U.S. patent application number 13/333790 was filed with the patent office on 2012-07-19 for chemically-treated outsole assembly for a golf shoe.
This patent application is currently assigned to CALLAWAY GOLF COMPANY. Invention is credited to JON BOBBETT, JAMES GORMAN, MICHAEL ROY.
Application Number | 20120180342 13/333790 |
Document ID | / |
Family ID | 40026078 |
Filed Date | 2012-07-19 |
United States Patent
Application |
20120180342 |
Kind Code |
A1 |
BOBBETT; JON ; et
al. |
July 19, 2012 |
CHEMICALLY-TREATED OUTSOLE ASSEMBLY FOR A GOLF SHOE
Abstract
An out-sole assembly for a golf shoe. The outsole assembly
includes an internal base member composed of EVA, an inner frame
member composed thermoplastic polyurethane subjected to an
isocyanate solution, an external base member composed of a
thermoplastic polyurethane, a dual looping frame composed of a
thermoplastic polyurethane, and a plurality of spike members.
Inventors: |
BOBBETT; JON; (PORTSMOUTH,
NH) ; ROY; MICHAEL; (KOWLOON, HK) ; GORMAN;
JAMES; (HOPKINGTON, MA) |
Assignee: |
CALLAWAY GOLF COMPANY
CARLSBAD
CA
|
Family ID: |
40026078 |
Appl. No.: |
13/333790 |
Filed: |
December 21, 2011 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
12961265 |
Dec 6, 2010 |
8087189 |
|
|
13333790 |
|
|
|
|
11952015 |
Dec 6, 2007 |
7845097 |
|
|
12961265 |
|
|
|
|
60869046 |
Dec 7, 2006 |
|
|
|
Current U.S.
Class: |
36/127 |
Current CPC
Class: |
A43B 13/04 20130101;
A43B 5/001 20130101; A43B 13/026 20130101; A43B 13/12 20130101 |
Class at
Publication: |
36/127 |
International
Class: |
A43B 5/00 20060101
A43B005/00 |
Claims
1. An outsole assembly for a golf shoe comprising: an inner frame
member composed thermoplastic polyurethane subjected to an
isocyanate solution; an external base member; a dual looping frame
comprising a plurality of traction teeth; and a plurality of spike
members; wherein a height of the out-sole assembly ranges from 30
mm to 50 mm.
2. A golf shoe comprising: an upper with an opening; a mid-sole; an
outsole assembly comprising an inner frame member, an external base
member, a dual looping frame, the dual looping frame comprising a
plurality of teeth, each of the plurality of traction teeth having
a height ranging from 1 mm to 6 mm, and a plurality of spike
members, wherein at least one of the components above has a Shore D
hardness of 60 or less and is molded from a thermoplastic material
comprising a polyurethane, polyurea or polyurethane/polyurea
composition having a flex modulus of 30,000 psi or less and a melt
index of 15 g/10 min or more at a temperature of 200.degree. C. to
210.degree. C. and a load of 8.71 g prior to molding, and wherein
the component is treated with a secondary curing agent comprising
an isocyanate subsequent to molding; wherein a height of the
out-sole assembly ranges from 30 mm to 50 mm.
3. The golf shoe according to claim 2 wherein said isocyanate is
selected from the group consisting of 4,4'-diphenylmethane
diisocyanate ("MDI"); 2,4-toluene diisocyanate ("TDI"); m-xylylene
diisocyanate ("XDI"); methylene bis-(4-cyclohexyl isocyanate)
("HMDI"); hexamethylene diisocyanate ("HDI");
naphthalene-1,5,-diisocyanate ("NDI"); 3,3'-dimethyl-4,4'-biphenyl
diisocyanate ("TODI"); 1,4-diisocyanate benzene ("PPDI");
phenylene-1,4-diisocyanate; 2,2,4- or 2,4,4-trimethyl hexamethylene
diisocyanate ("TMDI"); isophorone diisocyanate ("IPDI");
1,4-cyclohexyl diisocyanate ("CHDI");
diphenylether-4,4'-diisocyanate; p,p'-diphenyl diisocyanate; lysine
diisocyanate ("LDI"); 1,3-bis(isocyanato methyl)cyclohexane;
polymethylene polyphenyl isocyanate ("PMDI");
meta-tetramethylxylylene diisocyanate ("TMXDI"); and combinations
thereof.
4. The golf shoe according to claim 2 wherein each of a plurality
of the components has a Shore D hardness of 60 or less and is
molded from a thermoplastic material comprising a polyurethane,
polyurea or polyurethane/polyurea composition having a flex modulus
of 30,000 psi or less and a melt index of 15 g/10 min or more at a
temperature of 200.degree. C. to 210.degree. C. and a load of 8.7
kg prior to molding, and wherein the component is treated with a
secondary curing agent comprising an isocyanate subsequent to
molding.
Description
CROSS REFERENCES TO RELATED APPLICATIONS
[0001] The present application is a continuation application of
U.S. patent application Ser. No. 12/961,265, filed on Dec. 6, 2010,
which is a continuation application of U.S. patent application Ser.
No. 11/952,015, filed on Dec. 6, 2007, now U.S. Pat. No. 7,845,097,
issued on Dec. 7, 2010, which claims priority to U.S. Provisional
Patent Application No. 60/869,046, filed on Dec. 7, 2006, now
abandoned.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not Applicable
BACKGROUND OF THE INVENTION
[0003] 1. Field of the Invention
[0004] The present invention relates to golf shoes. More
specifically, the present invention relates to an outsole assembly
for a golf shoe.
[0005] 2. Description of the Related Art
[0006] The traction portion of a golf shoe is subject to tremendous
wear and tear during a round of golf. Typically, spikes composed of
a polymer materials should be replaced after ten rounds of
golf.
[0007] Erickson et al., U.S. Pat. No. 6,708,426 for a Torsion
Management Outsoles And Shoes Including Such Outsoles discloses an
outsole with a forward portion and a rearward portion connected by
a ball-and-socket connection to allow the forward portion and
rearward portion to flex freely.
[0008] Allen et al., U.S. Pat. No. 5,987,783, for a Golf Shoe
Having Spike Socket Spine System, discloses a golf shoe with a
spike frame that receives spike receptacles and is embedded within
the outsole.
[0009] Robinson et al., U.S. Pat. No. 5,979,083, for a Multi-Layer
Outsole, discloses a two-layers outsole for a golf shoe with the
layers formed from thermoplastic polyurethane.
[0010] Robinson et al., U.S. Pat. No. 7,143,529, for a Torsion
Management Outsoles And Shoes Including Such Outsoles, discloses an
outsole with a forward portion and a rearward portion connected by
a ball-and-socket connection to allow the forward portion and
rearward portion to flex freely, and also includes a gel
cushion.
[0011] There is a need for a better outsole assembly.
BRIEF SUMMARY OF THE INVENTION
[0012] An out-sole assembly for a golf shoe having improved
durability and dynamic flexibility is disclosed herein. The
out-sole assembly has components that are subjected to an
isocyanate solution for added durability.
[0013] One aspect of the present invention is an outsole assembly
for a golf shoe. The outsole assembly includes an internal base
member composed of EVA, an inner frame member composed
thermoplastic polyurethane subjected to an isocyanate solution, an
external base member composed of a thermoplastic polyurethane, a
dual looping frame composed of a thermoplastic polyurethane, and a
plurality of spike members.
[0014] Another aspect of the present invention is a golf shoe. The
golf shoe includes an internal base member, an inner frame member,
an external base member, a dual looping frame, and a plurality of
spike members. At least one of the components above is molded from
a thermoplastic material comprising a polyurethane, polyurea or
polyurethane/polyurea composition having a melt index of 15 g/10
min or more at a temperature of 200.degree. C. to 210.degree. C.
and a load of 8.7 kg prior to molding, and the component is treated
with a secondary curing agent comprising an isocyanate subsequent
to molding.
[0015] Alternatively, all of the components are molded from a
thermoplastic material comprising a polyurethane, polyurea or
polyurethane/polyurea composition having a melt index of 15 g/10
min or more at a temperature of 200.degree. C. to 210.degree. C.
and a load of 8.7 kg prior to molding, and the component is treated
with a secondary curing agent comprising an isocyanate subsequent
to molding.
[0016] Yet another aspect of the present invention is a golf shoe
having a component composed of a certain material. The golf shoe
includes an internal base member, an inner frame member, an
external base member, a dual looping frame, and a plurality of
spike members. At least one of the components above has a Shore D
hardness of 60 or less and is molded from a thermoplastic material
comprising a polyurethane, polyurea or polyurethane/polyurea
composition having a flex modulus of 30,000 psi or less and a melt
index of 15 g/10 min or more at a temperature of 200.degree. C. to
210.degree. C. and a load of 8.7 kg prior to molding, and the
component is treated with a secondary curing agent comprising an
isocyanate subsequent to molding.
[0017] Alternatively, all of the components have a Shore D hardness
of 60 or less and are molded from a thermoplastic material
comprising a polyurethane, polyurea or polyurethane/polyurea
composition having a flex modulus of 30,000 psi or less and a melt
index of 15 g/10 min or more at a temperature of 200.degree. C. to
210.degree. C. and a load of 8.7 kg prior to molding, and the
component is treated with a secondary curing agent comprising an
isocyanate subsequent to molding.
[0018] Having briefly described the present invention, the above
and further objects, features and advantages thereof will be
recognized by those skilled in the pertinent art from the following
detailed description of the invention when taken in conjunction
with the accompanying drawings.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0019] FIG. 1 is a top perspective view of a golf shoe of the
present invention.
[0020] FIG. 2 is a bottom view of a out-sole assembly of the
present invention.
[0021] FIG. 3 is a medial view of the out-sole assembly of FIG.
2.
[0022] FIG. 4 is an isolated view of an internal base member of the
out-sole assembly of the present invention.
[0023] FIG. 5 is an isolated view of an inner frame member of the
out-sole assembly of the present invention.
[0024] FIG. 6 is an isolated view of an external base member of the
out-sole assembly of the present invention.
[0025] FIG. 7 is an isolated view of a dual looping member, spike
members and logo medallion of the out-sole assembly of the present
invention.
[0026] FIG. 8 is a bottom view of a out-sole assembly of the
present invention.
[0027] FIG. 9 is a medial view of the out-sole assembly of FIG.
8.
[0028] FIG. 10 is a lateral view of the out-sole assembly of FIG.
8.
[0029] FIG. 11 is a heel end view of the out-sole assembly of FIG.
8.
[0030] FIG. 12 is a toe end view of the out-sole assembly of FIG.
8.
[0031] FIG. 13 is a top plan view of the out-sole assembly of FIG.
8.
[0032] FIG. 14 is a cross-sectional view of the out-sole assembly
of FIG. 8 along line 1414.
[0033] FIG. 15 is a cross-sectional view of the out-sole assembly
of FIG. 8 along line 15-15.
[0034] FIG. 16 is a cross-sectional view of the out-sole assembly
of FIG. 8 along line 16-16.
[0035] FIG. 17 is a cross-sectional view of the out-sole assembly
of FIG. 8 along line 17-17.
[0036] FIG. 18 is a cross-sectional view of the out-sole assembly
of FIG. 8 along line 18-18.
[0037] FIG. 19 is a cross-sectional view of the out-sole assembly
of FIG. 8 along line 19-19.
[0038] FIG. 20 is a cross-sectional view of the out-sole assembly
of FIG. 8 along line 20-20.
[0039] FIG. 21 is a cross-sectional view of the out-sole assembly
of FIG. 8 along line 21-21.
[0040] FIG. 22 is an isolated view of a spike member with partial
cross-sectional views.
[0041] FIG. 23 is an isolated view of a spike member with partial
cross-sectional views.
[0042] FIG. 24 is an isolated view of a tooth of the plurality of
teeth of the dual loop member of the out-sole assembly of the
present invention along with a partial cross-sectional view.
DETAILED DESCRIPTION OF THE INVENTION
[0043] As shown in FIG. 1, a golf shoe is generally designated 20.
The golf shoe 20 preferably comprises an out-sole assembly 25, a
mid-sole 30, an upper 35 with an opening 40. The golf shoe 20 also
has a heel end 45 and a toe end 50.
[0044] As shown in FIGS. 2-7, the out-sole assembly 25 of the
present invention comprises an internal base member 55, an inner
frame member 60, an external base member 65, a dual looping frame
member 70 and a plurality of spike members 75a, 75b, 75c and 75d.
The out-sole assembly 25 optionally comprises a logo medallion 80.
The dual looping frame 70 comprises a plurality of traction teeth
85.
[0045] A height, Ho, of the out-sole assembly preferably ranges
from 30 mm to 50 mm, and is most preferably 39 mm. The thickness of
the external base member 65 is preferably between 2 mm and 5 mm,
and most preferably 3 mm. The thickness of the internal base member
55 preferably ranges from 5 mm to 30 mm. The height of each of the
teeth 85 is preferably between 1 mm and 6 mm, and most preferably 4
mm.
[0046] In a preferred embodiment, the internal base member 55 is
composed of an ethylene vinyl acetate ("EVA") material. The inner
frame member 60 is preferably composed of a thermoplastic
polyurethane material subjected to an additional isocyanate
treatment as set forth below. The external base member 65 is
preferably composed of a thermoplastic polyurethane material. The
dual looping frame member 70 is preferably composed of a
thermoplastic polyurethane material subjected to an additional
isocyanate treatment as set forth below. Each of the plurality of
spike members 75a-d is preferably composed of a thermoplastic
polyurethane material subjected to an additional isocyanate
treatment as set forth below.
[0047] Along these lines, the present invention concerns the
production of a thermoplastic polyurethane, polyurea or
polyurethane/polyurea golf ball component wherein the melt index of
polyurethane, polyurea or polyurethane/polyurea material is high
(i.e., 15 g/10 min or more, preferably 20 g/10 min or more, more
preferably greater than 25 grams per 10 minutes at the temperature
of 200.degree. C. to 210.degree. C. and a load of 8.7 Kg) or
substantially increased prior to molding. For example, the melt
index of the material can be increased, from supplied or base
material to refined or processed material, at least 10% or more,
preferably 20% to 720%, more preferably 50% to 720%, and most
preferably 100% or more prior to molding of the components of the
out-sole assembly 25.
[0048] The enhanced melt index of the material may be achieved by
secondary processing or refining steps, such as by mechanical,
chemical or electrical means. Preferably, the melt index is
increased by mechanical means such as by extrusion. While not
wanting to be limited to the theory of such an increase, it is
believed that the melt index increases after extrusion due to a
decrease in molecular weight, either by mechanical shearing or
chemical changes or both. Additional processes for decreasing the
molecular weight of the material can also be used. For example,
other methods for decreasing the molecular weight and/or increasing
the melt index of the material include the use of, or the
incorporation of, heat, light, irradiation, moisture, flow
additives, plasticizers, extenders, lubricants or other
thermoplastic materials having a higher melt index, etc. The melt
index of the material is adjusted to the high melt index range
desired prior to molding.
[0049] In a further embodiment, each of the components of the
out-sole assembly 25 is treated with a secondary curing or treating
agent, such as a solution containing one or more isocyanates, to
improve durability of the component. It is believed that the
isocyanate further cross-links the material to provide additional
scuff resistance while maintaining the other desirable features of
the component, such as flexibility. The solution containing the
isocyanate is preferably added to the material by any suitable
method known in the art, although dipping, wiping, soaking,
brushing or spraying the components of the out-sole assembly 25 in
or with the isocyanate solution is preferred. The method of adding
the isocyanate to the components of the out-sole assembly 25 is
discussed in more detail below.
[0050] The solution of the isocyanate that is added to the material
to improve scuff resistance can be any aliphatic or aromatic
isocyanate or diisocyanate or blends thereof known in the art. The
isocyanate or diisocyanate used may have a solids content in the
range of about 1 to about 100 weight %, preferably about 5 to about
50 weight %, most preferably about 10 to about 30 weight %. If it
is necessary to adjust the solids content, any suitable solvent
that will allow penetration of the isocyanate into the
polyurethane, polyurea or polyurethane/polyurea material without
causing distortion may be used. Examples of suitable solvents
include ketone and acetate.
[0051] In a particularly preferred aspect of the present invention,
the components of the out-sole assembly 25 are formed from a
thermoplastic polyurethane, polyurea or polyurethane/polyurea
material having a relatively high melt index, or that which is
adjusted prior to molding so as to exhibit a relatively high melt
index. In this regard, the melt of the material is 25 g/10 min or
more at a temperature of 200.degree. C. to 210.degree. C. and a
load of 8.7 kg prior to molding. Preferably, the melt index of the
material is of 30 g/10 min or more, more preferably 35 g/10 min or
more and most preferably 40 g/10 min or more at the above noted
temperature and conditions.
[0052] In accordance with the present invention, it has been
discovered that the higher the melt index of a polymer, the better
the flow and lower the injection molding pressures. Melt index or
melt flow values referred to herein are determined (unless
specified differently) in accordance with ASTM Standard D1238,
herein incorporated by reference.
[0053] The previously noted preferred thermoplastic polyurethane
materials may be adjusted into higher melt index materials. It is
preferably to raise the melt index to allow for the molding of the
components of the out-sole assembly 25. For example, Bayer
TEXIN.RTM. DP7-1097 has (according to Bayer Corporation) a melt
index of about 7 to 12 g/10 min at 200.degree. C. and 8.7 kg. The
base material received from Bayer is then further processed to
exhibit a melt index of from about 25 to about 45 g/10 min at
200.degree. C. and 8.7 kg. This material, when used for forming the
components of the out-sole assembly 25, preferably has an increased
melt index of about 35 to about 85 g/10 min at 200.degree. C. and
8.7 kg.
[0054] Similarly, Bayer TEXIN.RTM. 245 has (according to Bayer
Corporation) a melt index of about 20 to 40 g/10 min at 230.degree.
C. and 1.2 kg. It can be further processed or refined to exhibit a
melt index of about 25 to about 45 g/10 min at 210.degree. C. and
8.7 kg.
[0055] As also noted herein, it has been discovered that as the
melt index of a polymer increases, some of the physical properties
of the polymer decrease. As a result, in the more preferred
embodiments of the invention the high melt index of the components
of the out-sole assembly 25 are further treated with a liquid
isocyanate solution. By performing an isocyanate post-molding
treatment process to the components of the out-sole assembly 25,
the physical properties of the thermoplastic polyurethane, polyurea
or polyurethane/polyurea material may not only increase, but may
increase beyond the values of the non-refined material. This
physical property improvement yields a significant improvement in
durability, namely improved cut and scuff resistance.
[0056] This post-application of isocyanate is believed to allow for
the use of relatively high melt index thermoplastic polyurethane,
polyurea or polyurethanes/polyureas to be used in conventional
injection molding machines and/or in reaction injection molding
("RIM") equipment to mold the components of the out-sole assembly
25. The components of the out-sole assembly 25 are preferably
dipped in an isocyanate solution for 1 to 10 minutes (preferably 1
to 5 minutes); the isocyanate may be aliphatic or aromatic, such as
HDI, IPDI, MDI, TDI type or others as discussed below and the
isocyanate solution may range from 10 to 100% solids. The solvent
used to reduce the solids and make the isocyanate solutions may be
a ketone or acetate or any solvent that will allow penetration of
the isocyanate into the material without distortion. After dipping,
the components of the out-sole assembly 25 are preferably air-dried
for 1 hour and then post-cured at 175.degree. F. for 4 hours. After
the post-cure the components of the out-sole assembly 25 may be
cleaned with isopropanol to remove any excess isocyanate and then
finished in a normal manner. Preferably, the isocyanate used is of
the MDI type at 15-30% solids reduced with a ketone (such as MONDUR
ML.TM. from Bayer Corporation) and dipped for 2-3 minutes. Most
preferably, the solids level is about 16 to 24% (20.+-.4). It is
beneficial that the MDI remain in a liquid state at room
temperature. However, this method shall not be limited to the type
of polyurethane, polyurea or polyurethane/polyurea material,
isocyanate used, concentration of the isocyanate solution, solvent
used, dip time, or method of application described above.
[0057] In a preferred embodiment, the material of the components of
the out-sole assembly 25 comprises a polyurethane, a polyurea or a
blend of polyurethanes/polyureas. Polyurethanes/polyureas are
polymers that are used to form a broad range of products. They are
generally formed by mixing two primary ingredients during
processing. For the most commonly used polyurethanes, the two
primary ingredients are a polyisocyanate (for example,
diphenylmethane diisocyanate monomer ("MDI") and toluene
diisocyanate ("TDI") and their derivatives) and a polyol (for
example, a polyester polyol or a polyether polyol). Various chain
extenders known in the art, are also commonly used.
[0058] A wide range of combinations of polyisocyanates and polyols,
as well as other ingredients, are available. Furthermore, the
end-use properties of polyurethanes can be controlled by the type
of polyurethane utilized, such as whether the material is thermoset
(cross-linked molecular structure) or thermoplastic (linear
molecular structure).
[0059] Cross-linking occurs between the isocyanate groups (--NCO)
and the polyol's hydroxyl end-groups (--OH), and/or with already
formed urethane groups. Additionally, the end-use characteristics
of polyurethanes can also be controlled by different types of
reactive chemicals and processing parameters. For example,
catalysts are utilized to control polymerization rates. Depending
upon the processing method, reaction rates can be very quick (as in
the case for some reaction injection molding systems ("RIM") or may
be on the order of several hours or longer (as in several coating
systems). Consequently, a great variety of polyurethanes are
suitable for different end-uses.
[0060] Polyurethanes are typically classified as thermosetting or
thermoplastic. A polyurethane becomes irreversibly "set" when a
polyurethane prepolymer is cross-linked with a polyfunctional
curing agent, such as a polyamine or a polyol. The prepolymer
typically is made from polyether or polyester. Diisocyanate
polyethers are typically preferred because of their hydrolytic
properties.
[0061] The physical properties of thermoset polyurethanes are
controlled substantially by the degree of cross-linking. Tightly
cross-linked polyurethanes are fairly rigid and strong. A lower
amount of cross-linking results in materials that are flexible and
resilient. Thermoplastic polyurethanes have some cross-linking, but
primarily by physical means. The cross-link bonds can be reversibly
broken by increasing temperature, as occurs during molding or
extrusion. In this regard, thermoplastic polyurethanes can be
injection molded, and extruded as sheet and blow film. They can be
used up to about 350.degree. F. to 450.degree. F. and are available
in a wide range of hardnesses.
[0062] Polyurethane materials suitable for the present invention
are formed by the reaction of a polyisocyanate, a polyol, and
optionally one or more chain extenders. The polyol component
includes any suitable polyether- or polyester-polyol. Additionally,
in an alternative embodiment, the polyol component is polybutadiene
diol. The chain extenders include, but are not limited, to diols,
triols and amine extenders. Any suitable polyisocyanate may be used
to form a polyurethane according to the present invention. The
polyisocyanate is preferably selected from the group of
diisocyanates including, but not limited, to 4,4'-diphenylmethane
diisocyanate ("MDI"); 2,4-toluene diisocyanate ("TDI"); m-xylylene
diisocyanate ("XDI"); methylene bis-(4-cyclohexyl isocyanate)
("HMDI"); hexamethylene diisocyanate ("HDI");
naphthalene-1,5,-diisocyanate ("NDI"); 3,3'-dimethyl-4,4'-biphenyl
diisocyanate ("TODI"); 1,4-diisocyanate benzene ("PPDI");
phenylene-1,4-diisocyanate; and 2,2,4- or 2,4,4-trimethyl
hexamethylene diisocyanate ("TMDI").
[0063] Other less preferred diisocyanates include, but are not
limited to, isophorone diisocyanate ("IPDI"); 1,4-cyclohexyl
diisocyanate ("CHDI"); diphenylether-4,4'-diisocyanate;
p,p'-diphenyl diisocyanate; lysine diisocyanate ("LDI");
1,3-bis(isocyanato methyl)cyclohexane; and polymethylene polyphenyl
isocyanate ("PMDI").
[0064] One polyurethane component that can be used in the present
invention incorporates TMXDI ("META") aliphatic isocyanate (Cytec
Industries, West Paterson, N.J.). Polyurethanes based on
meta-tetramethylxylylene diisocyanate (TMXDI) can provide improved
gloss retention UV light stability, thermal stability, and
hydrolytic stability. Additionally, TMXDI ("META") aliphatic
isocyanate has demonstrated favorable toxicological properties.
Furthermore, because it has a low viscosity, it is usable with a
wider range of diols (to polyurethane) and diamines (to polyureas).
If TMXDI is used, it typically, but not necessarily, is added as a
direct replacement for some or all of the other aliphatic
isocyanates in accordance with the suggestions of the supplier.
Because of slow reactivity of TMXDI, it may be useful or necessary
to use catalysts to have practical demolding times. Hardness,
tensile strength and elongation can be adjusted by adding further
materials in accordance with the supplier's instructions.
[0065] The polyurethane, polyurea or polyurethane/polyurea which is
selected for use as a component of the out-sole assembly 25
preferably has a Shore D hardness of from about 10 to about 60,
more preferably from about 25 to about 60, and most preferably from
about 30 to about 55 for a soft cover layer. The polyurethane,
polyurea or polyurethane/polyurea which is to be used preferably
has a flex modulus from about 1 to about 310 Kpsi, more preferably
from about 5 to about 100 Kpsi, and most preferably from about 5 to
about 20 Kpsi for a soft component and 30 to 70 Kpsi for a hard
component.
[0066] Non-limiting examples of a polyurethane, polyurea or
polyurethane/polyurea suitable for use include a thermoplastic
polyester polyurethane such as Bayer Corporation's TEXIN.RTM.
polyester polyurethane (such as TEXIN.RTM. DP7-1097, TEXIN.RTM. 285
and TEXIN.RTM. 245 grades). According to Bayer Corporation,
TEXIN.RTM. DP7-1097 has the following properties:
TABLE-US-00001 TABLE 1 Properties of TEXIN .RTM. DP7-1097 Tensile
Strength (ASTM D412) 6000 lb/in.sup.2 @50% (ASTM D412) 875
lb/in.sup.2 @200%(ASTM D412) 950 lb/in.sup.2 @300% (ASTM D412) 2200
lb/in.sup.2 Ultimate Elongation (ASTM D412) 450% Flexural Modulus
(ASTM D790) 158.degree. F. (70.degree. C.) 3841 lb/in.sup.2
73.degree. F. (23.degree. C.) 6500 lb/in.sup.2 -22.degree. F.
(-30.degree. C.) 57400 lb/in.sup.2 Hardness (Shore A/Shore D) 90/40
Bayshore Resilience (ASTM D2632) 35% Solubility in Water Insoluble
Tear Strength, Die "C" (ASTM D624) 600 lbf/in Specific Gravity
(ASTM D792) 1.20 Vicat Softening Temp. (ASTM D1525) 216.degree. F.
Melt Index 7-14 g/10 min at 200.degree. C. and 8.7 kg, L/D = 4
(Method 1103-A)
According to Bayer Corporation, TEXIN.RTM. 245 has the following
properties:
TABLE-US-00002 TABLE 2 Properties of TEXIN .RTM. 245 Melt Flow
20-40 (230.degree. C., 1.2 kg load) Hardness 40-50D Tensile
Strength 4000 psi Minimum 100% Modulus 1090-1400 psi
[0067] The melt indexes of the base thermoplastic polyurethanes
received from Bayer Corporation are then increased to the following
specifications:
TPU Melt Index ("MI") Specifications
A. DP7-1097
[0068] As received from Bayer Corporation: 7-14, measured at
20.degree. C., 8.7 kg. load "Refined" or extruded specification:
30-50, measured at 20.degree. C., 8.7 kg. load % flow increase:
114%-614%
B. TEXIN.RTM. 245
[0069] As received from Bayer Corporation: 20-40, measured at
23.degree. C., 1.2 kg. load "Refined" specification: 30-50,
measured at 21.degree. C., 8.7 kg. load % flow increase:
Approximately 100%
General TPU Extrusion Conditions
[0070] dry material below 0.03% moisture [0071] single screw
extruder, with a single stage screw having an L/D of at least 24:1
and a compression ratio of 3:1 [0072] processing temps. [0073]
hopper: 180-220 F [0074] rear: 360-390 F [0075] middle: 360-400 F
[0076] front: 360-410 F [0077] adapter: 365-410 F [0078] die:
370-415 F [0079] melt: 385-465 F [0080] cushion--0.125'' max.
[0081] back pressure--200 psi. max. [0082] screw speed--40-80 rpm
[0083] screen packs--optional
Procedure for Raising Melt Index ("MI") to Desired Refined
Specification of 30-50
[0083] [0084] 1. Measure M.I. of dried material as received from
Bayer Corporation; [0085] 2. Adjust extruder machine settings to
achieve a nominal M.I. 40, measured at the appropriate test
conditions for either DP7-1097 or Texin 245; and [0086] 3.
Periodically check the M.I. throughout the extrusion run to ensure
a target M.I. value of 40.
[0087] Typically, there are two classes of thermoplastic
polyurethane materials: aliphatic polyurethanes and aromatic
polyurethanes. The aliphatic materials are produced from a polyol
or polyols and aliphatic isocyanates, such as H.sub.12MDI or HDI,
and the aromatic materials are produced from a polyol or polyols
and aromatic isocyanates, such as MDI or TDI. The thermoplastic
polyurethanes may also be produced from a blend of both aliphatic
and aromatic materials, such as a blend of HDI and TDI with a
polyol or polyols.
[0088] Generally, the aliphatic thermoplastic polyurethanes are
lightfast, meaning that they do not yellow appreciably upon
exposure to ultraviolet light. Conversely, aromatic thermoplastic
polyurethanes tend to yellow upon exposure to ultraviolet light.
One method of stopping the yellowing of the aromatic materials is
to paint the outer surface with a coating containing a pigment,
such as titanium dioxide, so that the ultraviolet light is
prevented from reaching the surface. Another method is to add UV
absorbers and stabilizers to the clear coating, as well as to the
thermoplastic polyurethane material itself. By adding UV absorbers
and stabilizers to the thermoplastic polyurethane and the
coating(s), aromatic polyurethanes can be effectively used. This is
advantageous because aromatic polyurethanes typically have better
scuff resistance characteristics than aliphatic polyurethanes, and
the aromatic polyurethanes are typically lower cost than aliphatic
polyurethanes.
[0089] Non-limiting examples of suitable RIM systems for use in the
present invention are Bayflex.RTM. elastomeric polyurethane RIM
systems, Baydur.RTM. GS solid polyurethane RIM systems, Prism.RTM.
solid polyurethane RIM systems, all from Bayer Corp. (Pittsburgh,
Pa.), SPECTRIM.RTM. reaction moldable polyurethane and polyurea
systems from Dow Chemical USA (Midland, Mich.), including
SPECTRIM.RTM. MM 373-A (isocyanate) and 373-B (polyol), and
ELASTOLIT.RTM. SR systems from BASF (Parsippany, N.J.). Preferred
RIM systems include BAYFLEX.RTM. MP-5000 and BAYFLEX.RTM. 110-50,
filled and unfilled. Further preferred examples are polyols,
polyamines and isocyanates formed by processes for recycling
polyurethanes and polyureas. Additionally, these various systems
may be modified by incorporating a butadiene component in the diol
agent.
[0090] The isocyanate that is added to improve scuff resistance can
be any aliphatic or aromatic isocyanate or diisocyanate or blends
thereof known in the art. Examples of suitable isocyanates include,
but are not limited to, 4,4'-diphenylmethane diisocyanate ("MDI");
2,4-toluene diisocyanate ("TDI"); m-xylylene diisocyanate ("XDI");
methylene bis-(4-cyclohexyl isocyanate) ("HMDI"); hexamethylene
diisocyanate ("HDI"); naphthalene-1,5,-diisocyanate ("NDI");
3,3'-dimethyl-4,4'-biphenyl diisocyanate ("TODI"); 1,4-diisocyanate
benzene ("PPDI"); phenylene-1,4-diisocyanate; and 2,2,4- or
2,4,4-trimethyl hexamethylene diisocyanate ("TMDI"). Other less
preferred diisocyanates include, but are not limited to, isophorone
diisocyanate ("IPDI"); 1,4-cyclohexyl diisocyanate ("CHDI");
diphenylether-4,4'-diisocyanate; p,p'-diphenyl diisocyanate; lysine
diisocyanate ("LDI"); 1,3-bis(isocyanato methyl)cyclohexane;
polymethylene polyphenyl isocyanate ("PMDI"); and
meta-tetramethylxylylene diisocyanate ("TMXDI"). Preferably, the
diisocyanate is MDI. The term "isocyanate" as used herein includes
all of these compounds and other isocyanates.
[0091] As mentioned generally above, the isocyanate or diisocyanate
used may have a solids content in the range of about 1 to about 100
weight %, preferably about 5 to about 50 weight %, most preferably
about 10 to about 30 weight %. If it is necessary to adjust the
solids content, any suitable solvent (such as ketone and acetate)
that will allow penetration of the isocyanate into the polyurethane
material without causing distortion may be used.
[0092] More preferably, the isocyanate utilized is MONDUR ML.TM.,
an aromatic diisocyanate manufactured by the Bayer Corporation.
According to Bayer, MONDUR ML.TM. is an isomer mixture of diphenyl
methane diisocyanate (MDI) containing a high percentage of 2,4
isomer. More particularly, MONDUR ML.TM. reportedly has the
following specifications and proportions:
[0093] A. Product Specifications
TABLE-US-00003 Assay, wt. % 99.5 minimum Acidity as HCI, ppm 30
maximum 2',4' isomer content, % 50-60 Dimer, wt. % 0.3 maximum
[0094] B. Typical Properties*
TABLE-US-00004 Appearance Clear to light yellow liquid Equivalent
weight 125 NCO Content, % 33.4-33.6 Viscosity @25.degree. C., mPa*s
10 Weight per gallon, lb. @25.degree. C. .sup. 9.9 Specific Gravity
@ 25.degree. C. 1.19 Freezing point 59.degree.-68.degree. F.
(15-20.degree. C.) Flash point (Setaflash) 388.degree. F.
(198.degree. C.) Equivalent wt., avg. (as supplied) 125 *These
items are provided as general information only. They are
approximate values and are not considered part of the product
specification.
[0095] The isocyanate is preferably added by dipping, soaking or
spraying in or with the isocyanate solution for about 1 to 10
minutes, more preferably about 1 to 5 minutes. The isocyanate
solution may be any desired isocyanate or diisocyanate solution,
and the solids content is preferably 1 to 100 weight percent,
preferably 5 to 50 weight percent, more preferably 15 to 30 weight
percent, and most preferably 16 to 24 weight percent. The
components of the out-sole assembly 25 are preferably heated to a
temperature such as 110.degree. F. to 120.degree. F. before adding
the isocyanate to facilitate the penetration of the isocyanate into
the material, although heating is not required. After the
components of the out-sole assembly 25 are dipped in the isocyanate
solution for the appropriate amount of time, the components of the
out-sole assembly 25 are air dried for approximately 30 minutes to
24 hours, more preferably 1 to 2 hours, and most preferably at
least about 1 hour. The components of the out-sole assembly 25 are
then post-cured to promote cross-linking of the material,
preferably at a temperature of about 150.degree. F. to 250.degree.
F., more preferably about 175.degree. F. for about 2 to 24 hours,
more preferably about 4 hours. After post-curing, the components of
the out-sole assembly 25 may be cleaned using a suitable cleaner,
such as an alcohol, if needed. An example of a suitable alcohol is
isopropanol, although any suitable alcohol that does not damage or
react with the material may be used. After addition of the
isocyanate, the components of the out-sole assembly 25 finished as
desired.
[0096] The procedure for dipping was further refined for production
to improve efficiency and reduce the processing time. The
components of the out-sole assembly 25 could be oven dried for only
4 hours at 175.degree. F. instead of 16 hours at 180.degree. F.,
and the isopropanol rinse could be eliminated without adversely
affecting the scuff results.
[0097] From the foregoing it is believed that those skilled in the
pertinent art will recognize the meritorious advancement of this
invention and will readily understand that while the present
invention has been described in association with a preferred
embodiment thereof, and other embodiments illustrated in the
accompanying drawings, numerous changes, modifications and
substitutions of equivalents may be made therein without departing
from the spirit and scope of this invention which is intended to be
unlimited by the foregoing except as may appear in the following
appended claims. Therefore, the embodiments of the invention in
which an exclusive property or privilege is claimed are defined in
the following appended claims.
* * * * *