U.S. patent application number 17/018814 was filed with the patent office on 2021-03-18 for foam compositions and uses thereof.
The applicant listed for this patent is NIKE, Inc.. Invention is credited to Hossein A. Baghdadi, Jay Constantinou, Joseph Thomas Muth, Brian G. Prevo, Bradley C. Tutmark.
Application Number | 20210078275 17/018814 |
Document ID | / |
Family ID | 1000005121960 |
Filed Date | 2021-03-18 |
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United States Patent
Application |
20210078275 |
Kind Code |
A1 |
Baghdadi; Hossein A. ; et
al. |
March 18, 2021 |
FOAM COMPOSITIONS AND USES THEREOF
Abstract
Components for articles of footwear and athletic equipment
including a foam are provided. The foam portion of the components
and articles include a composition which includes a thermoplastic
copolyester, the composition having a foam structure. A polymer
layer is provided on at least on surface of the foam portion. The
polymer layer can control or reduce the water uptake of the foam
portion. Methods of making the compositions, foams, and components
are provided, as well as methods of making an article of footwear
including one of the foam components. In some aspects, the foams
and foam components can be made by injection molding, or injection
molding followed by compression molding.
Inventors: |
Baghdadi; Hossein A.;
(Portland, OR) ; Constantinou; Jay; (Beaverton,
OR) ; Muth; Joseph Thomas; (North Plains, OR)
; Prevo; Brian G.; (Portland, OR) ; Tutmark;
Bradley C.; (Aloha, OR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
NIKE, Inc. |
Beaverton |
OR |
US |
|
|
Family ID: |
1000005121960 |
Appl. No.: |
17/018814 |
Filed: |
September 11, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62899696 |
Sep 12, 2019 |
|
|
|
62899688 |
Sep 12, 2019 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08J 9/122 20130101;
B29K 2067/00 20130101; C08J 2367/02 20130101; C08J 2205/05
20130101; A43B 17/14 20130101; C08J 2205/044 20130101; B29D 35/142
20130101; C08J 2201/03 20130101; B29D 35/0018 20130101; C08J
2203/08 20130101 |
International
Class: |
B29D 35/00 20060101
B29D035/00; C08J 9/12 20060101 C08J009/12; A43B 17/14 20060101
A43B017/14; B29D 35/14 20060101 B29D035/14 |
Claims
1. A cushioning element for an article of footwear, the cushioning
element comprising: a first foam, wherein the first foam is a
thermoplastic multicellular foam having an open cell foam
microstructure, an average cell size of from about 50 micrometers
to about 500 micrometers, and a specific gravity of about 0.15 to
about 0.25; wherein the first foam compositionally comprises a
first thermoplastic composition comprising one or more
copolyesters; wherein the first foam is the physically foamed
product of a single-phase solution of a supercritical fluid and the
first thermoplastic composition in a molten state; and wherein the
first thermoplastic composition of the first foam is free or
essentially free of nucleating agents, or is free or essentially
free of fillers, or is free or essentially free of both nucleating
agents and fillers.
2. The cushioning element of claim 1, wherein the cushioning
element is produced by the method comprising: forming a
single-phase solution of the first thermoplastic composition
comprising the one or more thermoplastic copolyesters and the
supercritical fluid, wherein the first thermoplastic composition is
molten in the single-phase solution; injecting the single-phase
solution into a mold cavity, the single-phase solution having an
injection temperature during the injecting; reducing pressure in
the mold cavity and foaming the molten first thermoplastic
composition, the single-phase solution having a foaming temperature
during the foaming, thereby forming a first foam, wherein the first
foam is a thermoplastic multicellular foam having an open cell foam
microstructure; solidifying the first foam; and removing the
solidified first foam from the mold cavity, forming the cushioning
element.
3. The cushioning element of claim 1, wherein the supercritical
fluid comprises supercritical carbon dioxide or supercritical
nitrogen.
4. The cushioning element of claim 1, wherein the supercritical
fluid is present in the single-phase solution in an amount of about
1 percent to about 3 percent by weight based on upon a total weight
of the single-phase solution.
5. The cushioning element of claim 1, wherein the foaming
temperature is from about the melting temperature of the
thermoplastic copolyester as determined by dynamic scanning
calorimetry to about 50 degrees centigrade above the tail
temperature of the thermoplastic copolyester as determined by
dynamic scanning calorimetry.
6. The cushioning element of claim 1, wherein the first foam has a
split tear greater than or equal to about 2.0 kg/cm, or an energy
efficiency greater than or equal to about 60 percent, or both.
7. The cushioning element of claim 1, wherein the first
thermoplastic composition of the first foam comprises less than 5
weight percent of dyes or pigments.
8. The cushioning element of claim 1, wherein the first
thermoplastic composition of the first foam further comprises a
non-polymeric component comprising all non-polymeric ingredients
present in the first thermoplastic composition, and the
non-polymeric component makes up less than one weight percent of
the first thermoplastic composition based on a total weight of the
first thermoplastic composition.
9. The cushioning element of claim 1, wherein the first
thermoplastic composition of the first foam comprises a polymeric
component comprising all polymers present in the first
thermoplastic composition, and the polymeric component makes up at
least 95 weight percent of the first thermoplastic composition
based on a total weight of the first thermoplastic composition.
10. The cushioning element of claim 1, wherein the first
thermoplastic composition of the first foam comprises a polymeric
component comprising all polymers present in the first
thermoplastic composition, and, in addition to the one or more
copolyesters, the polymeric component further comprises a
polyester, a polyolefin, or both.
11. The cushioning element of claim 1, wherein the first
thermoplastic composition of the first foam comprises a polymeric
component comprising all polymers present in the first
thermoplastic composition, and the polymeric component consists
essentially of the one or more copolyesters.
12. The cushioning element of claim 1, wherein the thermoplastic
copolyester comprises (a) a plurality of first segments, each first
segment derived from a dihydroxy-terminated polydiol; (b) a
plurality of second segments, each second segment derived from a
diol; and (c) a plurality of third segments, each third segment
derived from an aromatic dicarboxylic acid.
13. The cushioning element of claim 1, wherein the open cell foam
microstructure of the first foam comprises less than 10 percent of
cells having a closed cell foam microstructure.
14. The cushioning element of claim 1, wherein the open cell foam
microstructure of the first foam comprises less than 5 percent of
cells having a closed cell foam microstructure.
15. The cushioning element of claim 1, wherein the open cell foam
microstructure of the first foam comprises less than 1 percent of
cells having a closed cell foam microstructure.
16. The cushioning element of claim 1, wherein up to 80% of the
open cells in the first foam have an average diameter of from about
50 micrometers to about 200 micrometers.
17. The cushioning element of claim 1, wherein the thermoplastic
copolyester comprises, (a) a plurality of first copolyester units,
each first copolyester unit of the plurality comprising the first
segment derived from a dihydroxy-terminated polydiol and the third
segment derived from an aromatic dicarboxylic acid, wherein the
first copolyester unit has a structure represented by a formula 1:
##STR00027## wherein R.sub.1 is a group remaining after removal of
terminal hydroxyl groups from the poly(alkylene oxide) diol of the
first segment, wherein the poly(alkylene oxide) diol of the first
segment is a poly(alkylene oxide) diol having a number-average
molecular weight of about 400 to about 6000; and wherein R.sub.2 is
a group remaining after removal of carboxyl groups from the
aromatic dicarboxylic acid of the third segment; and (b) a
plurality of second copolyester units, each second copolyester unit
of the plurality comprising the second segment derived from a diol
and the third segment derived from an aromatic dicarboxylic acid,
wherein the second copolyester unit has a structure represented by
a formula 2: ##STR00028## wherein R.sub.3 is a group remaining
after removal of hydroxyl groups from the diol of the second
segment derived from a diol, wherein the diol is a diol having a
molecular weight of less than about 250; and wherein R.sub.2 is the
group remaining after removal of carboxyl groups from the aromatic
dicarboxylic acid of the third segment.
18. The cushioning element of claim 1, wherein the one or more
thermoplastic copolyesters comprise at least one thermoplastic
copolyester elastomer.
19. The cushioning element of claim 1, wherein the cushioning
element is a midsole or a heel cushion.
20. An article of footwear comprising the cushioning element of
claim 1.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to, and the benefit of,
co-pending U.S. provisional applications entitled "FOAM
COMPOSITIONS AND USES THEREOF" having Ser. Nos. 62/899,688 and
62/899,696, both filed on Sep. 12, 2019, the contents of which are
incorporated by reference in its entirety.
TECHNICAL FIELD
[0002] The present disclosure generally relates to foams formed of
thermoplastic copolyesters, and in particular to foams formed of
thermoplastic copolyesters which are suitable for the footwear and
related industries and uses thereof.
BACKGROUND
[0003] The design of athletic equipment and apparel as well as
footwear involves a variety of factors from the aesthetic aspects,
to the comfort and feel, to the performance and durability. While
design and fashion may be rapidly changing, the demand for
increasing performance in the market is unchanging. To balance
these demands, designers employ a variety of materials and designs
for the various components that make up athletic equipment and
apparel as well as footwear.
BRIEF DESCRIPTION OF THE DRAWINGS
[0004] Further aspects of the present disclosure will be readily
appreciated upon review of the detailed description, described
below, when taken in conjunction with the accompanying
drawings.
[0005] FIG. 1 is an elevation view of an article of footwear with a
sole component according to an aspect of the invention.
[0006] FIG. 2 is an exploded view of the sole component of the
article of footwear of FIG. 1.
[0007] FIG. 3 is a plan view of the bottom of the sole component of
the article of footwear of FIG.
[0008] FIG. 4 is a bottom view of an insert for use in a sole
component of an article of footwear.
[0009] FIG. 5 is a top view of the insert of FIG. 4 inserted in a
first portion to form a sole component.
[0010] FIG. 6 shows representative compression data for
representative foam plaques comprising a disclosed composition and
prepared using a disclosed method.
[0011] FIG. 7 shows a representative schematic illustrating a
disclosed foam component or article with a second thermoplastic
composition.
[0012] FIG. 8 shows a representative schematic illustrating a
disclosed method for determining peak and tail temperatures.
[0013] FIGS. 9A-9D show representative images of cross-sectional
views of foam plaques prepared using a disclosed thermoplastic
copolyester elastomer at different temperatures. Each image shows a
scalar bar (500 micrometers). Foamed plaques were prepared at the
following temperatures: 175 degrees centigrade (FIG. 9A); 190
degrees centigrade (FIG. 9B); 205 degrees centigrade (FIG. 9C); and
245 degrees centigrade (FIG. 9D).
[0014] FIG. 10 shows a representative image of a cross-sectional
view of a foam plaque prepared using a disclosed thermoplastic
copolyester elastomer 160 degrees centigrade. The image shows a
scalar bar (500 micrometers).
[0015] FIG. 11 shows representative coefficient of friction on a
wood surface data for various polymeric materials.
[0016] FIG. 12 shows representative coefficient of friction on a
concrete surface data for various polymeric materials.
[0017] FIG. 13 shows representative coefficient of friction on a
concrete surface data for various polymeric materials used in a
blown outsole.
[0018] FIG. 14 shows representative specific gravity data for
various polymeric materials in unfoamed samples and various foamed
samples.
DETAILED DESCRIPTION
[0019] The present disclosure is directed to a foam article which
includes a first component, i.e., a thermoplastic foam component
compositionally comprising a foamed first thermoplastic
composition. In other words, the foamed first thermoplastic
composition retains its thermoplastic properties, and can be
recycled by melting the foamed first thermoplastic composition, and
re-forming the first thermoplastic composition it into a new foamed
article or a new solid (i.e., unfoamed) article. The first
component is a foam component that includes a foamed first
thermoplastic composition having a multicellular foam structure. In
some aspects, the multicellular foam structure is an open-cell foam
structure. In other aspects, the multicellular foam structure is a
closed-cell foam structure. In some aspects, the foamed first
thermoplastic composition comprises one or more copolyesters, such
as, for example, one or more copolyester elastomers. In some
aspects, the first thermoplastic composition further comprises one
or more non-polymeric ingredients, such as a filler or a nucleating
agent or a pigment. The one or more non-polymeric ingredients can
comprise 5 weight percent or less of the first thermoplastic
composition based on the total weight of the first thermoplastic
composition. It has been found, for thermoplastic foams,
particularly thermoplastic foams compositionally comprising at
least one thermoplastic copolyester elastomer, that including low
levels (e.g., 5 weight percent or less) of non-polymeric
ingredients such as fillers, nucleating agents and pigments can
improve the consistency of the sizes of the cells in the
multicellular thermoplastic foam. In addition to improving the cell
structure, including low levels of non-polymeric ingredients in the
first thermoplastic composition can also increase recyclability of
the first thermoplastic composition, due to the high polymeric
content of these thermoplastic compositions. The first
thermoplastic composition can be free of or essentially free of
fillers. The first thermoplastic composition can be free of or
essentially free of nucleating agents. The first thermoplastic
composition can be free or essentially free of pigments. The first
thermoplastic composition can be free of or essentially free of
fillers and nucleating agents, or can be free or essentially free
of fillers, nucleating agents, and pigments. The first
thermoplastic composition can be free of or essentially free of
non-polymeric ingredients. The foam article is particularly useful
as a cushioning element.
[0020] In some aspects, the disclosed foam article also includes a
second component comprising a second thermoplastic composition. In
such aspects, the second component can be disposed on or in at
least a portion of the first component. The second component can
comprise a polymeric layer disposed on at least a portion of an
external surface of the foamed first thermoplastic composition of
the first component. The second component comprises a second
thermoplastic composition which retains its thermoplastic
properties and can be recycled by melting the second thermoplastic
composition, and re-forming the second thermoplastic composition it
into a new foamed article or a new solid (i.e., unfoamed) article.
As both the first component and the second component are formed of
thermoplastic compositions, the first and the second components
need not be separated before being recycled. For example, the foam
article can be recycled by grinding or shredding the entire article
and forming a molten polymeric composition which is a mixture of
both the first thermoplastic composition and the second
thermoplastic composition. The second thermoplastic composition can
comprise a thermoplastic elastomer or a thermoplastic vulcanizate
material. The second thermoplastic composition can comprise a one
or more thermoplastic styrene copolymer elastomers, including
styrene-ethylene-butene-styrene (SEBS) copolymer elastomers. The
second thermoplastic composition can comprise one or more
thermoplastic polyurethane elastomers, alone or blended with other
polymers such as, for example, an ethylene-vinyl alcohol copolymer,
or a styrene copolymer elastomer. Second thermoplastic compositions
which comprise a thermoplastic copolyester elastomer, or a
thermoplastic polyurethane elastomer, or a thermoplastic styrene
copolymer elastomer, or a thermoplastic vulcanizate material, have
been found to form strong thermal bonds with foamed first
thermoplastic compositions comprising one or more thermoplastic
copolyester elastomers. The foam article disclosed herein is
particularly useful as a cushioning element. The foam article
including the first component and the second component is
particularly useful as a cushioning element for an article of
footwear, apparel or sporting equipment. For example, the first
component of the foam article can be a midsole or a midsole
component. The second component of the foam article can be a ground
contacting component such as an outsole, or a protective element
such as a rand, on an article of footwear, which provides a greater
level of abrasion resistance or provides better traction or which
provides both, as compared to the first foam component alone. The
second component of the foam article can be a protective or
reinforcing layer or a containment layer on the first foam
component, such as when the first foam component is a cushioning
element, or in other applications. In some aspects, when the first
component has an open-cell foam structure, the second component can
be a water-resistant barrier to reduce or prevent water uptake by
the open cell structure of the foam.
[0021] Conventionally, vulcanized and peroxide-cured natural and
synthetic rubbers such as isoprene and polybutadiene rubbers have
been used to form durable, abrasion-resistant outer protective
layers for a wide variety of articles, including outsoles for
articles of footwear. Rubber formulations used for outsoles also
typically provide traction. One disadvantage of using conventional
rubber materials is that these materials are highly crosslinked
during the curing process, rendering the cured rubber a thermoset
material and making it difficult to recycle or reuse the cured
rubber. Also, it can be difficult to bond other materials to the
cured rubber. Both the rubber materials and foam materials
typically used in a wide variety of consumer good are highly
crosslinked materials, which are formed and cured separately and
then adhered to each other using an adhesive system. These adhesive
systems require several manually-intensive processing steps, such
as cleaning the surfaces, priming the surfaces, applying adhesive
to the surfaces, and pressing the surfaces together to bond
them.
[0022] It has been found that thermoplastic compositions (e.g.,
thermoplastic compositions comprising one or more thermoplastic
copolyester elastomer) can be used to form multicellular foams
having advantageous properties for use in consumer articles such as
cushioning elements. When foamed as described herein, these foams
retain thermoplastic properties, making it possible to readily
recycle and reuse the thermoplastic compositions. Additionally, it
has been found that these foams can be directly molded and foamed
onto other polymeric materials (i.e., onto second thermoplastic
compositions as described herein), which bonds the foam securely to
the second thermoplastic composition with a thermal bond without
the need for additional adhesives, or the manual process steps of
applying an adhesive system. The second thermoplastic composition
which is bonded to the thermoplastic foam can be a thermoplastic
elastomeric material, such as a second thermoplastic composition as
described herein. Examples of both second thermoplastic
compositions which, when used either in solid form or in a lightly
foamed form (e.g., having a specific gravity of 0.85 or greater)
have been found which both bond well to the thermoplastic
copolyester-based foam during a molding and foaming process, and
which also provide high levels of abrasion resistance and traction
under wet and dry conditions, are described herein. When the second
thermoplastic composition comprises a second thermoplastic
copolyester, the fact that the foam comprises a first thermoplastic
copolyester and that the polymeric layer comprises a second
thermoplastic copolyester composition provides the advantage that
the entire article can easily be melted down and the combined
material can be recycled. In this scenario, the second copolyester
composition can each individually include one or more of the same
individual copolyesters present in the first thermoplastic
copolyester composition, either in the same proportions or in
different proportions. Alternatively, the first and second
copolyester compositions can each individually comprise different
copolyesters.
[0023] The foam components disclosed herein are formed by foaming
thermoplastic compositions comprising one or more thermoplastic
elastomer into a multicellular foam having an open-cell or
closed-cell foam structure. In some examples, the one or more
thermoplastic elastomer can comprise or consist essentially of a
thermoplastic copolyester elastomer. Examples of thermoplastic
copolyester elastomers include polymers which have one or more
carboxylic acid moieties present in the polymeric backbone, on one
or more side chains, or both in the polymeric backbone and on one
or more side chains. The one or more carboxylic acid moieties of
the thermoplastic copolyester can include a free carboxylic acid, a
salt of a carboxylic acid, or an anhydride of a carboxylic acid. In
particular examples, the carboxylic acid moiety can be an acrylic
acid moiety or a methacrylic acid moiety. The foam articles
comprising a multicellular open-cell or closed-cell thermoplastic
foam and a polymeric layer of the present disclosure are suitable
for use in a variety of articles including for athletic equipment
and apparel, particularly footwear (e.g., athletic footwear
midsoles/outsoles). As discussed below, the multicellular open-cell
or closed-cell thermoplastic foam exhibits a unique balance of
properties such as high energy efficiency or energy return, and low
specific gravity. In some examples, the multicellular foam also
exhibits a high split tear and low compression set. The presence of
the polymeric layer on at least a portion of the exterior surface
of the foam can reduce or prevent liquid uptake by the
multicellular foams, particularly multicellular open-cell foams,
increasing their performance when used under conditions where the
foam come into contact with liquids. Furthermore, the thermoplastic
foam can also be reprocessed with minimal loss in physical
properties (e.g., for recycling), providing a solution for
materials sustainability.
[0024] The second thermoplastic composition of the polymeric layer
can be selected to allow the entire foam article to be recycled in
a single step, without the need to remove or separate the polymeric
layer from the foam. For example, the second thermoplastic
composition can comprise one or more thermoplastic
copolyesters.
[0025] The foam article or foam component comprising the
thermoplastic c foam can be formed by injection molding and foaming
the thermoplastic composition as described herein, or by injection
molding and foaming the thermoplastic composition as described
herein into a foam pre-form and subsequently compression molding
the foam-preform into a finished foam. The second thermoplastic
composition can be disposed onto an exterior surface of the foam
component during an injection molding and foaming process, in which
the first thermoplastic composition is injected into a mold which
includes the second thermoplastic composition, and the second
thermoplastic composition bonds to the foam during the molding
process. Alternatively or additionally, the second thermoplastic
composition can be disposed onto the exterior surface of the foam
component during a compression molding step, in which the foam
component is compression molded in a mold which includes the second
thermoplastic composition, and the second thermoplastic composition
bonds to the foam during the molding process. Alternatively or
additionally, the second thermoplastic composition can be disposed
onto the foam component after the foam component has been formed,
such as, for example, by vacuum forming a film comprising the
second thermoplastic composition to the foam component.
Articles Manufactured Using the Disclosed Foams.
[0026] Footwear 10 is an exemplary article of athletic footwear
that includes the thermoplastic foam of the present disclosure.
While illustrated as a running shoe, footwear 10 may alternatively
be configured for any suitable athletic performance, such as
baseball shoes, basketball shoes, soccer/global football shoes,
American football shoes, running shoes, cross-trainer shoes,
cheerleading shoes, golf shoes, and the like. While an athletic
shoe is exemplified in FIG. 1, it will be readily understood that
some of the terminology employed will also apply to other articles
of footwear or to other styles of shoe. Footwear 10 includes an
upper 12 and a sole component 14 secured to upper 12. Sole
component 14 can be secured to upper 12 by adhesive or any other
suitable means. As used herein, the sole component 14 can be a
monolithic component formed entirely of the thermoplastic foam
material as described herein, or a multi-component assembly formed
of a plurality of monolithic components, where at least one of the
monolithic components is formed entirely of the thermoplastic foam
material as described herein.
[0027] Footwear 10 has a medial, or inner, side 16 and a lateral,
or outer, side 18. For ease of discussion, footwear 10 can be
divided into three portions: a forefoot portion 20, a midfoot
portion 22, and a heel portion 24. Portions 20, 22, and 24 are not
intended to demarcate precise areas of footwear 10. Rather,
portions 20, 22, and 24 are intended to represent respective areas
of footwear 10 that provide a frame of reference during the
following discussion. Unless indicated otherwise, directional terms
used herein, such as rearwardly, forwardly, top, bottom, inwardly,
downwardly, upwardly, etc., refer to directions relative to
footwear 10 itself. Footwear 10 is shown in FIG. 1 in a
substantially horizontal orientation, as it would be positioned on
a horizontal surface when worn by a wearer. However, it is to be
appreciated that footwear 10 need not be limited to such an
orientation. Thus, in FIG. 1, rearwardly is toward heel portion 24
(to the right as seen in FIG. 1), forwardly is toward forefoot
portion 20 (to the left as seen in FIG. 1), and downwardly is
toward the bottom of the page as seen in FIG. 1. Top refers to
elements toward the top of the view in FIG. 1, while bottom refers
to elements toward the bottom of the view in FIG. 1. Inwardly is
toward the center of footwear 10, and outwardly is toward the outer
peripheral edge of footwear 10.
[0028] The component can be a sole component, such as a sole
component 14 depicted in FIGS. 1-5, that includes a thermoplastic
foam, including a thermoplastic copolyester foam, as described
herein. The component can be an insert such as insert 36 or insert
60 depicted in FIGS. 4-5 that includes a thermoplastic foam
described herein. The sole components and inserts for sole
components can be made partially or entirely of a thermoplastic
foam described herein. Any portion of a sole component or an insert
for a sole component can be made of a thermoplastic foam described
herein. For example, first portion 26 of the sole component
(optionally including the ground engaging lower surface 44, such as
the plurality of projections 46 and/or the groove 48 surrounding
the projections), the entire insert 36, portions 62 or 64 of insert
60, a separate outsole component, or any combination thereof, can
include a thermoplastic foam as described herein. The sole
components and inserts can be made by foaming thermoplastic
compositions as described herein, for example by injection molding
or by injection molding, optionally followed by compression
molding, as described herein. In some aspects, the thermoplastic
foams can be formed by physical foaming of the thermoplastic
compositions. The thermoplastic foams and components can
demonstrate improved physical properties including one or more of
an enhanced energy efficiency or energy return, an enhanced split
tear, a decreased specific gravity, or a combination thereof.
[0029] Sole component 14, which is generally disposed between the
foot of the wearer and the ground, provides attenuation of ground
reaction forces (i.e., imparting cushioning), traction, and may
control foot motions, such as pronation. As with conventional
articles of footwear, sole component 14 can include an insole (not
shown) located within upper 12. In some aspects, the sole component
is an insole or sockliner or is a multi-component assembly
including an insole or sockliner, can further include an insole or
sockliner located within the upper, where the insole or sockliner
is formed entirely or partially of a thermoplastic foam described
herein. Articles of footwear described herein can include an insole
or sockliner formed entirely or partially of a thermoplastic foam
described herein.
[0030] As can be seen in FIG. 2, sole component 14 consists of a
first portion 26 having an upper surface 27 with a recess 28 formed
therein. Upper surface 27 is secured to upper 12 with adhesive or
other suitable fastening means. A plurality of substantially
horizontal ribs 30 is formed on the exterior of first portion 26.
In certain aspects, ribs 30 extend from a central portion of
forefoot portion 20 on medial side 16 rearwardly along first
portion 26, around heel portion 24 and forwardly on lateral side 18
of first portion 26 to a central portion of forefoot portion
20.
[0031] First portion 26 provides the external traction surface of
sole component 14. In certain aspects it is to be appreciated that
a separate outsole component could be secured to the lower surface
of first portion 26. When a separate outsole component is secured
to the lower surface of first portion 26, the first portion 26 is a
midsole component. In some aspects, the article is a midsole
component for an article of footwear. In other aspects, the article
is a combination midsole-outsole component for an article of
footwear.
[0032] The article can be an insert. An insert 36 can be received
in recess 28. As illustrated in FIG. 2, insert 36 can provide
cushioning or resiliency in the sole component. First portion 26
can provide structure and support for insert 36. In such aspects,
first portion 26 can be formed of a material of higher specific
gravity and/or hardness as compared to insert 36 such as, for
example, non-foam materials including rubber and thermoplastic
polyurethane, as well as foam materials. In certain aspects, insert
36 can be formed of a thermoplastic foam as disclosed herein.
[0033] Insert 36 has a curved rear surface 38 to mate with curved
rear surface 32 of recess 28 and a transverse front surface 40 to
mate with transverse front surface 34 of recess 28. An upper
surface 42 of insert 36 is in contact with and secured to upper 12
with adhesive or other suitable fastening means. For example, when
there is an insert 36, a recess 28 can extend from heel portion 24
to forefoot portion 20. In certain aspects, the rear surface 32 of
recess 28 is curved to substantially follow the contour of the rear
of heel portion 24 and the front surface 34 of recess 28 extends
transversely across first portion 26.
[0034] As seen best in FIG. 3, a ground engaging lower surface 44
of first portion 26 includes a plurality of projections 46. Each
projection 46 is surrounded by a groove 48. A plurality of
transverse slots 50 are formed in lower surface 44, extending
between adjacent projections 46. A longitudinal slot 52 extends
along lower surface 44 from heel portion 26 to forefoot portion
20.
[0035] FIGS. 4 and 5 show bottom and top views of an insert 60
which can be used in a sole component as described herein. Insert
60 is similar to insert 36, but as illustrated in FIGS. 4 and 5,
insert 60 is formed of two types of materials 62 and 64, where at
least one of the materials is a thermoplastic foam as disclosed
herein. FIG. 4 shows a bottom view of insert 60, while FIG. 5 shows
a top view of insert 60 formed of two types of materials 62 and 64,
with the insert placed inside a first portion 66 to form a sole
component 14. Inserts with more than two types of materials, at
least one of which is a thermoplastic foam as disclosed herein, can
also be used. In the example illustrated in FIGS. 4 and 5, a
portion of a first material 62 can be used in the heel region of
the insert, and a portion of a second material 64 can be used in
the toe region of the insert. A higher specific gravity material
can be used to support the heel region, while a lower specific
gravity material can be used to support the toe region. For
example, the specific gravity of the first material can be at least
0.02 units greater than the specific gravity of the second
material. The shape of the portions of the two materials 62 and 64
of the insert can be any suitable shape. For example, the heel
region can be in the shape of a wedge. Inserts formed of two types
of materials can be useful in running shoes, as well as in
basketball shoes.
[0036] In the articles comprising the foam articles or components
including the thermoplastic foam, for example a thermoplastic
copolyester foam having an open cell structure, and the layer of a
second thermoplastic composition disposed on at least a portion of
an exterior surface of the foam as described herein. Referring to
FIG. 7, in an aspect, a foam component 70 can have a foam portion
72, comprising a polymeric material that comprises a thermoplastic
copolyester multicellular foam having an open-cell or closed-cell
foam structure. The foam portion 72 has one or more sides that,
when the foam component 70 is disposed in an article such as an
article of footwear, are oriented toward an exterior facing side or
surface of the article (e.g. an outer peripheral edge of article of
footwear 10 of FIG. 1). A polymeric layer 74 is disposed on at
least a portion of an exterior facing side or surface of the foam
portion 72. The polymeric layer 74 comprises a second thermoplastic
composition that may be the same as or different from the first
thermoplastic composition of the foam portion 72. According to
aspects, the polymeric layer 74 is not a foamed material. The
polymeric layer 74 can function as an outsole, for example, which
can provide improved abrasion resistance on one or more surfaces of
the foam portion 72.
[0037] In some aspects, the article can be something other than a
sole component. For example, the article can be an upper or an
upper component. An upper component refers to a piece that is
stitched or otherwise joined with one or more other pieces to form
an upper portion for an article of footwear. The materials in the
upper generally contribute to characteristics such as
breathability, conformability, weight, and suppleness or softness.
A lower component refers to a piece that is joined with one or more
other pieces to form the lower portion of an article of footwear.
The lower can include, for example, the outsole and midsole. The
choice of outsole materials and design will contribute, for
instance, to the durability, traction, as well as to the pressure
distribution during use. The midsole materials and design
contribute to factors such as the cushioning and support. Grindery
components include all of the additional components that can be
attached to the upper, lower, or both. Grindery components can
include, for example, eyelets, toe puffs, shanks, nails, laces,
velcro, catches, backers, linings, padding, heel backings, heel
foxings, toe caps, etc.
[0038] The upper can be a lasted upper. A "lasted upper," as used
herein, refers to an upper that is formed into the shoe shape prior
to attachment to the sole by one or more mechanical means. The
lasted upper can include a heel counter formed to shape the heel of
the upper. The lasted upper can include a strobel or a strobel
board attached to the upper, typically via a strobel stitch.
[0039] While the thermoplastic foams described herein, including
the thermoplastic copolyester foams described herein, can be used
for making any of a variety of components, including a variety of
components for an article of footwear, in particular aspects the
components include a midsole, an outsole, an insole, or an insert.
Additional articles can include a tongue padding, a collar padding,
and a combination thereof. As described above and detailed more
completely below, the articles comprising the thermoplastic foams
described herein can exhibit a unique balance of beneficial
physical properties such as high energy efficiency or energy
return, and low specific gravity. Furthermore, the thermoplastic
foam can also be reprocessed with minimal loss in physical
properties (e.g., for recycling), providing a solution for
materials sustainability.
[0040] In some instances a disclosed article can comprise a first
component comprising a foamed thermoplastic composition, such as a
foamed thermoplastic copolyester composition, and a second
component comprising a second thermoplastic composition. An article
comprising the first component with the second thermoplastic
composition can be characterized by good bonding strength between
the second thermoplastic composition and the foam component. The
ply adhesion strength between the second thermoplastic composition
and the foam component is greater than 2.5 kg force/centimeter or
greater than 3.0 kg force/centimeter, when determined using the Ply
Adhesion Test method described herein.
First Components
[0041] The first component is a foam component comprising a
thermoplastic composition comprising one or more thermoplastic
elastomers. In one aspect, the thermoplastic composition is a
thermoplastic copolyester composition comprising one or more
thermoplastic copolyester elastomers. The first component can be a
component such as, but not limited to, a component of a midsole or
a midsole component. It is understood that the first component
comprises a foamed thermoplastic composition. For example, a
thermoplastic composition includes at least 90 weight percent, or
at least 95 weight percent, or at least 99 weight percent of
thermoplastic polymers, such as, for example, the thermoplastic
copolyester disclosed herein, based on the total weight of the
thermoplastic composition. In some instances, the polymeric
component of the thermoplastic composition, which includes all the
polymers present in the thermoplastic composition, includes or
consists essentially of one or more thermoplastic elastomers, such
as one or more of the disclosed thermoplastic copolyester
elastomers. In other words, the only polymers present in the
thermoplastic composition can be thermoplastic elastomers, or the
only polymers present in the thermoplastic composition can be
thermoplastic copolyester elastomers.
Second Components
[0042] The second component comprising a second thermoplastic
composition can be a component such as, but not limited to, a
component of an outsole or an outsole component. It is understood
that the second component can be foamed, partially foamed, or
essentially unfoamed. In some instances the second component is a
foamed component, i.e., a second foam component. In other
instances, the second component is an unfoamed component, i.e., a
solid component. In some instances, the second thermoplastic
composition is a disclosed thermoplastic composition, such as a
thermoplastic copolyester composition. For example, a second
thermoplastic composition can include at least 90 weight percent,
or at least 95 weight percent, or at least 99 weight percent of
thermoplastic elastomers as disclosed herein, based on the total
weight of the second thermoplastic composition. In some instances,
the second thermoplastic composition includes a polymeric component
consisting essentially of one or more disclosed thermoplastic
elastomers, including one or more disclosed copolyester elastomers.
In other instances, the second thermoplastic composition can
include a polymeric component which is essentially free of a
thermoplastic copolyester, e.g., the polymeric component can
consist essentially of a thermoplastic polyurethane elastomer or a
thermoplastic vulcanizate material as disclosed herein. In still
other instances, a second thermoplastic composition can include a
mixture of a disclosed thermoplastic copolyester and a polymeric
material that is not a disclosed thermoplastic copolyester, e.g., a
thermoplastic elastomer or thermoplastic vulcanizate material.
Characteristics of Thermoplastic Copolyester Foam Components.
[0043] As discussed herein above, a first component can be foam
component, i.e., a first foam component, comprising a disclosed
first thermoplastic composition. In some instances, a second
component can be foam component, i.e., a second foam component,
comprising a disclosed second thermoplastic composition. That is,
each of the first or second foam components can independently
comprise a disclosed thermoplastic foam component. It is understood
herein throughout that reference to a "thermoplastic foam" is
inclusive of a first foam component, a second component, or both a
first and a second foam components, and that each of the first and
second foam components can independently comprise one or more
disclosed thermoplastic compositions as disclosed herein below. A
disclosed thermoplastic foam can exhibit various beneficial
properties.
[0044] For example, the thermoplastic foam can exhibit a beneficial
split tear, for example a high split tear for a sole component in
an article of footwear. In some aspects, the thermoplastic foam can
have a split tear value of greater than about 1.5
kilogram/centimeter (kg/cm), or greater than about 2.0 kg/cm, or
greater than about 25 kg/cm, when determined using the Split Tear
Test Method described herein. In some aspects, the thermoplastic
foam can have about 1.0 kg/cm to 4.5 kg/cm, about 1.5 kg/cm to 4.0
kg/cm, about 2.0 kg/cm to 4.0 kg/cm, about 2.0 kg/cm to 3.5 kg/cm,
or about 2.5 kg/cm to 3.5 kg/cm, when determined using the Split
Tear Test method described herein. In some aspects, the
thermoplastic foam is injection molded, or is injection molded and
subsequently compression molded in a separate compression mold
having different dimensions than the mold used in the injection
molding step. The thermoplastic foam can have a split tear of about
0.08 kg/cm to 4.0 kg/cm, about 0.9 kg/cm to 3.0 kg/cm, about 1.0 to
2.0 kg/cm, about 1.0 kg/cm to 1.5 kg/cm, or about 2 kg/cm. In some
aspects, the thermoplastic foam the thermoplastic foam is injection
molded, and has have a split tear of about 0.07 kg/cm to 2.0 kg/cm,
or about 0.8 kg/cm to 1.5 kg/cm, or about 0.9 to 1.2 kg/cm, about
1.5 kg/cm to 2.2 kg/cm.
[0045] The specific gravity of a disclosed thermoplastic foam is
also an important physical property to consider when using a foam
for in an article of footwear or athletic equipment. As discussed
above, the thermoplastic foam of the present disclosure exhibits a
low specific gravity, which beneficially reduces the weight of
midsoles or other components containing the thermoplastic foam. The
thermoplastic foams of the present disclosure can have a specific
gravity of from 0.02 to 0.22, or of from 0.03 to 0.12, or of from
0.04 to 0.10, or from 0.11 to 0.12, or from 0.10 to 0.12, from 0.15
to 0.2; 0.15 to 0.30, when determined using the Specific Gravity
Test Method described herein. Alternatively or in addition, the
thermoplastic foam can have a specific gravity of from 0.01 to
0.10, or of from 0.02 to 0.08, or of from 0.03 to 0.06; 0.08 to
0.15; or from 0.10 to 0.12, when determined using the Specific
Gravity Test Method described herein. For example, the specific
gravity of the thermoplastic foam can be from or from 0.15 to 0.20,
or can be from 0.10 to 0.12. The thermoplastic foam can be
injection molded, or can be injection molded and subsequently
compression molded. In some aspects, the thermoplastic foam has a
specific gravity of about 0.7 or less, or 0.5 or less, or 0.4 or
less, or 0.3 or less, when determined using the Specific Gravity
Test Method described herein. In some aspects, the thermoplastic
foam, including thermoplastic foam present in midsoles and midsole
components, can have a specific gravity of about 0.05 to 0.25,
about 0.05 to 0.2, about 0.05 to 0.15, about 0.08 to 0.15, about
0.08 to 0.20, about 0.08 to 0.25, or about 0.1 to 0.15, when
determined using the Specific Gravity Test Method described herein.
In some aspects the thermoplastic foam has a specific gravity of
about 0.15 to 0.3, about 0.2 to 0.35, or about 0.15 to 0.25, when
determined using the Specific Gravity Test Method described
herein.
[0046] In a particular example, the first component is a cushioning
element for an article of footwear, and the thermoplastic foam of
the first component has a specific gravity from 0.05 to 0.25, or
from 0.17 to 0.22, or from 0.18 to 0.20, when determined using the
Specific Gravity Test Method described herein. The thermoplastic
foam can be a physically foamed thermoplastic foam, such as
physically foamed thermoplastic foam formed using a single-phase
solution of a supercritical fluid and a thermoplastic composition
described herein. The thermoplastic composition can be a
thermoplastic copolyester composition comprising one or more
thermoplastic copolyester elastomer.
[0047] The thermoplastic foam portion of the article or component
of an article can have a stiffness of about 200 kPa to about 1000
kPa, or about 300 to about 900 kPa or about 400 to about 800 kPa or
about 500 to about 700 kPa, when determined using the Cyclic
Compression Test with the 45-millimeter diameter cylindrical
sample. The thermoplastic foam portion of the article or component
of an article can have a stiffness of about 200 kPa to about 1000
kPa, or about 300 to about 900 kPa or about 400 to about 800 kPa or
about 500 to about 700 kPa, when determined using the Cyclic
Compression Test with the footform sample. The thermoplastic foam
article or article component can be formed by injection molding, or
by injection molding and subsequently compression molding.
[0048] The thermoplastic foam portion of the article or component
of an article can have an Asker C durometer hardness of from about
30 to about 50, or from about 35 to about 45, or from about 30 to
about 45, or from about 30 to about 40, when determined using the
Durometer Hardness Test described herein
[0049] The energy input of a foam is the integral of the force
displacement curve during loading of the foam during the Cyclic
Compression test. The energy return of a foam is the integral of
the force displacement curve during unloading of the foam during
the Cyclic Compression test. The thermoplastic foam portion of the
article or component of an article can have an energy return of
about 200 millijoules (mJ) to about 1200 mJ, or from about 400 mJ
to about 1000 mJ, or from about 600 mJ to about 800 mJ, when
determined using the Cyclic Compression Test with a 45-millimeter
diameter cylindrical sample.
[0050] The energy efficiency, a measure of the percentage of energy
the thermoplastic foam portion of the article or component returns
when it is released after being compressed under load, can provide
improved performance for athletic shoes, e.g. for reducing energy
loss or dissipation when running. This is especially true for
running and other athletic shoes. In some aspects, the
thermoplastic foam portion of the articles and components provided
herein have an energy efficiency of about 50 percent to 97 percent,
about 60 percent to 95 percent, about 60 percent to 90 percent,
about 60 percent to 85 percent, about 65 percent to 85 percent, or
about 70 percent to 85 percent, when determined using the Cyclic
Compression Test with a 45-millimeter diameter cylindrical
sample.
[0051] By modifying the conditions and components used to make the
foams one or more properties of the foam can be modified. In one
aspect, when the foam is the physically foamed product of a
single-phase solution of a supercritical fluid and the first
thermoplastic composition in a molten state, the resulting foam can
have a reduced specific gravity as well as high energy efficiency
or energy return. In one aspect, additives such as nucleating
agents and fillers are not used or are used at low levels, as it
has been found that the use of non-polymeric ingredients can
decrease the consistency of the size of the cells in the
multicellular foam, particularly when foaming thermoplastic
copolyester compositions. Additionally, the inclusion of higher
levels of non-polymeric additives such as fillers, nucleating
agents and pigments, can make recycling the foams more
challenging.
[0052] In other aspects, the temperature at which the molten first
thermoplastic composition is foamed can modify the properties of
the foam. In one aspect, the foaming temperature of the
thermoplastic composition, i.e., the temperature of the
thermoplastic composition at the point that foaming is initiated,
is from about the melting temperature of the thermoplastic
composition to about 50 degrees centigrade, or about 40 degrees
centigrade, or about 30 degrees centigrade, or about 20 degrees
centigrade above the tail temperature of the thermoplastic
composition. Alternatively, the foaming temperature can be from the
crystallization temperature of the thermoplastic composition to
about 50 degrees centigrade, or about 40 degrees centigrade, or
about 30 degrees centigrade, or about 20 degrees centigrade above
the crystallization temperature of the thermoplastic composition.
The melting temperature, the tail temperature, and the
crystallization temperature of the thermoplastic composition can be
determined using differential scanning calorimetry (DSC). In this
aspect, properties such as reduced specific gravity, consistent
foam cell size, and/or high energy efficiency or energy return can
be achieved, particularly when foaming thermoplastic copolyester
compositions.
[0053] The resulting foams can have a multicellular closed cell or
open cell foam structure. Cells are the hollow structures formed
during the foaming process, in which bubbles are formed in the
polymeric material by the blowing agents. The cell walls are
generally defined by the polymeric material. The cells can be
entirely enclosed by the polymeric material, or they can be at
least partially open, e.g., interconnected with one or more
adjacent cells. "Closed cell" structures refer to structures in
which at least 60 percent or more of the cells are closed cells, or
at least 80 percent of the cells are closed cells, or at least 90
percent of the cells are closed cells, or at least 95 percent of
the cells are closed cells. As described herein "open cell"
structures refers to foam structures in which less than about 15
percent or less than about 10 percent or 5 percent or less than 4
percent, or less than 3 percent or less than 1 percent of the cells
are closed cells.
[0054] The disclosed thermoplastic foams may have an average cell
diameter of from about 50 micrometers to about 1000 micrometers, or
from about 80 micrometers to about 800 micrometers, or from about
100 micrometers to about 500 micrometers. The disclosed
thermoplastic foams can have an average cell diameter of from about
50 micrometers to about 500 micrometers, or from about 70
micrometers to about 300 micrometers, or from about 80 micrometers
to about 200 micrometers, or from about 50 micrometers to about 200
micrometers.
[0055] The proportion of cells in the foam having an average cell
diameter of about 50 micrometers to about 300 micrometers is
preferably not less than 40 percent relative to all the cells, or
not less than 50 percent or not less than 60 percent relative to
all the cells. If the proportion of cells is less than 40 percent,
the cell structure will tend to be nonuniform and/or have a coarse
cell structure. As used herein, a "coarse cell structure" refers to
a foam structure in which the average cell diameter is greater than
1 millimeter, and/or for greater than 20 percent of the cells, a 1
millimeter line drawn across the largest dimension of the cell,
will not cross a cell wall or a strut (i.e., an open cell wall or
portion thereof).
[0056] The number of open cells and/or closed cells and cell
diameter of the cells of the foam can be determined visually, for
example by capturing an image of a cut surface with a camera or
digital microscope, determining the number of cells, number of open
cells and/or number of closed cells, and determining the average
cell diameters of a cross-section of a sample of the foam. For
cells of a closed cell foam, the diameters are determined from cell
wall to cell wall. For cells of an open cell foam, the diameters
are determined between planes formed by the intersections of
supporting struts between cells (i.e., an open cell wall or portion
thereof). In one aspect, a portion of the foam can be cut and the
cells in the cross-sectional area can be examined visually under a
microscope or by software to determine the percentage of the cells
within a region which are open or closed and to determine the
average size of the cells. In one aspect, a sample from a region of
the foam article which represents from about 75 percent to about
100 percent of the maximum thickness of the foam article can be
used to determine the nature and size of the cells.
Methods of Manufacturing Disclosed Foams.
[0057] In some examples, the disclosed foams can be prepared by
various methods as disclosed herein and as known in the art. That
is, disclosed articles or components of articles such as midsoles,
midsole components, inserts and insert components can be prepared
by injection molding a melt composition comprising a first
thermoplastic composition as described herein using a physical
blowing agent and/or chemical blowing agent. A disclosed foam
component, e.g., a disclosed first foam component or a disclosed
foam second foam component, can be prepared by the methods
disclosed herein below.
[0058] Disclosed herein are methods for making a foam article or
component, the method comprising: forming a mixture of molten first
thermoplastic composition and a blowing agent, wherein the first
thermoplastic composition comprises a disclosed thermoplastic
elastomer; injecting the mixture into a mold cavity; foaming the
molten first thermoplastic composition, thereby forming a foamed
molten first thermoplastic composition; solidifying the foamed
molten first thermoplastic composition, thereby forming a foam
article having a multicellular foam structure; and removing the
foam article from the mold cavity. In one aspect, the first
thermoplastic composition is a first thermoplastic copolyester
composition comprising a disclosed thermoplastic copolyester
elastomer, and the multicellular foam structure is an open cell
multicellular foam structure.
[0059] Also disclosed are methods for making a foam article or
component, the method comprising: forming a mixture of molten first
thermoplastic composition and a blowing agent, wherein the first
thermoplastic composition comprises a disclosed thermoplastic
elastomer; injecting the mixture into a mold cavity; foaming the
molten first thermoplastic composition, thereby forming a foamed
molten first thermoplastic composition; solidifying the foamed
molten first thermoplastic composition, thereby forming a foam
article having a multicellular foam structure; and removing the
foam article from the mold cavity; wherein, during the injecting,
the mixture has an injection temperature; and wherein the injection
temperature is from about the melting temperature of the
thermoplastic elastomer to about 50 degrees centigrade above the
tail temperature of the thermoplastic composition. In one aspect,
the first thermoplastic composition is a first thermoplastic
copolyester composition comprising a disclosed thermoplastic
copolyester elastomer, and the multicellular foam structure is an
open cell multicellular foam structure.
[0060] Also disclosed are methods for making a foam article or
component, the method comprising: forming a mixture of molten first
thermoplastic composition and a blowing agent, wherein the first
thermoplastic composition comprises a disclosed thermoplastic
elastomer; injecting the mixture into a mold cavity; foaming the
molten first thermoplastic composition, thereby forming a foamed
molten first thermoplastic composition; solidifying the foamed
molten first thermoplastic composition, thereby forming a foam
article having a multicellular foam structure; and removing the
foam article from the mold cavity; wherein the foaming occurs at a
foaming temperature; and wherein the foaming temperature is from
about the melting temperature of the thermoplastic elastomer to
about 50 degrees centigrade above the tail temperature of the
thermoplastic elastomer. In one aspect, the first thermoplastic
composition is a first thermoplastic copolyester composition
comprising a disclosed thermoplastic copolyester elastomer, and the
multicellular foam structure is an open cell multicellular foam
structure.
[0061] Dynamic scanning calorimetry (DSC) is used to determine the
melting temperature, the tail temperature, and the crystallization
temperature of a thermoplastic elastomer, and an exemplary method
is described herein below. Briefly, 10-30 mg pieces of undried
resin pellets are cycled from -90 degrees centigrade to 225 degrees
centigrade at 20 degrees centigrade/min and cooled to -90.degree.
C. at 10.degree. C./min. In some instances, experiments are run
using a heat-cool-heat profile with a ramp rate of 10 degrees
centigrade per min, minimum temperature of 0 degrees centigrade and
maximum temperature of 250 degrees centigrade. Analyses should be
determined in duplicate and averaged. The melting temperature and
crystallization temperature values are recorded. The melt "peak" is
and the crystallization "peak" are identified as the local maximum
of the melting or crystallization. If there is more than one peak
in the DSC curve, the peak occurring at hotter temperatures is
chosen as the temperature reference. The tail is identified as the
intersection of the tangent of the line of the higher temperature
side of the peak with the extrapolated baseline. A schematic
illustrating the method for determining melting peak and tail
temperatures is shown in FIG. 8.
[0062] For example, the disclosed foamed first thermoplastic
compositions can be prepared using a suitable extruder. An extruder
(e.g., single or twin screw) can be used to provide a composition.
The extruder can have a motor to turn a screw inside the extruder.
Extruder may be a single screw or twin screws made of individual
elements of various sizes and pitches appropriate for mixing or
kneading the specific materials used. In some examples, the
extruder has a twin screw.
[0063] The various components that make up the first thermoplastic
composition used to form the thermoplastic foam of the various
examples described herein are added into the extruder through one
or more port. The various components can be added as a melt or as
appropriately-sized solid particles, for example chips or pellets,
that are melted in section as they are mixed in the barrel of the
extruder. The contents of the extruder can be heated to melt the
composition. A supercritical fluid can be added into the melt as a
physical blowing agent. In particular examples, the thermoplastic
foam is prepared by using a physical blowing agent which foams the
thermoplastic composition after the pressure is dropped to a level
at which the supercritical fluid phase transitions into a gas, such
as after it exits the extruder, and the thermoplastic foam is thus
substantially free of a chemical blowing agent or decomposition
product thereof.
[0064] The compositions can be added as a melt at a temperature
close to the melting temperature of the first thermoplastic
composition.
[0065] If a chemical blowing agent is used, the processing
temperature within the extruder used can be sufficiently below the
temperature that would trigger the blowing agent. In order to foam
the first thermoplastic composition, the temperature near the exit
of the extruder or within the barrel of the injector can be
increased in order to heat the thermoplastic composition to a
temperature close to or at the triggering temperature of a chemical
blowing agent, thereby producing a chemically foamed thermoplastic
foam as the composition exits the extruder (e.g., as the
composition is injected into an injection mold).
[0066] Alternatively or in addition, a physical blowing agent can
be used to foam the composition to form a physically foamed
thermoplastic foam, or a physically and chemically foamed
thermoplastic foam. For example, a supercritical fluid such as
supercritical carbon dioxide or supercritical nitrogen can be mixed
with the molten first thermoplastic composition in the barrel of
the extruder to form a single-phase solution. As used herein,
"single-phase" refers to a composition where two or more components
are present where there is no discernible phase separation amongst
the components. For example, when a supercritical fluid is mixed
with molten first thermoplastic composition, the resulting
composition is a homogeneous solution where droplets of
supercritical fluid are not detected. As the single-phase solution
exits the extruder or the injector, the pressure drop between the
higher pressure in the extruder or injector and the lower pressure
outside the extruder or injector causes the supercritical fluid to
transition to the gas phase and foam the first thermoplastic
composition.
[0067] Various examples include methods of manufacturing an article
of footwear or components for an article of footwear. In some
examples, the methods of manufacturing an article of footwear
include injection molding a first thermoplastic composition to form
a thermoplastic foam described herein to produce a foam article or
component of an article, such as an article of footwear. The
article or component of an article can be a midsole or a component
of a midsole, and the method can include providing an upper and an
outsole for an article of footwear; and combining the midsole or
midsole component, the upper, and the outsole to make an article of
footwear. In some examples, the method of manufacturing the article
of footwear includes combining an article comprising a
thermoplastic foam and an upper to make an article of footwear.
[0068] The articles or components of articles such as midsoles,
midsole components, inserts and insert components can be prepared
by injection molding a molten first thermoplastic composition
described herein using a physical blowing agent. The injection
molding can use a screw-type injector that allows for maintaining
and controlling the pressure in the injector barrel. The injection
molding machine can allow metering and delivering a supercritical
fluid such as supercritical carbon dioxide or nitrogen into the
composition prior to injection. The supercritical fluid can be
mixed into the first thermoplastic composition within the injection
barrel to form a single-phase solution, and then the single-phase
solution can be injected into the mold cavity. A drop in pressure
within the mold cavity can cause the supercritical fluid to expand
to create cell nuclei and expand the cells to form the foam within
the mold cavity. The injection molding system used to form the
thermoplastic foam can include a physical foaming process, such as,
for example the "MUCELL" process (Trexel, Wilmington, Del.,
USA).
[0069] The thermoplastic r foams described herein can be made using
a process that involves impregnating a first thermoplastic
composition (e.g., at or above a softening temperature of the
composition) with a physical blowing agent at a first concentration
or first pressure. As used herein, the term "impregnating"
generally means dissolving or suspending a physical blowing agent
in a first thermoplastic composition. The impregnated first
thermoplastic composition can then be foamed, or can be cooled
(when applicable) and re-softened (when applicable) for foaming at
a later time. In particular examples, the impregnated first
thermoplastic composition is a single-phase solution comprising
supercritical carbon dioxide or nitrogen and the molten
thermoplastic composition.
[0070] The impregnated first thermoplastic composition is foamed by
reducing the solubility of the physical blowing agent in the
single-phase solution through pressure or temperature changes. The
reduction in solubility of the physical blowing agent can release
additional amounts (e.g., to create a secondary expansion of an
originally-formed foam) of the impregnated physical blowing agent
from the first thermoplastic composition, to further foam the first
thermoplastic composition, forming a thermoplastic foam having a
multicellular foam structure.
[0071] In addition to injection molding, the thermoplastic foam of
the present disclosure can be foamed and molded using various
processes known in the art. For example, the thermoplastic foam can
be formed into slab foam, filament or strand foams, particulate
(e.g., bead) foams of various shapes and sizes, etc. These various
forms of foam can then be used in different ways. For example, like
injection molded foam, slab foam and filament or strand foam can be
used directly as a finished foam article, or can be shaped (e.g.,
cut, buffed, or trimmed) to form a finished foam article, or can be
compression molded to form a finished foam article. Optionally, the
thermoplastic foam can be subjected to annealing processes as part
of forming the finished foam article. Pellets of the compositions
can be used to form individual particulate thermoplastic foams, or
can be foamed and molded to form unitary molded foam articles
composed of individual portions of foam affixed to each other.
[0072] The thermoplastic foams of the various examples described
herein may be further shaped or molded by any of the methods known
for forming articles from thermoplastic materials. Optionally, the
thermoplastic foams of the present disclosure which have been
foamed using any suitable foaming process (e.g., foaming using a
physical and/or chemical blowing agent), including by injection
molding using only a physical blowing agent, can then be
compression molded to form a compression molded foam.
[0073] The thermoplastic foam of the present disclosure can be
prepared by a process comprising (i) softening a first
thermoplastic composition (e.g., by heating at a first temperature
at or above a softening temperature of the composition); (ii)
simultaneously or sequentially with the softening (when
applicable), contacting the first thermoplastic composition with a
first concentration or first pressure of a physical blowing agent
sufficient to drive an amount of the physical blowing agent into
the first thermoplastic composition or combine the physical blowing
agent with the first thermoplastic composition; (iii) changing the
concentration or pressure (e.g., decreasing the pressure or
concentration) of the physical blowing agent to a second
concentration or second pressure that is effective to foam the
first thermoplastic composition, thereby forming a thermoplastic
foam (e.g., a thermoplastic foam having a multicellular structure);
and, (iv) following the changing, cooling (when applicable) the
thermoplastic foam to (e.g., cooling to a temperature below the
softening temperature of the composition), to form a solidified
thermoplastic foam.
[0074] The thermoplastic foam of the present disclosure can be
prepared by (i) contacting (e.g., dissolving or suspending) the
first thermoplastic composition with a first concentration of a
chemical blowing agent, in some examples, at or above a softening
temperature of the first thermoplastic composition (ii) triggering
the chemical blowing agent to foam the first thermoplastic
composition, thereby forming a thermoplastic foam (e.g., a
thermoplastic foam having a multicellular structure); and, (iii)
following the triggering, in some examples, cooling the
thermoplastic foam to, e.g., a temperature below its softening
temperature, to form a solidified thermoplastic foam. In some
examples, the "triggering" of the chemical blowing agent is
performed by any suitable method, including heating the composition
comprising a concentration of the chemical blowing agent to a
temperature sufficient to "trigger" the chemical blowing agent,
wherein the concentration of the chemical blowing agent is
effective to foam the first thermoplastic composition, thereby
forming a thermoplastic foam (e.g., a thermoplastic foam having a
multicellular structure). In some examples, the contacting
comprises contacting at a pressure of from about 10 MPa to about
100 MPa (e.g., from about 30 MPa to about 100 MPa, about 20 MPa to
about 80 MPa, about 30 MPa to about 60 MPa or about 40 MPa to about
70 MPa).
[0075] Chemical blowing agents may be endothermic or exothermic,
which refers to a type of decomposition they undergo to produce the
gas for foaming. The decomposition may be a result of inputting
thermal energy into the system. Endothermic blowing agents absorb
energy and typically release a gas, such as carbon dioxide, upon
decomposition. Exothermic blowing agents release energy and
generate a gas, such as nitrogen, when decomposed. Regardless of
the chemical blowing agent used, thermal variables of the first
thermoplastic composition being molded and thermal variables of the
blowing agent to be decomposed are coupled together such that
process parameters are selected so that the first thermoplastic
composition can be molded and the blowing agent can decompose at an
appropriate phase of the molding operation.
[0076] The disclosed foamed first thermoplastic compositions and
articles can be prepared by using all or some of the elements of
conventional injection molding systems such as those disclosed in
U.S. Patent Appl. No. 62/734,912, which is incorporated herein by
reference. Briefly, the system provides for decreased pressure
losses across the system as well as to control (e.g., deliberately
increase or decrease) the elongation, apparent shear, and/or zero
shear viscosities of the molten first thermoplastic composition
that is flowed into the mold. The method can include flowing a
molten first thermoplastic composition into a shot tuning chamber
from an upstream device and adjusting a temperature, a pressure, or
both, within the shot tuning chamber to create a tuned molten first
thermoplastic composition. The method additionally includes flowing
the tuned molten first thermoplastic composition into a mold cavity
from the shot tuning chamber. It will be appreciated that
fine-tuning the temperature of and/or pressure applied to the
molten first thermoplastic composition enables the system to have a
desired impact on the physical and mechanical properties of the
molded article. In particular, the temperature of the molten first
thermoplastic composition may be controlled to achieve a desired
range of shear/extensional viscosities, which reduces (e.g.,
substantially eliminates) uncontrolled bubble growth and/or
nucleation. In one example, the method may also include adjusting
(e.g., increasing and/or decreasing) a pressure in the mold cavity
via a gas counter pressure (GCP) assembly prior to or while the
molten first thermoplastic composition is flowed from the shot
tuning chamber or directly from the injector into the mold cavity.
In such an example, the molten first thermoplastic composition may
be flowed into the mold cavity at pressures well above ambient
pressure. Furthermore, GCP may be introduced into the mold cavity
to control nucleation and bubble growth during polymer foaming as
well as increase surface quality of the molded article. Nucleation
and bubble growth control can enhance cell density uniformity,
consistency of cell diameters, and mechanical properties of the
thermoplastic foam. In some examples, the improvement in cell
density homogeneity or consistency of cell diameters may be
particularly beneficial in thermoplastic foams having low specific
gravities such less than or equal to 0.3 and/or in foam components
having large dimensions such as articles having a thickness that is
1.0 cm, for instance.
[0077] The system can include a shot tuning chamber configured to
receive a molten first thermoplastic composition from an upstream
device. The shot tuning chamber is also configured to adjust one or
more of a temperature of and a pressure applied to the molten first
thermoplastic composition to create an adjusted molten first
thermoplastic composition and to dispense the adjusted molten first
thermoplastic composition. In this way, the system can selectively
adjust tuning chamber temperature and/or pressure to achieve
desired properties, as previously mentioned. In one example, the
system may further include an adjustable mold runner configured to
regulate fluidic communication between the shot tuning chamber and
a mold cavity in a mold.
[0078] In another example, the system can comprise a GCP assembly
coupled to the mold cavity and configured to regulate an amount of
counter pressure gas flow into and out of the mold cavity.
Providing GCP adjustment allows for tuning of the first
thermoplastic composition as it enters and cools in the mold.
[0079] Alternatively, the disclosed foams and articles can be
prepared using methods and systems as described in International
Patent Appl. No. PCT/US2018/035128. Briefly, the method can
comprise a method for molding a single-phase solution comprised of
a thermoplastic composition and a supercritical fluid. The
single-phase solution is maintained under pressure during the
molding operation to prevent a cellular structure from being formed
by the supercritical fluid in the single-phase composition coming
out of solution. The mold cavity in which the single-phase solution
is introduced for molding purposes is pressurized to a mold
pressure that is sufficient to maintain the single-phase solution
as a single-phase solution as the mold cavity is filled. Subsequent
to filling the mold cavity with the single-phase solution under
pressure, the single-phase solution may solidify, entrapping the
supercritical fluid. Alternatively, before being solidified, the
single-phase solution may be exposed to a reduction in pressure
causing the entrapped supercritical fluid to phase transition to a
gas and expand the softened thermoplastic composition to form a
multicellular structure before the thermoplastic composition is
solidified into a solidified multicellular foam.
[0080] The method can include forming the single-phase solution,
such as through introduction of a supercritical fluid with a first
thermoplastic composition that is melted, e.g., at a temperature of
from about the melting temperature of the thermoplastic elastomer
of the thermoplastic composition up to about 50 degrees centigrade
above the melting tail temperature of the thermoplastic elastomer
as described herein, in an injection molding apparatus's barrel
(e.g., screw) that is effective to mix the supercritical fluid and
the molten thermoplastic composition, forming a single-phase
solution while under pressure. The method continues with
pressurizing a mold cavity of a mold above atmospheric pressure to
a mold pressure. Atmospheric pressure is a pressure of the
environment in which the mold cavity is exposed (e.g., general
environment pressure). The mold pressure is at least a pressure to
maintain the single-phase solution as a single single-phase. The
method further includes injecting the single-phase solution into
the pressurized mold cavity. The method also includes maintaining
at least the mold pressure in the mold cavity during the injecting
of the single-phase solution. As a result, the pressure in the mold
cavity prevents the supercritical fluid from phase-transitioning to
a gas and from coming out of solution to form a two-phase mixture
(e.g., foaming) upon exit from the injection molding apparatus. As
the pressure is maintained, premature foaming as the thermoplastic
composition is injected from the injection molding apparatus is
avoided to allow a decoupling of process parameters associated with
the blowing agent and the thermoplastic composition.
[0081] A molding system can be utilized to prepare the disclosed
foams that includes a device configured to receive a first
thermoplastic composition and heat the first thermoplastic
composition to form a molten first thermoplastic composition or a
single-phase solution. The molding system optionally can include a
shot tuning chamber configured to receive the molten first
thermoplastic composition or the single-phase solution from the
device and adjust a temperature of or a pressure applied to the
molten first thermoplastic composition or the single-phase
solution. The molding system optionally can also include an
adjustable mold runner configured to regulate the flow of the
molten first thermoplastic composition or the single-phase solution
between the shot tuning chamber and a mold cavity. In one example,
the device may be an injection device or an extrusion device. The
molding system allows the characteristics of the first
thermoplastic composition or the single-phase solution to be
adapted to achieve desired end-use goals, such as, for example, to
achieve a desired injection temperature or a desired foaming
temperature or to achieve both.
[0082] In some aspects, the present disclosure is directed to a
compression molded thermoplastic foam, and to a method of forming
compression molded thermoplastic foam for, among other
applications, articles of footwear or athletic equipment. In some
examples, the method can be a process comprising providing (e.g.,
preparing) a thermoplastic foam preform and then compression
molding the thermoplastic foam preform to form a compression molded
thermoplastic foam. For example, the thermoplastic foam can be
compression molded by placing the thermoplastic foam preform in a
compression mold having a height less than the initial height of
the thermoplastic foam preform and closing the mold, thereby
compressing the thermoplastic foam preform to the height of the
mold. Simultaneously or sequentially with the compressing, the
thermoplastic foam preform can be heated in the closed compression
mold. During the compression molding, the temperature of at least a
portion of the thermoplastic foam preform in the closed mold can be
raised to a temperature within .+-.30 degrees centigrade of the
softening temperature of the composition. The temperature can be
raised by heating the closed mold. Following the raising of the
temperature, while the thermoplastic foam preform remains closed in
the compression mold, the temperature of at least a portion of the
thermoplastic foam preform can be lowered. The temperature can be
lowered by cooling the closed mold. The lowering can lower the
temperature of at least a portion of the thermoplastic foam preform
to a temperature at least 35 degrees centigrade below the softening
temperature of the composition, thereby forming the compression
molded thermoplastic foam. Following the cooling, the compression
mold can be opened, and the compression molded thermoplastic foam
can be removed from the compression mold.
[0083] Examples contemplated herein are directed to methods of
manufacturing articles of footwear, apparel, or athletic equipment.
For example, the method can comprise providing components such as
midsoles and inserts of an article of footwear in accordance with
the present disclosure, and combining the component with a footwear
upper and an outsole to form the article of footwear.
[0084] The thermoplastic foam can be made using a process that
involves impregnating a first thermoplastic composition (e.g., at
or above a softening temperature of the composition) with a
physical blowing agent at a first concentration or first pressure.
The impregnated first thermoplastic composition can then be foamed,
or can be cooled (when applicable) and re-softened (when
applicable) for blowing at a later time. In some instances, the
impregnated first thermoplastic composition is foamed by reducing
the temperature or pressure, impacting the solubility of the
physical blowing agent. The reduction in solubility of the physical
blowing agent can release additional amounts of the impregnated
physical blowing agent from the first thermoplastic composition to
further blow the composition forming a thermoplastic foam (e.g., a
thermoplastic foam having a multicellular structure).
[0085] The thermoplastic foam can have a closed skin. A closed skin
can be formed by foaming and molding a thermoplastic copolyester
foam in a closed mold. A closed skin can also be formed by
compression molding a thermoplastic foam preform in a compression
mold. However, care should be taken during the compression molding
not to subject the thermoplastic foam preform to conditions such
that more than a desired amount of the cell structures of the foam
collapse. One way to avoid collapsing more than a desired amount of
the cell structures is to control the temperature of the
thermoplastic foam during the compression molding process, for
example, by controlling the temperature of the mold. For example,
during the compression molding step, the heating of the
thermoplastic foam preform in the compression mold can be conducted
for time of from 100 seconds to 1,000 seconds, or of from 150
seconds to 700 seconds.
[0086] Once the thermoplastic foam has been heated in the
compression mold at the appropriate temperature for the desired
length of time to soften the thermoplastic foam to the desired
level, the softened preform is cooled, for example, to a
temperature at least 35 degrees centigrade below its softening
temperature, or at least 50 degrees centigrade below its softening
temperature, or at least 80 degrees centigrade below its softening
temperature, to re-solidify the softened foam, thereby forming the
compression molded foam. Once cooled, the compression molded
thermoplastic foam is removed from the compression mold. Following
the heating, the cooling of the foam preform in the compression
mold can be conducted for a time of from 50 to 1,000 seconds, or
for a time of from 100 to 400 seconds.
[0087] The thermoplastic foam can be foamed using any one of the
methods described above. The thermoplastic foam can be included in
components of articles of footwear as described above, for example
a midsole 146 as depicted in FIGS. 1A-1B.
Methods of Manufacturing Disclosed Articles.
[0088] Various examples include methods of manufacturing an article
comprising a first component and a second component. As discussed
herein above, the first component can be a foam component, e.g., a
first foam component, and the second component can be a foam
component, e.g., a second foam component. The first component can
be, but is not limited to, a midsole or component of a midsole. The
second component can be, but is not limited to, an outsole or an
upper. It is understood that the second component can be foamed,
partially foamed, or essentially unfoamed. In some instances, the
second thermoplastic composition comprises one or more disclosed
thermoplastic elastomers. For example, a second thermoplastic
composition includes at least 90 weight percent, or at least 95
weight percent, or at least 99 weight percent of the thermoplastic
elastomer disclosed herein, based on the total weight of the second
thermoplastic composition. In some instances, the second
thermoplastic composition includes a greater concentration of
fillers, pigments or dyes as compared to the first thermoplastic
composition of the first foam component. The disclosed methods of
manufacturing an article comprising a first component and a second
component may further comprise steps or adjustments as known to the
skilled artisan.
[0089] In some aspects, the methods of manufacturing an article of
footwear include injection molding a first thermoplastic
composition to form a thermoplastic foam described herein to
produce a foam article or component of an article, such as a
cushioning element for an article of footwear. The methods can
further comprise manufacturing an article or component of an
article comprising providing a midsole or a component of a midsole,
then providing an upper and/or an outsole or outsole component for
an article of footwear; and followed by combining the midsole or
midsole component with the upper and/or the outsole or outsole
component to make an article of footwear. In some instances, the
method of manufacturing the article of footwear includes combining
an article comprising a thermoplastic foam, an upper, and an
outsole to make an article of footwear. In various aspects, the
upper and/or outsole can comprise the same or a different
thermoplastic composition, a second thermoplastic composition, or
combinations thereof. In some instances, the outsole used in the
method can be foamed, partially foamed, or substantially unfoamed.
It is understood that a midsole, midsole component, outsole, or
outsole component can be foamed or partially foamed using the
methods disclosed herein for the preparation of a foam article.
[0090] The various disclosed methods can include coupling a first
component to a second component. In certain aspects, the disclosed
methods comprise forming the first component and second component
together. For example, the first thermoplastic composition for the
first component, i.e., a disclosed thermoplastic composition, and
the second thermoplastic composition can be added to a mold
sequentially during an injection molding process to provide a
unitary component having a first component, i.e., a foam portion
comprising the first thermoplastic composition and a second
component, e.g., a polymeric layer comprising the second
thermoplastic composition. In this aspect, a mold can be provided
having a first mold portion having a mold surface. The second
thermoplastic composition can be added to the mold, so as to form a
polymeric layer on at least a portion of the mold surface. The
second thermoplastic composition can be added to the mold as a film
or coating applied to a mold surface. The process of adding the
second thermoplastic composition can comprise injecting the second
thermoplastic composition into the mold cavity prior to injecting
the first thermoplastic composition into the mold cavity.
Optionally, after injecting the second thermoplastic composition
into the mold cavity but before injecting the first thermoplastic
composition into the mold cavity, the pressure within the mold
cavity, or the temperature of the mold cavity, or both, can be
altered. For example, after injecting the second thermoplastic
composition into the mold, the pressure within the mold can be
increased in order to better cover the surfaces of the mold cavity
with the second thermoplastic composition and create a polymeric
layer on the surfaces of the mold cavity. The first thermoplastic
composition for the first component, i.e., a disclosed
thermoplastic composition, can be injected into the mold containing
the second component, i.e., the polymeric layer comprising the
second thermoplastic composition, and foamed while in contact with
the polymeric layer. The resultant injection-molded component is a
unitary component, with the second component, i.e., the polymeric
layer, thermally bonded to the first component, i.e., the foam
component.
[0091] In one example, when injecting the second thermoplastic
composition and the first thermoplastic composition to form a
unitary component as described above, the second thermoplastic
composition can be free of blowing agents or essentially free of
blowing agents, in order to form a unitary foamed article including
an unfoamed polymer layer comprising the second thermoplastic
composition covering the thermoplastic foam having a multicellular
foam structure compositionally comprising the first thermoplastic
composition. For example, the step of injecting the second
thermoplastic composition can comprise injecting a molten second
thermoplastic composition that is free of or essentially free of
physical or chemical blowing agents, and the step of injecting the
first thermoplastic composition can comprise injecting a
single-phase solution of the first thermoplastic composition and a
supercritical fluid. In this way, the second thermoplastic
composition can be used to form a decorative layer or a protective
layer on the thermoplastic foam. One advantage of this method is
that the detail level of the unfoamed polymeric layer can be
greater, as an unfoamed material will retain a greater level of
mold detail than a foamed layer. Another advantage of this method
is that the second thermoplastic composition can have different
physical properties or coloration or both physical properties and
coloration as compared to the first thermoplastic composition, or
the second thermoplastic composition and the first thermoplastic
composition can be structurally different as described herein. For
example, the second thermoplastic composition can have a greater
Durometer hardness, or a greater level of abrasion resistance, or a
greater coefficient of friction in order to provide a greater level
of traction, as compared to the thermoplastic foam comprising the
first thermoplastic composition. In another example, the second
thermoplastic composition can comprise a greater concentration of
pigments or dyes or both as compared to the first thermoplastic
composition. For example, the second thermoplastic composition can
comprise greater than 3 weight percent, or greater than 4 weight
percent, or greater than 5 weight percent, or greater than 6 weight
percent or greater than 10 weight percent of pigments, while the
first thermoplastic composition can be free of or essentially free
of pigments. This can reduce the total amount of pigments used to
impart coloration to the unitary component without the need to
include pigments in both the first and second thermoplastic
compositions, which increases the recyclability of the unitary
component.
[0092] Alternatively or additionally, the second component
comprising the second thermoplastic composition can be disposed
onto the exterior surface of the first component comprising the
first thermoplastic composition during a compression molding step,
or during a vacuum forming step. For example, a first component can
be made such as by injection molding, and the foam component can
thereafter be compression molded or vacuum formed in a mold which
includes the second component (optionally with heating), such that
the first component bonds to the surface of the second component
during the compression molding or vacuum forming process. As
described above, the second thermoplastic composition can have a
greater Durometer hardness, or a greater level of abrasion
resistance, or a greater coefficient of friction in order to
provide a greater level of traction, as compared to the
thermoplastic foam comprising the first thermoplastic composition.
The second and the first thermoplastic compositions can be
structurally different. In another example, the second
thermoplastic composition can comprise a greater concentration of
pigments or dyes or both as compared to the first thermoplastic
composition.
[0093] The second component can be provided as an already formed
component, e.g., a second component, to the injection mold or
compression mold. For example, the second component, e.g., a film,
can be inserted into an injection mold and held in place against a
target surface of the mold via vacuum ports, electrostatic charge
or other method. The second component may be conformed to the
target surface of the mold, for example, with the application of
heat or vacuum before or after it is inserted into the mold. The
first thermoplastic composition for the first component, i.e., a
disclosed thermoplastic copolyester composition, can then be
injected into the mold containing the film, and foamed as described
herein. As a result the second component becomes an integral part
of the molded component.
[0094] Alternatively or additionally, the second component can be
disposed onto the foam component after the foam component has been
formed. According to some of the disclosed methods, the second
component that is provided separately from the first component, and
are thereafter operably coupled so that the second component is in
contact with a targeted portion of an exterior surface of the first
component. The second component may be coupled with the exterior
surface of a first component using any suitable method. In an
aspect, the second component may be adhesively laminated to the
first component. In another aspect, the second component may be
coupled with the first component may be thermally laminated to an
exterior surface of the first component. For example, heat may be
applied to an exterior surface of the first component, to a surface
of the second component, or both, to soften or melt the heated
surface(s), and the two surfaces may be joined when one or both are
in the softened or melted state. In an aspect, the second component
may be coupled with the first component using a flame lamination
process.
[0095] The second component can be provided as a polymeric layer.
For example, a polymeric coating can be formed by applying a liquid
second thermoplastic composition onto the foam component, such as
by spraying, dip coating, tumble-coating, brushing, or a
combination thereof. The liquid polymeric material can then be
dried or cured while in contact with the first component.
[0096] The polymeric layer can be disposed on at least one exterior
surface of the foam component. For example, where the foam article
is a midsole, the coating can be on all or part of the sidewall of
the midsole, or on all or part of a ground-facing (bottom) surface
of the midsole, or on all or part of an upper-facing (top) surface
of the midsole, or any combination thereof. The polymeric layer can
be disposed on at least one surface that may be exposed to moisture
during normal use of the finished article, e.g., an article of
footwear.
[0097] As disposed on the foam component, the polymeric layer has
an average thickness of about 0.01 millimeter to about 3
millimeter, or about 0.03 millimeter to about 2 millimeter, or from
about 0.1 millimeter to about 1 millimeter.
[0098] According to various aspect, the foam component or article
having the disclosed polymeric layer has similar physical
properties when compared to an equivalent foam component or article
that lacks the polymeric layer.
[0099] In a particular aspect, when the second thermoplastic
composition is a film, the film can be a multi-layer film. The
multi-layer film can include one or more layers of the second
thermoplastic composition, and one or more layers of a different
(i.e., third) thermoplastic composition. The third thermoplastic
composition can be a material having a lower level of oxygen
transmission or water vapor transmission or both, as compared to
the second thermoplastic composition. For example, the third
thermoplastic composition can comprise a barrier polymer such as
ethylene-vinyl alcohol (EVOH). One example of a multi-layer film
includes a first layer comprising a second thermoplastic
composition including TPU, and a second layer comprising a third
thermoplastic composition including EVOH. Alternatively, the third
thermoplastic composition can be an adhesive layer comprising one
or more adhesive polymers, such as one or more hot melt adhesive
polymers. Another example of a multi-layer film includes a first
layer comprising a second thermoplastic composition including a
first TPU, and a second layer comprising a third thermoplastic
composition including a second hot melt adhesive TPU having a lower
melting temperature than the first TPU.
[0100] The polymeric layer can be formed by applying a powdered
second thermoplastic composition onto the foam component, such as
by spraying, powder-coating, electrostatically coating,
tumble-coating, or a combination thereof. In some aspects, an
adhesive could be used to affix the powder to the midsole, and/or a
coating can be applied over the powder to hold it in place on the
foam component. Once the powder is affixed to the midsole, it can
be left in the form of a powder, or it can be treated so as to form
a more uniform coating, such as by heating it to melt it, by
applying a solvent to solubilize it, etc.
[0101] Alternatively, the polymeric layer can take the form of a
separate element which is applied to all or a portion of an
exterior surface of the foam component when incorporating the
midsole into an article of footwear. For example, the foam
component can be a midsole component of an article of footwear, and
the polymeric layer can be a rand or foxing tape applied around a
perimeter of the midsole. The polymeric layer can be an extension
of an outsole covering all or a portion of the bottom surface of
the midsole, and which wraps up and covers at least a portion of
the sidewall of the midsole. The polymeric layer can be the "shell"
portion of a core-shell sole structure, which covers both the
bottom surface and the sidewalls of the midsole, and which is
attached to the upper of the article of footwear.
[0102] The foam articles and components can be foamed using any one
of the methods described above.
[0103] In various aspects, the disclosed methods of manufacturing
articles comprising a first component and a second component, the
second component comprising a second thermoplastic composition can
be produced separately via injection molding with or without the
addition of compressed gas, supercritical fluids or other blowing
agents upon which the foam article is produced.
[0104] In some instances, the disclosed methods of manufacturing
articles comprising a first component and a second component
comprise injection via overmolding. In some instances, overmolding
can comprise sequential injection of a polymeric material for the
first component, i.e., a disclosed thermoplastic copolyester, and a
second thermoplastic composition in the same process, or wherein
the second thermoplastic composition was produced in a separate
process, and subsequently inserted into the mold after which foam
article from the first thermoplastic composition is over molded.
The second component can be produced separately via injection
molding with only sufficient compressed gas, supercritical fluids
or other blowing agents to achieve a density of 0.90 grams per
cubic centimeter, 0.85 grams per cubic centimeter, or 0.80 grams
per cubic centimeter.
[0105] In some instances, the disclosed methods of manufacturing
articles comprising a first component and a second component
comprise a step of corona treatment. That is, for example, the
second component can be a film or an outsole or a rand that is
pretreated with a plasma or corona treatment prior to receiving the
overmolding assembly described herein.
[0106] In some instances, the disclosed methods of manufacturing
articles comprising a first component and a second component
comprise a step of pretreatment with a primer. That is, for
example, the second component can be a film or an outsole or a rand
that is pretreated with a primer alone, or a primer plus and an
adhesive prior to receiving the overmolding assembly method
described herein.
[0107] In some instances, the disclosed methods of manufacturing
articles comprising a first component and a second component
comprise a step of fused deposition 3D printing. That is, for
example, the second component can be fused deposition 3D printed
onto a first component. In such instances, a second thermoplastic
composition can be extruded into a fused deposition 3D printing
filament of about 1.5 mm, about 1.75 mm, about 1.85 mm, about 2.85
mm, about 3.0 mm, or other relevant diameter for deposition and
attachment to first component in such a way that it comprises the
ground contact layer, print-on outsole, or other exterior features.
Any grade commonly used in injection molding will typically suffice
for 3D print filament for fused deposition applications.
[0108] The resulting article comprising the first and second
components can be characterized by good bonding strength between
the first and the second components. The ply adhesion strength
between the polymeric layer and the foam component is greater than
2.5 kg force/centimeter or greater than 3.0 kg force/centimeter,
when determined using the Ply Adhesion Test method described
herein. Alternatively additionally, the bonding strength between
the first and the second components can be determined according to
the Hand Pull Test, described herein. The disclosed articles or
components can have a bond between the first and the second
components that has an average hand pull test result of greater
than or equal to 2.0, or greater than or equal to 2.5, or greater
than or equal to 3.0, or greater than or equal to 3.5, or greater
than or equal to 4.0, or greater than or equal to 4.5, when
determined according to the Hand Pull Test method described
herein.
[0109] Each of the first and/or the second components can be
characterized by one or more properties. For example, a first
and/or a second component can have an Akron abrasion of less than
0.50 cubic centimeters lost, optionally less than 0.40 cubic
centimeters lost, less than 0.30 cubic centimeters lost, less than
0.20 cubic centimeters lost, or less than 0.10 cubic centimeters
lost as determined using the Akron Abrasion Test. The first and/or
the second components can have an Akron abrasion of about 0.05
cubic centimeters lost, about 0.10 cubic centimeters lost, about
0.15 cubic centimeters lost, about 0.20 cubic centimeters lost,
about 0.25 cubic centimeters lost, about 0.30 cubic centimeters
lost, about 0.35 cubic centimeters lost, about 0.40 cubic
centimeters lost, about 0.45 cubic centimeters lost, or about 0.50
cubic centimeters lost as determined using the Akron Abrasion Test,
any range of abrasion values encompassed by any of the foregoing
values, or any combination of the foregoing abrasion values.
[0110] The first and/or a second component can have an Akron
abrasion of less than 500 milligrams lost, optionally less than 400
milligrams lost, less than 300 milligrams lost, less than 200
milligrams lost, or less than 100 milligrams lost as determined
using the Akron Abrasion Test. The first and/or a second component
can have an can have an Akron abrasion of about 50 milligrams lost,
about 100 milligrams lost, about 150 milligrams lost, about 200
milligrams lost, about 250 milligrams lost, about 300 milligrams
lost, about 350 milligrams lost, about 400 milligrams lost, about
450 milligrams lost, or about 500 milligrams lost as determined
using the Akron Abrasion Test, any range of abrasion values
encompassed by any of the foregoing values, or any combination of
the foregoing abrasion values.
[0111] The first and/or a second component can have a DIN abrasion
of less than 0.30 cubic centimeters lost, optionally less than 0.20
cubic centimeters lost, less than 0.10 cubic centimeters lost, less
than 0.05 cubic centimeters lost, or less than 0.03 cubic
centimeters lost as determined using the DIN Abrasion Test. The
first and/or a second component can have a DIN abrasion of about
0.01 cubic centimeters lost, about 0.05 cubic centimeters lost,
about 0.10 cubic centimeters lost, about 0.15 cubic centimeters
lost, about 0.20 cubic centimeters lost, about 0.25 cubic
centimeters lost, or about 0.30 cubic centimeters lost as
determined using the DIN Abrasion Test, any range of abrasion
values encompassed by any of the foregoing values, or any
combination of the foregoing abrasion values.
[0112] The first and/or a second component can have a DIN abrasion
of less than 300 milligrams lost, optionally less than 250
milligrams lost, optionally less than 200 milligrams lost,
optionally less than 150 milligrams lost, optionally less than 100
milligrams lost, optionally less than 80 milligrams lost,
optionally less than 50 milligrams lost, or optionally less than 30
milligrams as determined using the DIN Abrasion Test. The first
and/or a second component can have a DIN abrasion of about 10
milligrams lost, about 50 milligrams lost, about 100 milligrams
lost, about 150 milligrams lost, about 200 milligrams lost, about
250 milligrams lost, or about 300 milligrams lost as determined
using the DIN Abrasion Test, any range of abrasion values
encompassed by any of the foregoing values, or any combination of
the foregoing abrasion values.
[0113] The first and/or a second component described herein when
incorporated into an article the product can have improved traction
properties. In one aspect, the coefficient of friction of the
polymer layer can be used to measure traction properties.
[0114] The first and/or a second component can have a dry dynamic
coefficient of friction (COF) on a dry surface (e.g., a smooth,
flat, or textured surface such as, for example, wooden parquet
court, concrete, asphalt, laminate, brick, or ceramic tile) of
greater than 0.5, optionally of greater than 0.7, greater than 0.8,
greater than 0.9, greater than 1.0, as determined using the Dry
Outsole Coefficient of Friction Test. The polymer layer can have a
dry dynamic COF of greater than 0.15, optionally of greater than
0.2, greater than 0.25, or greater than 0.3, using the Dry Upper
Coefficient of Friction Test.
[0115] The first and/or a second component can have a wet dynamic
COF of greater than 0.25, optionally of greater than 0.30, greater
than 0.35, greater than 0.40, or greater than 0.50, as determined
using the Wet Outsole Coefficient of Friction Test. The polymer
layer can have a wet dynamic COF of greater than 0.15, optionally
of greater than 0.2, greater than 0.25, or greater than 0.3, using
the Wet Upper Coefficient of Friction Test.
[0116] It may be desirable for the dynamic coefficient of friction
for the same dry and wet surface (e.g., smooth concrete or court)
to be as close as possible. In one aspect, the difference between
the dynamic coefficient of friction of the dry surface and the wet
surface is less than 15 percent. In another aspect, the difference
between the dynamic coefficient of friction of the dry surface and
the wet surface is about 0 percent, about 1 percent, about 2
percent, about 3 percent, about 4 percent, about 5 percent, about 6
percent, about 7 percent, about 8 percent, about 9 percent, about
10 percent, about 11 percent, about 12 percent, about 13 percent,
about 14 percent, or about 15 percent, any range of percentage
values encompassed by any of the foregoing values, or any
combination of the foregoing percentage values.
[0117] The first and/or a second component can have a durometer
Shore A hardness of less than 90 or less than 85 or less than 80.
The polymer layer can have a durometer Shore A hardness of greater
than 60 or greater than 65. The polymer layer can have a durometer
Shore A hardness of about 50 to about 90 Shore A, optionally from
about 55 to about 85 Shore A, from about 60 to about 80 Shore A, or
from about 60 to about 70 Shore A. The polymer layer can have a
durometer Shore A hardness of about 50A, about 55A, about 60A,
about 65A, about 70A, about 75A, about 80A, about 85A, or about
90A, any range of Shore A hardness values encompassed by any of the
foregoing values, or any combination of the foregoing Shore A
hardness values.
Thermoplastic Copolyester Composition
[0118] The thermoplastic compositions disclosed herein (i.e., the
polymeric material for the first component of the foam portion
and/or the second thermoplastic composition) can include or consist
essentially of one or more thermoplastic copolyesters, including
one or more thermoplastic copolyester elastomers. In some aspects,
the first thermoplastic composition for the first component
includes at least 90 percent or at least 95 weight percent, or at
least 99 weight percent of a thermoplastic copolyester disclosed
herein, based on the total weight of the first thermoplastic
composition.
[0119] The thermoplastic copolyester compositions include or
consist essentially of one or more thermoplastic copolyesters. The
disclosed thermoplastic copolyester composition can include at
least about 90 weight percent or at least about 95 weight percent
or at least about 99 weight percent of the one or more
thermoplastic copolyesters, based on the total weight of the
thermoplastic copolyester composition. In some aspects, the
polymeric component of the thermoplastic copolyester composition,
which is comprised of all the polymeric materials present in the
thermoplastic copolyester composition, consists essentially of the
one or more thermoplastic copolyesters. The thermoplastic
copolyesters can include chain units derived from one or more
olefins and chain units derived from one or more
ethylenically-unsaturated acid groups.
[0120] The thermoplastic copolyester compositions can have a melt
flow index of from about 5 to about 40, or about 10 to about 20, or
about 20 to about 30 as determined at 210 degrees centigrade using
a 2.16 kilogram weight. Alternatively or additionally, the
thermoplastic copolyester compositions can have a melt flow index
of from about 5 to about 40, or about 10 about 20, or about 20 to
about 30 as determined at 220 degrees centigrade using a 2.16
kilogram weight. Alternatively or additionally, the thermoplastic
copolyester compositions can have a melt flow index of from about 5
to about 40, or about 10 to about 20, or about 20 to about 30 as
determined at 230 degrees centigrade using a 2.16 kilogram
weight.
[0121] The thermoplastic copolyesters can be terpolymers of
moieties derived from ethylene, acrylic acid, and methyl acrylate
or butyl acrylate. In some aspects, a ratio of a total parts by
weight of the acrylic acid in the thermoplastic copolyesters to a
total weight of the thermoplastic copolyesters is about 0.05 to
about 0.6, about 0.1 to about 0.6, about 0.1 to about 0.5, about
0.15 to about 0.5, or about 0.2 to about 0.5.
[0122] The thermoplastic compositions provided herein can include a
thermoplastic copolyester comprising: (a) a plurality of first
segments, each first segment derived from a dihydroxy-terminated
polydiol; (b) a plurality of second segments, each second segment
derived from a diol; and (c) a plurality of third segments, each
third segment derived from an aromatic dicarboxylic acid. In
various aspects, the thermoplastic copolyester is a block
copolymer. In some aspects, the thermoplastic copolyester is a
segmented copolymer. In further aspects, the thermoplastic
copolyester is a random copolymer. In still further aspects, the
thermoplastic copolyester is a condensation copolymer.
[0123] The thermoplastic copolyester can have a weight average
molecular weight of about 50,000 Daltons to about 1,000,000
Daltons; about 50,000 Daltons to about 500,000 Daltons; about
75,000 Daltons to about 300,000 Daltons; about 100,000 Daltons to
about 250,000 Daltons; about 100,000 Dalton to about 500,000
Dalton; or a value or values of weight average molecular weight
within any of the foregoing ranges or a weight average molecular
weight range encompassing any sub-range of the foregoing
ranges.
[0124] The thermoplastic copolyester can have a ratio of first
segments to third segments from about 1:1 to about 1:5 based on the
weight of each of the first segments and the third segments; about
1:1 to about 1:3 based on the weight of each of the first segments
and the third segments; about 1:1 to about 1:2 based on the weight
of each of the first segments and the third segments; about 1:1 to
about 1:3 based on the weight of each of the first segments and the
third segments; or a value or values of have a ratio of first
segments to third segments within any of the foregoing ranges or a
have a range of ratio of first segments to third segments
encompassing any sub-range of the foregoing ranges.
[0125] The thermoplastic copolyester can a ratio of second segments
to third segments from about 1:1 to about 1:2 based on the weight
of each of the first segments and the third segments; about 1:1 to
about 1:1.52 based on the weight of each of the first segments and
the third segment; or a value or values of have a ratio of second
segments to third segments within any of the foregoing ranges or a
have a range of ratio of second segments to third segments
encompassing any sub-range of the foregoing ranges.
[0126] The thermoplastic copolyester can have first segments
derived from a poly(alkylene oxide)diol having a number-average
molecular weight of about 250 Daltons to about 6000 Daltons; about
400 Daltons to about 6,000 Daltons; about 350 Daltons to about
5,000 Daltons; about 500 Daltons to about 3,000 Daltons; about
2,000 Daltons to about 3,000 Daltons; or a value or values of
weight average molecular weight within any of the foregoing ranges
or a weight average molecular weight range encompassing any
sub-range of the foregoing ranges.
[0127] The thermoplastic copolyester can have first segments
derived from a poly(alkylene oxide)diol such as poly(ethylene
ether)diol; poly(propylene ether)diol; poly(tetramethylene
ether)diol; poly(pentamethylene ether)diol; poly(hexamethylene
ether)diol; poly(heptamethylene ether)diol; poly(octamethylene
ether)diol; poly(nonamethylene ether)diol; poly(decamethylene
ether)diol; or mixtures thereof. In a still further aspect, the
thermoplastic copolyester can have first segments derived from a
poly(alkylene oxide)diol such as poly(ethylene ether)diol;
poly(propylene ether)diol; poly(tetramethylene ether)diol;
poly(pentamethylene ether)diol; poly(hexamethylene ether)diol. In a
yet further aspect, the thermoplastic copolyester can have first
segments derived from a poly(tetramethylene ether)diol.
[0128] The thermoplastic copolyester can have second segments
derived from a diol having a molecular weight of less than about
250. The diol from which the second segments are derived can be a
C2-C8 diol. In a still further aspect, the second segments can be
derived from ethanediol; propanediol; butanediol; pentanediol;
2-methyl propanediol; 2,2-dimethyl propanediol; hexanediol;
1,2-dihydroxy cyclohexane; 1,3-dihydroxy cyclohexane; 1,4-dihydroxy
cyclohexane; and mixtures thereof. In a yet further aspect, the
second segments can be derived from 1,2-ethanediol,
1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and mixtures
thereof. In an even further aspect, the second segments can be
derived from 1,2-ethanediol. In a still further aspect, the second
segments can be derived from 1,4-butanediol.
[0129] The thermoplastic copolyester can have third segments
derived from an aromatic C5-C16 dicarboxylic acid. The aromatic
C5-C16 dicarboxylic acid can have a molecular weight less than
about 300 Daltons; about 120 Daltons to about 200 Daltons; or a
value or values of molecular weight within any of the foregoing
ranges or a molecular weight range encompassing any sub-range of
the foregoing ranges. In some instances, the aromatic C5-C16
dicarboxylic acid is terephthalic acid, phthalic acid, isophthalic
acid, or a derivative thereof. In a still further aspect, the
aromatic C5-C16 dicarboxylic acid is a diester derivative of the
terephthalic acid, phthalic acid, or isophthalic acid. In a yet
further aspect, the aromatic C5-C16 dicarboxylic acid is
terephthalic acid or the dimethyl ester derivative thereof.
[0130] The thermoplastic copolyester can comprise: (a) a plurality
of first copolyester units, each first copolyester unit of the
plurality comprising the first segment derived from a
dihydroxy-terminated polydiol and the third segment derived from an
aromatic dicarboxylic acid, wherein the first copolyester unit has
a structure represented by a Formula 1:
##STR00001##
wherein R.sub.1 is a group remaining after removal of terminal
hydroxyl groups from the poly(alkylene oxide) diol of the first
segment, wherein the poly(alkylene oxide) diol of the first segment
is a poly(alkylene oxide) diol having a number-average molecular
weight of about 400 to about 6000; and wherein R.sub.2 is a group
remaining after removal of carboxyl groups from the aromatic
dicarboxylic acid of the third segment; and (b) a plurality of
second copolyester units, each second copolyester unit of the
plurality comprising the second segment derived from a diol and the
third segment derived from an aromatic dicarboxylic acid, wherein
the second copolyester unit has a structure represented by a
Formula 2:
##STR00002##
wherein R.sub.3 is a group remaining after removal of hydroxyl
groups from the diol of the second segment derived from a diol,
wherein the diol is a diol having a molecular weight of less than
about 250; and wherein R.sub.2 is the group remaining after removal
of carboxyl groups from the aromatic dicarboxylic acid of the third
segment.
[0131] The thermoplastic copolyester can comprise a plurality of
first copolyester units having a structure represented by a Formula
3:
##STR00003##
wherein R is H or methyl; wherein y is an integer having a value
from 1 to 10; wherein z is an integer having a value from 2 to 60;
and wherein a weight average molecular weight of each of the
plurality of first copolyester units is from about 300 Daltons to
about 7,000 Daltons. In some aspects, in the foregoing formula, y
can be is an integer having a value of 1, 2, 3, 4, 5, 6, 7, 8, 9,
10; or y can be any set or range of the foregoing integer values.
In some aspects, the foregoing formula, z is an integer having a
value from 5 to 60; an integer having a value from 5 to 50; an
integer having a value from 5 to 40; an integer having a value from
4 to 30; an integer having a value from 4 to 20; an integer having
a value from 2 to 10; or z can be any set or range of the foregoing
integer values. In some aspects, R is hydrogen. In a still further
aspect, R is methyl. In some instances, R is hydrogen and y is an
integer having a value of 1, 2, or 3. Alternatively, in other
instances, R is methyl and y is an integer having a value of 1.
[0132] The thermoplastic copolyester can comprise a plurality of
first copolyester units having a structure represented by a Formula
4:
##STR00004##
wherein z is an integer having a value from 2 to 60; and wherein a
weight average molecular weight of each of the plurality of first
copolyester units is from about 300 Daltons to about 7,000 Daltons.
In some aspects, in the foregoing formula, y can be is an integer
having a value of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10; or y can be any
set or range of the foregoing integer values. In some aspects, the
foregoing formula, z is an integer having a value from 5 to 60; an
integer having a value from 5 to 50; an integer having a value from
5 to 40; an integer having a value from 4 to 30; an integer having
a value from 4 to 20; an integer having a value from 2 to 10; or z
can be any integer value or set of integer values within the
foregoing ranges or values, or any range of integer values
encompassing a sub-range the foregoing integer value ranges.
[0133] The thermoplastic copolyester can comprise a plurality of
first copolyester units having a weight average molecular weight
from about 400 Daltons to about 6,000 Daltons; about 400 Daltons to
about 5,000 Daltons; about 400 Daltons to about 4,000 Daltons;
about 400 Daltons to about 3,000 Daltons; about 500 Daltons to
about 6,000 Daltons; about 500 Daltons to about 5,000 Daltons;
about 500 Daltons to about 4,000 Daltons; about 500 Daltons to
about 3,000 Daltons; about 600 Daltons to about 6,000 Daltons;
about 600 Daltons to about 5,000 Daltons; about 600 Daltons to
about 4,000 Daltons; about 600 Daltons to about 3,000 Daltons;
about 2,000 Daltons to about 3,000 Daltons; or a value or values of
weight average molecular weight within any of the foregoing ranges
or a weight average molecular weight range encompassing any
sub-range of the foregoing ranges.
[0134] The thermoplastic copolyester can comprise a plurality of
second copolyester units, each second copolyester unit of the
plurality having represented by a Formula 5:
##STR00005##
wherein x is an integer having a value from 1 to 20; wherein the
foam article has a multicellular closed-cell or open-cell foam
structure. In some aspects, in the foregoing formula, x is an
integer having a value from 2 to 18; 2 to 17; 2 to 16; 2 to 15; 2
to 14; 2 to 13; 2 to 12; 2 to 11; 2 to 10; 2 to 9; 2 to 8; 2 to 7;
2 to 6; 2 to 5; 2 to 4; or x can be any integer value or set of
integer values within the foregoing ranges or values, or any range
of integer values encompassing a sub-range the foregoing integer
value ranges. In a further aspect, x is an integer having a value
of 2, 3, or 4.
[0135] The thermoplastic copolyester can comprise a plurality of
second copolyester units, each second copolyester unit of the
plurality having represented by a Formula 6:
##STR00006##
[0136] The thermoplastic copolyester can comprise a weight percent
range of the plurality of first copolyester units based on total
weight of the thermoplastic copolyester such that the weight
percent range is about 30 weight percent to about 80 weight
percent; about 40 weight percent to about 80 weight percent; about
50 weight percent to about 80 weight percent; about 30 weight
percent to about 70 weight percent; about 40 weight percent to
about 70 weight percent; about 50 weight percent to about 70 weight
percent; about 40 weight percent to about 65 weight percent; about
45 weight percent to about 65 weight percent; about 50 weight
percent to about 65 wt; about 55 weight percent to about 65 weight
percent; about 40 weight percent to about 60 weight percent; about
45 weight percent to about 60 weight percent; about 50 weight
percent to about 60 weight percent; about 55 weight percent to
about 60 weight percent; or any weight percent value or set of
weight percent values within any of the foregoing ranges of weight
percent, or any range of weight percent values encompassing a
sub-set of any of the foregoing ranges.
[0137] In some aspects, when in solid form, the thermoplastic
copolyester can comprise phase separated domains. For example, a
plurality of first segments derived from a dihydroxy-terminated
polydiol can phase-separate into domains comprising primarily the
first segments. Moreover, a plurality of second segments derived
from a diol can phase-separate into domains comprising primarily
the second segments. In other aspects, the thermoplastic
copolyester can comprise phase-separated domains comprising
primarily of a plurality of first copolyester units, each first
copolyester unit of the plurality comprising the first segment
derived from a dihydroxy-terminated polydiol and the third segment
derived from an aromatic dicarboxylic acid, wherein the first
copolyester unit has a structure represented by a Formula 1:
##STR00007##
wherein R.sub.1 is a group remaining after removal of terminal
hydroxyl groups from the poly(alkylene oxide) diol of the first
segment, wherein the poly(alkylene oxide) diol of the first segment
is a poly(alkylene oxide) diol having a number-average molecular
weight of about 400 to about 6000; and wherein R.sub.2 is a group
remaining after removal of carboxyl groups from the aromatic
dicarboxylic acid of the third segment; and other phase-separated
domains comprising primarily of a plurality of second copolyester
units, each second copolyester unit of the plurality comprising the
second segment derived from a diol and the third segment derived
from an aromatic dicarboxylic acid, wherein the second copolyester
unit has a structure represented by a Formula 2:
##STR00008##
wherein R.sub.3 is a group remaining after removal of hydroxyl
groups from the diol of the second segment derived from a diol,
wherein the diol is a diol having a molecular weight of less than
about 250; and wherein R.sub.2 is the group remaining after removal
of carboxyl groups from the aromatic dicarboxylic acid of the third
segment.
[0138] In other aspects, when in solid form, the thermoplastic
copolyester can comprise phase-separated domains comprising
primarily of a plurality of first copolyester units, each first
copolyester unit of the plurality having a structure represented by
a Formula 3:
##STR00009##
wherein R is H or methyl; wherein y is an integer having a value
from 1 to 10; wherein z is an integer having a value from 2 to 60;
and wherein a weight average molecular weight of each of the
plurality of first copolyester units is from about 300 Daltons to
about 7,000 Daltons. In some aspects, in the foregoing formula, y
can be is an integer having a value of 1, 2, 3, 4, 5, 6, 7, 8, 9,
10; or y can be any set or range of the foregoing integer values.
In some aspects, the foregoing formula, z is an integer having a
value from 5 to 60; an integer having a value from 5 to 50; an
integer having a value from 5 to 40; an integer having a value from
4 to 30; an integer having a value from 4 to 20; an integer having
a value from 2 to 10; or z can be any set or range of the foregoing
integer values. In some aspects, R is hydrogen. In a still further
aspect, R is methyl. In some instances, R is hydrogen and y is an
integer having a value of 1, 2, or 3. Alternatively, in other
instances, R is methyl and y is an integer having a value of 1.
[0139] In other aspects, when in solid form, the thermoplastic
copolyester can comprise phase-separated domains comprising
primarily of a plurality of first copolyester units, each first
copolyester unit of the plurality having a structure represented by
a Formula 4:
##STR00010##
wherein z is an integer having a value from 2 to 60; and wherein a
weight average molecular weight of each of the plurality of first
copolyester units is from about 300 Daltons to about 7,000 Daltons.
In some aspects, in the foregoing formula, y can be is an integer
having a value of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10; or y can be any
set or range of the foregoing integer values. In some aspects, the
foregoing formula, z is an integer having a value from 5 to 60; an
integer having a value from 5 to 50; an integer having a value from
5 to 40; an integer having a value from 4 to 30; an integer having
a value from 4 to 20; an integer having a value from 2 to 10; or z
can be any integer value or set of integer values within the
foregoing ranges or values, or any range of integer values
encompassing a sub-range the foregoing integer value ranges.
[0140] When in solid form, the thermoplastic copolyester can
comprise phase-separated domains comprising primarily of a
plurality of first copolyester units having a weight average
molecular weight from about 400 Daltons to about 6,000 Daltons;
about 400 Daltons to about 5,000 Daltons; about 400 Daltons to
about 4,000 Daltons; about 400 Daltons to about 3,000 Daltons;
about 500 Daltons to about 6,000 Daltons; about 500 Daltons to
about 5,000 Daltons; about 500 Daltons to about 4,000 Daltons;
about 500 Daltons to about 3,000 Daltons; about 600 Daltons to
about 6,000 Daltons; about 600 Daltons to about 5,000 Daltons;
about 600 Daltons to about 4,000 Daltons; about 600 Daltons to
about 3,000 Daltons; about 2,000 Daltons to about 3,000 Daltons; or
a value or values of weight average molecular weight within any of
the foregoing ranges or a weight average molecular weight range
encompassing any sub-range of the foregoing ranges.
[0141] In other aspects, when in solid form, the thermoplastic
copolyester can comprise phase-separated domains comprising a
plurality of second copolyester units, each second copolyester unit
of the plurality having represented by a Formula 5:
##STR00011##
wherein x is an integer having a value from 1 to 20; wherein the
foam article has a multicellular closed-cell or open-cell foam
structure. In some aspects, in the foregoing formula, x is an
integer having a value from 2 to 18; 2 to 17; 2 to 16; 2 to 15; 2
to 14; 2 to 13; 2 to 12; 2 to 11; 2 to 10; 2 to 9; 2 to 8; 2 to 7;
2 to 6; 2 to 5; 2 to 4; or x can be any integer value or set of
integer values within the foregoing ranges or values, or any range
of integer values encompassing a sub-range the foregoing integer
value ranges. In a further aspect, x is an integer having a value
of 2, 3, or 4.
[0142] In other aspects, when in solid form, the thermoplastic
copolyester can comprise phase-separated domains comprising a
plurality of second copolyester units, each second copolyester unit
of the plurality having represented by a Formula 6:
##STR00012##
[0143] When in solid form, the thermoplastic copolyester can
comprise phase-separated domains comprising a weight percent range
of the plurality of first copolyester units based on total weight
of the thermoplastic copolyester such that the weight percent range
is about 30 weight percent to about 80 weight percent; about 40
weight percent to about 80 weight percent; about 50 weight percent
to about 80 weight percent; about 30 weight percent to about 70
weight percent; about 40 weight percent to about 70 weight percent;
about 50 weight percent to about 70 weight percent; about 40 weight
percent to about 65 weight percent; about 45 weight percent to
about 65 weight percent; about 50 weight percent to about 65 wt;
about 55 weight percent to about 65 weight percent; about 40 weight
percent to about 60 weight percent; about 45 weight percent to
about 60 weight percent; about 50 weight percent to about 60 weight
percent; about 55 weight percent to about 60 weight percent; or any
weight percent value or set of weight percent values within any of
the foregoing ranges of weight percent, or any range of weight
percent values encompassing a sub-set of any of the foregoing
ranges.
[0144] The disclosed thermoplastic copolyester composition, the
polymeric component of the composition or an individual
thermoplastic copolyester copolymer in neat form can be
characterized by one or more properties. In some aspects, the
thermoplastic copolyester composition or the polymeric component,
or the polymer has a maximum load of about 10 newtons to about 100
newtons, or from about 15 newtons to about 50 newtons, or from
about 20 newtons to about 40 newtons; or any load value or set of
load values within any of the foregoing ranges of load value, or
any range of load values encompassing a sub-set of any of the
foregoing ranges, when determined using the Cyclic Tensile Test
method described herein.
[0145] The tensile strength of the thermoplastic copolyester
composition or of the component of the thermoplastic copolyester
composition or of a thermoplastic copolyester copolymer in neat
form is another important physical characteristic. The
thermoplastic copolyester composition or component or copolymer can
have a tensile strength of from 5 kilograms per square centimeter
to 25 kilograms per square centimeter, or of from 10 kilograms per
square centimeter to 23 kilograms per square centimeter, or of from
15 kilograms per square centimeter to 22 kilograms per square
centimeter; or any load value or set of load values within any of
the foregoing ranges of load value, or any range of load values
encompassing a sub-set of any of the foregoing ranges, when
determined using the Cyclic Tensile Test method described
herein.
[0146] The thermoplastic copolyester composition or polymeric
component of the thermoplastic copolyester composition or a
thermoplastic copolyester copolymer in neat form can have a tensile
modulus of about 2 megapascals to about 20 megapascals or from
about 5 megapascals to about 15 megapascals when determined using
the Cyclic Tensile Test method described herein; or any load value
or set of load values within any of the foregoing ranges of load
value, or any range of load values encompassing a sub-set of any of
the foregoing ranges.
[0147] Exemplary, but non-limiting, thermoplastic polyester
elastomers, including thermoplastic copolyesters, that can be used
in the disclosed methods, foams, and articles include "HYTREL"
3078, "HYTREL" 4068, and "HYTREL" 4556 (DuPont, Wilmington, Del.,
USA); "PELPRENE" P30B, P40B, and P40H (Toyobo U.S.A. Inc., New
York, N.Y., USA); "TRIEL" 5300, "TRIEL" 5400, and blends thereof
(Samyang Corporation, Korea); "KEYFLEX" BT1028D, BT1033D, BT1035D,
BT1040D, BT1045D, and BT1047D (LG Chem, Korea); and "KOPEL" KP3340,
KP3346, KP3347, KP3942 (Kolon Plastics, Inc., Korea).
[0148] The disclosed thermoplastic copolyester compositions can
further include one or more ionomers, such as any of the "SURLYN"
polymers (DuPont, Wilmington, Del., USA). Ionic foams described
herein can be made by a process/method including receiving a
composition described herein, and physically foaming the
composition to form a thermoplastic copolyester foam having a
density of about 0.7 gram per cubic centimeter or less, or 0.5 gram
per cubic centimeter or less, or 0.4 gram per cubic centimeter or
less, or 0.3 gram per cubic centimeter or less. The process can
include blowing the composition to produce an article or component
comprising the thermoplastic copolyester foam. In some examples,
the process for forming the thermoplastic copolyester foam
comprises injection molding a mixture including a composition as
described herein and a supercritical fluid (e.g., supercritical
carbon dioxide or supercritical nitrogen) in a mold, and removing
the thermoplastic copolyester foam from the mold.
[0149] The disclosed thermoplastic copolyester compositions can
further include one or more thermoplastic polyurethanes, including
thermoplastic polyurethane elastomers, such as "FORTIMO" (Mitsui
Chemicals, Inc., Tokyo, Japan); "TEXIN" (Covestro LLC, Pittsburgh,
Pa., USA); and "BOUNCELL-X" (Lubrizol Advanced Materials, Inc.,
Brecksville, Ohio, USA).
[0150] The disclosed thermoplastic copolyester compositions can
further include one or more olefinic polymers. Olefinic polymers
can include ethylene-based copolymers, propylene-based copolymers,
and butene-based copolymers. In some aspects, the olefinic polymer
is an ethylene-based copolymer such as a
styrene-ethylene/butylene-styrene (SEBS) copolymer; an
ethylene-propylene diene monomer (EPDM) copolymer; an
ethylene-vinyl acetate (EVA) copolymer; an ethylene alkyl acrylate
(EAA) copolymer; an ethylene alkyl methacrylate (EAMA) copolymer;
any copolymer thereof, and any blend thereof. In some aspects, a
ratio V of a total parts by weight of the olefinic polymers present
in the composition to a total parts by weight of the thermoplastic
copolyesters in the composition is about 0.0 to about 0.6, about
0.0 to about 0.4, about 0.01 to about 0.4, or about 0.01 to about
0.6, or about 0.1 to about 0.4.
[0151] The disclosed thermoplastic copolyester compositions can
further include an ethylene-vinyl acetate (EVA) copolymer. The
ethylene-vinyl acetate (EVA) copolymer can have a range of vinyl
acetate contents, for example about 50 percent to about 90 percent,
about 50 percent to about 80 percent, about 5 percent to about 50
percent, about 10 percent to about 45 percent, about 10 percent to
about 30 percent, about 30 percent to about 45 percent, or about 20
percent to about 35 percent, based on a total weight of the
copolymer.
[0152] The disclosed thermoplastic copolyester compositions can
further include an ethylene-vinyl alcohol (EVOH) copolymer. The
EVOH copolymer can have a range of vinyl alcohol contents, for
example about 50 percent to about 90 percent, about 50 percent to
about 80 percent, about 5 percent to about 50 percent, about 10
percent to about 45 percent, about 10 percent to about 30 percent,
about 30 percent to about 45 percent, or about 20 percent to about
35 percent, based on a total weight of the copolymer.
Second Thermoplastic Compositions
[0153] Having described the foams and methods of forming them, we
turn to the second thermoplastic composition. According to the
various aspects, the disclosed foam article has a second
thermoplastic composition disposed on at least one exterior surface
of the foam. For example, the second thermoplastic composition can
be a polymeric layer or a polymeric coating or a polymeric film. In
some aspects, the second thermoplastic composition has a higher
abrasion resistance than the foam component. In another aspect, the
second thermoplastic composition has a higher coefficient of
friction than the first thermoplastic composition of the foam
component. In another aspect, the second thermoplastic composition
has a higher Durometer hardness than the foam component. In other
aspects, the second thermoplastic composition has a higher specific
gravity than the foam component. In other aspect, the second
thermoplastic composition comprises a higher concentration of
non-polymeric ingredients, such as fillers and pigments, than the
first thermoplastic composition of the foam component. In yet
another aspect, the second thermoplastic composition has two or
more of a higher abrasion resistance, a higher coefficient of
friction, a higher Durometer hardness, a higher specific gravity,
and a higher concentration of non-polymeric ingredients, as
compared to the foam component or the first thermoplastic
composition of the foam component. In one aspect, the second
thermoplastic composition is structurally different than the first
thermoplastic composition as described below. Alternatively, the
second thermoplastic composition is structurally the same as the
first thermoplastic composition. The second thermoplastic
composition may be integral with the foam component, or may be a
separate component that is operably coupled with the foam
component, as described herein.
[0154] In one aspect, the first thermoplastic composition can be
structurally the same as or structurally different from the second
thermoplastic composition. Here, the first thermoplastic
composition has one or more structural chemical features that are
the same as or different than the second thermoplastic composition.
In one aspect, the structural difference is based on the chemical
structure of the first thermoplastic elastomer being different from
the chemical structure of all of the second thermoplastic
elastomers present in the second thermoplastic composition (e.g.,
different positional or stereochemical groups). In another aspect,
the structural difference is based on a number-average molecular
weight of the first thermoplastic elastomer being different from a
number-average molecular weight of second thermoplastic elastomer,
where the first and second thermoplastic elastomers have the same
chemical structure. In another aspect, the first structural
difference is based on a concentration of the first thermoplastic
elastomer in the first thermoplastic composition being different
from a concentration of the second thermoplastic elastomer in the
second thermoplastic composition, where the first and second
thermoplastic elastomers have the same chemical structure and the
same number average molecular weights. In yet another aspect, the
structural difference is based on any combination of the chemical
structure, the number-average molecular weight, and the
concentration being different. For example, a first thermoplastic
composition comprising a thermoplastic copolyester elastomer is
structurally different from a second thermoplastic composition
comprising a thermoplastic styrene copolymer elastomer, or
comprising a thermoplastic polyurethane elastomer, based on the
first and second thermoplastic compositions comprising
thermoplastic elastomers having different chemical structures In
another example, a first thermoplastic composition comprising a
first 50,000 Dalton thermoplastic copolyester elastomer is
structurally different than a second thermoplastic composition
comprising a second 100,000 Dalton thermoplastic copolyester
elastomer having the same chemical structure as the first 50,000
Dalton thermoplastic copolyester, based on the number average
molecular weight. In another example, a second thermoplastic
composition comprising the second 100,000 Dalton thermoplastic
copolyester elastomer having the same chemical structure as the
first 50,000 Dalton thermoplastic copolyester and also comprising
the first 50,000 Dalton thermoplastic copolyester would still be
structurally different from the first thermoplastic composition,
due to the presence of the 100,000 Dalton thermoplastic composition
in the second thermoplastic composition. In yet another example, a
first thermoplastic elastomer comprising 5 weight percent of a
first 50,000 Dalton thermoplastic copolyester is structurally
different than a second thermoplastic elastomer comprising 95
weight percent of the first 50,000 Dalton thermoplastic
copolyester.
[0155] In some aspects, a second thermoplastic composition includes
at least 90 weight percent, or at least 95 weight percent, or at
least 99 weight percent of a thermoplastic copolyester as disclosed
herein, based on the total weight of the second thermoplastic
composition. In some instances, the polymeric component of the
second thermoplastic composition consists essentially of only one
or more disclosed thermoplastic copolyester.
[0156] The second thermoplastic composition can be disposed on at
least one exterior surface of the foam component. For example,
where the foam article is a midsole, the second thermoplastic
composition can be on all or part of the ground-facing (bottom)
surface of the midsole, or on all or part of a side surface of the
midsole, or any combination thereof.
[0157] In certain aspects, the disclosed methods comprise forming
the second thermoplastic composition integrally with the first
component. For example, the polymeric material for the first
component, e.g., a disclosed first thermoplastic copolyester
composition, and the second thermoplastic composition can be added
to a mold sequentially during an injection molding process to
provide a unitary component having a foam portion and a second
portion comprising the second thermoplastic composition. In this
aspect, a mold can be provided having a first mold portion having a
mold surface. The second thermoplastic composition can be added to
the mold, so as to form a layer of second thermoplastic composition
on at least a portion of the mold surface. The first thermoplastic
composition for the first component, e.g., a disclosed
thermoplastic copolyester composition, can be injected into the
mold containing the second thermoplastic composition, and foamed
while in contact with the second thermoplastic composition. The
resultant injection-molded component is a unitary component, with
the second thermoplastic composition bonded to the foam component.
Alternatively or additionally, the second thermoplastic composition
can be disposed onto the exterior surface of the foam component
during a compression molding step. For example, a foam component
can be made such as by injection molding, and the foam component
can thereafter be compression molded in a mold which includes the
second thermoplastic composition, and the second thermoplastic
composition bonds to the surface of the foam during the compression
molding process.
[0158] The second thermoplastic composition can be provided as a
discrete layer or film to the injection mold or compression mold.
For example, the layer or film forming the second thermoplastic
composition can be inserted into an injection mold and held in
place against a target surface of the mold via vacuum ports,
electrostatic charge or other method. The layer or film may be
conformed to the target surface of the mold, for example, with the
application of heat or vacuum before or after it is inserted into
the mold. The first thermoplastic composition can then be injected
into the mold containing the film, and foamed as described herein.
As a result the second thermoplastic composition of the layer or
film becomes an integral part of the molded component.
[0159] Alternatively or additionally, the second thermoplastic
composition can be disposed onto the foam component after the foam
component has been formed. According to some of the disclosed
methods, the second thermoplastic composition is provided as a
layer or film that is provided separately from the foam component,
and are thereafter operably coupled so that the second
thermoplastic composition forms a layer on the targeted portion of
the exterior surface of the foam. The second thermoplastic
composition may be coupled with the exterior surface of a foam
component or article using any suitable method. In an aspect, the
second thermoplastic composition may be adhesively laminated to the
foam component. In another aspect, the second thermoplastic
composition may be coupled with the foam component such as by
thermally laminating to an exterior surface of the foam. For
example, heat may be applied to an exterior surface of the foam
component, to a surface of the second thermoplastic composition, or
both, to soften or melt the respective heated surface(s), and the
two surfaces may be joined when one or both are in the softened or
melted state. In an aspect, the second thermoplastic composition
may be coupled with the foam component using a flame lamination
process.
[0160] The second thermoplastic composition can be provided as a
polymeric coating. For example, a polymeric coating can be formed
by applying a liquid polymeric material onto the foam component,
such as by spraying, dip coating, tumble-coating, brushing, or a
combination thereof. The liquid second thermoplastic composition
can then be dried or cured while in contact with the midsole.
[0161] The polymeric coating can be formed by applying a powdered
second thermoplastic composition onto the foam component, such as
by spraying, powder-coating, electrostatically coating,
tumble-coating, or a combination thereof. In some aspects, an
adhesive could be used to affix the powder to the midsole, and/or a
coating can be applied over the powder to hold it in place on the
foam component. Once the powder is affixed to the midsole, it can
be left in the form of a powder, or it can be treated so as to form
a more uniform coating, such as by heating it to melt it, by
applying a solvent to solubilize it, etc.
[0162] Alternatively, the second thermoplastic composition can take
the form of a separate element which is applied to all or a portion
of an exterior surface of the foam component when incorporating the
midsole into an article of footwear. For example, the foam
component can be a midsole component of an article of footwear, and
the second thermoplastic composition can be a rand or foxing tape
applied around a perimeter of the midsole. The second thermoplastic
composition can be an extension of an outsole covering all or a
portion of the bottom surface of the midsole, and which wraps up
and covers at least a portion of the sidewall of the midsole. The
second thermoplastic composition can be the "shell" portion of a
core-shell sole structure, which covers both the bottom surface and
the sidewalls of the midsole, and which is attached to the upper of
the article of footwear.
[0163] The resulting article comprising the first component with
the second thermoplastic composition can be characterized by good
bonding strength between the second thermoplastic composition and
the foam component. The ply adhesion strength between the second
thermoplastic composition and the foam component is greater than
2.5 kg force/centimeter or greater than 3.0 kg force/centimeter,
when determined using the Ply Adhesion Test method described
herein.
[0164] Second Thermoplastic Composition Properties
[0165] The disclosed second thermoplastic composition can be
characterized by one or more properties.
[0166] In one aspect, the polymeric layer composed of the second
thermoplastic composition forms a water-resistant barrier on the at
least a portion of the exterior surface of the first foam
component. Here, the second thermoplastic composition of the
polymeric layer reduces or prevents water uptake by the open cell
foam microstructure of first foam component.
[0167] In one aspect, the foams and articles described herein
having the polymeric layer exhibit a beneficial Water Uptake
Capacity. In other words, the foam articles having a polymeric
layer as disclosed herein do not uptake either any water or a
significant amount of water during the use of the article. For
example, the foam articles or foam components having the polymeric
layer have a Water Uptake Capacity at 2 hours of less than 5
percent, or less than 4 percent, or less than 3 percent, or less
than 2 percent, when determined using the Water Uptake Capacity
Test method described herein. In comparison, an equivalent foam
article or foam component that lacks the polymeric layer may have a
water uptake capacity at 2 hours of greater than 2 percent, or from
about 2 percent to about 30 percent, or from about 3 percent to
about 25 percent or from about 5 percent to about 20 percent, when
determined using the Water Uptake Capacity Test method described
herein. The disclosed foam component or article having the
disclosed polymeric layer can have a reduced water uptake when
compared to an equivalent foam component or article that lacks the
polymeric layer. For example, the disclosed foam component or
article can have a water uptake capacity at 2 hours that is about
20 percent less, or about 30 percent less, or about 50 percent less
than a water uptake capacity at 5 minutes for an equivalent foam
component or article that lacks the polymeric layer, when
determined using the Water Uptake Capacity Test method describe
herein. The disclosed foam component or article can have a water
uptake capacity at 5 minutes that is at least 2 percentage points
less, or at least 3 percentage points less, or at least 4
percentage points less, or at least 5 percent less, or at least 6
percentage points less, or at least 7 percentage points less, or at
least 8 percentage points less, or at least 9 percentage points
less, or at least 10 percentage points less, or at least 11
percentage points less, or at least 12 percentage points less, or
at least 13 percentage points less, or at least 14 percentage
points less, or at least 15 percentage points less, or at least 20
percentage points less, or at least 25 percentage points less, or
at least 30 percentage points less than a water uptake capacity at
5 minutes for an equivalent foam component or article that lacks
the polymeric layer, when determined using the Water Uptake
Capacity Test method describe herein
[0168] In some aspects, the second thermoplastic composition or the
second thermoplastic elastomer has a maximum load of about 10
newtons to about 100 newtons, or from about 15 newtons to about 50
newtons, or from about 20 newtons to about 40 newtons; or any load
value or set of load values within any of the foregoing ranges of
load value, or any range of load values encompassing a sub-set of
any of the foregoing ranges, when determined using the Cyclic
Tensile Test method described herein.
[0169] The tensile strength of the second thermoplastic composition
or second thermoplastic elastomer is another important physical
characteristic. The second thermoplastic composition or resin can
have a tensile strength of from 5 kilograms per square centimeter
to 25 kilograms per square centimeter, or of from 10 kilograms per
square centimeter to 23 kilograms per square centimeter, or of from
15 kilograms per square centimeter to 22 kilograms per square
centimeter; or any load value or set of load values within any of
the foregoing ranges of load value, or any range of load values
encompassing a sub-set of any of the foregoing ranges, when
determined using the Cyclic Tensile Test method described
herein.
[0170] The second thermoplastic composition or second thermoplastic
elastomer can have a tensile modulus of about 2 megapascals to
about 20 megapascals or from about 5 megapascals to about 15
megapascals when determined using the Cyclic Tensile Test method
described herein; or any load value or set of load values within
any of the foregoing ranges of load value, or any range of load
values encompassing a sub-set of any of the foregoing ranges.
[0171] The second thermoplastic composition can have an Akron
abrasion of less than 0.50 cubic centimeters lost, optionally less
than 0.40 cubic centimeters lost, less than 0.30 cubic centimeters
lost, less than 0.20 cubic centimeters lost, or less than 0.10
cubic centimeters lost as determined using the Akron Abrasion Test.
The second thermoplastic composition can have an Akron abrasion of
about 0.05 cubic centimeters lost, about 0.10 cubic centimeters
lost, about 0.15 cubic centimeters lost, about 0.20 cubic
centimeters lost, about 0.25 cubic centimeters lost, about 0.30
cubic centimeters lost, about 0.35 cubic centimeters lost, about
0.40 cubic centimeters lost, about 0.45 cubic centimeters lost, or
about 0.50 cubic centimeters lost as determined using the Akron
Abrasion Test, any range of abrasion values encompassed by any of
the foregoing values, or any combination of the foregoing abrasion
values.
[0172] The second thermoplastic composition can have an Akron
abrasion of less than 500 milligrams lost, optionally less than 400
milligrams lost, less than 300 milligrams lost, less than 200
milligrams lost, or less than 100 milligrams lost as determined
using the Akron Abrasion Test. The second thermoplastic composition
can have an Akron abrasion of about 50 milligrams lost, about 100
milligrams lost, about 150 milligrams lost, about 200 milligrams
lost, about 250 milligrams lost, about 300 milligrams lost, about
350 milligrams lost, about 400 milligrams lost, about 450
milligrams lost, or about 500 milligrams lost as determined using
the Akron Abrasion Test, any range of abrasion values encompassed
by any of the foregoing values, or any combination of the foregoing
abrasion values.
[0173] The second thermoplastic composition can have a DIN abrasion
of less than 0.30 cubic centimeters lost, optionally less than 0.20
cubic centimeters lost, less than 0.10 cubic centimeters lost, less
than 0.05 cubic centimeters lost, or less than 0.03 cubic
centimeters lost as determined using the DIN Abrasion Test. The
second thermoplastic composition can have a DIN abrasion of about
0.01 cubic centimeters lost, about 0.05 cubic centimeters lost,
about 0.10 cubic centimeters lost, about 0.15 cubic centimeters
lost, about 0.20 cubic centimeters lost, about 0.25 cubic
centimeters lost, or about 0.30 cubic centimeters lost as
determined using the DIN Abrasion Test, any range of abrasion
values encompassed by any of the foregoing values, or any
combination of the foregoing abrasion values.
[0174] The second thermoplastic composition can have a DIN abrasion
of less than 300 milligrams lost, optionally less than 250
milligrams lost, optionally less than 200 milligrams lost,
optionally less than 150 milligrams lost, optionally less than 100
milligrams lost, optionally less than 80 milligrams lost,
optionally less than 50 milligrams lost, or optionally less than 30
milligrams as determined using the DIN Abrasion Test. The second
thermoplastic composition can have a DIN abrasion of about 10
milligrams lost, about 50 milligrams lost, about 100 milligrams
lost, about 150 milligrams lost, about 200 milligrams lost, about
250 milligrams lost, or about 300 milligrams lost as determined
using the DIN Abrasion Test, any range of abrasion values
encompassed by any of the foregoing values, or any combination of
the foregoing abrasion values.
[0175] The second thermoplastic composition described herein when
incorporated into an article the product has improved traction
properties. In one aspect, the coefficient of friction of the
second thermoplastic composition can be used to measure traction
properties.
[0176] The second thermoplastic composition can have a dry dynamic
coefficient of friction (COF) on a dry surface (e.g., a smooth,
flat, or textured surface such as, for example, wooden parquet
court, concrete, asphalt, laminate, brick, or ceramic tile) of
greater than 0.5, optionally of greater than 0.7, greater than 0.8,
greater than 0.9, greater than 1.0, as determined using the Dry
Outsole Coefficient of Friction Test. The second thermoplastic
composition can have a dry dynamic COF of greater than 0.15,
optionally of greater than 0.2, greater than 0.25, or greater than
0.3, using the Dry Upper Coefficient of Friction Test.
[0177] The second thermoplastic composition can have a wet dynamic
COF of greater than 0.25, optionally of greater than 0.30, greater
than 0.35, greater than 0.40, or greater than 0.50, as determined
using the Wet Outsole Coefficient of Friction Test. The second
thermoplastic composition can have a wet dynamic COF of greater
than 0.15, optionally of greater than 0.2, greater than 0.25, or
greater than 0.3, using the Wet Upper Coefficient of Friction
Test.
[0178] It may be desirable for the dynamic coefficient of friction
for the same dry and wet surface (e.g., smooth concrete or court)
to be as close as possible. In one aspect, the difference between
the dynamic coefficient of friction of the dry surface and the wet
surface is less than 15 percent. In another aspect, the difference
between the dynamic coefficient of friction of the dry surface and
the wet surface is about 0 percent, about 1 percent, about 2
percent, about 3 percent, about 4 percent, about 5 percent, about 6
percent, about 7 percent, about 8 percent, about 9 percent, about
10 percent, about 11 percent, about 12 percent, about 13 percent,
about 14 percent, or about 15 percent, any range of percentage
values encompassed by any of the foregoing values, or any
combination of the foregoing percentage values.
[0179] The second thermoplastic composition can have a melting
temperature from about 100 degrees centigrade to about 210 degrees
centigrade, optionally from about 110 degrees centigrade to about
195 degrees centigrade, from about 120 degrees centigrade to about
180 degrees centigrade, or from about 120 degrees centigrade to
about 170 degrees centigrade. The melting temperature of the second
thermoplastic composition can be within about 50 degrees
centigrade, or about 40 degrees centigrade, or about 30 degrees
centigrade, or about 20 degrees centigrade of the first
thermoplastic composition.
[0180] The second thermoplastic composition can have a melt flow
rate of at least 0.2 grams per 10 minutes, optionally at least 5,
at least 10, at least 15, at least 20, at least 25, at least 30, at
least 40, or at least 50 grams per 10 minutes, as determined using
ASTM D1238-13 at 160 degrees centigrade using a weight of 2.16 kg.
The second thermoplastic composition can have a melt flow rate of
at least 0.2 grams per 10 minutes, optionally at least 5, at least
10, at least 15, at least 20, at least 25, at least 30, at least
40, or at least 50 grams per 10 minutes, as determined using ASTM
D1238-13 at 200 degrees centigrade using a weight of 10 kg.
[0181] The second thermoplastic composition can have a melting
temperature from about 100 degrees centigrade to about 210 degrees
centigrade, optionally from about 110 degrees centigrade to about
195 degrees centigrade, from about 120 degrees centigrade to about
180 degrees centigrade, or from about 120 degrees centigrade to
about 170 degrees centigrade.
[0182] The second thermoplastic composition can have a melt flow
index of from about 5 to about 40, or about 10 to about 20, or
about 20 to about 30 as determined at 210 degrees centigrade using
a 2.16 kilogram weight. Alternatively or additionally, the second
thermoplastic composition can have a melt flow index of from about
5 to about 40, or about 10 about 20, or about 20 to about 30 as
determined at 220 degrees centigrade using a 2.16 kilogram weight.
Alternatively or additionally, the second thermoplastic composition
can have a melt flow index of from about 5 to about 40, or about 10
to about 20, or about 20 to about 30 as determined at 230 degrees
centigrade using a 2.16 kilogram weight.
[0183] The second thermoplastic composition can have a durometer
Shore A hardness of less than 90 or less than 85 or less than 80.
The second thermoplastic composition can have a durometer Shore A
hardness of greater than 60 or greater than 65. The second
thermoplastic composition can have a durometer Shore A hardness of
about 50 to about 90 Shore A, optionally from about 55 to about 85
Shore A, from about 60 to about 80 Shore A, or from about 60 to
about 70 Shore A.
[0184] In the foamed article, the second thermoplastic composition
can have a specific gravity from about 0.8 to about 1.5, optionally
from about 0.85 to about 1.30, or from about 0.88 to about 1.20.
Alternatively, in the foamed article, the second thermoplastic
composition can be a multicellular foam having a specific gravity
of from about 0.15 to about 0.60, or from about 0.15 to about 0.40,
or from about 0.15 to about 0.25.
[0185] The second thermoplastic composition can have two or more of
the first properties, or optionally three or more, four or more,
five or more, six or more, seven or more, or all ten first
properties provided above.
[0186] In addition to the first properties, the second
thermoplastic composition can have one or more second properties.
The second thermoplastic composition can have a glass transition
temperature less than 50 degrees centigrade, optionally less than
30 degrees centigrade, less than 0 degrees centigrade, less than
-10 degrees centigrade, or less than -20 degrees centigrade. The
second thermoplastic composition can have a stress at break greater
than 7 megapascals, optionally greater than 8 megapascals, or
greater than 8 megapascals as determined using ASTM DE-412 at 25
degrees centigrade The second thermoplastic composition can have a
tensile stress at 300 percent modulus greater than 2 megapascals,
optionally greater than 2.5 megapascals, or greater than 3
megapascals as determined using ASTM DE-412 at 25 degrees
centigrade The second thermoplastic composition can have an
elongation at break greater than 450 percent, optionally greater
than 500 percent, or greater than 550 percent as determined using
ASTM DE-412 at 25 degrees centigrade. The second thermoplastic
composition can have two or more of the second properties, or
optionally three or more, or all four second properties.
[0187] According to the various aspects, the disclosed foam article
has a polymeric layer disposed on at least one exterior surface of
the foam component. For example, the polymeric layer can be a
polymeric coating or a polymeric film. In some aspects, the
polymeric layer acts as a fluid barrier that controls or prevents
water uptake by the foam article. The polymeric layer may be
integral with the foam component, or may be a separate component
that is operably coupled with the foam component, as described
herein.
[0188] The polymeric layer can be disposed on at least one exterior
surface of the foam component. For example, where the foam article
is a midsole, the coating can be on all or part of the sidewall of
the midsole, or on all or part of a ground-facing (bottom) surface
of the midsole, or on all or part of an upper-facing (top) surface
of the midsole, or any combination thereof. The polymeric layer can
be disposed on at least one surface that may be exposed to moisture
during normal use of the finished article, e.g., an article of
footwear.
[0189] As disposed on the foam component, the polymeric layer has
an average thickness of about 0.01 millimeter to about 3
millimeter, or about 0.03 millimeter to about 2 millimeter, or from
about 0.1 millimeter to about 1 millimeter.
[0190] Thermoplastic Elastomers
[0191] The first and second thermoplastic compositions described
herein can comprise one or more thermoplastic elastomers. Exemplary
thermoplastic elastomers include thermoplastic homo-polymer
elastomer and thermoplastic co-polymer elastomers. The
thermoplastic elastomer can be a thermoplastic random co-polymer
elastomer. The thermoplastic elastomer can be a thermoplastic block
co-polymer elastomer. The term "polymer" refers to a polymerized
molecule having one or more monomer species, and includes
homopolymers and copolymers. The term "copolymer" refers to a
polymer having two or more monomer species, and includes
terpolymers (i.e., copolymers having three monomer species). For
example, the thermoplastic elastomer can be a block co-polymer
having repeating blocks of polymeric units of the same chemical
structure (segments) which are relatively harder (hard segments),
and repeating blocks of polymeric segments which are relatively
softer (soft segments). In various aspects, in block co-polymers,
including block co-polymers 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.
Particular examples of hard segments include isocyanate segments
and polyamide segments. Particular examples of soft segments
include polyether segments and polyester segments. As used herein,
the polymeric segment can be referred to as being a particular type
of polymeric segment such as, for example, an isocyanate segment, a
polyamide segment, a polyether segment, a polyester segment, and
the like. It is understood that the chemical structure of the
segment is derived from the described chemical structure. For
example, an isocyanate segment is a polymerized unit including an
isocyanate functional group. When referring to a block of polymeric
segments of a particular chemical structure, the block can contain
up to 10 mol percent of segments of other chemical structures. For
example, as used herein, a polyether segment is understood to
include up to 10 mol percent of non-polyether segments.
[0192] The thermoplastic elastomer can include one or more of a
thermoplastic polyester elastomer, a thermoplastic polyurea
elastomer, a thermoplastic polyimide elastomer, a thermoplastic
polyamide elastomer, a thermoplastic polyether elastomer, a
thermoplastic polyurethane elastomer, a thermoplastic polyolefin
elastomer, a thermoplastic ionomer elastomer, any copolymer
thereof, or any blend thereof. It should be understood that other
thermoplastic polymeric materials not specifically described below
are also contemplated for use in the coated fiber as described
herein and/or the uncoated fiber.
[0193] The second thermoplastic composition can include one or more
of thermoplastic polyamide elastomers, such as PEBA or polyether
block polyamides. The second thermoplastic composition can comprise
one or more metallocene-catalyzed block copolymers of ethylene and
.alpha.-olefins having 4 to about 8 carbon atoms. The second
thermoplastic composition can comprise one or more thermoplastic
styrene copolymers, including styrene block copolymers such as
poly(styrene-butadiene-styrene),
poly(styrene-ethylene-co-butylene-styrene), and
poly(styrene-isoprene-styrene), and combinations thereof.
[0194] The second thermoplastic composition can include at least
one thermoplastic polyester, including at least one thermoplastic
copolyester. Exemplary, but non-limiting, thermoplastic copolyester
elastomers, including thermoplastic copolyesters, that can be used
in the disclosed methods, foams, and articles include "HYTREL"
3078, "HYTREL" 4068, and "HYTREL" 4556 (DuPont, Wilmington, Del.,
USA); "PELPRENE" P30B, P40B, and P40H (Toyobo U.S.A. Inc., New
York, N.Y., USA); "TRIEL" 5300, "TRIEL" 5400, and blends thereof
(Samyang Corporation, Korea); "KEYFLEX" BT1028D, BT1033D, BT1035D,
BT1040D, BT1045D, and BT1047D (LG Chem, Korea); and "KOPEL" KP3340,
KP3346, KP3347, KP3942 (Kolon Plastics, Inc., Korea). The polymeric
component of second thermoplastic composition (i.e., the component
consisting of all the polymers present in the second polymeric
material) can comprise at least 80 weight percent of thermoplastic
copolyester elastomers, or at least 90 weight percent of
thermoplastic copolyester elastomers, or at least 95 weight percent
of thermoplastic copolyester elastomers, based on a total weight of
the second thermoplastic composition.
[0195] The second thermoplastic composition can include one or more
thermoplastic polyurethanes (TPUs), such as "FORTIMO" (Mitsui
Chemicals, Inc., Tokyo, Japan); "TEXIN" (Covestro LLC, Pittsburgh,
Pa., USA); and "BOUNCELL-X" (Lubrizol Advanced Materials, Inc.,
Brecksville, Ohio, USA). The polymeric component of second
thermoplastic composition (i.e., the component consisting of all
the polymers present in the second thermoplastic composition) can
comprise at least 80 weight percent of TPU elastomers, or at least
90 weight percent of TPU elastomers, or at least 95 weight percent
of TPU elastomers, based on a total weight of the second
thermoplastic composition. The second thermoplastic composition can
include one or more thermoplastic polyurethane hot-melt adhesives,
such as, for example, "NASA-T" hot-melt film (Sambu Fine Chemicals,
Gimhae-si, Gyeongsangdam-do, Korea).
[0196] The second thermoplastic composition can comprise a blend of
one or more thermoplastic polyurethane elastomers with one or more
thermoplastic polymers having a different chemical structure. In
one aspect, the second thermoplastic composition comprises one or
more thermoplastic polyurethane elastomers and one or more
ethylene-vinyl alcohol copolymers. In another aspect, the second
thermoplastic composition comprises one or more thermoplastic
elastomers and one or more thermoplastic polystyrene elastomers,
such as, for example, one or more SEBS copolymer elastomers.
[0197] The thermoplastic composition can include one or more
olefinic polymers. Olefinic polymers can include ethylene-based
copolymers, propylene-based copolymers, and butene-based
copolymers. The olefinic polymer can be an ethylene-based copolymer
such as a styrene-ethylene/butylene-styrene (SEBS) copolymer; an
ethylene-propylene diene monomer (EPDM) copolymer; an
ethylene-vinyl acetate (EVA) copolymer; an ethylene-vinyl alcohol
(EVOH) copolymer; an ethylene alkyl acrylate (EAA) copolymer; an
ethylene alkyl methacrylate (EAMA) copolymer; any copolymer
thereof, and any blend thereof.
[0198] The thermoplastic composition can include one or more
olefinic polymers. Olefinic polymers can include ethylene-based
copolymers, propylene-based copolymers, and butene-based
copolymers. In some aspects, the olefinic polymer is an
ethylene-based copolymer such as a
styrene-ethylene/butylene-styrene (SEBS) copolymer; an
ethylene-propylene diene monomer (EPDM) copolymer; an
ethylene-vinyl acetate (EVA) copolymer; an ethylene alkyl acrylate
(EAA) copolymer; an ethylene alkyl methacrylate (EAMA) copolymer;
any copolymer thereof, and any blend thereof. In some aspects, a
ratio of a total parts by weight of the olefinic polymers present
in the composition to a total parts by weight of the thermoplastic
copolyesters or of the second thermoplastic composition in the
composition is about 0.0 to about 0.6, about 0.0 to about 0.4,
about 0.01 to about 0.4, or about 0.01 to about 0.6, or about 0.1
to about 0.4.
[0199] The thermoplastic composition can include an ethylene-vinyl
acetate (EVA) copolymer. The ethylene-vinyl acetate (EVA) copolymer
can have a range of vinyl acetate contents, for example about 50
percent to about 90 percent, about 50 percent to about 80 percent,
about 5 percent to about 50 percent, about 10 percent to about 45
percent, about 10 percent to about 30 percent, about 30 percent to
about 45 percent, or about 20 percent to about 35 percent.
[0200] The second thermoplastic composition can include one or more
ionomers, such as any of the "SURLYN" polymers (DuPont, Wilmington,
Del., USA).
[0201] The thermoplastic elastomer can have a melting temperature
greater than about 110 degrees centigrade and less than about 210
degrees centigrade or less than about 170 degrees centigrade.
[0202] The thermoplastic elastomer can have a glass transition
temperature less than 50 degrees centigrade, or less than 20
degrees centigrade, or less than 0 degrees centigrade, or less than
-10 degrees centigrade, when determined in accordance with ASTM
D3418-97 as described herein below. Thermoplastic Polyurethane
Elastomers
[0203] The thermoplastic elastomer can be a thermoplastic
polyurethane elastomer. The thermoplastic polyurethane elastomer
can be a thermoplastic block polyurethane co-polymer. The
thermoplastic block polyurethane co-polymer can be a block
copolymer having blocks of hard segments and blocks of soft
segments. The hard segments can comprise or consist of isocyanate
segments. The soft segments can comprise or consist of polyether
segments, or polyester segments, or a combination of polyether
segments and polyester segments. The thermoplastic material can
comprise or consist essentially of an elastomeric thermoplastic
polyurethane having repeating blocks of hard segments and repeating
blocks of soft segments.
[0204] One or more of the thermoplastic polyurethane elastomer can
be produced by polymerizing one or more isocyanates with one or
more polyols to produce copolymer chains having carbamate linkages
(--N(CO)O--) as illustrated below in Formula 7 below,
##STR00013##
where the isocyanate(s) each preferably include two or more
isocyanate (--NCO) groups per molecule, such as 2, 3, or 4
isocyanate groups per molecule (although, single-functional
isocyanates can also be optionally included, e.g., as chain
terminating units). In these aspects, each R.sub.1 and R.sub.2
independently is an aliphatic or aromatic segment. Optionally, each
R.sub.2 can be a hydrophilic segment.
[0205] 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.
[0206] Additionally, the isocyanates can also be chain extended
with one or more chain extenders to bridge two or more isocyanates.
This can produce polyurethane copolymer chains as illustrated below
in Formula 8,
##STR00014##
wherein R.sub.3 includes the chain extender. As with each R.sub.1
and R.sub.3, each R.sub.3 independently is an aliphatic or aromatic
segment.
[0207] Each segment R.sub.1, or the first segment, in Formulas 7
and 8 can independently include a linear or branched C.sub.3-30
segment, 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 that does not include a
cyclically conjugated ring system having delocalized pi electrons.
In comparison, the term "aromatic" refers to a cyclically
conjugated ring system having delocalized pi electrons, which
exhibits greater stability than a hypothetical ring system having
localized pi electrons.
[0208] Each segment R.sub.1 can be present in an amount of 5
percent to 85 percent by weight, from 5 percent to 70 percent by
weight, or from 10 percent to 50 percent by weight, based on the
total weight of the reactant monomers.
[0209] In aliphatic aspects (from aliphatic isocyanate(s)), each
segment R.sub.1 can include a linear aliphatic group, a branched
aliphatic group, a cycloaliphatic group, or combinations thereof.
For instance, each segment R.sub.1 can include a linear or branched
C.sub.3-20 alkylene segment (e.g., C.sub.4-15 alkylene or
C.sub.6-10 alkylene), one or more C.sub.3-8cycloalkylene segments
(e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
cycloheptyl, or cyclooctyl), and combinations thereof.
[0210] Examples of suitable aliphatic diisocyanates for producing
the polyurethane copolymer chains include hexamethylene
diisocyanate (HDI), isophorone diisocyanate (IPDI),
butylenediisocyanate (BDI), bisisocyanatocyclohexylmethane (HMDI),
2,2,4-trimethylhexamethylene diisocyanate (TMDI),
bisisocyanatomethylcyclohexane, bisisocyanatomethyltricyclodecane,
norbornane diisocyanate (NDI), cyclohexane diisocyanate (CHDI),
4,4'-dicyclohexylmethane diisocyanate (H12M DI),
diisocyanatododecane, lysine diisocyanate, and combinations
thereof.
[0211] In aromatic aspects (from aromatic isocyanate(s)), each
segment R.sub.1 can include one or more aromatic groups, such as
phenyl, naphthyl, tetrahydronaphthyl, phenanthrenyl, biphenylenyl,
indanyl, indenyl, anthracenyl, and fluorenyl. Unless otherwise
indicated, an aromatic group can be an unsubstituted aromatic group
or a substituted aromatic group, and can also include
heteroaromatic groups. "Heteroaromatic" refers to monocyclic or
polycyclic (e.g., fused bicyclic and fused tricyclic) aromatic ring
systems, where one to four ring atoms are selected from oxygen,
nitrogen, or sulfur, and the remaining ring atoms are carbon, and
where the ring system is joined to the remainder of the molecule by
any of the ring atoms. Examples of suitable heteroaryl groups
include pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl,
imidazolyl, thiazolyl, tetrazolyl, oxazolyl, isooxazolyl,
thiadiazolyl, oxadiazolyl, furanyl, quinolinyl, isoquinolinyl,
benzoxazolyl, benzimidazolyl, and benzothiazolyl.
[0212] Examples of suitable aromatic diisocyanates for producing
the polyurethane copolymer chains include toluene diisocyanate
(TDI), TDI adducts with trimethyloylpropane (TMP), methylene
diphenyl diisocyanate (MDI), xylene diisocyanate (XDI),
tetramethylxylylene diisocyanate (TMXDI), hydrogenated xylene
diisocyanate (HXDI), naphthalene 1,5-diisocyanate (NDI),
1,5-tetrahydronaphthalene diisocyanate, para-phenylene diisocyanate
(PPDI), 3,3'-dimethyldiphenyl-4, 4'-diisocyanate (DDDI),
4,4'-dibenzyl diisocyanate (DBDI), 4-chloro-1,3-phenylene
diisocyanate, and combinations thereof. In some aspects, the
copolymer chains are substantially free of aromatic groups.
[0213] The polyurethane copolymer chains can be produced from
diisocyanates including HMDI, TDI, MDI, H.sub.12 aliphatics, and
combinations thereof. For example, the coated fiber as described
herein of the present disclosure can comprise one or more
polyurethane copolymer chains are produced from diisocynates
including HMDI, TDI, MDI, H.sub.12 aliphatics, and combinations
thereof.
[0214] Commercially available thermoplastic polyurethane elastomers
having greater hydrophilicity suitable for the present use include,
but are not limited to those under the tradename "TECOPHILIC", such
as TG-500, TG-2000, SP-80A-150, SP-93A-100, SP-60D-60 (Lubrizol,
Countryside, Ill.), "ESTANE" (e.g., 58238, T470A-, 2350-75A-030;
Lubrizol, Countryside, Ill.), and "ELASTOLLAN" (e.g., 9500, B70A;
BASF).
[0215] The thermoplastic polyurethane elastomer can be partially
covalently crosslinked, as previously described herein.
[0216] The second thermoplastic composition can include one or more
thermoplastic polyurethanes (TPUs), such as "FORTIMO" (Mitsui
Chemicals, Inc., Tokyo, Japan); "TEXIN" (Covestro LLC, Pittsburgh,
Pa., USA); and "BOUNCELL-X" (Lubrizol Advanced Materials, Inc.,
Brecksville, Ohio, USA). The polymer component of second
thermoplastic composition (i.e., the component consisting of all
the polymers present in the second thermoplastic composition) can
comprise at least 80 weight percent of TPUs, or at least 90 weight
percent of TPUs, or at least 95 weight percent of TPUs, based on a
total weight of the second thermoplastic composition. The second
thermoplastic composition can include one or more thermoplastic
polyurethane hot-melt adhesives, such as, for example, "NASA-T"
hot-melt film (Sambu Fine Chemicals, Gimhae-si, Gyeongsangdam-do,
Korea).
[0217] Thermoplastic Block Co-Polyamide Elastomers
[0218] In various aspects, the second thermoplastic composition as
described herein can comprise one or more thermoplastic elastomers
comprising a thermoplastic block co-polyamide elastomer. The
thermoplastic block co-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.
[0219] The block co-polyamide can have repeating blocks of hard
segments, and repeating blocks soft segments. The hard segments can
comprise polyamide segments, and the soft segments can comprise
non-polyamide segments. The thermoplastic elastomer can be an
elastomeric thermoplastic co-polyamide comprising or consisting of
block co-polyamides having repeating blocks of hard segments and
repeating blocks of soft segments. In block co-polymers, including
block co-polymers 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.
[0220] The polyamide segments of the block 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 blocks. In a particular
example, the polyamide segments can comprise or consist of
polyamide 6 segments, or polyamide 12 segments, or both polyamide 6
segment and polyamide 12 segments. In the example where the
polyamide segments of the co-polyamide include of polyamide 6
segments and polyamide 12 segments, the segments can be arranged
randomly. The non-polyamide segments of the co-polyamide can
comprise or consist of polyether segments, polyester segments, or
both polyether segments and polyester segments. The co-polyamide
can be a block co-polyamide, or can be a random co-polyamide. The
thermoplastic copolyamide can be formed from the polycodensation of
a polyamide oligomer or prepolymer with a second oligomer
prepolymer to form a block copolyamide (i.e., a block co-polymer
including polyamide segments. Optionally, the second prepolymer can
be a hydrophilic prepolymer.
[0221] Exemplary commercially available copolymers include, but are
not limited to, those available under the tradenames of
VESTAMID.RTM. (Evonik Industries); PELATAMID.RTM. (Arkema), e.g.,
product code H2694; PEBAX.RTM. (Arkema), e.g., product code "PEBAX
MH1657" and "PEBAX MV1074"; PEBAX.RTM. RNEW (Arkema); GRILAMID.RTM.
(EMS-Chemie AG), or also to other similar materials produced by
various other suppliers.
[0222] Thermoplastic Polyolefin Elastomers
[0223] In some aspects, the thermoplastic elastomers can comprise
or consist essentially of a thermoplastic polyolefin. Exemplary of
thermoplastic polyolefins useful in the disclosed second
thermoplastic compositions can include, but are not limited to,
thermoplastic olefin elastomers (e.g., metallocene-catalyzed block
copolymers of ethylene and .alpha.-olefins having 4 to about 8
carbon atoms). The thermoplastic polyolefin can be a polymer
comprising an ethylene-.alpha.-olefin copolymer, an
ethylene-propylene rubber (EPDM), a polybutene, a polyisobutylene,
a poly-4-methylpent-1-ene, a polyisoprene, a polybutadiene, an
ethylene-methacrylic acid copolymer, and an olefin elastomer such
as a dynamically cross-linked polymer obtained from polypropylene
(PP) and an ethylene-propylene rubber (EPDM), and blends or
mixtures of the foregoing. Further exemplary thermoplastic
polyolefins useful in the disclosed second thermoplastic
compositions are polymers of cycloolefins such as cyclopentene or
norbornene.
[0224] The polyolefin can 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 wt percent vinyl
acetate-derived composition.
[0225] The thermoplastic polyolefin can be a mixture of
thermoplastic polyolefins, such as a mixture of two or more
polyolefins disclosed herein above. For example, a suitable mixture
of thermoplastic polyolefins can be a mixture of polypropylene with
polyisobutylene, polypropylene with polyethylene (for example
PP/HDPE, PP/LDPE) or mixtures of different types of polyethylene
(for example LDPE/HDPE).
[0226] The thermoplastic polyolefin can be a copolymer of suitable
monolefin monomers or a copolymer of a suitable monolefin monomer
and a vinyl monomer. Exemplary thermoplastic polyolefin copolymers
include, but are not limited to, ethylene/propylene copolymers,
linear low density polyethylene (LLDPE) and mixtures thereof with
low density polyethylene (LDPE), propylene/but-1-ene copolymers,
propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,
ethylene/hexene copolymers, ethylene/methylpentene copolymers,
ethylene/heptene copolymers, ethylene/octene copolymers,
propylene/butadiene copolymers, isobutylene/isoprene copolymers,
ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate
copolymers, ethylene/vinyl acetate copolymers and their copolymers
with carbon monoxide or ethylene/acrylic acid copolymers and their
salts (ionomers) as well as terpolymers of ethylene with propylene
and a diene such as hexadiene, dicyclopentadiene or
ethylidene-norbornene; and mixtures of such copolymers with one
another and with polymers mentioned in 1) above, for example
polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl
acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers
(EAA), LLDPE/EVA, LLDPE/EAA and alternating or random
polyalkylene/carbon monoxide copolymers and mixtures thereof with
other polymers, for example polyamides.
[0227] 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.
[0228] 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.
[0229] Thermoplastic Ionomer Elastomers
[0230] In certain aspects, the thermoplastic elastomer can be one
or more ionomeric polymers. The ionomeric polymers can include
chain units derived from one or more olefins and chain units
derived from one or more ethylenically-unsaturated acid groups. The
compositions can also include a plurality of cations ionically
crosslink anionic form of the acid groups in the ionomeric
copolymers. The compositions can be essentially just the ionomeric
copolymers and metal cations. The ionomeric copolymers can have a
melt flow index of about 30 or less, about 20 or less, about 15 or
less, about 10 or less, or about 5 or less.
[0231] The ionomeric copolymers can be terpolymers of ethylene,
acrylic acid, and methyl acrylate or butyl acrylate. In some
aspects, a ratio III of a total parts by weight of the acrylic acid
in the ionomeric copolymers to a total weight of the ionomeric
copolymers is about 0.05 to about 0.6, about 0.1 to about 0.6,
about 0.1 to about 0.5, about 0.15 to about 0.5, or about 0.2 to
about 0.5.
[0232] The second thermoplastic composition can include one or more
ionomers, such as any of the "SURLYN" polymers (DuPont, Wilmington,
Del., USA.
[0233] The second thermoplastic composition can include acrylic
block copolymer elastomers, such as block copolymers comprising a
first PMMA block, an acrylate block, and a second PMMA block.
[0234] Thermoplastic Styrenic Copolymer Elastomers
[0235] In certain aspects, the thermoplastic elastomer is a
thermoplastic elastomeric styrenic copolymer. Examples of these
copolymers include, but are not limited to, styrene butadiene
styrene (SBS) block copolymer, a styrene ethylene/butylene styrene
(SEBS) resin, a polyacetal resin (POM) or a styrene acrylonitrile
resin (SAN). Exemplary commercially available thermoplastic
elastomeric styrenic copolymers include MONOPRENE IN5074, SP066070,
and SP16975 (Teknor Apex), which are styrene ethylene/butylene
styrene (SEBS) resins.
[0236] Thermoplastic Vulcanizate Materials
[0237] The second thermoplastic composition can include an
injection processible thermoplastic vulcanizate (TPV) material.
Injection-processible TPV materials are typically cross-linked or
partially cross-linked rubbers dispersed into thermoplastic host
phases. Exemplary TPV materials include ethylene propylene diene
rubber in polypropylene hosts (EPDM/PP), such as "SARLINK" or
"SANTOPRENE" TPV materials. Other exemplary TPV materials include
alkyl acrylic copolymer rubbers in polyamide hosts (ACM/PA), such
as "ZEOTHERM" TPVs. Yet other exemplary TPV materials include
silicone rubbers dispersed in "HYTREL" based copolyesters (e.g.,
so-called TSiPVs).
Additives
[0238] In various aspects, the disclosed first thermoplastic
composition and second thermoplastic composition can independently
further comprise an additive. The additive can be incorporated
directly into the disclosed first thermoplastic composition or
second thermoplastic composition, or alternatively, applied
thereto, prior to foaming the first thermoplastic composition or
second thermoplastic composition. Additives that can be used in the
disclosed compositions and materials include, but are not limited
to, dyes, pigments, colorants, ultraviolet light absorbers,
hindered amine light stabilizers, antioxidants, processing aids or
agents, plasticizers, lubricants, emulsifiers, pigments, dyes,
optical brighteners, rheology additives, catalysts, flow-control
agents, slip agents, crosslinking agents, crosslinking boosters,
halogen scavengers, smoke inhibitors, flameproofing agents,
antistatic agents, fillers, or mixtures of two or more of the
foregoing. In some aspects, the additive can be a wax, an
anti-oxidant, a UV-absorbing agent, a coloring agent, or
combinations thereof.
[0239] The additive can be present in an amount from about 0.1
weight percent to about 10 weight percent, or from 0.1 to 6 weight
percent, based on the total weight of the first or second
thermoplastic composition. In a particular aspect, the additive can
be present in the first or second thermoplastic composition in an
amount from about 0.1 weight percent to about 4 weight percent,
based on a total weight of the first or second thermoplastic
composition. The first or second thermoplastic composition can
comprise less than 4 weight percent, or less than 3 weight percent,
or less than 2 weight percent, or less than 1 weight percent of
additives, based on a total weight of the first or second
thermoplastic composition.
[0240] The first and/or second thermoplastic composition can be
essentially free of additives, where the amount of additive is less
than about 0.1 weight percent, about 0.08 weight percent, about
0.06 weight percent, about 0.04 weight percent, or about 0.02
weight percent of the first and/or second thermoplastic
composition. In another aspect, the first and/or second
thermoplastic composition is free of any additives (i.e., contains
no additives).
[0241] In some instances, an additive can be present in an amount
of from about 0.01 weight percent to about 10 weight percent, about
0.025 weight percent to about 5 weight percent, or about 0.1 weight
percent to 3 weight percent, where the weight percent is based upon
the sum of the material components in the first thermoplastic
composition or second thermoplastic composition.
[0242] Individual components can be mixed together with the other
components of the first thermoplastic composition or second
thermoplastic composition in a continuous mixer or a batch mixer,
e.g., in an intermeshing rotor mixer, such as an Intermix mixer, a
twin screw extruder, in a tangential rotor mixer such as a Banbury
mixer, using a two-roll mill, or some combinations of these to make
a composition comprising a thermoplastic polymer and an additive.
The mixer can blend the components together via a single step or
multiple steps, and can mix the components via dispersive mixing or
distributive mixing to form the resulting thermoplastic
composition. This step is often referred to as "compounding."
[0243] The first thermoplastic composition and second thermoplastic
composition can independently further comprise a solid
non-polymeric material such as a chemical blowing agent, nucleating
agent, filler, pigment, or a combination thereof. The solid
non-polymeric material can be present in an amount from about 0.05
weight percent to about 20 weight percent based on the total weight
of the first thermoplastic composition and/or second thermoplastic
composition; about 0.1 weight percent to about 10 weight percent
based on the total weight of the first thermoplastic composition
and/or second thermoplastic composition; or 0.5 weight percent to
about 5 weight percent based on the total weight of the first
thermoplastic composition and/or second thermoplastic composition.
The first or the second thermoplastic composition can comprise
about 5 weight percent or less, or about 3 weight percent or less,
or about 2 weight percent or less, or about 1 weight percent or
less of solid non-polymeric material, based on the total weight of
the first thermoplastic composition and/or second thermoplastic
composition. The foamed polymeric material can comprise less than
about 5 weight percent, or less than 4 weight percent, or less than
3 weight percent, or less than 2 weight percent, or less than 1
weight percent of solid non-polymeric material, based on the total
weight of the first thermoplastic composition and/or second
thermoplastic composition.
[0244] The first thermoplastic composition and/or second
thermoplastic composition can comprise essentially no, or can
comprise no non-polymeric materials such as chemical blowing
agents, nucleating agents, fillers, pigments, or a combination
thereof. In other words, the first thermoplastic composition and/or
second thermoplastic composition can be essentially free of
non-polymeric materials. In other aspects, the first thermoplastic
composition and/or second thermoplastic composition can comprise 5
weight percent or less of a non-polymeric material such as a
chemical blowing agent, nucleating agent, filler, pigment, or a
combination thereof. The first thermoplastic composition and/or
second thermoplastic composition can comprise less than 4 weight
percent, less than 3 weight percent, less than 2 weight percent,
less than 1 weight percent, less than 0.5 weight percent, less than
0.1 weight percent, less than 0.08 weight percent, less 0.06 weight
percent, less than 0.04 weight percent, or less than 0.02 weight
percent of non-polymeric material, based on a total weight of the
first thermoplastic composition and/or second thermoplastic
composition. In other aspects, the first thermoplastic composition
and/or second thermoplastic composition is free of (i.e., contains
no) non-polymeric material such as a chemical blowing agent,
nucleating agent, filler, or a combination thereof.
[0245] In some instances, the solid non-polymeric material is a
filler. The filler can be a particulate filler. In further aspects,
the filler is a carbonaceous filler. The carbonaceous filler can be
carbon black, activated carbon, graphite, carbon fibers, carbon
fibrils, carbon nanoparticles, or combinations thereof. In various
aspects, the carbonaceous filler can be chemically-modified.
Alternatively, the filler can be an inorganic filler. The inorganic
filler can be an oxide, a hydroxide, a salt, a silicate, a metal,
or combinations thereof. Examples of an inorganic filler include,
but are not limited to, glass spheres, glass fibers, glass hollow
spheres, glass flakes, MgO, SiO.sub.2, Sb.sub.2O.sub.3,
Al.sub.2O.sub.3, ZnO, talc, mica, kaolin, wollastonite, or
combinations thereof.
[0246] Nucleating agents are widely used to modify the properties
of various polymers. Nucleating agents can aid in decreasing foam
specific gravity, increasing the number of cells present in the
foam, and decreasing cell size in the foam by providing a surface
for heterogeneous nucleation of gas bubbles from the supercritical
fluid state. For the first thermoplastic compositions and second
thermoplastic compositions of the present disclosure, nucleating
agents can influence the properties of the final foam article by
modifying the quantity, distribution and rate of supercritical
fluid conversion from a liquid to a gas during the foaming process
as lower pressures. The addition of nucleating agents provides a
surface on which the supercritical fluid can be transformed from a
liquid to a gas. As a consequence, many nucleation sites will
result in many gas cell domains. In a particular example, the
nucleating agent can include a metal salt of a fatty acid. In some
aspects, the nucleating agent is zinc stearate. In some aspects,
the composition or material contains about 0.1 weight percent to
about 10 weight percent, about 0.1 weight percent to about 5 weight
percent, about 0.1 weight percent to about 2 weight percent, or
about 0.5 weight percent to about 2 weight percent of the
nucleating agent based upon a total weight of the composition or
material.
[0247] In some aspects, the additive is a nucleating agent such as
talcum, metal oxides such as titanium dioxide or magnesium oxide,
phosphates, carbonates or sulfates of, preferably, alkaline earth
metals, or mixtures thereof. Alternatively, the nucleating agent
can be a mono- or polycarboxylic acids, and the salts thereof,
e.g., 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid,
sodium succinate, sodium benzoate, or mixtures thereof. In a
further aspect, the additive can be a nucleating agent comprising
both an inorganic and an organic material as disclosed herein
above.
[0248] In some aspects, the rheology modifier can be a
nano-particles having comparatively high aspect ratios, nano-clays,
nano-carbon, graphite, nano-silica, and the like.
[0249] In some aspects, the additive is a filler or reinforcing
agent such as clay, kaolin, talc, asbestos, graphite, glass (such
as glass fibers, glass particulates, and glass bulbs, spheres, or
spheroids), mica, calcium metasilicate, barium sulfate, zinc
sulfide, aluminum hydroxide, silicates, diatomaceous earth,
carbonates (such as calcium carbonate, magnesium carbonate and the
like), metals (such as titanium, tungsten, zinc, aluminum, bismuth,
nickel, molybdenum, iron, copper, brass, boron, bronze, cobalt,
beryllium, and alloys of these), metal oxides (such as zinc oxide,
iron oxide, aluminum oxide, titanium oxide, magnesium oxide,
zirconium oxide and the like), metal hydroxides, particulate
synthetic plastics (such as polyethylene, polypropylene,
polystyrene, polyamide, polyester, polyurethane, polyimide, and the
like), synthetic fibers (such as fibers comprising high molecular
weight polyethylene, polypropylene, polystyrene, polyamide,
polyester, polyurethane, polyimide, and the like), particulate
carbonaceous materials (such as carbon black and the like), wood
flour and flours or fibers of other natural products, as well as
cotton flock, non-cotton cellulose flock, cellulose pulp, leather
fiber, and combinations of any of the above. Non-limiting examples
of heavy density filler components that can be used to increase the
specific gravity of the cured elastomer composition can include
titanium, tungsten, aluminum, bismuth, nickel, molybdenum, iron,
steel, lead, copper, brass, boron, boron carbide whiskers, bronze,
cobalt, beryllium, zinc, tin, metal oxides (such as zinc oxide,
iron oxide, aluminum oxide, titanium oxide, magnesium oxide, and
zirconium oxide), metal sulfates (such as barium sulfate), metal
carbonates (such as calcium carbonate), and combinations of these.
Non-limiting examples of light density filler components that can
be used to decrease the specific gravity of the elastomer compound
can include particulate plastics, hollow glass spheres, ceramics,
and hollow spheres, regrinds, and foams, which can be used in
combinations.
[0250] In some examples, the non-polymeric materials can also
include a nanofiller. Nanofillers can not only serve as mechanical
reinforcement but also nucleating agents. A variety of nanofillers
can be used in lieu of or in addition to the zinc stearate.
Nanofillers can include nanomaterials having one-dimensional
structures such as of plates, laminas and/or shells;
two-dimensional structures such as nanotubes and nanofibres having
a diameter lower than 0.1 micrometer; or three-dimensional
nanostructures such as nanoparticles or beads. Nanoplate fillers
can be natural or synthetic clays, as well as phosphates of
transition metals. Clay-based nanocomposites generate an overall
improvement in physical performances. The most widely used ones are
the phyllosilicates. Nanofillers can include nano-oxides such as
nanoparticles of Titanium dioxide or Rutile. Other nanofillers can
include nanoparticles of alumina or aluminum oxide, diatomite, and
nanoscale carbon materials such as single-wall carbon nanotubes
(SWCNT) or double-wall carbon nanotubes (DWCNT).
Definitions
[0251] Unless defined otherwise, all technical and scientific terms
used herein have the same meaning as commonly understood by one of
ordinary skill in the art to which this disclosure belongs. It will
be further understood that terms, such as those defined in commonly
used dictionaries, should be interpreted as having a meaning that
is consistent with their meaning in the context of the
specification and relevant art and should not be interpreted in an
idealized or overly formal sense unless expressly defined
herein.
[0252] The terms "comprises," "comprising," "including," and
"having," are inclusive and therefore specify the presence of
features, steps, operations, elements, and/or components, but do
not preclude the presence or addition of one or more other
features, steps, operations, elements, components, and/or groups
thereof.
[0253] As used in the specification and the appended claims, the
singular forms "a," "an" and "the" include plural referents unless
the context clearly dictates otherwise. Thus, for example,
reference to "a foam particle," "a midsole," or "an adhesive,"
including, but not limited to, two or more such foam particles,
midsoles, or adhesives, and the like.
[0254] As used herein, the term "and/or" includes any and all
combinations of one or more of the associated listed items.
[0255] As used herein, in substance or substantially means at least
50 percent, 60 percent, 75 percent, 90 percent, 95 percent, or
more, as determined based on weight or volume.
[0256] The terms first, second, third, etc. can be used herein to
describe various elements, components, regions, layers and/or
sections. These elements, components, regions, layers and/or
sections should not be limited by these terms. These terms can be
only used to distinguish one element, component, region, layer or
section from another region, layer or section. Terms such as
"first," "second," and other numerical terms do not imply a
sequence or order unless clearly indicated by the context. Thus, a
first element, component, region, layer or section discussed below
could be termed a second element, component, region, layer or
section without departing from the teachings of the example
configurations.
[0257] As used herein, the modifiers "upper," "lower," "top,"
"bottom," "upward," "downward," "vertical," "horizontal,"
"longitudinal," "transverse," "front," "back" etc., unless
otherwise defined or made clear from the disclosure, are relative
terms meant to place the various structures or orientations of the
structures of the article of footwear in the context of an article
of footwear worn by a user standing on a flat, horizontal
surface.
[0258] The term "receiving", such as for "receiving an upper for an
article of footwear", when recited in the claims, is not intended
to require any particular delivery or receipt of the received item.
Rather, the term "receiving" 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.
[0259] 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 can also be
represented by the suffix "(s)" at the end of the element. For
example, "at least one polyamide", "one or more polyamides", and
"polyamide(s)" can be used interchangeably and have the same
meaning.
[0260] It should be noted that ratios, concentrations, amounts, and
other numerical data can be expressed herein in a range format.
Where the stated range includes one or both of the limits, ranges
excluding either or both of those included limits are also included
in the disclosure, e.g. the phrase "x to y" includes the range from
`x` to `y` as well as the range greater than `x` and less than `y`.
The range can also be expressed as an upper limit, e.g. `about x,
y, z, or less` and should be interpreted to include the specific
ranges of `about x`, `about y`, and `about z` as well as the ranges
of `less than x`, less than y', and `less than z`. Likewise, the
phrase `about x, y, z, or greater` should be interpreted to include
the specific ranges of `about x`, `about y`, and `about z` as well
as the ranges of `greater than x`, greater than y', and `greater
than z`. In addition, the phrase "about `x` to `y`", where `x` and
`y` are numerical values, includes "about `x` to about `y`". It is
to be understood that such a range format is used for convenience
and brevity, and thus, should be interpreted in a flexible manner
to include not only the numerical values explicitly recited as the
limits of the range, but also to include all the individual
numerical values or sub-ranges encompassed within that range as if
each numerical value and sub-range is explicitly recited. To
illustrate, a numerical range of "about 0.1% to 5%" should be
interpreted to include not only the explicitly recited values of
about 0.1 percent to about 5 percent, but also include individual
values (e.g., 1 percent, 2 percent, 3 percent, and 4 percent) and
the sub-ranges (e.g., 0.5 percent, 1.1 percent, 2.4 percent, 3.2
percent, and 4.4 percent) within the indicated range.
[0261] The terms "about" and "substantially" are used herein with
respect to measurable values and ranges due to expected variations
known to those skilled in the art (e.g., limitations and
variabilities in measurements).
[0262] As used herein, the terms "optional" or "optionally" means
that the subsequently described component, event or circumstance
can or cannot occur, and that the description includes instances
where said component, event or circumstance occurs and instances
where it does not.
[0263] As used herein, the term "units" can be used to refer to
individual (co)monomer units such that, for example, styrenic
repeat units refers to individual styrene (co)monomer units in the
polymer. In addition, the term "units" can be used to refer to
polymeric block units such that, for example, "styrene repeating
units" can also refer to polystyrene blocks; "units of
polyethylene" refers to block units of polyethylene; "units of
polypropylene" refers to block units of polypropylene; "units of
polybutylene" refers to block units of polybutylene, and so on.
Such use will be clear from the context.
[0264] The term "copolymer" refers to a polymer having two or more
monomer species, and includes terpolymers (i.e., copolymers having
three monomer species).
[0265] Reference to "a" chemical compound refers one or more
molecules of the chemical compound, rather than being limited to a
single molecule of the chemical compound. Furthermore, the one or
more molecules may or may not be identical, so long as they fall
under the category of the chemical compound. Thus, for example, "a"
polyamide is interpreted to include one or more polymer molecules
of the polyamide, where the polymer molecules may or may not be
identical (e.g., different molecular weights and/or isomers).
[0266] As used herein the terms "percent by weight" or "weight
percent," which can be used interchangeably, indicate the weight
percent of a given component based on the total weight of the
composition or article, unless otherwise specified. That is, unless
otherwise specified, all weight percent values are based on the
total weight of the composition. It should be understood that the
sum of weight percent values for all components in a disclosed
composition or formulation or article are equal to 100.
[0267] Similarly, the terms "percent by volume" or "volume
percent," which can be used interchangeably, indicate the percent
by volume of a given component based on the total volume of the
composition or article, unless otherwise specified. That is, unless
otherwise specified, all volume percent values are based on the
total volume of the composition or article. It should be understood
that the sum of volume percent values for all components in a
disclosed composition or formulation or article are equal to
100.
[0268] Compounds are described using standard nomenclature. For
example, any position not substituted by any indicated group is
understood to have its valence filled by a bond as indicated, or a
hydrogen atom. A dash ("-") that is not between two letters or
symbols is used to indicate a point of attachment for a
substituent. For example, --CHO is attached through carbon of the
carbonyl group. Unless defined otherwise, technical and scientific
terms used herein have the same meaning as is commonly understood
by one of skill in the art to which this invention belongs.
[0269] Unless otherwise specified, temperatures referred to herein
are based on atmospheric pressure (i.e. one atmosphere).
[0270] Before proceeding to the Examples, it is to be understood
that this disclosure is not limited to particular aspects
described, and as such may, of course, vary. Other systems,
methods, features, and advantages of foam compositions and
components thereof will be or become apparent to one with skill in
the art upon examination of the following drawings and detailed
description. It is intended that all such additional systems,
methods, features, and advantages be included within this
description, be within the scope of the present disclosure, and be
protected by the accompanying claims. It is also to be understood
that the terminology used herein is for the purpose of describing
particular aspects only, and is not intended to be limiting. The
skilled artisan will recognize many variants and adaptations of the
aspects described herein. These variants and adaptations are
intended to be included in the teachings of this disclosure and to
be encompassed by the claims herein.
Test Methods
[0271] Below are certain sampling procedures and testing methods
referenced in the Description and in the Examples.
Sampling Procedures
[0272] Various properties of the compositions and foams and other
articles formed therefrom can be characterized using samples
prepared with the following sampling procedures:
[0273] a. Neat Sampling Procedure
[0274] The neat sampling procedure can be used to obtain a neat
sample of a foamed or unfoamed first thermoplastic composition, an
unfoamed or foamed second thermoplastic composition, or, in some
instances, a sample of a material (e.g., polymer) used to form a
first thermoplastic composition or second thermoplastic
composition. The material can be provided in media form, such as
flakes, granules, powders, pellets, and the like. If a source of
the first thermoplastic composition or second thermoplastic
composition is not available in a neat form, the sample can be cut
from another component containing the composition or material,
thereby isolating a sample of the composition or material.
[0275] b. Plaque Sampling Procedure--Solid Composition or
Material
[0276] The first thermoplastic composition or second thermoplastic
composition is molded into a plaque having dimensions of about six
inches by about 4 inches and a thickness of about 20 millimeters
(or as otherwise specified by the test method). The sample is
prepared by mixing together the components of the composition or
material, melting the composition or material, pouring, extruding,
or injecting the melted composition into a mold cavity, cooling the
melted composition or material to solidify it in the mold cavity to
form the plaque, and then removing the plaque from the mold
cavity.
[0277] c. Plaque Sampling Procedure--Foam Composition or
Material
[0278] The foamed first thermoplastic composition or second
thermoplastic composition is foamed into a sheet. The skin is
removed from a portion of the sheet, and the skinned portion of the
sheet is cut into a plaque having dimensions of about six inches by
about four inches and a thickness of about 20 millimeter (mm) (or
as otherwise specified by the test method).
[0279] d. Component Sampling Procedure
[0280] This procedure can be used to obtain a sample of a foamed or
unfoamed composition or material when the composition or material
is incorporated into a component such as a sole structure or
midsole or outsole of an article of footwear. A sample of the
component which includes the composition or material is obtained as
formed into the component, or cut from the article of footwear
using a blade. This process is performed by separating the
component from an associated footwear upper, if present, and
removing any materials from the article's top surface (e.g.,
corresponding to the top surface). 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 interfere with the test results.
[0281] The resulting component sample includes the composition or
material. As such, any test using a Component Sampling Procedure
can simulate how the composition or material will perform as part
of an article of footwear. As specified by the test method, the
component may be tested as a full component (e.g., full midsole
component), or it can be extracted as a sample having a certain
geometry. A sample of a component is taken at a location along the
component 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. Unless otherwise specified, the desired
harvested geometry is a cylindrical puck with a 45-millimeter
diameter and a cylinder height of at least about 10 millimeters,
preferably from about 20 to 25 millimeters. Compression testing of
the harvested component samples should be tested along the length
of the cylinder using compression platens that are at least twice
the diameter of the cylindrical puck sample.
Solid Polymer, Thermoplastic Copolyester Composition, and Second
thermoplastic composition Characterization.
[0282] Glass Transition Temperature, Melting Temperature, and
Crystallization Temperature Test
[0283] Dynamic scanning calorimetry (DSC) is performed on samples
prepared using the Neat Sampling Procedure, or on a portion of a
sample prepared using the Plaque Sampling Procedure or the
Component Sampling Procedure. The test is conducted using a DSC
system such as a TA instruments Q2000. 10-30 mg samples are cycled
from negative 90 degrees centigrade to 225 degrees centigrade at a
rate of 20 degrees centigrade/min and cooled to negative 90 degrees
centigrade at a rate of 10 degrees centigrade/min. Each sample is
run in duplicate. The melting temperature, crystallization
temperature, and glass transition temperature values are recorded
from the second cycle. The melt, crystallization, or glass
transition "peak" is identified as the local maximum of the second
heating cycle. If there was more than one melt peak in the DSC
curve, the melt peak occurring at hotter temperatures was chosen as
the injecting or foaming temperature reference. The tail was
identified as the intersection of the tangent of the line of the
higher temperature side of the melt peak with the extrapolated
baseline. A schematic illustrating the method for determining peak
and tail temperatures is shown in FIG. 8.
[0284] Cyclic Tensile Test
[0285] The cyclic tensile testing is carried out on solid samples
prepared using the Plaque Sampling Procedure or the Component
Sampling Procedure, having a dog-bone shape as described in ASTM
D638 with a 2 mm thickness. In the test, the specimen is placed
under a pre-load of 5 N. Strain is controlled to extend the sample
to an extension 6 percent at a strain rate of 5 Hz. The stiffness
is the load at 6 percent strain divided by the extension at 6
percent strain, giving a value in N/mm. The maximum load (N)
observed over the test cycle of 500 cycles is also recorded.
[0286] Melt Flow Index Test
[0287] The melt flow index is determined using a sample prepared
using the Neat Sampling Procedure, or on a portion of a sample
prepared using the Plaque Sampling Procedure or the Component
Sampling Procedure, according to the test method detailed in ASTM
D1238-13 Standard Test Method for Melt Flow Rates of Thermoplastics
by Extrusion Plastometer, using Procedure A described therein.
Briefly, the melt flow index measures the rate of extrusion of
thermoplastics through an orifice at a prescribed temperature and
load. In the test method, approximately 7 grams of the sample is
loaded into the barrel of the melt flow apparatus, which has been
heated to a specified temperature of 210 degrees centigrade, 220
degrees centigrade, or 230 degrees centigrade. A weight of 2.16
kilograms is applied to a plunger and the molten sample is forced
through the die. A timed extrudate is collected and weighed. Melt
flow rate values are calculated in g/10 min, and are reported with
the specified temperature (i.e., 210, 220 or 230 degrees
centigrade) and the weight applied to the plunger (i.e., 2.15
kilograms).
[0288] Solid Polymer Abrasion Test (Akron)
[0289] Abrasion loss is tested on a sample sheet having a thickness
of 3 millimeters, prepared using the Plaque Sampling procedure or
the Component Sampling Procedure. The sample sheet is adhered onto
an Akron abrasion test specimen with JIS-A hardness of 70 by using
an adhesive to prepare a test specimen. Abrasion loss in volume is
measured by using an Akron abrasion test machine at a load of 27N,
an inclination angle of 15 degree, a preliminary abrasion of 500
times and a test abrasion of 1,000 times according to JIS K6254.
The mass and/or volume of the sample is measured before and after
the test, with the difference being the abrasion loss. The smaller
the abrasion loss volume or mass, the better the abrasion
resistance.
[0290] Solid Polymer Abrasion Test (DIN)
[0291] Abrasion loss is tested on samples cut from sheets having a
minimum thickness of 6 millimeters to 12 millimeters, prepared
using the Plaque Sampling Procedure or the Component Sampling
Procedure. The cut samples have a cylindrical shape with a diameter
of 16 millimeters plus or minus 0.2 millimeters and a minimum
thickness of 6 mm to 12 mm cut from sheets using an ASTM standard
hole drill. The abrasion loss is measured using Method B of ASTM D
5963-97a on a standard abrasion test machine such as a Gotech
GT-7012-D abrasion test machine. The tests are performed at 22
degrees centigrade with an abrasion path of 40 meters. The sample
is abraded with a standard sandpaper such as VSM-VITEX-KK511X-60P
sandpaper (commercially available from VSM Abrasives Corp.), using
an abrasion load of 10 Newton. The mass and/or volume of the sample
is measured before and after the test, with the difference being
the abrasion loss. The smaller the abrasion loss, the better the
abrasion resistance of the material.
[0292] Solid Polymer Coefficient of Friction Test (Wet &
Dry)
[0293] This test measures the coefficient of friction of the
Coefficient of Friction Test for a sample (e.g., taken with the
above-discussed Component Sampling Procedure, Plaque Sampling
Procedure, or the Neat Sampling Procedure). The sample is cut into
a rectangular shape measuring approximately 3.0 inches by 3.3
inches, and having a thickness of about 2 millimeters. The sample
is permanently adhered to a 1 centimeter thick piece of EVA foam
having a density of approximately 0.25 grams/cubic centimeters and
having a Durometer hardness of 50 C.
[0294] For a dry test (i.e., to determine a dry-state coefficient
of friction), the sample is initially equilibrated at 25 degree C.
and 20 percent humidity for 24 hours. For a wet test (i.e., to
determine a wet-state coefficient of friction), the sample is fully
immersed in a deionized water bath maintained at 25 degree C. for
24 hours. After that, the sample is removed from the bath and
blotted with a cloth to remove surface water.
[0295] The measurement is performed with an aluminum sled mounted
on a test track, which is used to perform a sliding friction test
for test sample on the surface of the test track. The surface of
the test track may include a specified test track material, such as
aluminum, wood court surface (wet or dry), smooth concrete surface
(wet or dry). The test track measures 127 millimeters wide by 610
millimeters long. The aluminum sled measures 76.2 millimeters by
76.2 millimeters, with a 9.5 millimeter radius cut into the leading
edge. The contact area of the aluminum sled with the track is 76.2
millimeters by 66.6 millimeters, or 5,100 square millimeters).
[0296] The dry or wet sample is attached to the bottom of the sled
using a room temperature-curing two-part epoxy adhesive such as the
adhesive commercially available under the tradename "LOCTITE 608"
from Henkel, Dusseldorf, Germany. The adhesive is used to maintain
the planarity of the wet sample, which can curl when saturated. A
polystyrene foam having a thickness of about 25.4 millimeters is
attached to the top surface of the sled (opposite of the test
sample) for structural support.
[0297] The sliding friction test is conducted using a screw-driven
load frame. A tow cable is attached to the sled with a mount
supported in the polystyrene foam structural support, and is
wrapped around a pulley to drag the sled across the aluminum test
track. The sliding or frictional force is measured using a load
transducer with a capacity of 2,000 Newtons. The normal force is
controlled by placing weights on top of the aluminum sled,
supported by the foam structural support, for a total sled weight
of 1000 Newtons). The crosshead of the test frame has a speed of
0.4 meters/second, and the total test displacement is 250
millimeters. The coefficient of friction is calculated based on the
steady-state force parallel to the direction of movement required
to pull the sled at constant velocity. The coefficient of friction
itself is found by dividing the steady-state pull force by the
applied normal force. Any transient value relating static
coefficient of friction at the start of the test is ignored.
[0298] Ply Adhesion Testing
[0299] Ply adhesion testing determines the adhesion between two
bonded plies of material (e.g., a thermoplastic copolyester
composition and a second thermoplastic composition) using a tensile
testing device such as an Instron Electropuls E10000 (Instron,
Norwood, Mass., USA). Sample plies of each material may be provided
using the Neat Sampling Procedure or the Plaque Sampling Procedure
or Component Sampling Procedure, and the plies are thereafter
bonded using a specified method. Alternatively, a sample of bonded
plies may be provided by using the Component Sampling Procedure. On
one end of the sample, the bond between the plies is carefully
separated to provide approximately 0.5 centimeter unbonded length
that may be inserted into the crossheads of the tensile testing
device. A first ply is inserted into a first grip of the tensile
tester, and a second ply is inserted into a second grip of the
tensile tester so that the sample between the grips is
substantially straight. The crosshead speed is set to 50
millimeters per minute. The peel strength is measured throughout
the separation of the bonded sample until the bond fully separates
or the sample fails. The force per peel distance is reported
(kilograms force/centimeter), and the mode of failure (either
adhesive or cohesive) is recorded for each sample.
Foam Characterization.
[0300] Density Test
[0301] The density is measured for samples taken using the Plaque
Sampling Procedure, or the Component Sampling Procedure, using a
digital balance or a Densicom Tester (Qualitest, Plantation, Fla.,
USA). For each sample a sample volume is determined in cubic
centimeters, and then each sample is weighed (g). The density of
the sample is the mass divided by the sample volume, given in
grams/cubic centimeters.
[0302] Specific Gravity Test
[0303] The specific gravity (SG) is measured for samples taken
using the Plaque Sampling Procedure, or the Component Sampling
Procedure, using a digital balance or a Densicom Tester (Qualitest,
Plantation, Fla., USA). Each sample is weighed (g) and then is
submerged in a distilled water bath (at 22 degrees centigrade plus
or minus 2 degrees centigrade). To avoid errors, air bubbles on the
surface of the samples are removed, e.g., by wiping isopropyl
alcohol on the sample before immersing the sample in water, or
using a brush after the sample is immersed. The weight of the
sample in the distilled water is recorded. The specific gravity is
calculated with the following formula:
S . G . = Weight of the sample in air ( g ) Weight of sample in air
( g ) - Weight of sample in water ( g ) ##EQU00001##
[0304] Water Uptake Test
[0305] This test measures the water uptake capacity of a foam
sample after a soaking duration of 5 minutes. A 1-centimeter core
sample is removed from a foam sample prepared using the Plaque
Sampling Procedure or Component Sampling Procedure, starting from
the side wall of the foamed article, e.g., the midsole of an
article of footwear. The core is then cut to provide a cylindrical
sample having a 1-centimeter cylinder height, ensuring that the
side wall remains as part of the core sample. The sample is
conditioned in an oven for 24 hours at 50 degrees centigrade plus
or minus 3 degrees centigrade. After conditioning, the sample is
cooled for 30 minutes in a lab environment at a temperature of 22
degrees centigrade plus or minus 2 degrees centigrade, and then is
immediately weighed, and the weight recorded in grams (W_0). The
surface of the side wall is masked with masking tape, while all
other surfaces are sealed with a nonpermeable coating. When the
surfaces are fully coated, the sidewall surface is unmasked. The
coated sample is then conditioned in an oven for 24 hours at 50
degrees centigrade plus or minus 3 degrees centigrade, cooled for
30 minutes in a lab environment at a temperature of 22 degrees
centigrade plus or minus 2 degrees centigrade, and then is
immediately weighed and the weight recorded in grams (W_i). The
dried sample is fully immersed in a deionized water bath maintained
at 22 degrees centigrade plus or minus 2 degrees centigrade, for a
duration of 2 hours. After the 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
(W_f) is measured in grams (W_f). The water uptake for the time
period is calculated as follows:
Water Uptake Capacity = W_f - W_i W_i .times. 100 %
##EQU00002##
[0306] Force/Displacement Test (Cyclic Compression Test)
[0307] Force/displacement behavior for the foams and the foamed
articles is measured using samples having a diameter of 45
millimeters and a thickness of at least 10 millimeters (preferably
20 to 25 millimeters) prepared using the Plaque Sampling Procedure
or the Component Sampling Procedure with a cyclic compression
testing device such an Instron Electropuls E10000 (Instron,
Norwood, Mass., USA) with a stainless steel circular cross section
impact geometry having a diameter at least twice the diameter of
the foam sample (e.g., for a 45-millimeter diameter sample, a
90-millimeter diameter platen). Each sample is compressed to 50%
strain at 5 Hz for 500 cycles. Stiffness, efficiency, and energy
return are measured from the force vs. displacement curves for
cycles 200, 300, 400, and 500. Stiffness of a particular foam
sample is the stress at the maximum strain divided by the maximum
strain, giving a value in kPa or N/mm. Efficiency of a foam sample
is the integral of the unloading force-displacement curve divided
by the integral of the loading force-displacement curve. Energy
return of a foam sample is the integral of the unloading
force-displacement curve, giving a value in mJ. The reported value
for each metric is the average of each metric between cycles 200,
300, 400, and 500. All fatigue metrics are defined as relative
differences in properties at the end of the test compared to the
same properties at the beginning of the test (i.e., cycle 1).
[0308] In some cases, a full midsole is tested using a footform for
impact instead of a cylindrical tupp to more accurately simulate
full gate loading. For these tests, a US mens size 10 midsole is
tested, and a mens size 9 footform used for impact, with a load of
2000N being applied to the midsole with the footform at a loading
rate of 5 Hz. All of the metrics from the footform test are
collected and analyzed as described above.
[0309] As with when a cylindrical tupp is used, when a footform is
used, energy input is taken as the integral of the
force-displacement curve during compression force loading. Energy
return is taken as the integral of the force displacement curve
during unloading. Hysteresis is taken as the ratio: (energy
return)/(energy input), which can also be viewed as the energy
efficiency of the foam. Fatigue behavior is judged by changes in
the foam displacement at the max load of a cycle. All measured
properties: stiffness, hysteresis, and fatigue are measured for
thousands of cycles for both running and walking compression
cycles.
[0310] Durometer Hardness Test--Shore A
[0311] The test used to obtain the hardness values for the foam
articles is as follows. A flat foam sample is prepared using the
Plaque Sampling Procedure or the Component Sampling Procedure,
where the sample has a minimum of 6 mm thick for Shore A durometer
testing. If necessary, samples are stacked to make up the minimum
thickness. Samples are large enough to allow all measurements to be
performed at a minimum of 12 mm from the edge of the sample and at
least 12 mm from any other measurement. Regions tested are flat and
parallel with an area at least 6 mm in diameter. A minimum of five
hardness measurements are taken and tested using a 1 kilogram head
weight.
[0312] Split Tear Test
[0313] The split tear test can determine the internal tear strength
for a foam material. A sample may be provided either using the
Plaque Sampling Procedure or the Component Sampling Procedure. The
sample is die cut into a rectangular shape having a width of 1.54
centimeters and a length of 15.24 centimeters (1 inch by 6 inches),
and having a thickness of 10 millimeters, plus or minus 1
millimeter. On one end, a cut is made into the sample that bisects
the thickness, the cut extending the full width of the sample, and
3 centimeters from the end of the sample. Starting from the end of
the cut, 5 marks are placed along the length of the sample spaced 2
centimeters apart. The cut ends of the sample are placed in the
clamps of a tensile tester. Each section of the sample is held in a
clamp in such a manner that the original adjacent cut edges form a
straight line joining the centers of the clamps. The crosshead
speed is set to 50 millimeters per minute. The tear strength is
measured throughout the separation of the crossheads. If necessary,
a sharp knife may be used to keep separating the foam in the center
of the sample, discarding the readings caused by cutting of the
knife. The lowest split tear strength values are recorded for each
of the five marked segments of the sample (between each of the
2-centimeter markings). An average split tear strength value is
recorded for each sample. If a segment of a sample has an air
bubble measuring more than 2 millimeters, the tear strength for the
segment is discarded, and the air bubble recorded as a test defect.
If more than one segment of a sample has an air bubble measuring
more than 2 millimeters, the entire sample is discarded.
[0314] Hand Pull Test
[0315] The hand pull test can evaluate the bond strength between
two foams, compositions or materials, such as between a solid and a
foam or between two different foams. Depending upon the bonding
method used, a sample of two pre-bonded foams, compositions or
materials may be provided either using the Plaque Sampling
Procedure or the Component Sampling Procedure. Alternatively,
separate samples of a foam, a composition or a material can be
prepared using the Plaque Sampling Procedure or the Component
Sampling Procedure, and then can be bonded together using the
bonding method to be evaluated. The sample is die cut into a
rectangular shape having a width of 1.54 centimeters and a length
of 15.24 centimeters (1 inch by 6 inches), and having a thickness
of 10 millimeters, plus or minus 1 millimeter. On one end, a cut is
made into the sample that bisects the thickness, the cut extending
the full width of the sample, and 3 centimeters from the end of the
sample. Starting from the end of the cut, 5 marks are placed along
the length of the sample spaced 2 centimeters apart. The cut ends
of the sample are held in the tester's hand and pulled at a rate of
approximately 50 millimeters per minute. If necessary, a sharp
knife may be used to keep separating the material in the center of
the sample, discarding the readings caused by cutting of the knife.
Tear strength values are recorded for each of the five marked
segments of the sample (between each of the 2-centimeter markings),
using the following scoring rubric: easy to peel or adhesive
failure is given a score of 1; an adhesive failure but some
resistance is given a score of 2; cohesive foam failure is given a
score of 3 to 4.5 based on the accompanying level of foam skin
failure, where 3 is the highest level of foam skin failure and 4.5
is the lowest level of foam skin failure; and unable to separate is
given a score of 5. The scores for each segment are averaged to
give value recorded for each sample. If a segment of a sample has
an air bubble measuring more than 2 millimeters, the tear strength
for the segment is discarded, and the air bubble recorded as a test
defect. If more than one segment of a sample has an air bubble
measuring more than 2 millimeters, the entire sample is
discarded.
Aspects
[0316] The following listing of exemplary aspects supports and is
supported by the disclosure provided herein.
Aspect 1. A foam comprising a thermoplastic multicellular foam
having an open cell foam microstructure, an average cell size of
from about 50 micrometers to about 500 micrometers, and a specific
gravity of about 0.15 to about 0.25; wherein the first foam
compositionally comprises a first thermoplastic composition
comprising one or more copolyesters; and wherein the first
thermoplastic composition of the first foam is free or essentially
free of nucleating agents, or is free or essentially free of
fillers, or is free or essentially free of both nucleating agents
and fillers. Aspect 2. A foam comprising a thermoplastic
multicellular foam having an open cell foam microstructure, an
average cell size of from about 50 micrometers to about 500
micrometers, and a specific gravity of about 0.15 to about 0.25;
wherein the first foam compositionally comprises a first
thermoplastic composition comprising one or more copolyesters;
wherein the first foam is the physically foamed product of a
single-phase solution of a supercritical fluid and the first
thermoplastic composition in a molten state; and wherein the first
thermoplastic composition of the first foam is free or essentially
free of nucleating agents, or is free or essentially free of
fillers, or is free or essentially free of both nucleating agents
and fillers. Aspect 3. The foam of Aspects 1-2, wherein the foam is
produced by the method comprising: forming a single-phase solution
of the first thermoplastic composition comprising the one or more
thermoplastic copolyesters and the supercritical fluid, wherein the
first thermoplastic composition is molten in the single-phase
solution; injecting the single-phase solution into a mold cavity,
the single-phase solution having an injection temperature during
the injecting; reducing pressure in the mold cavity and foaming the
molten first thermoplastic composition, the single-phase solution
having a foaming temperature during the foaming, thereby forming a
first foam, wherein the first foam is a thermoplastic multicellular
foam having an open cell foam microstructure; solidifying the first
foam; and removing the solidified first foam from the mold cavity,
forming the cushioning element. Aspect 4. The foam of any one of
Aspects 1-3, wherein the supercritical fluid comprises
supercritical carbon dioxide or supercritical nitrogen. Aspect 5.
The foam of any one of Aspects 1-4, wherein the supercritical fluid
is present in the single-phase solution in an amount of about 1
percent to about 3 percent by weight based on upon a total weight
of the single-phase solution. Aspect 6. The foam of any one of
Aspects 1-5, wherein the foaming temperature is from about the
melting temperature of the thermoplastic copolyester as determined
by dynamic scanning calorimetry to about 50 degrees C. above the
tail temperature of the thermoplastic copolyester as determined by
dynamic scanning calorimetry. Aspect 7. The foam of any one of
Aspects 1-6, wherein the thermoplastic copolyester is a block
copolymer; a segmented copolymer; a random copolymer; or a
condensation copolymer. Aspect 8. The foam of any one of Aspects
1-7, wherein the thermoplastic copolyester has a weight average
molecular weight of about 50,000 Daltons to about 1,000,000
Daltons. Aspect 9. The foam of any one of Aspects 1-8, wherein the
thermoplastic copolyester has a weight average molecular weight of
about 50,000 Daltons to about 500,000 Daltons; about 75,000 Daltons
to about 300,000 Daltons; or about 100,000 Daltons to about 200,000
Daltons. Aspect 10. The foam of any one of Aspects 1-9, wherein the
thermoplastic copolyester has a ratio of first segments to third
segments from about 1:1 to about 1:5 based on the weight of each of
the first segments and the third segments. Aspect 11. The foam of
any one of Aspects 1-10, wherein the thermoplastic copolyester has
a ratio of first segments to third segments from about 1:1 to about
1:3 or about 1:1 to about 1:2 based on the weight of each of the
first segments and the third segments. Aspect 12. The foam of any
one of Aspects 1-11, wherein the thermoplastic copolyester has a
ratio of second segments to third segments from about 1:1 to about
1:3 based on the weight of each of the first segments and the third
segments. Aspect 13. The foam of any one of Aspects 1-12, wherein
the thermoplastic copolyester has a ratio of second segments to
third segments from about 1:1 to about 1:2 or about 1:1 to about
1:1.52 based on the weight of each of the first segments and the
third segments. Aspect 14. The foam of any one of Aspects 1-13,
wherein the first segments derived from a dihydroxy-terminated
polydiol comprise segments derived from a poly(alkylene oxide)diol
having a number-average molecular weight of about 250 Daltons to
about 6000 Daltons. Aspect 15. The foam of Aspect 14, wherein the
number-average molecular weight is about 400 Daltons to about 6,000
Daltons; about 350 Daltons to about 5,000 Daltons; or about 500
Daltons to about 3,000 Daltons. Aspect 16. The foam of any one of
Aspects 14-15, wherein the poly(alkylene oxide)diol is
poly(ethylene ether)diol; poly(propylene ether)diol;
poly(tetramethylene ether)diol; poly(pentamethylene ether)diol;
poly(hexamethylene ether)diol; poly(heptamethylene ether)diol;
poly(octamethylene ether)diol; poly(nonamethylene ether)diol;
poly(decamethylene ether)diol; or mixtures thereof. Aspect 17. The
foam of Aspect 16, wherein the poly(alkylene oxide)diol is
poly(ethylene ether)diol; poly(propylene ether)diol;
poly(tetramethylene ether)diol; poly(pentamethylene ether)diol; or
poly(hexamethylene ether)diol. Aspect 18. The foam of Aspect 16,
wherein the poly(alkylene oxide)diol is poly(tetramethylene
ether)diol. Aspect 19. The foam of any one of Aspects 1-18, wherein
the second segments derived from a diol comprise a diol having a
molecular weight of less than about 250. Aspect 20. The foam of
Aspect 19, wherein the diol is a C2-C8 diol. Aspect 21. The foam of
Aspect 20, wherein the second segments derived from a diol comprise
a diol selected from ethanediol; propanediol; butanediol;
pentanediol; 2-methyl propanediol; 2,2-dimethyl propanediol;
hexanediol; 1,2-dihydroxy cyclohexane; 1,3-dihydroxy cyclohexane;
1,4-dihydroxy cyclohexane; and mixtures thereof. Aspect 22. The
foam of Aspect 21, wherein the diol is selected from
1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol,
and mixtures thereof. Aspect 23. The foam of any one of Aspects
1-22, wherein the third segments derived from an aromatic
dicarboxylic acid comprise an aromatic C5-C16 dicarboxylic acid.
Aspect 24. The foam of Aspect 23, wherein the aromatic C5-C16
dicarboxylic acid has a molecular weight less than about 300
Daltons or about 120 Daltons to about 200 Daltons. Aspect 25. The
foam of Aspect 23, wherein the aromatic C5-C16 dicarboxylic acid is
terephthalic acid, phthalic acid, isophthalic acid, or a derivative
thereof. Aspect 26. The foam of Aspect 25, wherein the aromatic
C5-C16 dicarboxylic acid is terephthalic acid or the dimethyl ester
derivative thereof. Aspect 27. The foam of any one of Aspects 1-26,
wherein the first thermoplastic composition of the first foam
further comprises a non-polymeric component comprising all
non-polymeric ingredients present in the first thermoplastic
composition, and the non-polymeric component makes up less than 5
weight percent, less than 4 weight percent, less than 3 weight
percent, less than 2 weight percent, less than 1 weight percent, or
less than 0.5 weight percent of the first thermoplastic composition
based on a total weight of the first thermoplastic composition.
Aspect 28. The foam of any one of Aspects 1-27, wherein the first
thermoplastic composition of the first foam comprises a polymeric
component comprising all polymers present in the first
thermoplastic composition, and the polymeric component makes up at
least 95 weight percent of the first thermoplastic composition
based on a total weight of the first thermoplastic composition.
Aspect 29. The foam of any one of Aspects 1-28, wherein the first
thermoplastic composition of the first foam comprises a polymeric
component comprising all polymers present in the first
thermoplastic composition, and the polymeric component makes up at
least 97 weight percent, at least 98 weight percent, or at least 99
weight percent of the first thermoplastic composition based on a
total weight of the first thermoplastic composition. Aspect 30. The
foam of any one of Aspects 1-29, wherein the first thermoplastic
composition of the first foam comprises a polymeric component
comprising all polymers present in the first thermoplastic
composition, and, in addition to the one or more copolyesters, the
polymeric component further comprises a polyester, a polyolefin, or
both. Aspect 31. The foam of any one of Aspects 1-30, wherein the
first thermoplastic composition of the first foam comprises a
polymeric component comprising all polymers present in the first
thermoplastic composition, and the polymeric component consists
essentially of the one or more copolyesters. Aspect 32. The foam of
any one of Aspects 1-31, wherein the thermoplastic copolyester
comprises
[0317] a plurality of first segments, each first segment derived
from a dihydroxy-terminated polydiol;
[0318] a plurality of second segments, each second segment derived
from a diol; and
[0319] a plurality of third segments, each third segment derived
from an aromatic dicarboxylic acid.
Aspect 33. The foam of any one of Aspects 1-32, wherein the one or
more thermoplastic copolyesters comprise at least one thermoplastic
copolyester elastomer. Aspect 34. The foam of any one of Aspects
1-33, wherein the thermoplastic copolyester comprises, (a) a
plurality of first copolyester units, each first copolyester unit
of the plurality comprising the first segment derived from a
dihydroxy-terminated polydiol and the third segment derived from an
aromatic dicarboxylic acid, wherein the first copolyester unit has
a structure represented by a formula 1:
##STR00015##
wherein R.sub.1 is a group remaining after removal of terminal
hydroxyl groups from the poly(alkylene oxide) diol of the first
segment, wherein the poly(alkylene oxide) diol of the first segment
is a poly(alkylene oxide) diol having a number-average molecular
weight of about 400 to about 6000; and wherein R.sub.2 is a group
remaining after removal of carboxyl groups from the aromatic
dicarboxylic acid of the third segment; and (b) a plurality of
second copolyester units, each second copolyester unit of the
plurality comprising the second segment derived from a diol and the
third segment derived from an aromatic dicarboxylic acid, wherein
the the second copolyester unit has a structure represented by a
formula 2:
##STR00016##
wherein R.sub.3 is a group remaining after removal of hydroxyl
groups from the diol of the second segment derived from a diol,
wherein the diol is a diol having a molecular weight of less than
about 250; and wherein R.sub.2 is the group remaining after removal
of carboxyl groups from the aromatic dicarboxylic acid of the third
segment. Aspect 35. The foam of Aspect 34, wherein the first
copolyester unit has a structure represented by a formula 3:
##STR00017##
wherein R is H or methyl; wherein y is an integer having a value
from 1 to 10; wherein z is an integer having a value from 2 to 60;
and wherein a weight average molecular weight of each of the
plurality of first copolyester units is from about 300 Daltons to
about 7,000 Daltons. Aspect 36. The foam of Aspect 35, wherein y is
an integer having a value of 1, 2, 3, 4, or 5. Aspect 37. The foam
of Aspect 35 or 36, wherein R is hydrogen; wherein R is methyl;
wherein R is hydrogen and y is an integer having a value of 1, 2,
or 3; or wherein R is methyl and y is an integer having a value of
1. Aspect 38. The foam of Aspect 35, wherein the first copolyester
unit has a structure represented by a formula 4:
##STR00018##
wherein z is an integer having a value from 2 to 60; and wherein a
weight average molecular weight of each of the plurality of first
copolyester units is from about 300 Daltons to about 7,000 Daltons.
Aspect 39. The foam of any one of Aspects 35-38, wherein z is an
integer having a value from 5 to 60; from 5 to 50; from 5 to 40;
from 4 to 30; from 4 to 20; or from 2 to 10. Aspect 40. The foam of
any one of Aspects 35-39, wherein the weight average molecular
weight of each of the plurality of first copolyester units is from
about 400 Daltons to about 6,000 Daltons; from about 400 Daltons to
about 5,000 Daltons; from about 400 Daltons to about 4,000 Daltons;
from about 400 Daltons to about 3,000 Daltons; from about 500
Daltons to about 6,000 Daltons; from about 500 Daltons to about
5,000 Daltons; from about 500 Daltons to about 4,000 Daltons; from
about 500 Daltons to about 3,000 Daltons; from about 600 Daltons to
about 6,000 Daltons; from about 600 Daltons to about 5,000 Daltons;
from about 600 Daltons to about 4,000 Daltons; from about 600
Daltons to about 3,000 Daltons. Aspect 41. The foam of any one of
Aspects 35-40, wherein the second copolyester unit has a structure
represented by a formula 5:
##STR00019##
wherein x is an integer having a value from 1 to 20. Aspect 42. The
foam of Aspect 41, wherein x is an integer having a value from 2 to
18; a value from 2 to 17; a value from 2 to 16; a value from 2 to
15; a value from 2 to 14; a value from 2 to 13; a value from 2 to
12; a value from 2 to 11; a value from 2 to 10; a value from 2 to
9; a value from 2 to 8; a value from 2 to 7; a value from 2 to 6;
or a value of 2, 3, or 4. Aspect 43. The foam of Aspect 41, wherein
the second copolyester unit has a structure represented by a
formula 6:
##STR00020##
Aspect 44. The foam of any one of Aspects 1-43, wherein the
thermoplastic copolyester comprises a weight percent of the
plurality of first copolyester units based on total weight of the
thermoplastic copolyester of about 30 weight percent to about 80
weight; about 40 weight percent to about 80 weight percent; about
50 weight percent to about 80 weight percent; about 30 weight
percent to about 70 weight percent; about 40 weight percent to
about 70 weight percent; or about 50 weight percent to about 70
weight percent. Aspect 45. The foam of any one of Aspects 1-44,
wherein the thermoplastic copolyester comprises a weight percent of
the plurality of second copolyester units based on total weight of
the thermoplastic copolyester of about 40 weight percent to about
65 weight percent; about 45 weight percent to about 65 weight
percent; about 50 weight percent to about 65 weight percent; about
55 weight percent to about 65 weight percent; about 40 weight
percent to about 60 weight percent; about 45 weight percent to
about 60 weight percent; about 50 weight percent to about 60 weight
percent; or about 55 weight percent to about 60 weight percent.
Aspect 46. The foam of any one of Aspects 1-45, wherein the
thermoplastic copolyester comprises a weight percent of the
plurality of second copolyester units based on total weight of the
thermoplastic copolyester of about 40 weight percent to about 65
weight percent. Aspect 47. The foam of any one of Aspects 1-46,
wherein the thermoplastic copolyester has a ratio of first segments
to third segments from about 1:1 to about 1:5 based on the weight
of each of the first segments and the third segments, or wherein
the thermoplastic copolyester has a ratio of second segments to
third segments from about 1:1 to about 1:3 based on the weight of
each of the first segments and the third segments. Aspect 48. The
foam of any one of Aspects 1-47, wherein the thermoplastic
copolyester has a weight average molecular weight of about 50,000
Daltons to about 1,000,000 Daltons. Aspect 49. The foam of any one
of Aspects 1-48, wherein the thermoplastic copolyester composition
further comprises an additive. Aspect 50. The foam of Aspect 49,
wherein the additive is present in an amount from about 0.1 weight
percent to about 10 weight percent based on the total weight of the
foamed polymeric material. Aspect 51. The foam of Aspects 49 or 50,
wherein the additive is a wax, an anti-oxidant, a UV-absorbing
agent, a coloring agent, or combinations thereof. Aspect 52. The
foam of any one of Aspects 1-51, wherein the thermoplastic
copolyester composition consists essentially of one or more
thermoplastic copolyester. Aspect 53. The foam of any one of
Aspects 1-52, further comprising at least one ionomer. Aspect 54.
The foam of any one of Aspects 1-53, further comprising at least
one thermoplastic polyurethane. Aspect 55. The foam of any one of
Aspects 1-54, wherein the thermoplastic copolyester composition is
substantially free of a thermoplastic polyamide polymer, include
polyamide copolymers such as polyether block amide copolymers.
Aspect 56. The foam of any one of Aspects 1-55, wherein the
thermoplastic copolyester composition is substantially free of a
thermoplastic polyolefin polymers, including polyethylene and
polypropylene and/or polyolefin copolymers such as ethylene-vinyl
acetate copolymers. Aspect 57. The foam of any one of Aspects 1-56,
wherein the thermoplastic copolyester has a zero shear viscosity
when determined using a cyclic tensile test as described herein of
about 10 to about 10,000 pascal-second; about 100 to about 7,000
pascal-second; or about 1,000 to about 5,000 pascal-second. Aspect
58. The foam of any one of Aspects 1-57, wherein the first
thermoplastic composition of the first foam further comprises one
or more dyes or pigments. Aspect 59. The foam of Aspects 1-58,
wherein the first thermoplastic composition of the first foam
comprises 5 weight percent or less, 4 weight percent or less, 3
weight percent or less, 2 weight percent or less, or 1 weight
percent or less of dyes or pigments. Aspect 60. The foam of any one
of Aspects 1-59, wherein the first thermoplastic composition of the
first foam is substantially free of dyes or pigments. Aspect 61.
The foam of any one of Aspects 1-60, wherein the single-phase
solution is free or essentially free of chemical blowing agents,
and the first foam is free or essentially free of chemical blowing
agent decomposition products. Aspect 62. The foam of any one of
Aspects 1-61, wherein the multicellular foam does not include a
chemical foaming agent, or a decomposition product of a chemical
foaming agent. Aspect 63. The foam of Aspect 62, wherein the
chemical foaming agent comprises an inorganic substance. Aspect 64.
The foam of Aspect 62, wherein the chemical foaming agent comprises
an organic substance. Aspect 65. The foam of any one of Aspects
1-63, wherein the single-phase solution is essentially free of
cross-linking agents. Aspect 66. The foam of any one of Aspects
1-64, wherein the multicellular foam structure comprises less than
10 percent of cells having a closed cell microstructure. Aspect 67.
The foam of any one of Aspects 1-64, wherein the multicellular foam
structure comprises less than 5 percent of cells having a closed
cell microstructure. Aspect 68. The foam of any one of Aspects
1-64, wherein the multicellular foam structure comprises less than
1 percent of cells having a closed cell microstructure. Aspect 69.
The foam of any one of Aspects 1-68, wherein the multicellular foam
has an average cell size of from about 50 micron to about 5
millimeters; from about 100 micron to about 1 millimeters; or from
about 50 micron to about 1 millimeters. Aspect 70. The foam of any
one of Aspects 1-69, wherein up to 80% of the open cells in the
first foam have an average diameter of from about 50 micrometers to
about 200 micrometers. Aspect 71. The foam of any one of Aspects
1-70, wherein the first foam has a split tear greater than or equal
to about 2.0 kg/cm, or an energy efficiency greater than or equal
to about 60 percent, or both. Aspect 72. A method for making a foam
article, the method comprising: forming a mixture of molten first
thermoplastic composition comprising a thermoplastic elastomer and
a blowing agent; injecting the mixture into a mold cavity; foaming
the molten first thermoplastic composition, thereby forming a
foamed molten first thermoplastic composition; solidifying the
foamed molten first thermoplastic composition thereby forming a
multicellular foam article having a multicellular foam structure;
and removing the foam article from the mold cavity. Aspect 73. The
method of Aspect 72, wherein the blowing agent is a physical
blowing agent. Aspect 74. The method of Aspect 73, wherein the
physical blowing agent is a supercritical fluid. Aspect 75. The
method of Aspect 74, wherein the supercritical fluid comprises
nitrogen, or a supercritical fluid thereof. Aspect 76. The method
of Aspect 75, wherein the supercritical fluid comprises or consists
essentially of nitrogen, or a supercritical fluid thereof. Aspect
77. The method of Aspect 75, wherein the supercritical fluid
further comprises carbon dioxide, or a supercritical fluid thereof.
Aspect 78. The method of Aspect 75, wherein the carbon dioxide is
present in an amount of about 1% to about 3% or about 1% to about
5% by weight based on upon a total weight of the mixture. Aspect
79. The method of any one of Aspects 75-78, wherein the nitrogen is
present in an amount of about 1% to about 3% or about 1% to about
5% by weight based on upon a total weight of the mixture. Aspect
80. The method of any one of Aspects 72-79, wherein the forming the
mixture of the molten first thermoplastic composition and the
physical blowing agent comprises adding the physical blowing agent
to the molten first thermoplastic composition and forming a single
phase solution of the physical blowing agent dissolved in the
molten first thermoplastic composition. Aspect 81. The method of
any one of Aspects 72-79, wherein the forming the mixture of the
molten first thermoplastic composition and the physical blowing
agent comprises infusing a solid resin comprising the polymeric
material with the physical blowing agent to form infused resin, and
melting the infused resin to form a single phase solution of the
physical blowing agent dissolved in the molten first thermoplastic
composition. Aspect 82. The method of any one of Aspects 72-81,
wherein the injecting the mixture into the mold cavity comprises
injecting the mixture into a pressurized mold cavity, the
pressurized mold cavity having a first pressure greater than
atmospheric pressure; and the foaming the molten first
thermoplastic composition comprises decreasing the first pressure
to a second pressure and initiating formation of gas bubbles by the
physical blowing agent, thereby foaming the molten first
thermoplastic composition. Aspect 83. The method of any one of
Aspects 72-82, wherein the injecting the mixture into the mold
cavity comprises injecting the mixture into a pressurized mold
cavity having a first pressure greater than atmospheric pressure.
Aspect 84. The method of Aspect 83, wherein the method comprises
applying a gas counter pressure to the mold cavity of from about
100 psi to about 3,000 psi, or from about 550 psi to about 1500
psi, or from about 650 psi to about 1000 psi, and wherein the gas
counter pressure is applied to the mold cavity before the foaming.
Aspect 85. The method of Aspect 82, wherein the second pressure is
atmospheric pressure; and wherein decreasing the first pressure to
the second pressure comprises venting the pressurized mold cavity
to atmospheric pressure. Aspect 86. The method of Aspect 82,
wherein the second pressure is atmospheric pressure; and wherein
decreasing the first pressure to the second pressure comprises
using a controlled rate of pressure decrease until the mold cavity
has a pressure essentially equal to atmospheric pressure. Aspect
87. The method of Aspect 86, wherein the controlled rate of
pressure decrease is from about 10 psi per sec to about 600 psi per
sec, or from about 15 psi per sec to about 300 psi per sec, or from
about 20 psi per sec to about 150 psi per sec. Aspect 88. The
method of any one of Aspects 72-87, wherein the foam article is
substantially free of a chemical blowing agent or a decomposition
product thereof. Aspect 89. The method of any one of Aspects 72-88,
wherein the mixture has an injection temperature; and wherein the
injection temperature is from about the melting temperature of the
first thermoplastic composition to about 50 degrees C. above the
tail temperature of the first thermoplastic composition. Aspect 90.
The method of Aspect 89, wherein the injection temperature is from
about the melting temperature of the first thermoplastic
composition to a temperature that is above the tail temperature of
the first thermoplastic composition by about 0 degrees C., 5
degrees C., 10 degrees C., 15 degrees C., 20 degrees C., 25 degrees
C., 30 degrees C., 35 degrees C., 40 degrees C., 45 degrees C., or
50 degrees C. Aspect 91. The method of any one of Aspects 72-90,
wherein the foaming occurs at a foaming temperature; and wherein
the foaming temperature is from about the melting temperature of
the thermoplastic elastomer to about 50 degrees C. above the tail
temperature of the thermoplastic elastomer. Aspect 92. The method
of Aspect 91, wherein the foaming temperature is from about the
melting temperature of the first thermoplastic composition to a
temperature that is above the tail temperature of the first
thermoplastic composition by about 0 degrees C., 5 degrees C., 10
degrees C., 15 degrees C., 20 degrees C., 25 degrees C., 30 degrees
C., 35 degrees C., 40 degrees C., 45 degrees C., or 50 degrees C.
Aspect 93. The method of any one of Aspects 72-92, wherein the foam
article is a thermoplastic foam article. Aspect 94. The method of
any one of Aspects 72-93, wherein the solidifying comprises cooling
the mold cavity; or wherein the solidifying comprises cooling the
foamed first thermoplastic composition. Aspect 95. The method of
any one of Aspects 72-94, wherein the foaming comprises releasing
pressure from the mold cavity at a mold cavity pressure release
rate. Aspect 96. The method of Aspect 95, wherein the mold cavity
pressure release rate is about 10 psi per sec to about 600 psi per
sec, or about 15 psi per sec to about 300 psi per sec, or about 20
psi per sec to about 150 psi per sec. Aspect 97. The method of any
one of Aspects 72-96, wherein the foaming comprises providing a gas
counter pressure to the mold cavity. Aspect 98. The method of
Aspect 97, wherein the gas counter pressure is at least about 550
psi, about 550 psi to about 1500 psi, or about 650 psi to about
1000 psi. Aspect 99. The method of Aspect 98, wherein the blowing
agent is a physical blowing agent; or wherein the blowing agent is
supercritical nitrogen. Aspect 100. The method of any one of
Aspects 72-99, the method further comprising placing a textile
element in the mold cavity prior to injecting the mixture, and
foaming the molten first thermoplastic composition in contact with
the textile element. Aspect 101. The method of Aspect 100, wherein
the textile element comprises thermoplastic polyester fibers,
thermoplastic polyester yarns, thermoplastic polyurethane fibers,
thermoplastic polyurethane yarns, thermoplastic polyamide fibers,
thermoplastic polyamide yarns, or combinations thereof. Aspect 102.
The method of Aspects 100 or 101, wherein the textile element is a
component for an upper for an article of footwear. Aspect 103. The
method of any one of Aspects 72-102, wherein the foam article is a
component of an article of footwear. Aspect 104. The method of
Aspect 103, wherein the foam article is a midsole. Aspect 105. The
method of any one of Aspects 72-103, wherein the foam article is a
component of an article of apparel. Aspect 106. The method of any
one of Aspects 72-103, wherein the foam article is a component of
an article of sporting equipment. Aspect 107. The method of any one
of Aspects 72-106, wherein the injecting comprises monitoring an
injection pressure of the mixture prior or during the injecting,
and controlling the injecting based on the injection pressure of
the mixture. Aspect 108. The method of any one of Aspects 72-106,
wherein the injecting comprises controlling the injection
temperature of the mixture prior to the mixture entering the mold
cavity. Aspect 109. The method of any one of Aspects 72-106,
wherein the injecting comprises controlling a mold cavity
temperature prior to the mixture entering the mold cavity. Aspect
110. The method of any one of Aspects 72-109, wherein the mixture
has an expansion ratio of 1 as compared to a volume of the mold
cavity. Aspect 111. The method of any one of Aspects 72-109,
wherein, following removing the foam article from the mold cavity,
cooling the foam article to about 25 degrees C., and equilibrating
the foam article at about 25 degrees C. and about 1 atm of
pressure, a volume of the equilibrated foam article is within plus
or minus 5 percent of a volume of the mold cavity. Aspect 112. The
method of any one of Aspects 72-111, wherein the multicellular foam
article comprises less than 1 percent of cells having a closed cell
microstructure. Aspect 113. The method of any one of Aspects
72-112, wherein the multicellular foam article has an average cell
size of from about 50 micron to about 5 millimeters; from about 100
micron to about 1 millimeters; or from about 50 micron to about 1
millimeters. Aspect 114. The method of any one of Aspects 72-113,
wherein the multicellular foam article does not include a chemical
foaming agent. Aspect 115. The method of Aspect 114, wherein the
chemical foaming agent comprises an inorganic substance. Aspect
116. The method of Aspect 115, wherein the chemical foaming agent
comprises an organic substance. Aspect 117. The method of any one
of Aspects 72-116, wherein the thermoplastic copolyester is a block
copolymer; a segmented copolymer; a random copolymer; or a
condensation copolymer. Aspect 118. The method of any one of
Aspects 72-117, wherein the thermoplastic copolyester has a weight
average molecular weight of about 50,000 Daltons to about 1,000,000
Daltons. Aspect 119. The method of Aspect 118, wherein the
thermoplastic copolyester has a weight average molecular weight of
about 50,000 Daltons to about 500,000 Daltons; about 75,000 Daltons
to about 300,000 Daltons; or about 100,000 Daltons to about 200,000
Daltons. Aspect 120. The method of any one of Aspects 72-119,
wherein the thermoplastic copolyester has a ratio of first segments
to third segments from about 1:1 to about 1:5 based on the weight
of each of the first segments and the third segments. Aspect 121.
The method of Aspect 120, wherein the thermoplastic copolyester has
a ratio of first segments to third segments from about 1:1 to about
1:3 or about 1:1 to about 1:2 based on the weight of each of the
first segments and the third segments. Aspect 122. The method of
any one of Aspects 72-121, wherein the thermoplastic copolyester
has a ratio of second segments to third segments from about 1:1 to
about 1:3 based on the weight of each of the first segments and the
third segments. Aspect 123. The method Aspect 122, wherein the
thermoplastic copolyester has a ratio of second segments to third
segments from about 1:1 to about 1:2 or about 1:1 to about 1:1.52
based on the weight of each of the first segments and the third
segments. Aspect 124. The method of any one of Aspects 72-123,
wherein the first segments derived from a
dihydroxy-terminated polydiol comprise segments derived from a
poly(alkylene oxide)diol having a number-average molecular weight
of about 250 Daltons to about 6000 Daltons. Aspect 125. The method
of Aspect 124, wherein the number-average molecular weight is about
400 Daltons to about 6,000 Daltons; about 350 Daltons to about
5,000 Daltons; or about 500 Daltons to about 3,000 Daltons. Aspect
126. The method of any one of Aspects 124-125, wherein the
poly(alkylene oxide)diol is poly(ethylene ether)diol;
poly(propylene ether)diol; poly(tetramethylene ether)diol;
poly(pentamethylene ether)diol; poly(hexamethylene ether)diol;
poly(heptamethylene ether)diol; poly(octamethylene ether)diol;
poly(nonamethylene ether)diol; poly(decamethylene ether)diol; or
mixtures thereof. Aspect 127. The method of Aspect 126, wherein the
poly(alkylene oxide)diol is poly(ethylene ether)diol;
poly(propylene ether)diol; poly(tetramethylene ether)diol;
poly(pentamethylene ether)diol; or poly(hexamethylene ether)diol.
Aspect 128. The method of Aspect 126, wherein the poly(alkylene
oxide)diol is poly(tetramethylene ether)diol. Aspect 129. The
method of any one of Aspects 72-128, wherein the second segments
derived from a diol comprise a diol having a molecular weight of
less than about 250. Aspect 130. The method of Aspect 129, wherein
the diol is a C2-C8 diol. Aspect 131. The method of Aspect 130,
wherein the second segments derived from a diol comprise a diol
selected from ethanediol; propanediol; butanediol; pentanediol;
2-methyl propanediol; 2,2-dimethyl propanediol; hexanediol;
1,2-dihydroxy cyclohexane; 1,3-dihydroxy cyclohexane; 1,4-dihydroxy
cyclohexane; and mixtures thereof. Aspect 132. The method of Aspect
130, wherein the diol is selected from 1,2-ethanediol,
1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and mixtures
thereof. Aspect 133. The method of any one of Aspects 72-132,
wherein the third segments derived from an aromatic dicarboxylic
acid comprise an aromatic C5-C16 dicarboxylic acid. Aspect 134. The
method of Aspect 133, wherein the aromatic C5-C16 dicarboxylic acid
has a molecular weight less than about 300 Daltons or about 120
Daltons to about 200 Daltons. Aspect 135. The method of Aspect 133,
wherein the aromatic C5-C16 dicarboxylic acid is terephthalic acid,
phthalic acid, isophthalic acid, or a derivative thereof. Aspect
136. The method of Aspect 135, wherein the aromatic C5-C16
dicarboxylic acid is terephthalic acid or the dimethyl ester
derivative thereof. Aspect 137. The method of any one of Aspects
72-136, wherein the thermoplastic copolyester comprises, a. a
plurality of first copolyester units, each first copolyester unit
of the plurality comprising the first segment derived from a
dihydroxy-terminated polydiol and the third segment derived from an
aromatic dicarboxylic acid, wherein the first copolyester unit has
a structure represented by a formula 1:
##STR00021##
wherein R.sub.1 is a group remaining after removal of terminal
hydroxyl groups from the poly(alkylene oxide) diol of the first
segment, wherein the poly(alkylene oxide) diol of the first segment
is a poly(alkylene oxide) diol having a number-average molecular
weight of about 400 to about 6000; and wherein R.sub.2 is a group
remaining after removal of carboxyl groups from the aromatic
dicarboxylic acid of the third segment; and b. a plurality of
second copolyester units, each second copolyester unit of the
plurality comprising the second segment derived from a diol and the
third segment derived from an aromatic dicarboxylic acid, wherein
the the second copolyester unit has a structure represented by a
formula 2:
##STR00022##
wherein R.sub.3 is a group remaining after removal of hydroxyl
groups from the diol of the second segment derived from a diol,
wherein the diol is a diol having a molecular weight of less than
about 250; and wherein R.sub.2 is the group remaining after removal
of carboxyl groups from the aromatic dicarboxylic acid of the third
segment. Aspect 138. The method of Aspect 137, wherein the first
copolyester unit has a structure represented by a formula 3:
##STR00023##
wherein R is H or methyl; wherein y is an integer having a value
from 1 to 10; wherein z is an integer having a value from 2 to 60;
and wherein a weight average molecular weight of each of the
plurality of first copolyester units is from about 300 Daltons to
about 7,000 Daltons. Aspect 139. The method of Aspect 138, wherein
y is an integer having a value of 1, 2, 3, 4, or 5. Aspect 140. The
method of Aspect 138 or 139, wherein R is hydrogen; wherein R is
methyl; wherein R is hydrogen and y is an integer having a value of
1, 2, or 3; or wherein R is methyl and y is an integer having a
value of 1. Aspect 141. The method of Aspect 137, wherein the first
copolyester unit has a structure represented by a formula 4:
##STR00024##
wherein z is an integer having a value from 2 to 60; and wherein a
weight average molecular weight of each of the plurality of first
copolyester units is from about 300 Daltons to about 7,000 Daltons.
Aspect 142. The method of any one of Aspects 137-141, wherein z is
an integer having a value from 5 to 60; from 5 to 50; from 5 to 40;
from 4 to 30; from 4 to 20; or from 2 to 10. Aspect 143. The method
of any one of Aspects 137-142, wherein the weight average molecular
weight of each of the plurality of first copolyester units is from
about 400 Daltons to about 6,000 Daltons; from about 400 Daltons to
about 5,000 Daltons; from about 400 Daltons to about 4,000 Daltons;
from about 400 Daltons to about 3,000 Daltons; from about 500
Daltons to about 6,000 Daltons; from about 500 Daltons to about
5,000 Daltons; from about 500 Daltons to about 4,000 Daltons; from
about 500 Daltons to about 3,000 Daltons; from about 600 Daltons to
about 6,000 Daltons; from about 600 Daltons to about 5,000 Daltons;
from about 600 Daltons to about 4,000 Daltons; from about 600
Daltons to about 3,000 Daltons. Aspect 144. The method of any one
of Aspects 137-143, wherein the second copolyester unit has a
structure represented by a formula 5:
##STR00025##
wherein x is an integer having a value from 1 to 20. Aspect 145.
The method of Aspect 144, wherein x is an integer having a value
from 2 to 18; a value from 2 to 17; a value from 2 to 16; a value
from 2 to 15; a value from 2 to 14; a value from 2 to 13; a value
from 2 to 12; a value from 2 to 11; a value from 2 to 10; a value
from 2 to 9; a value from 2 to 8; a value from 2 to 7; a value from
2 to 6; or a value of 2, 3, or 4. Aspect 146. The method of Aspect
144, wherein the second copolyester unit has a structure
represented by a formula 6:
##STR00026##
Aspect 147. The foam of any one of Aspects 137-146, wherein the
thermoplastic copolyester comprises a weight percent of the
plurality of first copolyester units based on total weight of the
thermoplastic copolyester of about 30 weight percent to about 80
weight; about 40 weight percent to about 80 weight percent; about
50 weight percent to about 80 weight percent; about 30 weight
percent to about 70 weight percent; about 40 weight percent to
about 70 weight percent; or about 50 weight percent to about 70
weight percent. Aspect 148. The method of any one of Aspects
72-147, wherein the thermoplastic copolyester comprises a weight
percent of the plurality of second copolyester units based on total
weight of the thermoplastic copolyester of about 40 weight percent
to about 65 weight percent; about 45 weight percent to about 65
weight percent; about 50 weight percent to about 65 weight percent;
about 55 weight percent to about 65 weight percent; about 40 weight
percent to about 60 weight percent; about 45 weight percent to
about 60 weight percent; about 50 weight percent to about 60 weight
percent; or about 55 weight percent to about 60 weight percent.
Aspect 149. The method of any one of Aspects 72-148, wherein the
thermoplastic copolyester composition further comprises an
additive. Aspect 150. The method of Aspect 149, wherein the
additive is present in an amount from about 0.1 weight percent to
about 10 weight percent based on the total weight of the foamed
polymeric material. Aspect 151. The method of Aspects 149 or 150,
wherein the additive is a wax, an anti-oxidant, a UV-absorbing
agent, a coloring agent, or combinations thereof. Aspect 152. The
method of any one of Aspects 72-151, wherein the thermoplastic
copolyester composition consists essentially of one or more
thermoplastic copolyester. Aspect 153. The method of any one of
Aspects 72-151, further comprising at least one ionomer. Aspect
154. The method of any one of Aspects 72-151, further comprising at
least one thermoplastic polyurethane. Aspect 155. The method of any
one of Aspects 72-154, wherein the thermoplastic copolyester
composition is substantially free of a thermoplastic polyamide
polymer, include polyamide copolymers such as polyether block amide
copolymers. Aspect 156. The method of any one of Aspects 72-154,
wherein the thermoplastic copolyester composition is substantially
free of a thermoplastic polyolefin polymers, including polyethylene
and polypropylene and/or polyolefin copolymers such as
ethylene-vinyl acetate copolymers. Aspect 157. The method of any
one of Aspects 72-156, wherein the thermoplastic copolyester has a
zero shear viscosity when determined using a cyclic tensile test as
described herein of about 10 to about 10,000 pascal-second; about
100 to about 7,000 pascal-second; or about 1,000 to about 5,000
pascal-second. Aspect 158. The method of any one of Aspects 72-157,
wherein the foam article has a maximum load of about 100 N to about
4000 N when determined using the Cyclic Tensile test as described
herein. Aspect 159. The method of Aspect 158, wherein the foam
article has a maximum load of about 100 N to about 4000 N when
determined using the Cyclic Tensile test as described herein.
Aspect 160. The method of any one of Aspects 72-159, wherein the
foam article has an energy efficiency of greater than or equal to
about 50 percent when determined using the Cyclic Compression test
as described herein. Aspect 161. The foam article of Aspect 160,
wherein the foam article has an energy efficiency of greater than
or equal to about 60 percent when determined using the Cyclic
Compression test as described herein. Aspect 162. The method of
Aspect 160, wherein the foam article has an energy efficiency of
greater than or equal to about 70 percent when determined using the
Cyclic Compression test as described herein. Aspect 163. The method
of Aspect 160, wherein the foam article has an energy efficiency of
about 50 percent to about 97 percent when determined using the
Cyclic Compression test as described herein. Aspect 164. The method
of any one of Aspects 72-163, wherein the foam article has an
energy return of about 200 millijoules (mJ) to 1200 mJ when
determined using the Cyclic Compression test as described herein.
Aspect 165. The method of Aspect 164, wherein the foam article has
an energy return of about 400 mJ to 1000 mJ when determined using
the Cyclic Compression test as described herein. Aspect 166. The
method of Aspect 164, wherein the foam article has an energy return
of about 600 mJ to 800 mJ when determined using the Cyclic
Compression test as described herein. Aspect 167. The method of any
one of Aspects 72-166, wherein the foam article has a split tear
value of about 1.0 kilogram per centimeter to 4.5 kilogram per
centimeter, about 1.6 kilogram per centimeter to 4.0 kilogram per
centimeter, about 2.0 kilogram per centimeter to 4.0 kilogram per
centimeter, about 2.0 kilogram per centimeter to 3.5 kilogram per
centimeter, about 2.5 kilogram per centimeter to 3.5 kilogram per
centimeter, about 0.07 kilogram per centimeter to 2.0 kilogram per
centimeter, or about 0.8 kilogram per centimeter to 1.5 kilogram
per centimeter, or about 0.9 to 1.2 kilogram per centimeter, about
1.5 kilogram per centimeter to 2.2 kilogram per centimeter; about
0.08 kilogram per centimeter to 4.0 kilogram per centimeter, about
0.9 kilogram per centimeter to 3.0 kilogram per centimeter, about
1.0 to 2.0 kilogram per centimeter, about 1.0 kilogram per
centimeter to 1.5 kilogram per centimeter, or about 2 kilogram per
centimeter using a split tear test as described herein. Aspect 168.
The method of any one of Aspects 72-167, wherein the foam article
has a split tear value of greater than or equal to about 1.5 kg/cm,
greater than or equal to about 2.0 kg/cm, or greater than or equal
to about 2.5 kg/cm, when determined using a split tear test as
described herein. Aspect 169. The method of any one of Aspects
72-168, wherein the foam article has a specific gravity of less
than or equal to 0.9, less than or equal to 0.7, less than or equal
to 0.5, or less than or equal to 0.3. Aspect 170. The foam article
of Aspect 169, wherein the foam article has a specific gravity of
from about 0.02 to about 0.22; of from about 0.03 to about 0.12;
from about 0.04 to about 0.10; from about 0.11 to about 0.12; from
about 0.10 to about 0.12; from about 0.15 to about 0.2; 0.15 to
about 0.30; 0.01 to about 0.10; from about 0.02 to about 0.08; from
about 0.03 to about 0.06; 0.08 to about 0.15; from about 0.10 to
about 0.12; from about 0.15 to about 0.2; from about 0.10 to about
0.12; from about 0.1 to about 0.35; from about 0.12 to about 0.20;
from 0.02 to about 0.22; from about 0.02 to about 0.20; from about
0.02 to about 0.18; or from of about 0.02 to about 0.16. Aspect
171. The method of any one of Aspects 72-170, wherein the foam
article has a stiffness of about 200 kilopascals to about 1000
kilopascals, for a cylindrical sample having a diameter of about 45
millimeters as determined using the Cyclic Compression Test. Aspect
172. The method of Aspect 171, wherein the foam article has a
stiffness of about 400 kilopascals to about 900 kilopascals, for a
cylindrical sample having a diameter of about 45 millimeters as
determined using the Cyclic Compression Test. Aspect 173. The
method of any one of Aspects 72-172, wherein the foam article has a
change in displacement at max loading of about 1 millimeters to
about 5 millimeters when measured on foam slabs having a thickness
of about 1 centimeter, wherein the foam slabs are compressed for
about 5000 cycles of compression from 0 newtons to 300 newtons and
back to 0 N per cycle, using a 45 mm diameter cylindrical tupp as
the compression head. Aspect 174. The method of any one of Aspects
72-172, wherein the foam article has a change in displacement at
max loading of about 2 millimeters to about 4 millimeters when
measured on foam slabs having a thickness of about 1 centimeters,
wherein the foam slabs are compressed for about 5000 cycles of
compression from 0 newtons to 300 newtons and back to 0 newtons per
cycle, using a 45 mm diameter cylindrical tupp as the compression
head. Aspect 175. The method of any one of Aspects 72-174, further
comprising disposing a layer comprising a second thermoplastic
composition on an exterior surface of the foam article. Aspect 176.
The method of Aspect 175, further comprising a step of removing the
foam article from the mold cavity following the disposing step.
Aspect 177. The method of Aspect 175, further comprising a step of
removing the foam article from the mold cavity before the disposing
step. Aspect 178. The method of any one of Aspects 175-177, wherein
the thermoplastic composition comprises a thermoplastic elastomer
or thermoplastic vulcanizate material for use a type of ground
contact, reinforcing skin, containment layer, outsole, rand, or
other application. Aspect 179. The method of any one of Aspects
175-178, wherein the second thermoplastic composition comprises a
thermoplastic elastomer (TPE) from polymer chemical families such
as copolyesters, thermoplastic polyurethanes (TPU), styrenic
copolymers like styrene butadiene rubbers (SBRs), styrene ethylene
butadiene styrene (SEBSs), styrene ethylene propylene styrene
(SEPS), ethylenic copolymers such as ethylene-propylene copolymers,
olefinic block copolymers, Surlyns and other ionomers, and/or
acrylic copolymer elastomers wherein they are block copolymers
comprised of PMMA blocks--acrylate blocks--PMMA blocks, etc, Aspect
180. The method of any one of Aspects 175-179, wherein the second
thermoplastic composition is comprised of an injection processible
thermoplastic vulcanizate (TPV) material, which are typically
cross-linked or partially cross-linked rubbers dispersed into
thermoplastic host phases, such as an ethylene propylene diene
rubber in polypropylene (EPDM/PP) where examples include Sarlink or
Santoprene TPV tradenames, or alkyl acrylic copolymer rubbers in
polyamide hosts (ACM/PA) where examples include Zeotherm TPVs, or
silicone rubbers dispersed in Hytrel based copolyesters (e.g. so
called TSiPVs) Aspect 181. The method of any one of Aspects
175-180, wherein the second thermoplastic composition if used as a
solid polymer material without the addition of compressed gas,
supercritical fluid or other blowing agent has a durometer less
than Shore A 90, optionally less than Shore A 85, and preferably
less than Shore A 80, but greater than Shore A 60, and optionally
greater than Shore A 65. Aspect 182. The method of any one of
Aspects 175-181, wherein the thermoplastic composition if used as a
solid polymer is comprised of TPEs or TPVs with densities less than
1.25 g/cc, optionally less than 1.1 g/cc, or less than 0.95 g/cc
and preferably less than 0.9 g/cc. Aspect 183. The method of any
one of Aspects 175-182, wherein the second thermoplastic
composition is produced separately via injection molding with or
without the addition of compressed gas, supercritical fluids or
other blowing agents upon which the foam article is produced or
injected via overmolding. Aspect 184. The method of any one of
Aspects 175-183, wherein the second thermoplastic composition (TPE
or TPV) is extruded into a fused deposition 3D printing filament of
1.5 mm, 1.75 mm, 1.85 mm, 2.85 mm 3.0 mm, or other relevant
diameter for deposition and attachment to foamed article comprised
of the first thermoplastic composition in such a way that it
comprises the ground contact layer, print-on outsole, or other
exterior features. Aspect 185. The method of Aspect 184, wherein
the second thermoplastic composition was produced via sequential
injection in the same process, or wherein the second thermoplastic
composition was produced in a separate process, and subsequently
inserted into the mold after which foam article from the first
thermoplastic composition is over molded. Aspect 186. The method of
any one of Aspects 175-185, wherein the second thermoplastic
composition is produced separately via injection molding with only
sufficient compressed gas, supercritical fluids or other blowing
agents to achieve a density of 0.9 g/cc or less, 0.85 g/cc or less,
or 0.8 g/cc or less. Aspect 187. The method of any one of Aspects
175-185, wherein the second thermoplastic composition is a film or
an outsole or a rand that is pretreated with a plasma or corona
treatment prior to receiving an overmolding assembly method. Aspect
188. The method of any one of Aspects 175-187, wherein the second
thermoplastic composition is a film or an outsole or a rand that is
pretreated with a primer alone, or a primer plus and an adhesive
prior to receiving the overmolding assembly method described in
Aspects above. Aspect 189. The method of any one of Aspects
175-188, wherein the ply adhesion strength between the second
thermoplastic composition and the first thermoplastic composition
comprising overmolded foam article exceeds 2.5 kilogram force per
centimeter. Aspect 190. The method of Aspect 189, wherein the ply
adhesion strength between the second thermoplastic composition and
the first thermoplastic composition comprising the foam article
exceeds 3.0 kilogram force per centimeter. Aspect 191. The method
of any one of Aspects 72-190, wherein the foam article comprises
greater than about 90 weight percent of the thermoplastic
copolyester based on the total weight of the first thermoplastic
composition. Aspect 192. The method of Aspect 191, wherein the foam
article comprises greater than about 95 weight percent of the
thermoplastic copolyester based on the total weight of the first
thermoplastic composition. Aspect 193. The method of Aspect 191,
wherein the foam article comprises greater than about 97 weight
percent of the thermoplastic copolyester based on the total weight
of the first thermoplastic composition. Aspect 194. The method of
Aspect 191, wherein the foam article comprises greater than about
98 weight percent of the thermoplastic copolyester based on the
total weight of the first thermoplastic composition. Aspect 195.
The method of Aspect 191, wherein the foam article comprises
greater than about 99 weight percent of the thermoplastic
copolyester based on the total weight of the first thermoplastic
composition. Aspect 196. A foam article comprising a foamed
polymeric material comprising the foam of any one of Aspects 1-71;
wherein the foam article has a multicellular foam structure. Aspect
197. The foam article of Aspect 196, wherein the foam article is an
extruded foam article. Aspect 198. The foam article of Aspect 196,
wherein the foam article is an injection molded foam article.
Aspect 199. The foam article of Aspect 198, wherein the foam
article is a compression molded foam article. Aspect 200. The foam
article of any one of Aspects 196-199, wherein the multicellular
foam structure has a closed cell foam microstructure. Aspect 201.
The foam article of any one of Aspects 196-200, wherein the
multicellular foam structure comprises less than 5 percent of cells
having a closed cell microstructure. Aspect 202. The foam article
of any one of Aspects 196-200, wherein the multicellular foam
structure comprises less than 1 percent of cells having a closed
cell microstructure. Aspect 203. The foam article of any one of
Aspects 196-202, wherein the multicellular foam has an average cell
size of from about 50 micron to about 5 millimeters; from about 100
micron to about 1 millimeters; or from about 50 micron to about 1
millimeters. Aspect 204. The foam article of any one of Aspects
196-203, wherein the foam article has a ply adhesion strength
between the polymeric layer and the foam component that is greater
than 2.5 kg force/centimeter or greater than 3.0 kg
force/centimeter, when determined using the Ply Adhesion Test
method described herein. Aspect 205. The foam article of any one of
Aspects 196-204, wherein the foam article has an average hand pull
test result between the polymeric layer and the foam component that
is greater than or equal to 2.0, or greater than or equal to 2.5,
or greater than or equal to 3.0, or greater than or equal to 3.5,
or greater than or equal to 4.0, or greater than or equal to 4.5,
when determined according to the Hand Pull Test method described
herein. Aspect 206. The foam article of any one of Aspects 196-205,
wherein the layer has an Akron abrasion of less than 0.50 cubic
centimeters lost, optionally less than 0.40 cubic centimeters lost,
less than 0.30 cubic centimeters lost, less than 0.20 cubic
centimeters lost, or less than 0.10 cubic centimeters lost as
determined using the Akron Abrasion Test. Aspect 207. The foam
article of any one of Aspects 196-206, wherein the layer has an
Akron abrasion of less than 500 milligrams lost, optionally less
than 400 milligrams lost, less than 300 milligrams lost, less than
200 milligrams lost, or less than 100 milligrams lost as determined
using the Akron Abrasion Test. Aspect 208. The foam article of any
one of Aspects 196-207, wherein the layer has a DIN abrasion of
less than 0.30 cubic centimeters lost, optionally less than 0.20
cubic centimeters lost, less than 0.10 cubic centimeters lost, less
than 0.05 cubic centimeters lost, or less than 0.03 cubic
centimeters lost as determined using the DIN Abrasion Test. Aspect
209. The foam article of any one of Aspects 196-208, wherein the
layer has a DIN abrasion of less than 300 milligrams lost,
optionally less than 250 milligrams lost, optionally less than 200
milligrams lost, optionally less than 150 milligrams lost,
optionally less than 100 milligrams lost, optionally less than 80
milligrams lost, optionally less than 50 milligrams lost, or
optionally less than 30 milligrams as
determined using the DIN Abrasion Test. Aspect 210. The foam
article of any one of Aspects 196-209, wherein the layer has a dry
dynamic coefficient of friction (COF) on a dry surface of greater
than 0.5, optionally of greater than 0.7, greater than 0.8, greater
than 0.9, greater than 1.0, as determined using the Dry Outsole
Coefficient of Friction Test. Aspect 211. The foam article of any
one of Aspects 206-210, wherein the layer has a wet dynamic COF of
greater than 0.25, optionally of greater than 0.30, greater than
0.35, greater than 0.40, or greater than 0.50, as determined using
the Wet Outsole Coefficient of Friction Test. Aspect 212. The foam
article of any one of Aspects 196-211, wherein the foam article has
a maximum load of about 100 N to about 4000 N when determined using
the Cyclic Tensile test as described herein. Aspect 213. The foam
article of Aspect 212, wherein the foam article has a maximum load
of about 100 N to about 4000 N when determined using the Cyclic
Tensile test as described herein. Aspect 214. The foam article of
any one of Aspects 196-213, wherein the foam article has an energy
efficiency of greater than or equal to about 50 percent when
determined using the Cyclic Compression test as described herein.
Aspect 215. The foam article of Aspect 214, wherein the foam
article has an energy efficiency of greater than or equal to about
60 percent when determined using the Cyclic Compression test as
described herein. Aspect 216. The foam article of Aspect 214,
wherein the foam article has an energy efficiency of greater than
or equal to about 70 percent when determined using the Cyclic
Compression test as described herein. Aspect 217. The foam article
of Aspect 214, wherein the foam article has an energy efficiency of
about 50 percent to about 97 percent when determined using the
Cyclic Compression test as described herein. Aspect 218. The foam
article of any one of Aspects 196-217, wherein the foam article has
an energy return of about 200 millijoules (mJ) to 1200 mJ when
determined using the Cyclic Compression test as described herein.
Aspect 219. The foam article of Aspect 218, wherein the foam
article has an energy return of about 400 mJ to 1000 mJ when
determined using the Cyclic Compression test as described herein.
Aspect 220. The foam article of Aspect 218, wherein the foam
article has an energy return of about 600 mJ to 800 mJ when
determined using the Cyclic Compression test as described herein.
Aspect 221. The foam article of any one of Aspects 196-220, wherein
the foam article has a split tear value of about 1.0 kilogram per
centimeter to 4.5 kilogram per centimeter, about 1.6 kilogram per
centimeter to 4.0 kilogram per centimeter, about 2.0 kilogram per
centimeter to 4.0 kilogram per centimeter, about 2.0 kilogram per
centimeter to 3.5 kilogram per centimeter, about 2.5 kilogram per
centimeter to 3.5 kilogram per centimeter, about 0.07 kilogram per
centimeter to 2.0 kilogram per centimeter, or about 0.8 kilogram
per centimeter to 1.5 kilogram per centimeter, or about 0.9 to 1.2
kilogram per centimeter, about 1.5 kilogram per centimeter to 2.2
kilogram per centimeter; about 0.08 kilogram per centimeter to 4.0
kilogram per centimeter, about 0.9 kilogram per centimeter to 3.0
kilogram per centimeter, about 1.0 to 2.0 kilogram per centimeter,
about 1.0 kilogram per centimeter to 1.5 kilogram per centimeter,
or about 2 kilogram per centimeter using a split tear test as
described herein. Aspect 222. The foam article of any one of
Aspects 196-220, wherein the foam article has a split tear value of
greater than or equal to about 1.5 kg/cm, greater than or equal to
about 2.0 kg/cm, or greater than or equal to about 2.5 kg/cm, when
determined using a split tear test as described herein. Aspect 223.
The foam article of any one of Aspects 196-222, wherein the foam
article has a specific gravity of less than or equal to 0.9, less
than or equal to 0.7, less than or equal to 0.5, or less than or
equal to 0.3. Aspect 224. The foam article of Aspect 223, wherein
the foam article has a specific gravity of from about 0.02 to about
0.22; of from about 0.03 to about 0.12; from about 0.04 to about
0.10; from about 0.11 to about 0.12; from about 0.10 to about 0.12;
from about 0.15 to about 0.2; 0.15 to about 0.30; 0.01 to about
0.10; from about 0.02 to about 0.08; from about 0.03 to about 0.06;
0.08 to about 0.15; from about 0.10 to about 0.12; from about 0.15
to about 0.2; from about 0.10 to about 0.12; from about 0.1 to
about 0.35; from about 0.12 to about 0.20; from 0.02 to about 0.22;
from about 0.02 to about 0.20; from about 0.02 to about 0.18; or
from of about 0.02 to about 0.16. Aspect 225. The foam article of
any one of Aspects 196-224, wherein the foam article has a
stiffness of about 200 kilopascals to about 1000 kilopascals, for a
cylindrical sample having a diameter of about 45 millimeters as
determined using the Cyclic Compression Test. Aspect 226. The foam
article of Aspect 225, wherein the foam article has a stiffness of
about 400 kilopascals to about 900 kilopascals, for a cylindrical
sample having a diameter of about 45 millimeters as determined
using the Cyclic Compression Test. Aspect 227. The foam article of
any one of Aspects 196-226, wherein the foam article has a change
in displacement at max loading of about 1 millimeters to about 5
millimeters when measured on foam slabs having a thickness of about
1 centimeters, wherein the foam slabs are compressed for about 5000
cycles of compression from ON to 300 N and back to 0 N per cycle,
using a 45 mm diameter cylindrical tupp as the compression head.
Aspect 228. The foam article of any one of Aspects 196-226, wherein
the foam article has a change in displacement at max loading of
about 2 millimeters to about 4 millimeters when measured on foam
slabs having a thickness of about 1 centimeters, wherein the foam
slabs are compressed for about 5000 cycles of compression from ON
to 300 N and back to 0 N per cycle, using a 45 mm diameter
cylindrical tupp as the compression head. Aspect 229. The foam
article of any one of Aspects 196-228, wherein the foam article
comprises greater than about 90 weight percent of the thermoplastic
copolyester based on the total weight of the first thermoplastic
composition. Aspect 230. The foam article of Aspect 229, wherein
the foam article comprises greater than about 95 weight percent of
the thermoplastic copolyester based on the total weight of the
first thermoplastic composition. Aspect 231. The foam article of
Aspect 229, wherein the foam article comprises greater than about
97 weight percent of the thermoplastic copolyester based on the
total weight of the first thermoplastic composition. Aspect 232.
The foam article of Aspect 229, wherein the foam article comprises
greater than about 98 weight percent of the thermoplastic
copolyester based on the total weight of the first thermoplastic
composition. Aspect 233. The foam article of Aspect 229, wherein
the foam article comprises greater than about 99 weight percent of
the thermoplastic copolyester based on the total weight of the
first thermoplastic composition. Aspect 234. An article comprising
the foam article made by the method of any one of Aspects 72-195,
or the foam article of any one of Aspects 196-233. Aspect 235. The
article of Aspect 234, wherein the article is an article of
footwear. Aspect 236. The article of Aspect 234, wherein the foam
article is a cushioning element in the article of footwear. Aspect
237. The article of Aspect 234, wherein the cushioning element is a
component of a sole structure in the article of footwear. Aspect
238. The article of Aspect 234, wherein the foam article is a
component of a sole structure in the article of footwear. Aspect
239. The article of any one of Aspects 243-238, wherein the sole
structure has a first side that is configured to be ground-facing
when the sole structure is a component of an article of footwear, a
second side opposed to the first side, and a sidewall extending at
least partially between the first side and the second side; wherein
the layer comprising the second polymeric material is disposed on
one or more of the first side, the second side, or the sidewall.
Aspect 240. The article of any one of Aspects 234-239, wherein the
sole structure includes a midsole. Aspect 241. The article of any
one of Aspects 234-240, wherein the sole structure includes a
plate. Aspect 242. The article of any one of Aspects 234-241,
wherein the sole structure includes a chassis. Aspect 243. The
article of any one of Aspects 234-242, wherein the sole structure
includes a bladder. Aspect 244. The article of any one of Aspects
234-243, wherein the sole structure includes a bladder, and the
foam article is disposed on an exterior surface of the bladder.
Aspect 245. The article of any one of Aspects 234-244, wherein the
sole structure includes a heel counter, or wherein the foam article
is a heel counter. Aspect 246. The article of any one of Aspects
234-245, wherein the sole structure comprises a shell component
that at least partially encloses the foam article, wherein the
shell component comprises the layer comprising the second
thermoplastic composition. Aspect 247. The article of any one of
Aspects 234-246, wherein the shell component encloses the foam
article on the first side and the sidewall of the sole structure.
Aspect 248. The article of any one of Aspects 234-247, wherein the
shell component is attached to the upper of the article of
footwear. Aspect 249. The article of any one of Aspects 234-248,
wherein the sole structure further comprises an outsole component
on the ground-facing side of the sole structure. Aspect 250. The
article of Aspect 249, wherein the outsole component comprises a
thermoplastic elastomer (TPE) or thermoplastic vulcanizate (TPV).
Aspect 251. The article of Aspect 250, wherein the thermoplastic
vulcanizate is cross-linked. Aspect 252. The article of Aspect 250,
wherein the thermoplastic vulcanizate is comprises a partially
cross-linked rubber dispersed into a thermoplastic host phase.
Aspect 253. The article of Aspect 252, wherein the partially
cross-linked rubber of the thermoplastic vulcanizate comprises an
ethylene propylene diene rubber, an alkyl acrylic copolymer rubber,
or silicone rubber, or any combination thereof; or wherein the
thermoplastic host phase of the thermoplastic vulcanizate comprises
a polypropylene homopolymer or copolymer, a polyamide homopolymer
or copolymer, a polyester homopolymer or copolymer, or any
combination thereof; optionally wherein the partially cross-linked
rubber dispersed into a thermoplastic host phase comprises an
ethylene propylene diene rubber in polypropylene (EPDM/PP), an
alkyl acrylic copolymer rubber in a polyamide host (ACM/PA), a
silicone rubber dispersed in thermoplastic copolyester, or
combinations thereof. Aspect 254. The article of any one of Aspects
234-253, wherein the outsole component comprises a thermoplastic
elastomer (TPE). Aspect 255. The article of Aspect 254, wherein the
thermoplastic elastomer is selected from a copolyester, a
thermoplastic polyurethane (TPU), a styrenic copolymer, an
ethylenic copolymer, an ionomer, an acrylic copolymer, and
combinations thereof; optionally wherein the thermoplastic
elastomer is a TPU or a styrenic copolymer. Aspect 256. The article
of Aspect 255, wherein the styrenic copolymer is selected from a
styrene butadiene rubber (SBR), a styrene ethylene butadiene
styrene (SEBS), a styrene ethylene propylene styrene (SEPS), and
combinations thereof. Aspect 257. The article of Aspect 255,
wherein the ethylenic copolymer is selected from an
ethylene-propylene copolymer, an olefinic block copolymer, and
combinations thereof. Aspect 258. The article of Aspect 255,
wherein the olefinic block comprises poly(methyl methacrylate)
blocks, acrylate blocks, poly(methyl methacrylate)-acrylate
copolymeric blocks, and combinations thereof. Aspect 259. The
article of any one of Aspects 249-258, wherein the outsole
component comprises a solid polymeric material that was formed
without the addition of compressed gas, supercritical fluid or
other blowing agent. Aspect 260. The article of Aspect 259, wherein
the outsole component has a durometer less than Shore A 90, than
Shore A 85, or less than Shore A 80. Aspect 261. The article of
Aspect 259, wherein the outsole component has a durometer greater
than Shore A 60 or Shore A 65. Aspect 262. The article of Aspect
259, wherein the outsole component has a durometer less than Shore
A 90, than Shore A 85, or less than Shore A 80; and wherein the
outsole component has a durometer greater than Shore A 60 or Shore
A 65. Aspect 263. The article of any one of Aspects 249-262,
wherein the outsole component comprises a thermoplastic elastomer
(TPE) or thermoplastic vulcanizate (TPV); and wherein the outsole
component has a density less than about 1.25 grams per cubic
centimeter, about 1.1 grams per cubic centimeter, about 0.95 grams
per cubic centimeter, or about 0.9 grams per cubic centimeter.
Aspect 264. The article of any one of Aspects 249-263, wherein the
outsole component comprises a ground contact layer, outsole, or
other exterior feature; wherein the ground contact layer, outsole,
or other exterior feature is prepared using a fused deposition 3D
printing process; and wherein the fused deposition 3D printing
process comprises using a preformed filament comprising a
thermoplastic elastomer (TPE) or thermoplastic vulcanizate (TPV);
or wherein the ground contact layer, outsole, or other exterior
feature is prepared using a yarn having a coating comprising a
thermoplastic elastomer (TPE) or thermoplastic vulcanizate (TPV),
and the process of forming the ground contact layer, outsole, or
other exterior feature comprises melting, re-flowing and
re-solidifying the coating of the yarn to form the ground contact
layer, outsole, or other exterior feature. Aspect 265. The article
of Aspect 264, wherein the filament has a diameter of about 1.5
millimeters, 1.75 millimeters, 1.85 millimeters, 2.85 millimeters,
or 3.0 millimeters. Aspect 266. The article of Aspect 264, wherein
the filament has a linear density from about 100 denier to about
300 denier, or has a diameter of from about 60 to 200 microns.
Aspect 267. The article of Aspects 265 or 266, wherein the ground
contact layer, outsole, or other exterior feature has a durometer
less than Shore A 90, than Shore A 85, or less than Shore A 80; and
wherein the outsole component has a durometer greater than Shore A
60 or Shore A 65. Aspect 268. The article of any one of Aspects
265-267, wherein the ground contact layer, outsole, or other
exterior feature has a density less than about 1.25 grams per cubic
centimeter, about 1.1 grams per cubic centimeter, about 0.95 grams
per cubic centimeter, or about 0.9 grams per cubic centimeter.
Aspect 269. The article of any one of Aspects 259-268, wherein the
outsole component is injected molded; optionally wherein the
outsole component is injection molded and foamed. Aspect 270. The
article of Aspect 269, wherein the injection molding comprises the
use of a compressed gas, a supercritical fluid, or a combination
thereof. Aspect 271. The article of Aspect 269, wherein the
injection molding comprises the use of a chemical foaming agent.
Aspect 272. The article of Aspect 269, wherein the injection
molding comprises the use of a compressed gas, a supercritical
fluid, a chemical foaming agent, or a combination thereof. Aspect
273. The article of any one of Aspects 249-272, wherein the outsole
component exhibits a dry traction coefficient of friction of about
0.9, of about 1.0, or about 1.1 by methods as defined herein.
Aspect 274. The article of any one of Aspects 249-273, wherein the
outsole component exhibits a wet traction coefficient of friction
of about 0.3, about 0.4, or about 0.5 by methods as defined herein.
Aspect 275. The article of any one of Aspects 249-274, wherein the
outsole component comprising TPE or TPV polymers exhibits abrasion
resistance as defined per the DIN or rotary drum abrasion test of
less than 250 milligrams lost per test, optionally less than 200
milligrams lost per test, and preferably less than 150 milligrams
lost per test, or less than 100 milligrams lost per test, or less
than 80 milligrams lost per test by methods as defined herein.
Aspect 276. The article of any one of Aspects 249-275, wherein the
outsole component comprises a cured rubber. Aspect 277. The article
of any one of Aspects 249-276, wherein the outsole has a density of
less than or equal to about 0.90 grams per cubic centimeter. Aspect
278. The article of any one of Aspects 249-276, wherein the outsole
has a density of less than or equal to about 0.85 grams per cubic
centimeter. Aspect 279. The article of any one of Aspects 249-276,
wherein the outsole has a density of less than or equal to about
0.50 grams per cubic centimeter. Aspect 280. The article of any one
of Aspects 249-276, wherein the outsole has a density about 0.60
grams per cubic centimeter to about 0.90 grams per cubic
centimeter. Aspect 281. The article of any one of Aspects 249-276,
wherein the outsole has a density about 0.60 grams per cubic
centimeter to about 0.85 grams per cubic centimeter. Aspect 282.
The article of any one of Aspects 249-276, wherein the outsole has
a density about 0.60 grams per cubic centimeter to about 0.80 grams
per cubic centimeter. Aspect 283. The article of any one of Aspects
249-276, wherein a side of the foam article is bonded to an upper.
Aspect 284. The article of any one of Aspects 196-283, wherein the
upper comprises a polyester yarn, a polyester fiber, a
thermoplastic polyurethane yarn, a thermoplastic polyurethane
fiber, or
combinations thereof. Aspect 285. The article of any one of Aspects
196-284, wherein the side of the foam article bonded to an upper is
bonded using an adhesive. Aspect 286. The article of any one of
Aspects 196-285, wherein the side of the foam article bonded to an
upper is essentially free of an adhesive at a bond interface
between the side of the foam article and the upper. Aspect 287. The
article of any one of Aspects 196-286, wherein the sole structure
further comprises an outsole component on a ground-facing side of
the outsole component. Aspect 288. The article of any one of
Aspects 196-287, wherein the outsole component comprises a cured
rubber. Aspect 289. The article of any one of Aspects 196-288,
wherein the article comprises a side of the foam article bonded to
an upper. Aspect 290. The article of any one of Aspects 196-289,
wherein the upper comprises a thermoplastic polyester yarn, a
thermoplastic polyester fiber, a thermoplastic polyurethane yarn, a
thermoplastic polyurethane fiber, a thermoplastic polyamide yarn, a
thermoplastic polyamide fiber, or combinations thereof. Aspect 291.
The article of any one of Aspects 196-2690 wherein the side of the
foam article bonded to an upper is bonded using an adhesive. Aspect
292. The article of any one of Aspects 196-291, wherein the side of
the foam article bonded to an upper and is essentially free of an
adhesive at a bond interface between the side of the foam article
and the upper. Aspect 293. The article of any one of Aspects
196-292, wherein the article is an article of apparel. Aspect 294.
The article of any one of Aspects 196-293, wherein the article is
an article of sporting equipment. Aspect 295. A method for
manufacturing an article of footwear, the method comprising:
affixing a foam article and a textile element to each other;
wherein the foam article is a form article of any one of Aspects
196-294; or wherein the foam article is a form article is made by
the method one of Aspects 72-195. Aspect 296. A method for
manufacturing an article of footwear, the method comprising:
affixing an outsole to the midsole to a midsole; wherein the
outsole comprises an outsole thermoplastic copolyester; and wherein
the midsole comprises a form article of any one of Aspects 196-294,
or a form article is made by the method one of Aspects 72-195.
Aspect 297. The method of Aspect 296, wherein the outsole
thermoplastic copolyester comprises a thermoplastic copolyester of
any one of Aspects 1-71. Aspect 298. The method of Aspect 296,
wherein the outsole thermoplastic copolyester is substantially free
of a thermoplastic copolyester of any one of Aspects 1-71. Aspect
299. The method of any one of Aspects 296-298, wherein outsole is
substantially free of a foamed outsole thermoplastic copolyester.
Aspect 300. The method of any one of Aspects 296-298, wherein
outsole comprises a foamed outsole thermoplastic copolyester.
Aspect 301. The method of any one of Aspects 296-300, wherein the
midsole comprises a midsole foamed thermoplastic composition
comprising at least one first thermoplastic copolyester, and the
outsole comprises an outsole thermoplastic copolyester composition
comprising a second thermoplastic composition including at least
one second thermoplastic copolyester, and wherein a concentration
of an additive in the foamed thermoplastic copolyester composition
differs from a concentration of the additive in the outsole
thermoplastic copolyester composition by at least 10 weight
percent, or a first concentration of the first thermoplastic
composition in the foamed thermoplastic copolyester composition
differs from a second concentration of the second thermoplastic
composition in the outsole thermoplastic copolyester composition by
at least 10 weight percent, or a chemical structure of the first at
least one thermoplastic copolyester differs from a chemical
structure of the second at least one thermoplastic copolyester, or
a number average molecular weight of the first at least one
thermoplastic copolyester differs from a number average molecular
weight of the second at least one thermoplastic copolyester by at
least 10 percent, or any combination thereof. Aspect 302. The
method of any one of Aspects 296-301, wherein the affixing
comprises injection molding an outsole, and then injection molding
the midsole directly onto the outsole. Aspect 303. The method of
any one of Aspects 296-301, wherein the affixing comprises
thermally bonding the midsole to the outsole. Aspect 304. A molding
system for forming a foam article, the system comprising: a barrel
housing a screw configured to receive a molten first thermoplastic
composition and form a mixture of the molten first thermoplastic
composition comprising a thermoplastic elastomer and a blowing
agent, and to adjust a position of the screw in the barrel to
regulate a flowrate of the mixture out of the barrel; a mold cavity
configured to contain the mixture during foaming, mold the foamed
mixture, and solidify the molded foamed mixture into the foam
article; an injection or extrusion device configured to receive the
mixture and extrude or inject it into the mold cavity at an
injection pressure and temperature; and a temperature control and
monitoring system configured to control the injection temperature
or a foaming temperature at which the molten first thermoplastic
composition is foamed within the mold cavity, or both. Aspect 305.
The molding system of Aspect 304, wherein the temperature control
and monitoring system is configured to control the injection
temperature of the mixture or the foaming temperature of the molten
first thermoplastic composition or both within a temperature
ranging from about the melting temperature of the thermoplastic
elastomer to about 50 degrees C. above the tail temperature of the
thermoplastic elastomer. Aspect 306. The molding system of Aspect
304 or 305, further comprising a gas counter pressure assembly
coupled to the mold cavity, wherein the gas counter pressure
assembly is configured to regulate an amount of counter pressure
gas flow into the mold cavity before, during or after extruding or
injecting the mixture into the mold cavity, or during foaming of
the molten first thermoplastic composition in the mold cavity.
Aspect 307. The molding system of any one of Aspects 304-306,
further comprising a mold cavity venting system configured to
regulate a rate of pressure loss due to gas flow out of the mold
cavity. Aspect 308. The molding system of any one of Aspects
304-307, wherein the system further comprises a runner system in
fluid communication with the injection or extrusion device and the
mold cavity. Aspect 309. The molding system of Aspect 308, wherein
the runner system is configured to control a temperature of the
mixture as it flows through the runner. Aspect 310. The molding
system of Aspect 309, wherein the runner system is configured to
heat the mixture as it flows through the runner. Aspect 311. The
molding system of any one of Aspects 304-310, wherein the system
includes a pressure control assembly configured to control a
pressure of the mixture as it enters the mold cavity. Aspect 312. A
method for operation of a molding system for forming a foam
article, the method comprising: forming a mixture of a molten first
thermoplastic composition comprising a thermoplastic elastomer and
a blowing agent in a barrel housing a screw; adjusting a position
of the screw in the barrel to regulate a flowrate of the mixture
out of the barrel;
[0320] flowing the mixture from the barrel into a mold cavity;
extruding or injecting the mixture into the mold cavity at an
injection pressure and an injection pressure; foaming the molten
first thermoplastic composition in the mold cavity at a foaming
temperature, thereby forming a foamed molten first thermoplastic
composition; and solidifying the foamed molten first thermoplastic
composition in the mold cavity, thereby forming a foam article
having a multicellular foam structure. Aspect 313. The method of
operation of Aspect 312, wherein the method further comprises
monitoring and controlling the injection temperature of the mixture
or the foaming temperature of the molten first thermoplastic
composition or both within a temperature ranging from about the
melting temperature of the thermoplastic elastomer to about 50
degrees C. above the tail temperature of the thermoplastic
elastomer. Aspect 314. The method of operation of Aspect 312 or
313, further comprising regulating an amount of counter pressure
gas flowing into the mold cavity before, during or after extruding
or injecting the mixture into the mold cavity, or during foaming of
the molten first thermoplastic composition in the mold cavity.
Aspect 315. The method of operation of Aspect 312-314, further
comprising releasing gas from the mold cavity at a controlled rate
during the extruding or injecting or during the foaming. Aspect
316. The method of operation of Aspect 312-315, further comprising
controlling a temperature of the mixture as it flows through a
runner into the mold cavity. Aspect 317. The method of operation of
Aspect 312-316, further controlling the injection pressure of the
mixture as it enters the mold cavity. Aspect 318. The method of
operation of Aspect 312-317, wherein the molten first thermoplastic
composition comprises a thermoplastic copolyester according any one
of Aspects 1-49, or the method is a method of making a foam article
according to any one of Aspects 50-173 or the foam article
comprises a foam article according to any one of Aspects 174-271,
or any combination thereof.
EXAMPLES
[0321] Now having described the aspects of the present disclosure,
in general, the following Examples describe some additional aspects
of the present disclosure. While aspects of the present disclosure
are described in connection with the following examples and the
corresponding text and figures, there is no intent to limit aspects
of the present disclosure to this description. On the contrary, the
intent is to cover all alternatives, modifications, and equivalents
included within the spirit and scope of the present disclosure.
Materials.
[0322] HYTREL 3078 and HYTREL 4068 were obtained from DuPont
(Wilmington, Del., USA).
Processing Conditions.
[0323] Foam plaques were prepared according to the conditions shown
in Table 1 below:
TABLE-US-00001 TABLE 1 Melt Mold Injection Speed Fill MPP N.sub.2
GCP GCP Material temp (.degree. C.) Temp (.degree. C.) (cc/sec)
time (s) (Bar) (%) (PSI) release Hytrel 4068 210 54 100 2.5 175 0.5
600 End of fill Hytrel 3078 200 40 100 2.5 175 0.5 000 End of
fill
[0324] Foam midsoles were prepared according to the conditions
shown in Table 2 below:
TABLE-US-00002 TABLE 2 Melt Mold Injection Speed Fill Cooling MPP
N.sub.2 GCP GCP Material Temp (.degree. C.) Temp (.degree. C.)
(cc/sec) time (s) Time (s) (Bar) (%) (PSI) release Hytrel 4058 210
54 100 2.5 400 175 1.22 600 End of fill Hytrel 3078 200 40 100 2.5
400 175 1.5 600 End of fill
[0325] Foam plaques were prepared according to the conditions shown
in Table 3 below.
TABLE-US-00003 TABLE 3 Mold Mold Temperature Temperature relative
to relative to Mold peak tail Temperature temperature temperature
(degrees (degrees (degrees Foam No. Polyester centigrade)
centigrade) centigrade) Quality 1 Triel .RTM. 5400 160 +5 -16 Good
2 Toyobo P-30B 175 0 -18 Poor 3 Toyobo P-30B 190 +15 -3 Good 4
Toyobo P-30B 205 +30 +12 Coarse 5 Toyobo P-30B 245 +70 +52
Coarser
[0326] Cross-sectional views of the foam plaques described above
are shown in FIGS. 9A-9D (for Nos. 2-5 above) and FIG. 10 (for No.
1 above).
Example 1. Exemplary Data of Foam Plaques
[0327] Foam plaques were prepared as described above using HYTREL
4068. Exemplary compression data are shown in FIG. 6. The data were
obtained by a cyclic compression testing protocol on a plaque in
the form of a cylindrical tupp having the following dimensions:
thickness--20 mm; diameter--44.86 mm. The compression data in FIG.
6 are a representative compression curve. The data obtained from
these tests are summarized in Table 4 below.
TABLE-US-00004 TABLE 4 Average Average Energy Modulus Stiffness Max
Efficiency Return Material (kPa) (N/mm) Strain (%) (mJ) Hytrel 4068
554 80 0.377 87 397
[0328] The specific gravity for foam plaques, prepared as described
herein above, was determined to be 0.16-0.28 for HYTREL 4068 and
0.17-0.26 HYTREL 3078.
[0329] The foam plaques described in Table 3 above were subjected
to energy return analysis as described herein. The results are
shown in Table 5 below.
TABLE-US-00005 TABLE 5 Energy Return No. Polyester (mJ) 1 Triel
.RTM. 5400 2830 2 Toyobo P-30B 2050 3 Toyobo P-30B 2940 4 Toyobo
P-30B 3150 5 Toyobo P-30B 2950
Example 2. Exemplary Data of Foam Midsoles
[0330] Foam midsoles were prepared as described above using HYTREL
4068. Compression data were obtained by a cyclic compression
testing protocol using a footform as described above. The data
obtained from these tests are summarized in Table 6 below.
TABLE-US-00006 TABLE 6 Average Average Max Energy Modulus Stiffness
Displacement Efficiency Return Material (kPa) (N/mm) (mm) (%) (mJ)
Hytrel 4068 N/A 173 11.57 74 4078
[0331] The specific gravity for foam midsoles, prepared as
described herein above, was determined to be 0.19-0.27 for HYTREL
4068 and 0.19-0.26 HYTREL 3078.
Example 3. Exemplary Hand Pull Data
[0332] A foam article was prepared comprising a first foam
component and a second s component. The first foam component was an
open-cell foam formed from a first thermoplastic copolyester
composition comprising HYTREL 4068 which contained less than 1
weight percent of non-polymeric materials. The first thermoplastic
copolyester composition was injection molded, foamed and bonded in
place to the second solid component. The thermoplastic copolyester
composition was foamed using the MUCELL process by forming a
single-phase solution of carbon dioxide and the thermoplastic
copolyester composition. The first thermoplastic copolyester
composition was injection molded and foamed onto a preformed second
component as described herein below. The second solid component was
prepared as a solid plaque using a second thermoplastic copolyester
composition, i.e., a second thermoplastic composition comprising
one of the four listed polymers shown in the table below (MP
IN15074, HYTREL 3078, TRIEL 5202SU, and SP9339, which are further
described in Table 8). The first foam component was bonded to the
second foam component, i.e., a plaque comprising a solid second
thermoplastic composition, by injecting, foaming, and molding a
single-phase solution of carbon dioxide and a thermoplastic
copolyester composition comprising HYTREL 4068 onto the outsole
plaque in an injection mold. Prior to placing the outsole plaque
into the mold, one of the following treatments was used: a) no
surface preparation was conducted on the surface of the outsole
plaque onto which the foam was injected (i.e., control sample); b)
the outsole plaque surface was wiped with methyl ethyl ketone prior
to insertion into the mold; c) the outsole plaque surface was
treated using a rotating cone open air plasma treatment immediately
prior to insertion into the mold and injection of the foam
composition, where the plaque surface was held 1 cm away from the
emitting head, and the plaque was moved passed the emitting head at
a rate of about 100-200 mm/sec; or d) the outsole plaque was heated
using an infrared lamp for at least 30 seconds after insertion into
the mold and immediately prior to injection of the foam
composition. The equipment used was a Plasmatreat OPENAIR-PLASMA
System with an RD1004 head (Plasmatreat GmbH, Steinhagen,
Germany).
[0333] Hand pull data were obtained using the Hand Pull Test as
described herein above. The data obtained are shown in Table 7
below. The data in Table 7 indicate that good bonding of the foam
to an outsole material can be achieved using a direct bonding
process with little if any additional process steps prior to
foaming and molding in place the first foam component.
TABLE-US-00007 TABLE 7 Outsole Polymer* Surface Prep of MP TRIEL
Foam Plaque IN15074 HY3078 5202SU SP9339 No treatment 1 2 3.5 2 MEK
wipe 1 3 3 3 Plasmatreat 1.5 4.5 4 3.5 IR pre-treatment 1 4.5 4 4
*Values correspond to the following results in Hand Pull Test:
1-easy to peel adhesive failure; 2-adhesive failure, but some
resistance; 3-4.5 cohesive foam failure, varying levels of foam
skin failure; and 5-unable separate)
Example 4. Exemplary Data of Second Thermoplastic Composition
Characterization--Coefficient of Friction--Polymer Samples
[0334] Sample preparation, coefficient of friction, and other test
procedures were carried out as described herein above. The
coefficient of friction data for wood and concrete surfaces are
shown in the table shown in FIGS. 11 and 12, respectively. The
materials referred into FIGS. 11 and 12 are further described in
Table 8 below.
TABLE-US-00008 TABLE 8 Material Grade Polymer type Form Supplier BT
1030D CoPe TPE Solid LG Desmopan 8795A TPU Foam Covestro Ellastolan
b70a TPU Solid Lubrizol Ellastolan SP9339 TPU Foam BASF Ellastolan
SP9339 TPU Solid BASF Estane t470a-3 TPU Solid Lubrizol HPF AD1035
Ethlyenic TPE/Ionomer Solid DuPont HPF AD1172 Ethlyenic TPE/Ionomer
Solid DuPont Hytrel 3078 CoPe TPE Solid DuPont Hytrel 3078 CoPe TPE
Foam DuPont Hytrel 3078 CoPe TPE Solid DuPont Hytrel 4068 CoPe TPE
Foam DuPont Hytrel 4556 CoPe TPE Solid DuPont KP3340 CoPe TPE Solid
Kolon KP3347 CoPe TPE Solid Kolon Kurarity LA2250 Acrylic TPE Solid
Kuraray Kurarity LA4285 Acrylic TPE Solid Kuraray Monprene 12990
SEBS TPE Foam Teknor Apex Monprene 66070 SEBS TPE Solid Teknor Apex
Monprene CP28160-01 SEBS TPE Solid Teknor Apex Monprene IN15056
SEBS TPE Solid Teknor Apex Monprene IN15074 SEBS TPE Solid Teknor
Apex Monprene IN15074 SEBS TPE Foam Teknor Apex Monprene SP16074H
SEBS TPE Solid Teknor Apex Monprene SP16975 SEBS TPE Solid Teknor
Apex Santoprene 123-40 TPV: EPDM/PP Solid-Herringbone Exxon
Santoprene 201-64 TPV: EPDM/PP Solid-Herringbone Exxon Santoprene
103-50 TPV: EPDM/PP Solid-Herringbone Exxon Sarlink 3160 TPV:
EPDM/PP Solid Teknor Apex Sarlink 6755B TPV: EPDM/PP Solid Teknor
Apex Sarlink 6755N TPV: EPDM/PP Solid Teknor Apex Septon blends
w/PP SEBS/PP compound Solid Kuraray (16-011-4) Septon blends w/PP
SEBS/PP compound Solid Kuraray (16-051-1) Septon blends w/PP
SEBS/PP compound Solid Kuraray (16-078-2) Surlyn 8150 Ethlyenic
TPE/Ionomer Solid DuPont Surlyn 8320 Ethlyenic TPE/Ionomer Solid
DuPont Surlyn 9320 Ethlyenic TPE/Ionomer Solid DuPont Topgreen RH
1502-2 CoPe TPE Solid FENC Topgreen RH 1601-7 CoPe TPE Solid FENC
TPSiV-50A TPV: Silicone/Hytrel Solid DuPont TPSiV-60A TPV:
Silicone/Hytrel Solid DuPont Triel 5202SP CoPe TPE Solid SamYang
Triel 5202SP CoPe TPE Foam SamYang Triel 5300 CoPe TPE Solid
SamYang Triel 5401A CoPe TPE Solid SamYang Triel SY 5280 CoPe TPE
Solid SamYang Tuftec P1500 SEBS TPE Solid Asahi Tuftec P5051 SEBS
TPE Solid Asahi Zeotherm 100-70B TPV: ACM/PA Solid Zeon Chemical
Zeotherm 100-80B TPV: ACM/PA Solid Zeon Chemical Zeotherm 110-70B
TPV: ACM/PA Solid Zeon Chemical Zeotherm 130-90B TPV: ACM/PA Solid
Zeon Chemical
[0335] Table 8, the abbreviations used therein have the following
meaning: "TPU" means "Thermoplastic Polyurethane"; CoPe TPE means
"Copolyester Thermoplastic Elastomer"; "Ethylenic TPE/Ionomer"
means "Ethylenic Thermoplastic Elastomer/Ionomer"; "Acrylic TPE"
means "Acrylic Thermoplastic Elastomer"; "SEBS TPE" means
"Styrene-Ethylene-Butadiene-Styrene Thermoplastic Elastomer";
"TPV/EPDM/PP" means "Styrene-Ethylene-Butadiene-Styrene
Thermoplastic Elastomer Thermoplastic Vulcanizate of Ethylene
Propylene Diene Monomer Rubber and Thermoplastic Polypropylene";
"TPV: Silicone/Hytrel" means "Thermoplastic Vulcanizate of Silicone
Rubber and Thermoplastic Copolyester"; and "TPV: ACM/PA" means
"Thermoplastic Vulcanizate of Acryl Acrylate Copolymer Rubber and
Thermoplastic Polyamide".
Example 5. Exemplary Data of Second Thermoplastic Composition
Characterization--Coefficient of Friction--Blown Outsole
Samples
[0336] Sample preparation, coefficient of friction, and other test
procedures were carried out as described herein above. The
coefficient of friction data for concrete surfaces are shown in the
table shown in FIG. 13. The materials referred into FIG. 13 are
further described in Table 8 above.
Example 6. Exemplary Data of Second Thermoplastic Composition
Characterization--Specific Gravity--Blown Outsole Samples
[0337] Sample preparation and specific gravity test procedures were
carried out as described herein above. The coefficient of friction
data for concrete surfaces are shown in the table shown in FIG. 14.
The samples approximated `blown` rubber via physically foamed
thermoplastic resins using added compressed gas or SCF. The
materials referred into FIG. 14 are further described in Table 8
above.
[0338] It should be emphasized that the above-described aspects of
the present disclosure are merely possible examples of
implementations, and are set forth only for a clear understanding
of the principles of the disclosure. Many variations and
modifications may be made to the above-described aspects of the
disclosure without departing substantially from the spirit and
principles of the disclosure. All such modifications and variations
are intended to be included herein within the scope of this
disclosure.
* * * * *