U.S. patent application number 15/674577 was filed with the patent office on 2017-12-28 for medium gradient multi-piece urethane covered golf ball.
This patent application is currently assigned to Acushnet Company. The applicant listed for this patent is Acushnet Company. Invention is credited to Mark L. Binette, Brian Comeau, Michael J. Sullivan.
Application Number | 20170368422 15/674577 |
Document ID | / |
Family ID | 60675848 |
Filed Date | 2017-12-28 |
United States Patent
Application |
20170368422 |
Kind Code |
A1 |
Sullivan; Michael J. ; et
al. |
December 28, 2017 |
MEDIUM GRADIENT MULTI-PIECE URETHANE COVERED GOLF BALL
Abstract
A golf ball includes a core having an outer surface and a
geometric center; an inner cover layer, and an outer cover layer.
The inner cover layer includes an ionomeric material and has a
material hardness of about 60 Shore D or greater. The outer cover
layer is formed from a polyurea or polyurethane and has a material
hardness of about 60 Shore M or greater. The outer surface of the
core has a hardness of about 68 to 92 Shore C. The geometric center
of the core has a hardness of about 45 to 85 Shore C. The core
outer surface hardness is greater than the geometric center
hardness by about 5 to 21 Shore C to define a positive hardness
gradient. The core also has a volume weighted average hardness,
H.sub.V, of about 70 to 80, where H _ V = I V V c .
##EQU00001##
Inventors: |
Sullivan; Michael J.; (Old
Lyme, CT) ; Comeau; Brian; (Berkley, MA) ;
Binette; Mark L.; (Mattapoisett, MA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Acushnet Company |
Fairhaven |
MA |
US |
|
|
Assignee: |
Acushnet Company
Fairhaven
MA
|
Family ID: |
60675848 |
Appl. No.: |
15/674577 |
Filed: |
August 11, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15384414 |
Dec 20, 2016 |
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15674577 |
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15138371 |
Apr 26, 2016 |
9795836 |
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15384414 |
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14792803 |
Jul 7, 2015 |
9320945 |
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15138371 |
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14499320 |
Sep 29, 2014 |
9072945 |
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14792803 |
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13723469 |
Dec 21, 2012 |
8845456 |
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14499320 |
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13438947 |
Apr 4, 2012 |
8337330 |
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13723469 |
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12964343 |
Dec 9, 2010 |
8152655 |
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13438947 |
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12647584 |
Dec 28, 2009 |
8500575 |
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12964343 |
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12558826 |
Sep 14, 2009 |
7857714 |
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12647584 |
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12186877 |
Aug 6, 2008 |
7803069 |
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12558826 |
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11832197 |
Aug 1, 2007 |
7410429 |
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12186877 |
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11829461 |
Jul 27, 2007 |
7537530 |
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11832197 |
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11772903 |
Jul 3, 2007 |
7537529 |
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11829461 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A63B 37/0031 20130101;
A63B 37/0063 20130101; A63B 37/008 20130101; A63B 37/0003 20130101;
A63B 37/0027 20130101; A63B 37/0039 20130101; A63B 37/0064
20130101; A63B 37/0051 20130101; A63B 37/0062 20130101; A63B
37/0075 20130101; A63B 37/0032 20130101; A63B 37/0022 20130101;
A63B 37/0092 20130101; A63B 37/0043 20130101 |
International
Class: |
A63B 37/00 20060101
A63B037/00 |
Claims
1. A golf ball comprising: a core having a first outer surface and
a geometric center; an inner cover layer, the inner cover layer
comprising an ionomeric material and having a material hardness of
about 60 Shore D or greater; and an outer cover layer, the outer
cover layer comprising a polyurea or a polyurethane and having a
material hardness of about 60 Shore M or greater; wherein the first
outer surface has a hardness of about 68 to 92 Shore C, the
geometric center has a hardness of about 45 to 85 Shore C, and the
core has a positive hardness gradient of about 5 to 21 Shore C and
a volume weighted average hardness, H.sub.V, of about 70 to 80,
where H _ V = I V V c . ##EQU00006##
2. The golf ball of claim 1, wherein the volume weighted average
hardness, H.sub.V, of about 70 to 75, where H _ V = I V V c .
##EQU00007##
3. The golf ball of claim 2, wherein the volume weighted average
hardness, H.sub.V, of about 73 to 75, where H _ V = I V V c .
##EQU00008##
4. The golf ball of claim 1, wherein the positive hardness gradient
is about 11 to 19 Shore C.
5. The golf ball of claim 4, wherein the positive hardness gradient
is about 13 to 18 Shore C.
6. The golf ball of claim 1, wherein the core has an outer diameter
of about 1.45 to about 1.62 inches.
7. The golf ball of claim 1, wherein the hardness of the geometric
center is about 60 to 85 Shore C.
8. The golf ball of claim 1, wherein the hardness of the first
outer surface is about 74 to 88 Shore C.
9. The golf ball of claim 8, wherein the first outer surface
hardness is about 80 to 86 Shore C.
10. The golf ball of claim 1, wherein the outer cover layer
comprises a coating layer having a Shore M hardness of about 60 or
less.
11. The golf ball of claim 10, wherein the coating layer has a
Shore M hardness of about 50 or less.
12. The golf ball of claim 10, wherein the coating layer has an
instrumented hardness of about 0.1 MPa to about 23 MPa.
13. The golf ball of claim 1, wherein the golf ball comprises an
outer core layer disposed between the core and the inner cover
layer.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of co-pending
U.S. patent application Ser. No. 15/384,414, filed Dec. 20, 2016,
which is a continuation-in-part of co-pending U.S. patent
application Ser. No. 15/138,371, filed Apr. 26, 2016, which is a
continuation-in-part of U.S. patent application Ser. No.
14/792,803, filed Jul. 7, 2015 and now U.S. Pat. No. 9,320,945,
which is a continuation of U.S. patent application Ser. No.
14/499,320, filed Sep. 29, 2014 and now U.S. Pat. No. 9,072,945,
which is a continuation of U.S. patent application Ser. No.
13/723,469, filed Dec. 21, 2012 and now U.S. Pat. No. 8,845,456,
which is a continuation of U.S. patent application Ser. No.
13/438,947, filed Apr. 4, 2012 and now U.S. Pat. No. 8,337,330,
which is a continuation of U.S. patent application Ser. No.
12/964,343, filed Dec. 9, 2010 and now U.S. Pat. No. 8,152,655,
which is a continuation-in-part of co-pending U.S. patent
application Ser. No. 12/647,584, filed Dec. 28, 2009 and now U.S.
Pat. No. 8,500,575, which is a continuation-in-part of U.S. patent
application Ser. No. 12/558,826, filed Sep. 14, 2009 and now U.S.
Pat. No. 7,857,714, which is a continuation of U.S. patent
application Ser. No. 12/186,877, filed Aug. 6, 2008 and now U.S.
Pat. No. 7,803,069, which is a continuation of U.S. patent
application Ser. No. 11/832,197, filed Aug. 1, 2007 and now U.S.
Pat. No. 7,410,429, which is a continuation-in-part of U.S. patent
application Ser. No. 11/829,461, filed Jul. 27, 2007 and now U.S.
Pat. No. 7,537,530, which is a continuation-in-part of U.S. patent
application Ser. No. 11/772,903, filed Jul. 3, 2007 and now U.S.
Pat. No. 7,537,529, the disclosures of which are incorporated
herein by reference.
FIELD OF THE INVENTION
[0002] This invention relates generally to golf balls with cores
having one or more layers, any of the layers having a `negative` or
`positive` hardness gradient, trans-polybutadiene gradient, or
both. More particularly, the golf ball has a core of one or more
layers where at least one layer, preferably a solid core, has a
medium, positive hardness gradient.
BACKGROUND OF THE INVENTION
[0003] Solid golf balls are typically made with a solid core
encased by a cover, both of which can have multiple layers, such as
a dual core having a solid center and an outer core layer, or a
multi-layer cover having an inner. Generally, golf ball cores
centers are constructed with a thermoset rubber, typically a
polybutadiene-based composition. The cores are thermally
crosslinked to obtain certain desirable properties, such as higher
or lower compression or hardness. These and other characteristics
can be tailored to the needs of golfers of different abilities. It
is desirable to have cores exhibiting a wide range of properties,
such as resilience, durability, spin, and "feel," because this
enables the manufacturer to make and sell many different types of
golf balls suited to differing levels of ability.
[0004] Most solid golf ball cores have a conventional hard-to-soft
hardness gradient from the surface of the core to the center of the
core, known as a "positive hardness gradient." These gradients,
however, are typically quite large, upwards of 15, 20, even 25 or
more Shore C. The patent literature contains a number of
references, additionally, that discuss a
hard-surface-to-soft-center hardness gradient across a golf ball
core.
[0005] U.S. Pat. No. 4,650,193 to Molitor et al. generally
discloses a hardness gradient in the surface layers of a core by
surface treating a slug of curable elastomer with a cure-altering
agent and subsequently molding the slug into a core. This treatment
allegedly creates a core with two zones of different compositions,
the first part being the hard, resilient, central portion of the
core, which was left untreated, and the second being the soft,
deformable, outer layer of the core, which was treated by the
cure-altering agent. The two "layers" or regions of the core are
integral with one another and, as a result, achieve the effect of a
gradient of soft surface to hard center.
[0006] U.S. Pat. No. 3,784,209 to Berman, et al. generally
discloses a soft-to-hard hardness gradient. The '209 patent
discloses a non-homogenous, molded golf ball with a core of "mixed"
elastomers. A center sphere of uncured elastomeric material is
surrounded by a compatible but different uncured elastomer. When
both layers of elastomer are concurrently exposed to a curing
agent, they become integral with one another, thereby forming a
mixed core. The center of this core, having a higher concentration
of the first elastomeric material, is harder than the outer layer.
One drawback to this method of manufacture is the time-consuming
process of creating first elastomer and then a second elastomer and
then molding the two together.
[0007] Other patents discuss cores that receive a surface treatment
to provide a soft `skin`. However, since the interior portions of
these cores are untreated, they have the similar hard surface to
soft center gradient as conventional cores. For example, U.S. Pat.
No. 6,113,831 to Nesbitt et al. generally discloses a conventional
core and a separate soft skin wrapped around the core. This soft
skin is created by exposing the preform slug to steam during the
molding process so that a maximum mold temperature exceeds a steam
set point, and by controlling exothermic molding temperatures
during molding. The skin comprises the radially-outermost 1/32 inch
to 1/4 inch of the spherical core. U.S. Pat. Nos. 5,976,443 and
5,733,206, both to Nesbitt et al., disclose the addition of water
mist to the outside surface of the slug before molding in order to
create a soft skin. The water allegedly softens the compression of
the core by retarding crosslinking on the core surface, thereby
creating an even softer soft skin around the hard central
portion.
[0008] Additionally, a number of patents disclose multi-layer golf
ball cores, where each core layer has a different hardness thereby
creating a hardness gradient from core layer to core layer. There
remains a need, however, for a multi-layer golf ball having single
layer core that has a medium hard-to-soft ("positive") hardness
gradient, from the surface to the center, and to achieve a method
of producing such a core that is inexpensive and efficient.
SUMMARY OF THE INVENTION
[0009] The present invention is directed to a golf ball including a
single core and a double cover. The single core has an outer
surface and a geometric center, and is formed from a substantially
homogenous rubber composition. The double cover includes an inner
cover layer and an outer cover layer. The inner cover layer, which
is disposed about the core, is formed from an ionomeric material.
The inner cover layer has a material hardness of about 60 Shore D
or greater. The outer cover layer is disposed about the inner cover
layer and is typically formed from a castable polyurea or a
castable polyurethane. This layer has a material hardness of about
60 Shore D or less. In one preferred embodiment, the outer surface
of the core has a trans content of about 12% or less and a hardness
of about 71 to 88 Shore C, the geometric center has a trans content
of about 10% or less and a hardness of about 70 to 80 Shore C, and
the core surface hardness is greater than the geometric center
hardness by about 1 to 10 Shore C to define a shallow positive
hardness gradient.
[0010] In one embodiment, the positive hardness gradient is about 2
to 8 Shore C, more preferably about 2.5 to 7 Shore C. The core
preferably has an outer diameter of about 1.45 to about 1.62
inches, more preferably about 1.50 to about 1.58 inches. The
hardness of the geometric center of the core is generally about 72
to 78 Shore C and the hardness of the core surface is generally
about 73 to 80 Shore C, more preferably about 74 to 78 Shore C. In
another preferred embodiment, the outer surface of the core has a
trans content of about 10% or less and the geometric center of the
core has a trans content of about 8% or less.
[0011] The present invention is also directed to a golf ball formed
from a single core having an outer diameter of about 1.5 to 1.55
inches. The core is typically formed from a substantially
homogenous rubber composition. An inner cover layer is disposed
about the core and is typically formed from a thermoplastic
ionomeric material having a material hardness of about 66 to 80
Shore D. An outer cover layer is disposed about the inner cover
layer and has a thickness of about 0.04 inches. In this embodiment,
the outer cover layer is formed from an ionomer having a material
hardness of about 64 to 68 Shore D, or a thermosetting castable
polyurethane having a hardness of about 51 to 55 Shore D.
Preferably, the outer surface of the core has a trans content of
about 12% or less and a hardness of about 74 to 78 Shore C, the
geometric center has a trans content of about 10% or less and a
hardness of about 72 to 78 Shore C, and the core surface hardness
is greater than the geometric center hardness by about 1 to 5 Shore
C to define a shallow positive hardness gradient, the core having
an Atti compression of about 50 to 70.
[0012] In one embodiment, the golf ball further includes an
intermediate layer disposed between the inner cover layer and the
core, the intermediate layer having a thickness of about 0.06
inches and a hardness of about 43 to 47 Shore D. Generally, the
inner cover hardness is about 66 Shore D, the intermediate layer
hardness is about 45 Shore D, and the outer cover layer hardness is
about 53 Shore D.
[0013] The present invention is further directed to a golf ball
including a single core having an outer diameter of about 1.45
inches, an outer surface, and a geometric center, and being formed
from a substantially homogenous rubber composition. An inner cover
layer is disposed about the core. The inner cover has an outer
diameter of about 1.58 inches and is formed from a thermoplastic
non-ionomeric material having a material hardness of about 38 to 42
Shore D. An outer cover layer is disposed about the inner cover
layer. The outer cover has a thickness of about 0.05 inches and is
formed from an ionomer having a material hardness of about 66 to 70
Shore D. Preferably, the outer surface of the core has a trans
content of about 12% or less and a hardness of about 74 to 78 Shore
C, the geometric center has a trans content of about 10% or less
and a hardness of about 72 to 78 Shore C, and the core surface
hardness is greater than the geometric center hardness by about 1
to 5 Shore C to define a shallow positive hardness gradient.
[0014] Alternatively, the present invention is directed to a golf
ball including a core having an outer surface and a geometric
center. The core is typically formed from a substantially
homogenous rubber composition. An ionomeric inner cover layer is
formed about the core and has a material hardness of about 60 Shore
D or greater. The golf ball also includes an outer cover layer
formed over the inner cover layer. The outer cover includes a
polyurea or a polyurethane and generally has a material hardness of
about 60 Shore D or less. The outer surface of the core has a
trans-polybutadiene content of about 12% or less and a hardness of
about 71 to 88 Shore C. The geometric center of the core has a
trans-polybutadiene content of about 10% or less and a hardness of
about 60 to 80 Shore C. The core also has an outer surface hardness
greater than a geometric center hardness by about 5 to 19 Shore C
to define a positive hardness gradient.
[0015] Preferably, the positive hardness gradient is about 10 to 19
Shore C, more preferably about 12 to 19 Shore C, most preferably
about 14 to 17 Shore C. The core has an outer diameter of about
1.45 to 1.62 inches, more preferably about 1.50 to about 1.58
inches. The hardness of the geometric center of the core is
preferably about 60 to 70 Shore C and the hardness of the surface
of the core is preferably about 74 to 85 Shore C. More preferably,
the core surface hardness is about 80 to 84 Shore C. Alternatively,
the core surface hardness is about 75 to 79 Shore C. In one
embodiment, the outer surface has a trans-polybutadiene content of
about 10% or less and the geometric center has a
trans-polybutadiene content of about 8% or less.
[0016] The present invention is directed to a golf ball including a
core, an inner cover layer, and an outer cover layer. The core has
an outer surface and a geometric center and is formed from a
substantially homogenous rubber composition. The inner cover layer
is formed from an ionomeric material and has a material hardness of
about 60 Shore D or greater. The outer cover layer includes a
polyurea or a polyurethane and has a material hardness of about 60
Shore D or less. Preferably, the outer surface of the core has a
trans-polybutadiene content of about 12% or less and a hardness of
about 45 to 56 Shore D. The geometric center of the core has a
trans-polybutadiene content of about 10% or less and a hardness of
about 35 to 45 Shore D. The core outer surface hardness is greater
than the core geometric center hardness by about 3 to 15 Shore D to
define a positive hardness gradient.
[0017] The geometric center preferably has a hardness of about 38
to 43 Shore D and the outer surface hardness is preferably about 48
to 54 Shore D. The positive hardness gradient is preferably about 5
to 13 Shore D, more preferably about 7 to 11 Shore D.
[0018] The present invention is further directed to a
medium-hardness-gradient golf ball that includes a core having an
outer surface and a geometric center, an inner cover layer, and an
outer cover layer. The inner cover layer typically includes an
ionomeric material (including a fully-neutralized ionomer) and has
a material hardness of about 60 Shore D or greater. The outer cover
layer is formed from a polyurea or polyurethane and has a material
hardness of about 60 Shore M or greater. In one embodiment, the
outer cover layers has a material hardness of about 50 Shore M or
greater.
[0019] The outer surface of the core preferably has a hardness of
about 68 Shore C to about 92 Shore C, more preferably the outer
surface of the core has a hardness of about 74 Shore C to about 85
Shore C, and most preferably outer surface of the core preferably
has a hardness of about 80 Shore C to about 84 Shore C. In an
alternative embodiment, the outer surface of the core has a
hardness of about 45 Shore D to about 56 Shore D, preferably the
outer surface of the core has a hardness of about 48 Shore D to
about 54 Shore D.
[0020] The geometric center of the core may have a hardness of
about 45 Shore C to about 85 Shore C. Preferably, the geometric
center of the core has a hardness of about 60 Shore C to about 85
Shore C, more preferably the geometric center of the core has a
hardness of about 62 Shore C to about 80 Shore C, and most
preferably the geometric center of the core has a hardness of about
65 Shore C to about 72 Shore C. In an alternative embodiment, the
geometric center of the core has a hardness of about 35 Shore D to
about 45 Shore D, preferably the geometric center of the core has a
hardness of about 38 Shore D to about 43 Shore D.
[0021] While the core outer surface hardness may be greater than
the geometric center hardness by about 5 Shore C to about 55 Shore
C to define a positive hardness gradient, preferably the core outer
surface hardness is greater than the geometric center hardness by
about 5 Shore C to about 21 Shore C, more preferably the core outer
surface hardness is greater than the geometric center hardness by
about 11 Shore C to about 19 Shore C, and most preferably the core
outer surface hardness is greater than the geometric center
hardness by about 13 Shore C to about 18 Shore C. In an alternative
embodiment, the outer surface of the core has a hardness that is
greater than the hardness at the geometric center of the core by
about 3 Shore D to about 15 Shore D to define a positive hardness
gradient. More preferably, the positive hardness gradient is about
5 Shore D to about 13 Shore D, and most preferably, the positive
hardness gradient is about 7 Shore D to about 11 Shore D.
[0022] The outer surface of the core preferably has a trans content
of about 12% or less and the geometric center of the core
preferably has a trans content of about 10% or less. In one
alternative embodiment, the core has an outer diameter of about
1.45 to about 1.62 inches and, optionally, comprises an outer core
layer disposed between the core and the inner cover layer. The
outer cover layer may include a coating layer having a Shore M
hardness of about 60 or less, more preferably about 50 or less. The
coating layer has an instrumented hardness of about 0.1 MPa to
about 23 MPa.
[0023] The present invention is directed to a golf ball having a
core, an inner cover, and an outer cover. The core has an outer
surface hardness that is greater than the hardness at the geometric
center to define a positive hardness gradient across the core. The
inner cover layer includes an ionomeric material and has a material
hardness of about 60 Shore D or greater. The outer cover layer
includes a polyurea or a polyurethane and has a material hardness
of about 60 Shore M or greater. The core outer surface has a
hardness of about 68 to 92 Shore C, the geometric center has a
hardness of about 45 to 85 Shore C, and the positive hardness
gradient is about 5 to 21 Shore C. The core also has a volume
weighted average hardness, H.sub.V, of about 70 to 80, where
H _ V = I V V c . ##EQU00002##
More preferably, the volume weighted average hardness is about 70
to 75, most preferably about 73 to 75.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] These and other aspects of the present invention may be more
fully understood with reference to, but not limited by, the
following drawings.
[0025] FIG. 1 is a representative cross section of a golf ball of
the invention; and
[0026] FIG. 2 is a plot of hardness vs. volume for various
embodiments of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0027] The golf balls of the present invention may include a
single-layer (one-piece) golf ball, and multi-layer golf balls,
such as one having a core and a cover surrounding the core, but are
preferably formed from a core comprised of a solid center
(otherwise known as an inner core) and an outer core layer, an
inner cover layer and an outer cover layer. Of course, any of the
core and/or the cover layers may include more than one layer. In a
preferred embodiment, the core is formed of an inner core and an
outer core layer where both the inner core and the outer core layer
have a "soft-to-hard" hardness gradient (a "negative" hardness
gradient) radially inward from each component's outer surface
towards its innermost portion (i.e., the center of the inner core
or the inner surface of the outer core layer), although alternative
embodiments involving varying direction and combination of hardness
gradient amongst core components are also envisioned (e.g., a
"negative" gradient in the center coupled with a "positive"
gradient in the outer core layer, or vice versa).
[0028] The center of the core may also be a liquid-filled or hollow
sphere surrounded by one or more intermediate and/or cover layers,
or it may include a solid or liquid center around which tensioned
elastomeric material is wound. Any layers disposed around these
alternative centers may exhibit the inventive core hardness
gradient (i.e., "negative"). The cover layer may be a single layer
or, for example, formed of a plurality of layers, such as an inner
cover layer and an outer cover layer.
[0029] Alternatively, a preferred golf ball construction includes a
solid core, an inner cover layer, and an outer cover layer. The
core has an outer surface and a geometric center, both of which
have hardness values. The core is typically formed from a
substantially homogenous rubber composition, such as a
polybutadiene rubber. The inner cover layer is preferably formed
from an ionomeric material and has a material hardness of about 60
Shore D or greater. The outer cover layer, formed over the inner
cover layer, is preferably a polyurea or a polyurethane material
and has a material hardness of about 60 Shore D or less. The outer
surface of the core preferably has a trans-polybutadiene content of
about 12% or less, more preferably 10% or less, and most preferably
about 8% or less. The core outer surface hardness is preferably
about 71 to 88 Shore C. The geometric center of the core has a
trans-polybutadiene content of about 10% or less and a hardness of
about 60 to 80 Shore C. The core also has an outer surface hardness
greater than a geometric center hardness by about 5 to 19 Shore C
to define a positive hardness gradient.
[0030] Preferably, the positive hardness gradient is about 10 to 19
Shore C, more preferably about 12 to 19 Shore C, most preferably
about 14 to 17 Shore C. The hardness of the geometric center of the
core is preferably about 60 to 70 Shore C and the hardness of the
surface of the core is preferably about 74 to 85 Shore C. More
preferably, the core surface hardness is about 80 to 84 Shore C.
Alternatively, the core surface hardness is about 75 to 79 Shore C.
In one embodiment, the outer surface has a trans-polybutadiene
content of about 10% or less and the geometric center has a
trans-polybutadiene content of about 8% or less.
[0031] The present invention is directed to a golf ball including a
core, an inner cover layer, and an outer cover layer. The core has
an outer surface and a geometric center and is formed from a
substantially homogenous rubber composition. The inner cover layer
is formed from an ionomeric material and has a material hardness of
about 60 Shore D or greater. The outer cover layer includes a
polyurea or a polyurethane and has a material hardness of about 60
Shore D or less. Preferably, the outer surface of the core has a
trans-polybutadiene content of about 12% or less and a hardness of
about 45 to 56 Shore D. The geometric center of the core has a
trans-polybutadiene content of about 10% or less and a hardness of
about 35 to 45 Shore D. The core outer surface hardness is greater
than the core geometric center hardness by about 3 to 15 Shore D to
define a positive hardness gradient.
[0032] The geometric center preferably has a hardness of about 38
to 43 Shore D and the outer surface hardness is preferably about 48
to 54 Shore D. The positive hardness gradient is preferably about 5
to 13 Shore D, more preferably about 7 to 11 Shore D.
[0033] As discussed above, the inventive cores may have a hardness
gradient defined by hardness measurements made at the surface of
the inner core (or outer core layer) and radially inward towards
the center of the inner core, typically at 2-mm increments. As used
herein, the terms "negative" and "positive" refer to the result of
subtracting the hardness value at the innermost portion of the
component being measured (e.g., the center of a solid core or an
inner core in a dual core construction; the inner surface of a core
layer; etc.) from the hardness value at the outer surface of the
component being measured (e.g., the outer surface of a solid core;
the outer surface of an inner core in a dual core; the outer
surface of an outer core layer in a dual core, etc.). For example,
if the outer surface of a solid core has a lower hardness value
than the center (i.e., the surface is softer than the center), the
hardness gradient will be deemed a "negative" gradient (a smaller
number-a larger number=a negative number). It is preferred that the
inventive cores have a zero or a negative hardness gradient, more
preferably between zero (0) and -10, most preferably between 0 and
-5.
[0034] Preferably, the core layers (inner core or outer core layer)
is made from a composition including at least one thermoset base
rubber, such as a polybutadiene rubber, cured with at least one
peroxide and at least one reactive co-agent, which can be a metal
salt of an unsaturated carboxylic acid, such as acrylic acid or
methacrylic acid, a non-metallic coagent, or mixtures thereof.
Preferably, a suitable antioxidant is included in the composition.
An optional soft and fast agent (and sometimes a cis-to-trans
catalyst), such as an organosulfur or metal-containing organosulfur
compound, can also be included in the core formulation
[0035] Other ingredients that are known to those skilled in the art
may be used, and are understood to include, but not be limited to,
density-adjusting fillers, process aides, plasticizers, blowing or
foaming agents, sulfur accelerators, and/or non-peroxide radical
sources. The base thermoset rubber,130 which can be blended with
other rubbers and polymers, typically includes a natural or
synthetic rubber. A preferred base rubber is 1,4-polybutadiene
having a cis structure of at least 40%, preferably greater than
80%, and more preferably greater than 90%. Examples of desirable
polybutadiene rubbers include BUNA.RTM. CB22 and BUNA.RTM. CB23,
CB1221, CB1220, CB24, and CB21, commercially-available from LANXESS
Corporation; UBEPOL.RTM. 360L and UBEPOL.RTM. 150L and UBEPOL-BR
rubbers, commercially available from UBE Industries, Ltd. of Tokyo,
Japan; KINEX.RTM. 7245, KINEX.RTM. 7265, and BUDENE 1207 and 1208,
commercially available from Goodyear of Akron, Ohio; SE BR-1220;
Europrene.RTM. NEOCIS.RTM. BR 40 and BR 60, commercially available
from Polimeri Europa; and BR 01, BR 730, BR 735, BR 11, and BR 51,
commercially available from Japan Synthetic Rubber Co., Ltd;
PETROFLEX.RTM. BRNd-40; and KARBOCHEM.RTM. ND40, ND45, and ND60,
commercially available from Karbochem.
[0036] From the Lanxess Corporation , most preferred are the
neodymium and cobalt catalyzed grades, but all of the following may
be used.: Buna CB 21; Buna CB 22; Buna CB 23; Buna CB 24; Buna CB
25; Buna CB 29 MES; Buna CB Nd 40; Buna CB Nd 40 H; Buna CB Nd 60;
Buna CB 55 NF; Buna CB 60; Buna CB 45 B; Buna CB 55 B; Buna CB 55
H; Buna CB 55 L; Buna CB 70 B; Buna CB 1220; Buna CB 1221; Buna CB
1203; Buna CB 45. Additionally, numerous suitable rubbers are
available from JSR (Japan Synthetic Rubber), Ubepol sold by Ube
Industries Inc, Japan, BST sold by BST Elastomers, Thailand; IPCL
sold by Indian Petrochemicals Ltd, India; Nitsu sold by Karbochem
or Karbochem Ltd of South Africa; Petroflex of Brazil; LG of Korea;
and Kuhmo Petrochemical of Korea.
[0037] The base rubber may also comprise high or medium Mooney
viscosity rubber, or blends thereof. A "Mooney" unit is a unit used
to measure the plasticity of raw or unvulcanized rubber. The
plasticity in a "Mooney" unit is equal to the torque, measured on
an arbitrary scale, on a disk in a vessel that contains rubber at a
temperature of 100.degree. C. and rotates at two revolutions per
minute. The measurement of Mooney viscosity is defined according to
ASTM D-1646. The Mooney viscosity range is preferably greater than
about 40, more preferably in the range from about 40 to about 80
and more preferably in the range from about 40 to about 60.
Polybutadiene rubber with higher Mooney viscosity may also be used,
so long as the viscosity of the polybutadiene does not reach a
level where the high viscosity polybutadiene clogs or otherwise
adversely interferes with the manufacturing machinery. It is
contemplated that polybutadiene with viscosity less than 65 Mooney
can be used with the present invention. Gin one embodiment of the
present invention, glf ball cores made with mid- to high-Mooney
viscosity polybutadiene material exhibit increased resiliency (and,
therefore, distance) without increasing the hardness of the ball.
Such cores are soft, i.e., compression less than about 60 and more
specifically in the range of about 50-55. Cores with compression in
the range of from about 30 about 50 are also within the range of
this preferred embodiment.
[0038] Commercial sources of suitable mid- to high-Mooney viscosity
polybutadiene include Bayer AG CB23 (Nd-catalyzed), which has a
Mooney viscosity of around 50 and is a highly linear polybutadiene,
and CB1221 (Co-catalyzed). If desired, the polybutadiene can also
be mixed with other elastomers known in the art, such as other
polybutadiene rubbers, natural rubber, styrene butadiene rubber,
and/or isoprene rubber in order to further modify the properties of
the core. When a mixture of elastomers is used, the amounts of
other constituents in the core composition are typically based on
100 parts by weight of the total elastomer mixture. In one
preferred embodiment, the base rubber comprises a Nd-catalyzed
polybutadiene, a rare earth-catalyzed polybutadiene rubber, or
blends thereof. If desired, the polybutadiene can also be mixed
with other elastomers known in the art such as natural rubber,
polyisoprene rubber and/or styrene-butadiene rubber in order to
modify the properties of the core. Other suitable base rubbers
include thermosetting materials such as, ethylene propylene diene
monomer rubber, ethylene propylene rubber, butyl rubber, halobutyl
rubber, hydrogenated nitrile butadiene rubber, nitrile rubber, and
silicone rubber.
[0039] Thermoplastic elastomers (TPE) many also be used to modify
the properties of the core layers, or the uncured core layer stock
by blending with the base thermoset rubber. These TPEs include
natural or synthetic balata, or high trans-polyisoprene, high
trans-polybutadiene, or any styrenic block copolymer, such as
styrene ethylene butadiene styrene, styrene-isoprene-styrene, etc.,
a metallocene or other single-site catalyzed polyolefin such as
ethylene-octene, or ethylene-butene, or thermoplastic polyurethanes
(TPU), including copolymers, e.g. with silicone. Other suitable
TPEs for blending with the thermoset rubbers of the present
invention include PEBAX.RTM., which is believed to comprise
polyether amide copolymers, HYTREL.RTM., which is believed to
comprise polyether ester copolymers, thermoplastic urethane, and
KRATON.RTM., which is believed to comprise styrenic block
copolymers elastomers. Any of the TPEs or TPUs above may also
contain functionality suitable for grafting, including maleic acid
or maleic anhydride.
[0040] Additional polymers may also optionally be incorporated into
the base rubber. Examples include, but are not limited to,
thermoset elastomers such as core regrind, thermoplastic
vulcanizate, copolymeric ionomer, terpolymeric ionomer,
polycarbonate, polyamide, copolymeric polyamide, polyesters,
polyvinyl alcohols, acrylonitrile-butadiene-styrene copolymers,
polyarylate, polyacrylate, polyphenylene ether, impact-modified
polyphenylene ether, high impact polystyrene, diallyl phthalate
polymer, styrene-acrylonitrile polymer (SAN) (including
olefin-modified SAN and acrylonitrile-styrene-acrylonitrile
polymer), styrene-maleic anhydride copolymer, styrenic copolymer,
functionalized styrenic copolymer, functionalized styrenic
terpolymer, styrenic terpolymer, cellulose polymer, liquid crystal
polymer, ethylene-vinyl acetate copolymers, polyurea, and
polysiloxane or any metallocene-catalyzed polymers of these
species.
[0041] Suitable polyamides for use as an additional polymeric
material in compositions within the scope of the present invention
also include resins obtained by: (1) polycondensation of (a) a
dicarboxylic acid, such as oxalic acid, adipic acid, sebacic acid,
terephthalic acid, isophthalic acid, or 1,4-cyclohexanedicarboxylic
acid, with (b) a diamine, such as ethylenediamine,
tetramethylenediamine, pentamethylenediamine, hexamethylenediamine,
or decamethylenediamine, 1,4-cyclohexanediamine, or
m-xylylenediamine; (2) a ring-opening polymerization of cyclic
lactam, such as .epsilon.-caprolactam or .OMEGA.-laurolactam; (3)
polycondensation of an aminocarboxylic acid, such as 6-aminocaproic
acid, 9-aminononanoic acid, 11-aminoundecanoic acid, or
12-aminododecanoic acid; or (4) copolymerization of a cyclic lactam
with a dicarboxylic acid and a diamine. Specific examples of
suitable polyamides include NYLON 6, NYLON 66, NYLON 610, NYLON 11,
NYLON 12, copolymerized NYLON, NYLON MXD6, and NYLON 46.
[0042] Suitable peroxide initiating agents include dicumyl
peroxide; 2,5-dimethyl-2,5-di(t-butylperoxy) hexane;
2,5-dimethyl-2,5-di(t-butylperoxy)hexyne;
2,5-dimethyl-2,5-di(benzoylperoxy)hexane;
2,2'-bis(t-butylperoxy)-di-iso-propylbenzene;
1,1-bis(t-butylperoxy)-3,3,5-trimethyl cyclohexane; n-butyl
4,4-bis(t-butyl-peroxy)valerate; t-butyl perbenzoate; benzoyl
peroxide; n-butyl 4,4'-bis(butylperoxy) valerate; di-t-butyl
peroxide; or 2,5-di-(t-butylperoxy)-2,5-dimethyl hexane, lauryl
peroxide, t-butyl hydroperoxide, .alpha.-.alpha. bis(t-butylperoxy)
diisopropylbenzene, di(2-t-butyl-peroxyisopropyl)benzene, di-t-amyl
peroxide, di-t-butyl peroxide. Preferably, the rubber composition
includes from about 0.25 to about 5.0 parts by weight peroxide per
100 parts by weight rubber (phr), more preferably 0.5 phr to 3 phr,
most preferably 0.5 phr to 1.5 phr. In a most preferred embodiment,
the peroxide is present in an amount of about 0.8 phr. These ranges
of peroxide are given assuming the peroxide is 100% active, without
accounting for any carrier that might be present. Because many
commercially available peroxides are sold along with a carrier
compound, the actual amount of active peroxide present must be
calculated. Commercially-available peroxide initiating agents
include DICUP.TM. family of dicumyl peroxides (including DICUP.TM.
R, DICUP.TM. 40C and DICUP.TM. 40KE) available from Crompton (Geo
Specialty Chemicals). Similar initiating agents are available from
AkroChem, Lanxess, Flexsys/Harwick and R.T. Vanderbilt. Another
commercially-available and preferred initiating agent is
TRIGONOX.TM. 265-50B from Akzo Nobel, which is a mixture of
1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane and
di(2-t-butylperoxyisopropyl) benzene. TRIGONOX.TM. peroxides are
generally sold on a carrier compound.
[0043] Suitable reactive co-agents include, but are not limited to,
metal salts of diacrylates, dimethacrylates, and monomethacrylates
suitable for use in this invention include those wherein the metal
is zinc, magnesium, calcium, barium, tin, aluminum, lithium,
sodium, potassium, iron, zirconium, and bismuth. Zinc diacrylate
(ZDA) is preferred, but the present invention is not limited
thereto. ZDA provides golf balls with a high initial velocity. The
ZDA can be of various grades of purity. For the purposes of this
invention, the lower the quantity of zinc stearate present in the
ZDA the higher the ZDA purity. ZDA containing less than about 10%
zinc stearate is preferable. More preferable is ZDA containing
about 4-8% zinc stearate. Suitable, commercially available zinc
diacrylates include those from Sartomer Co. The preferred
concentrations of ZDA that can be used are about 10 phr to about 40
phr, more preferably 20 phr to about 35 phr, most preferably 25 phr
to about 35 phr. In a particularly preferred embodiment, the
reactive co-agent is present in an amount of about 29 phr to about
31 phr.
[0044] Additional preferred co-agents that may be used alone or in
combination with those mentioned above include, but are not limited
to, trimethylolpropane trimethacrylate, trimethylolpropane
triacrylate, and the like. It is understood by those skilled in the
art, that in the case where these co-agents may be liquids at room
temperature, it may be advantageous to disperse these compounds on
a suitable carrier to promote ease of incorporation in the rubber
mixture.
[0045] Antioxidants are compounds that inhibit or prevent the
oxidative breakdown of elastomers, and/or inhibit or prevent
reactions that are promoted by oxygen radicals. Some exemplary
antioxidants that may be used in the present invention include, but
are not limited to, quinoline type antioxidants, amine type
antioxidants, and phenolic type antioxidants. A preferred
antioxidant is 2,2'-methylene-bis-(4-methyl-6-t-butylphenol)
available as VANOX.RTM. MBPC from R.T. Vanderbilt. Other
polyphenolic antioxidants include VANOX.RTM. T, VANOX.RTM. L,
VANOX.RTM. SKT, VANOX.RTM. SWP, VANOX.RTM. 13 and VANOX.RTM.
1290.
[0046] Suitable antioxidants include, but are not limited to,
alkylene-bis-alkyl substituted cresols, such as
4,4'-methylene-bis(2,5-xylenol);
4,4'-ethylidene-bis-(6-ethyl-m-cresol);
4,4'-butylidene-bis-(6-t-butyl-m-cresol);
4,4'-decylidene-bis-(6-methyl-m-cresol);
4,4'-methylene-bis-(2-amyl-m-cresol);
4,4'-propylidene-bis-(5-hexyl-m-cresol);
3,3'-decylidene-bis-(5-ethyl-p-cresol);
2,2'-butylidene-bis-(3-n-hexyl-p-cresol);
4,4'-(2-butylidene)-bis-(6-t-butyl-m-cresol);
3,3'-4(decylidene)-bis-(5-ethyl-p-cresol);
(2,5-dimethyl-4-hydroxyphenyl) (2-hydroxy-3,5-dimethylphenyl)
methane; (2-methyl-4-hydroxy-5-ethylphenyl)
(2-ethyl-3-hydroxy-5-methylphenyl) methane;
(3-methyl-5-hydroxy-6-t-butylphenyl)
(2-hydroxy-4-methyl-5-decylphenyl)-n-butyl methane;
(2-hydroxy-4-ethyl-5-methylphenyl)
(2-decyl-3-hydroxy-4-methylphenyl)butylamylmethane;
(3-ethyl-4-methyl-5-hydroxyphenyl)-(2,3-dimethyl-3-hydroxy-phenyl)nonylme-
thane;
(3-methyl-2-hydroxy-6-ethylphenyl)-(2-isopropyl-3-hydroxy-5-methyl--
phenyl)cyclohexylmethane; (2-methyl-4-hydroxy-5-methylphenyl)
(2-hydroxy-3-methyl-5-ethylphenyl)dicyclohexyl methane; and the
like.
[0047] Other suitable antioxidants include, but are not limited to,
substituted phenols, such as 2-tert-butyl-4-methoxyphenol;
3-tert-butyl-4-methoxyphenol; 3-tert-octyl-4-methoxyphenol;
2-methyl-4-methoxyphenol; 2-stearyl-4-n-butoxyphenol;
3-t-butyl-4-stearyloxyphenol; 3-lauryl-4-ethoxyphenol;
2,5-di-t-butyl-4-methoxyphenol; 2-methyl-4-methoxyphenol;
2-(1-methycyclohexyl)-4-methoxyphenol;
2-t-butyl-4-dodecyloxyphenol; 2-(1-methylbenzyl)-4-methoxyphenol;
2-t-octyl-4-methoxyphenol; methyl gallate; n-propyl gallate;
n-butyl gallate; lauryl gallate; myristyl gallate; stearyl gallate;
2,4,5-trihydroxyacetophenone; 2,4,5-trihydroxy-n-butyrophenone;
2,4,5-trihydroxystearophenone; 2,6-ditert-butyl-4-methylphenol;
2,6-ditert-octyl-4-methylphenol; 2,6-ditert-butyl-4-stearylphenol;
2-methyl-4-methyl-6-tert-butylphenol; 2,6-distearyl-4-methylphenol;
2,6-dilauryl-4-methylphenol; 2,6-di(n-octyl)-4-methylphenol;
2,6-di(n-hexadecyl)-4-methylphenol;
2,6-di(1-methylundecyl)-4-methylphenol;
2,6-di(1-methylheptadecyl)-4-methylphenol;
2,6-di(trimethylhexyl)-4-methylphenol;
2,6-di(1,1,3,3-tetramethyloctyl)-4-methylphenol; 2-n-dodecyl-6-tert
butyl-4-methylphenol;
2-n-dodecyl-6-(1-methylundecyl)-4-methylphenol;
2-n-dodecyl-6-(1,1,3,3-tetramethyloctyl)-4-methylphenol;
2-n-dodecyl-6-n-octadecyl-4-methylphenol;
2-n-dodecyl-6-n-octyl-4-methylphenol;
2-methyl-6-n-octadecyl-4-methylphenol;
2-n-dodecyl-6-(1-methylheptadecyl)-4-methylphenol;
2,6-di(1-methylbenzyl)-4-methylphenol;
2,6-di(1-methylcyclohexyl)-4-methylphenol;
2,6-(1-methylcyclohexyl)-4-methylphenol;
2-(1-methylbenzyl)-4-methylphenol; and related substituted
phenols.
[0048] More suitable antioxidants include, but are not limited to,
alkylene bisphenols, such as 4,4'-butylidene bis(3-methyl-6-t-butyl
phenol); 2,2-butylidene bis (4,6-dimethyl phenol); 2,2'-butylidene
bis(4-methyl-6-t-butyl phenol); 2,2'-butylidene
bis(4-t-butyl-6-methyl phenol); 2,2'-ethylidene
bis(4-methyl-6-t-butylphenol); 2,2'-methylene bis(4,6-dimethyl
phenol); 2,2'-methylene bis(4-methyl-6-t-butyl phenol);
2,2'-methylene bis(4-ethyl-6-t-butyl phenol); 4,4'-methylene
bis(2,6-di-t-butyl phenol); 4,4'-methylene bis(2-methyl-6-t-butyl
phenol); 4,4'-methylene bis(2,6-dimethyl phenol); 2,2'-methylene
bis(4-t-butyl-6-phenyl phenol);
2,2'-dihydroxy-3,3',5,5'-tetramethylstilbene; 2,2'-isopropylidene
bis(4-methyl-6-t-butyl phenol); ethylene bis (beta-naphthol);
1,5-dihydroxy naphthalene; 2,2'-ethylene bis (4-methyl-6-propyl
phenol); 4,4'-methylene bis(2-propyl-6-t-butyl phenol);
4,4'-ethylene bis (2-methyl-6-propyl phenol); 2,2'-methylene
bis(5-methyl-6-t-butyl phenol); and 4,4'-butylidene
bis(6-t-butyl-3-methyl phenol);
[0049] Suitable antioxidants further include, but are not limited
to, alkylene trisphenols, such as 2,6-bis
(2'-hydroxy-3'-t-butyl-5'-methyl benzyl)-4-methyl phenol; 2,6-bis
(2'-hydroxy-3'-t-ethyl-5'-butyl benzyl)-4-methyl phenol; and
2,6-bis(2'-hydroxy-3'-t-butyl-5'-propyl benzyl)-4-methyl
phenol.
[0050] The antioxidant is typically present in an amount of about
0.1 phr to about 5 phr, preferably from about 0.1 phr to about 2
phr, more preferably about 0.1 phr to about 1 phr. In a
particularly preferred embodiment, the antioxidant is present in an
amount of about 0.4 phr.
[0051] In an alternative embodiment, the antioxidant should be
present in an amount to ensure that the hardness gradient of the
inventive cores is negative. Preferably, about 0.2 phr to about 1
phr antioxidant is added to the core layer (inner core or outer
core layer) formulation, more preferably, about 0.3 to about 0.8
phr, and most preferably 0.4 to about 0.7 phr. Preferably, about
0.25 phr to about 1.5 phr of peroxide as calculated at 100% active
can be added to the core formulation, more preferably about 0.5 phr
to about 1.2 phr, and most preferably about 0.7 phr to about 1.0
phr. The ZDA amount can be varied to suit the desired compression,
spin and feel of the resulting golf ball. The cure regime can have
a temperature range between from about 290.degree. F. to about
335.degree. F., more preferably about 300.degree. F. to about
325.degree. F., and the stock is held at that temperature for at
least about 10 minutes to about 30 minutes.
[0052] The thermoset rubber composition of the present invention
may also include an optional soft and fast agent. As used herein,
"soft and fast agent" means any compound or a blend thereof that
that is capable of making a core 1) be softer (lower compression)
at constant COR or 2) have a higher COR at equal compression, or
any combination thereof, when compared to a core equivalently
prepared without a soft and fast agent. Preferably, the composition
of the present invention contains from about 0.05 phr to about 10.0
phr soft and fast agent. In one embodiment, the soft and fast agent
is present in an amount of about 0.05 phr to about 3.0 phr,
preferably about 0.05 phr to about 2.0 phr, more preferably about
0.05 phr to about 1.0 phr. In another embodiment, the soft and fast
agent is present in an amount of about 2.0 phr to about 5.0 phr,
preferably about 2.35 phr to about 4.0 phr, and more preferably
about 2.35 phr to about 3.0 phr. In an alternative high
concentration embodiment, the soft and fast agent is present in an
amount of about 5.0 phr to about 10.0 phr, more preferably about
6.0 phr to about 9.0 phr, most preferably about 7.0 phr to about
8.0 phr. In a most preferred embodiment, the soft and fast agent is
present in an amount of about 2.6 phr.
[0053] Suitable soft and fast agents include, but are not limited
to, organosulfur or metal-containing organosulfur compounds, an
organic sulfur compound, including mono, di, and polysulfides, a
thiol, or mercapto compound, an inorganic sulfide compound, a Group
VIA compound, or mixtures thereof. The soft and fast agent
component may also be a blend of an organosulfur compound and an
inorganic sulfide compound.
[0054] Suitable soft and fast agents of the present invention
include, but are not limited to those having the following general
formula:
##STR00001##
where R.sub.1-R.sub.5 can be C.sub.1-C.sub.8 alkyl groups; halogen
groups; thiol groups (--SH), carboxylated groups; sulfonated
groups; and hydrogen; in any order; and also pentafluorothiophenol;
2-fluorothiophenol; 3-fluorothiophenol; 4-fluorothiophenol;
2,3-fluorothiophenol; 2,4-fluorothiophenol; 3,4-fluorothiophenol;
3,5-fluorothiophenol 2,3,4-fluorothiophenol;
3,4,5-fluorothiophenol; 2,3,4,5-tetrafluorothiophenol;
2,3,5,6-tetrafluorothiophenol; 4-chlorotetrafluorothiophenol;
pentachlorothiophenol; 2-chlorothiophenol; 3-chlorothiophenol;
4-chlorothiophenol; 2,3-chlorothiophenol; 2,4-chlorothiophenol;
3,4-chlorothiophenol; 3,5-chlorothiophenol; 2,3,4-chlorothiophenol;
3,4,5-chlorothiophenol; 2,3,4,5-tetrachlorothiophenol;
2,3,5,6-tetrachlorothiophenol; pentabromothiophenol;
2-bromothiophenol; 3-bromothiophenol; 4-bromothiophenol;
2,3-bromothiophenol; 2,4-bromothiophenol; 3,4-bromothiophenol;
3,5-bromothiophenol; 2,3,4-bromothiophenol; 3,4,5-bromothiophenol;
2,3,4,5-tetrabromothiophenol; 2,3,5,6-tetrabromothiophenol;
pentaiodothiophenol; 2-iodothiophenol; 3-iodothiophenol;
4-iodothiophenol; 2,3-iodothiophenol; 2,4-iodothiophenol;
3,4-iodothiophenol; 3,5-iodothiophenol; 2,3,4-iodothiophenol;
3,4,5-iodothiophenol; 2,3,4,5-tetraiodothiophenol;
2,3,5,6-tetraiodothiophenoland; and their zinc salts. Preferably,
the halogenated thiophenol compound is pentachlorothiophenol, which
is commercially available in neat form or under the tradename
STRUKTOL.RTM., a clay-based carrier containing the sulfur compound
pentachlorothiophenol loaded at 45 percent (correlating to 2.4
parts PCTP). STRUKTOL.RTM. is commercially available from Struktol
Company of America of Stow, Ohio. PCTP is commercially available in
neat form from eChinachem of San Francisco, Calif. and in the salt
form from eChinachem of San Francisco, Calif. Most preferably, the
halogenated thiophenol compound is the zinc salt of
pentachlorothiophenol, which is commercially available from
eChinachem of San Francisco, Calif.
[0055] As used herein when referring to the invention, the term
"organosulfur compound(s)" refers to any compound containing
carbon, hydrogen, and sulfur, where the sulfur is directly bonded
to at least 1 carbon. As used herein, the term "sulfur compound"
means a compound that is elemental sulfur, polymeric sulfur, or a
combination thereof. It should be further understood that the term
"elemental sulfur" refers to the ring structure of S.sub.8 and that
"polymeric sulfur" is a structure including at least one additional
sulfur relative to elemental sulfur.
[0056] Additional suitable examples of soft and fast agents (that
are also believed to be cis-to-trans catalysts) include, but are
not limited to, 4,4'-diphenyl disulfide; 4,4'-ditolyl disulfide;
2,2'-benzamido diphenyl disulfide; bis(2-aminophenyl) disulfide;
bis(4-aminophenyl) disulfide; bis(3-aminophenyl) disulfide;
2,2'-bis(4-aminonaphthyl) disulfide; 2,2'-bis(3-aminonaphthyl)
disulfide; 2,2'-bis(4-aminonaphthyl) disulfide;
2,2'-bis(5-aminonaphthyl) disulfide; 2,2'-bis(6-aminonaphthyl)
disulfide; 2,2'-bis(7-aminonaphthyl) disulfide;
2,2'-bis(8-aminonaphthyl) disulfide; 1,1'-bis(2-aminonaphthyl)
disulfide; 1,1'-bis(3-aminonaphthyl) disulfide;
1,1'-bis(3-aminonaphthyl) disulfide; 1,1'-bis(4-aminonaphthyl)
disulfide; 1,1'-bis(5-aminonaphthyl) disulfide;
1,1'-bis(6-aminonaphthyl) disulfide; 1,1'-bis(7-aminonaphthyl)
disulfide; 1,1'-bis(8-aminonaphthyl) disulfide;
1,2'-diamino-1,2'-dithiodinaphthalene;
2,3'-diamino-1,2'-dithiodinaphthalene; bis(4-chlorophenyl)
disulfide; bis(2-chlorophenyl) disulfide; bis(3-chlorophenyl)
disulfide; bis(4-bromophenyl) disulfide; bis(2-bromophenyl)
disulfide; bis(3-bromophenyl) disulfide; bis(4-fluorophenyl)
disulfide; bis(4-iodophenyl) disulfide; bis(2,5-dichlorophenyl)
disulfide; bis(3,5-dichlorophenyl) disulfide; bis
(2,4-dichlorophenyl) disulfide; bis(2,6-dichlorophenyl) disulfide;
bis(2,5-dibromophenyl) disulfide; bis(3,5-dibromophenyl) disulfide;
bis(2-chloro-5-bromophenyl) disulfide; bis(2,4,6-trichlorophenyl)
disulfide; bis(2,3,4,5,6-pentachlorophenyl) disulfide;
bis(4-cyanophenyl) disulfide; bis(2-cyanophenyl) disulfide;
bis(4-nitrophenyl) disulfide; bis(2-nitrophenyl) disulfide;
2,2'-dithiobenzoic acid ethylester; 2,2'-dithiobenzoic acid
methylester; 2,2'-dithiobenzoic acid; 4,4'-dithiobenzoic acid
ethylester; bis(4-acetylphenyl) disulfide; bis(2-acetylphenyl)
disulfide; bis(4-formylphenyl) disulfide; bis(4-carbamoylphenyl)
disulfide; 1,1'-dinaphthyl disulfide; 2,2'-dinaphthyl disulfide;
1,2'-dinaphthyl disulfide; 2,2'-bis(1-chlorodinaphthyl) disulfide;
2,2'-bis(1-bromonaphthyl) disulfide; 1,1'-bis(2-chloronaphthyl)
disulfide; 2,2'-bis(1-cyanonaphthyl) disulfide;
2,2'-bis(1-acetylnaphthyl) disulfide; and the like; or a mixture
thereof. Preferred organosulfur components include 4,4'-diphenyl
disulfide, 4,4'-ditolyl disulfide, or 2,2'-benzamido diphenyl
disulfide, or a mixture thereof. A more preferred organosulfur
component includes 4,4'-ditolyl disulfide. In another embodiment,
metal-containing organosulfur components can be used according to
the invention. Suitable metal-containing organosulfur components
include, but are not limited to, cadmium, copper, lead, and
tellurium analogs of diethyldithiocarbamate, diamyldithiocarbamate,
and dimethyldithiocarbamate, or mixtures thereof.
[0057] Suitable substituted or unsubstituted aromatic organic
components that do not include sulfur or a metal include, but are
not limited to, 4,4'-diphenyl acetylene, azobenzene, or a mixture
thereof. The aromatic organic group preferably ranges in size from
C.sub.6 to C.sub.20, and more preferably from C.sub.6 to C.sub.10.
Suitable inorganic sulfide components include, but are not limited
to titanium sulfide, manganese sulfide, and sulfide analogs of
iron, calcium, cobalt, molybdenum, tungsten, copper, selenium,
yttrium, zinc, tin, and bismuth.
[0058] A substituted or unsubstituted aromatic organic compound is
also suitable as a soft and fast agent. Suitable substituted or
unsubstituted aromatic organic components include, but are not
limited to, components having the formula
(R.sub.1).sub.x--R.sub.3-M-R.sub.4--(R.sub.2).sub.y, wherein
R.sub.1 and R.sub.2 are each hydrogen or a substituted or
unsubstituted C.sub.1-20 linear, branched, or cyclic alkyl, alkoxy,
or alkylthio group, or a single, multiple, or fused ring C.sub.6 to
C.sub.24 aromatic group; x and y are each an integer from 0 to 5;
R.sub.3 and R.sub.4 are each selected from a single, multiple, or
fused ring C.sub.6 to C.sub.24 aromatic group; and M includes an
azo group or a metal component. R.sub.3 and R.sub.4 are each
preferably selected from a C.sub.6 to C.sub.10 aromatic group, more
preferably selected from phenyl, benzyl, naphthyl, benzamido, and
benzothiazyl. R.sub.1 and R.sub.2 are each preferably selected from
a substituted or unsubstituted C.sub.1-10 linear, branched, or
cyclic alkyl, alkoxy, or alkylthio group or a C.sub.6 to C.sub.10
aromatic group. When R.sub.1, R.sub.2, R.sub.3, or R.sub.4, are
substituted, the substitution may include one or more of the
following substituent groups: hydroxy and metal salts thereof;
mercapto and metal salts thereof; halogen; amino, nitro, cyano, and
amido; carboxyl including esters, acids, and metal salts thereof;
silyl; acrylates and metal salts thereof; sulfonyl or sulfonamide;
and phosphates and phosphites. When M is a metal component, it may
be any suitable elemental metal available to those of ordinary
skill in the art. Typically, the metal will be a transition metal,
although preferably it is tellurium or selenium. In one embodiment,
the aromatic organic compound is substantially free of metal, while
in another embodiment the aromatic organic compound is completely
free of metal.
[0059] The soft and fast agent can also include a Group VIA
component. Elemental sulfur and polymeric sulfur are commercially
available from Elastochem, Inc. of Chardon, Ohio. Exemplary sulfur
catalyst compounds include PB(RM-S)-80 elemental sulfur and
PB(CRST)-65 polymeric sulfur, each of which is available from
Elastochem, Inc. An exemplary tellurium catalyst under the
tradename TELLOY.RTM. and an exemplary selenium catalyst under the
tradename VANDEX.RTM. are each commercially available from RT
Vanderbilt.
[0060] Other suitable soft and fast agents include, but are not
limited to, hydroquinones, benzoquinones, quinhydrones, catechols,
and resorcinols.
[0061] Suitable hydroquinone compounds include compounds
represented by the following formula, and hydrates thereof:
##STR00002##
wherein each R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are hydrogen;
halogen; alkyl; carboxyl; metal salts thereof, and esters thereof;
acetate and esters thereof; formyl; acyl; acetyl; halogenated
carbonyl; sulfo and esters thereof; halogenated sulfonyl; sulfino;
alkylsulfinyl; carbamoyl; halogenated alkyl; cyano; alkoxy; hydroxy
and metal salts thereof; amino; nitro; aryl; aryloxy; arylalkyl;
nitroso; acetamido; or vinyl.
[0062] Other suitable hydroquinone compounds include, but are not
limited to, hydroquionone; tetrachlorohydroquinone;
2-chlorohydroquionone; 2-bromohydroquinone;
2,5-dichlorohydroquinone; 2,5-dibromohydroquinone;
tetrabromohydroquinone; 2-methylhydroquinone;
2-t-butylhydroquinone; 2,5-di-t-amylhydroquinone; and
2-(2-chlorophenyl) hydroquinone hydrate.
[0063] More suitable hydroquinone compounds include compounds
represented by the following formula, and hydrates thereof:
##STR00003##
wherein each R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are a metal
salt of a carboxyl; acetate and esters thereof; hydroxy; a metal
salt of a hydroxy; amino; nitro; aryl; aryloxy; arylalkyl; nitroso;
acetamido; or vinyl.
[0064] Suitable benzoquinone compounds include compounds
represented by the following formula, and hydrates thereof:
##STR00004##
wherein each R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are hydrogen;
halogen; alkyl; carboxyl; metal salts thereof, and esters thereof;
acetate and esters thereof; formyl; acyl; acetyl; halogenated
carbonyl; sulfo and esters thereof; halogenated sulfonyl; sulfino;
alkylsulfinyl; carbamoyl; halogenated alkyl; cyano; alkoxy; hydroxy
and metal salts thereof; amino; nitro; aryl; aryloxy; arylalkyl;
nitroso; acetamido; or vinyl.
[0065] Other suitable benzoquinone compounds include one or more
compounds represented by the following formula, and hydrates
thereof:
##STR00005##
wherein each R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are a metal
salt of a carboxyl; acetate and esters thereof; hydroxy; a metal
salt of a hydroxy; amino; nitro; aryl; aryloxy; arylalkyl; nitroso;
acetamido; or vinyl.
[0066] Suitable quinhydrones include one or more compounds
represented by the following formula, and hydrates thereof:
##STR00006##
wherein each R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, and R.sub.8 are hydrogen; halogen; alkyl; carboxyl; metal
salts thereof, and esters thereof; acetate and esters thereof;
formyl; acyl; acetyl; halogenated carbonyl; sulfo and esters
thereof; halogenated sulfonyl; sulfino; alkylsulfinyl; carbamoyl;
halogenated alkyl; cyano; alkoxy; hydroxy and metal salts thereof;
amino; nitro; aryl; aryloxy; arylalkyl; nitroso; acetamido; or
vinyl.
[0067] Other suitable quinhydrones include those having the above
formula, wherein each R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5,
R.sub.6, R.sub.7, and R.sub.8 are a metal salt of a carboxyl;
acetate and esters thereof; hydroxy; a metal salt of a hydroxy;
amino; nitro; aryl; aryloxy; arylalkyl; nitroso; acetamido; or
vinyl. Suitable catechols include one or more compounds represented
by the following formula, and hydrates thereof:
##STR00007##
wherein each R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are hydrogen;
halogen; alkyl; carboxyl; metal salts thereof, and esters thereof;
acetate and esters thereof; formyl; acyl; acetyl; halogenated
carbonyl; sulfo and esters thereof; halogenated sulfonyl; sulfino;
alkylsulfinyl; carbamoyl; halogenated alkyl; cyano;
[0068] alkoxy; hydroxy and metal salts thereof; amino; nitro; aryl;
aryloxy; arylalkyl; nitroso; acetamido; or vinyl.
[0069] Suitable resorcinols include one or more compounds
represented by the following formula, and hydrates thereof:
##STR00008##
wherein each R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are hydrogen;
halogen; alkyl; carboxyl; metal salts thereof, and esters thereof;
acetate and esters thereof; formyl; acyl; acetyl; halogenated
carbonyl; sulfo and esters thereof; halogenated sulfonyl; sulfino;
alkylsulfinyl; carbamoyl; halogenated alkyl; cyano; alkoxy; hydroxy
and metal salts thereof; amino; nitro; aryl; aryloxy; arylalkyl;
nitroso; acetamido; or vinyl.
[0070] Fillers may also be added to the thermoset rubber
composition of the core to adjust the density of the composition,
up or down. Typically, fillers include materials such as tungsten,
zinc oxide, barium sulfate, silica, calcium carbonate, zinc
carbonate, metals, metal oxides and salts, regrind (recycled core
material typically ground to about 30 mesh particle),
high-Mooney-viscosity rubber regrind, trans-regrind core material
(recycled core material containing high trans-isomer of
polybutadiene), and the like. When trans-regrind is present, the
amount of trans-isomer is preferably between about 10% and about
60%. In a preferred embodiment of the invention, the core comprises
polybutadiene having a cis-isomer content of greater than about 95%
and trans-regrind core material (already vulcanized) as a filler.
Any particle size trans-regrind core material is sufficient, but is
preferably less than about 125 .mu.m.
[0071] Fillers added to one or more portions of the golf ball
typically include processing aids or compounds to affect
rheological and mixing properties, density-modifying fillers, tear
strength, or reinforcement fillers, and the like. The fillers are
generally inorganic, and suitable fillers include numerous metals
or metal oxides, such as zinc oxide and tin oxide, as well as
barium sulfate, zinc sulfate, calcium carbonate, barium carbonate,
clay, tungsten, tungsten carbide, an array of silicas, and mixtures
thereof. Fillers may also include various foaming agents or blowing
agents which may be readily selected by one of ordinary skill in
the art. Fillers may include polymeric, ceramic, metal, and glass
microspheres may be solid or hollow, and filled or unfilled.
Fillers are typically also added to one or more portions of the
golf ball to modify the density thereof to conform to uniform golf
ball standards. Fillers may also be used to modify the weight of
the center or at least one additional layer for specialty balls,
e.g., a lower weight ball is preferred for a player having a low
swing speed.
[0072] Materials such as tungsten, zinc oxide, barium sulfate,
silica, calcium carbonate, zinc carbonate, metals, metal oxides and
salts, and regrind (recycled core material typically ground to
about 30 mesh particle) are also suitable fillers.
[0073] The polybutadiene and/or any other base rubber or elastomer
system may also be foamed, or filled with hollow microspheres or
with expandable microspheres which expand at a set temperature
during the curing process to any low specific gravity level. Other
ingredients such as sulfur accelerators, e.g., tetramethylthiuram
di, tri, or tetrasulfide, and/or metal-containing organosulfur
components may also be used according to the invention. Suitable
metal-containing organosulfur accelerators include, but are not
limited to, cadmium, copper, lead, and tellurium analogs of
diethyldithiocarbamate, diamyldithiocarbamate, and
dimethyldithiocarbamate, or mixtures thereof. Other ingredients
such as processing aids e.g., fatty acids and/or their metal salts,
processing oils, dyes and pigments, as well as other additives
known to one skilled in the art may also be used in the present
invention in amounts sufficient to achieve the purpose for which
they are typically used.
[0074] Without being bound by theory, it is believed that the
percentage of double bonds in the trans configuration may be
manipulated throughout a core containing at least one main-chain
unsaturated rubber (i.e., polybutadiene), plastic, or elastomer
resulting in a trans gradient. The trans gradient may be influenced
(up or down) by changing the type and amount of cis-to-trans
catalyst (or soft-and-fast agent), the type and amount of peroxide,
and the type and amount of coagent in the formulation. For example,
a formulation containing about 0.25 phr ZnPCTP may have a trans
gradient of about 5% across the core whereas a formulation
containing about 2 phr ZnPCTP may have a trans gradient of about
10%, or higher. The trans gradient may also be manipulated through
the cure times and temperatures. It is believed that lower
temperatures and shorter cure times yield lower trans gradients,
although a combination of many of these factors may yield gradients
of differing and/or opposite directions from that resulting from
use of a single factor.
[0075] The % trans isomer in a core can also be manipulated by
adding organosulfur compounds, such as those listed above, to the
core formulation including but not limited to
pentachlorothiophenol, zinc pentachlorothiophenol, ditolyl
disulfide, and diphenyl disulfide. The amount of the organosulfur
compound and the overall state of cure affect the amount of the
trans isomer that is produced during the cure reaction. Another
method of increasing the trans content in a core is to introduce an
unsaturated rubber that contains a high level of trans isomer, such
as high trans containing polybutadiene or high trans containing
polyoctenamer into the core formulation. High trans rubber can be
used with or without the organosulfur compounds.
[0076] In general, higher and/or faster cure rates tend to yield
higher levels of trans content, as do higher concentrations of
peroxides, soft-and-fast agents, and, to some extent, ZDA
concentration. Even the type of rubber may have an effect on trans
levels, with those catalyzed by rare-earth metals, such as Nd,
being able to form higher levels of trans polybutadiene compared to
those rubbers formed from Group VIII metals, such as Co, Ni, and
Li.
[0077] The measurement of trans-isomer content of polybutadiene
referred to herein was and can be accomplished as follows.
Calibration standards are prepared using at least two polybutadiene
rubber samples of known trans content, e.g., high and low percent
trans-polybutadiene). These samples are used alone and blended
together in such a way as to create a ladder of trans-polybutadiene
content of at least about 1.5% to 50% or to bracket the unknown
amount, such that the resulting calibration curve contains at least
about 13 equally-spaced points.
[0078] Using a commercially-available FTIR spectrometer equipped
with a Photoacoustic ("PAS") cell, a PAS spectrum of each standard
was obtained using the following instrument parameters: scan at
speed of 2.5 KHz (0.16 cm/s optical velocity), use a 1.2 KHz
electronic filter, set an undersampling ratio of 2 (number of laser
signal zero crossings before collecting a sample), co-add a minimum
of 128 scans at a resolution of 4 cm.sup.-1 over a range of 375 to
4000 cm.sup.-1 with a sensitivity setting of 1.
[0079] The cis-, trans-, and vinyl-polybutadiene peaks are found
between 600-1100 cm.sup.-1 in the PAS spectrum. The area under each
of the trans-polybutadiene peaks can be integrated. Determining the
fraction of each peak area relative to the total area of the three
isomer peaks allow construction of a calibration curve of the
trans-polybutadiene area fraction versus the actual
trans-polybutadiene content. The correlation coefficient (R.sup.2)
of the resulting calibration curve must be a minimum of 0.95.
[0080] A PAS spectrum is obtained, using the parameters described
above, for the unknown core material at the point of interest
(e.g., the surface or center of the core) by filling the PAS cell
with a sample containing a freshly cut, uncontaminated surface free
of foreign matters, such as mold release and the like. The
trans-polybutadiene area fraction of the unknown is analyzed to
determine the actual trans-isomer content from the calibration
curve.
[0081] In one known circumstance when barium sulfate is included,
the above method for testing trans-content may be less accurate.
Thus, an additional or alternative test of the trans-content of
polybutadiene is as follows. Calibration standards are prepared
using at least two polybutadienes of known trans-content (e.g.,
high and low percent trans-polybutadiene). These samples are used
alone and blended together in such a way as to create a ladder of
trans-polybutadiene content of at least about 1.5% to 50% or to
bracket the unknown amount, such that the resulting calibration
curve contains at least about 13 equally-spaced points.
[0082] Using an FT-Raman spectrometer equipped with a near-infrared
laser, a Stokes Raman spectrum should be obtained from each
standard using the following instrument parameters: sufficient
laser power (typically 400-800 mW) to obtain good signal-to-noise
ratio without causing excessive heating or fluorescence; a
resolution of 2 cm.sup.-1; over a Raman shift spectral range of
400-4000 cm.sup.-1; and co-adding at least 300 scans.
[0083] A calibration curve may be constructed from the data
generated above, using a chemometrics approach and software, such
as PLSplus/IQ from Galactic Industries Corp. An acceptable
calibration was obtained with this software using a PLS-1 curve
generated using an SNV (detrend) pathlength correction, a mean
center data preparation, and a 5-point SG second derivative over
the spectral range of 1600-1700 cm.sup.-1. The correlation
coefficient (R.sup.2) of the resulting calibration curve must be at
least 0.95.
[0084] Preferably, the geometric center of the core has a trans
content of about 1% to 10%, more preferably 2% to 9%, and most
preferably 4% to 8%. The outer surface of the core preferably has a
trans content of about 5% to 15%, more preferably about 7% to 12%,
and most preferably about 8% to 10%. A half-radius point in the
core preferably has a trans content of about 5% to 16%, more
preferably about 6% to 14%, and most preferably about 7% to
13%.
[0085] Cores most suitable for the golf balls of the present
invention have an outer surface and a center and are formed from a
substantially homogenous rubber composition. An intermediate layer,
such as a casing layer (inner cover), is disposed about the core,
and a cover layer is formed around the intermediate layer, the
cover typically formed from a castable polyurea or a castable
polyurethane (i.e., meaning covers comprising castable polyurea
(100% urea linkages/no urethane linkages); castable polyurethane
(100% urethane linkages/no urea linkages); castable hybrid
poly(urethane/urea) (the prepolymer is all urethane linkages and is
cured with an amine); and castable hybrid poly(urea/urethane) (the
prepolymer is all urea linkages and is cured with a polyol). In a
preferred embodiment, the outer surface of the core has a
trans-polybutadiene content of about 6% to 10%, the center of the
core has a trans-polybutadiene content of about 1% to 3%, and the
trans content of the outer surface of the core is greater than the
trans content of the center by about 6% or greater to define a
positive trans gradient along the core radius (i.e., the surface
trans content is higher than the center trans content--a core
having the opposite disposition of trans content would be
considered to have a negative trans gradient and is also envisioned
herein).
[0086] Referring to FIG. 1, in one embodiment of the present
invention the golf ball 10 includes a core 12, an inner cover layer
14, and an outer cover layer 16.
[0087] The invention preferably includes a core of at least a
single layer, the core having a "low hardness gradient" formulation
and cure cycle, herein defined as a "LOG" core. Such LOG cores may
have a "positive" Shore C hardness gradient (defined as the core
surface hardness minus the geometric center hardness) of from about
1 Shore C to about 10 Shore C, more preferably about 2 Shore C to
less than 8 Shore C, and most preferably about 2.5 Shore C to 7.5
Shore C. Where the LOG core includes more than one layer, e.g., a
center surrounded by an outer core layer, either or both of the
layers may have a low (or shallow) "positive" hardness
gradient.
[0088] The balls of the present invention preferably include at
least a LOG core, a cover layer. Optionally, one or more
intermediate layer(s) between the core and cover layer is present.
Most preferably, a single layer LOG core having a diameter of about
1.45 to 1.62 inches, more preferably about 1.50 to 1.58 inches, and
most preferably about 1.51 to 1.55 inches, is enclosed with two
cover layers. The inner cover layer is preferably formed from an
ionomeric material, such as a conventional ionomer or a
highly-/fully-neutralized ionomer, having a hardness of about 60
Shore D or greater. The outer cover layer is preferably formed from
polyurethane, polyurea, or a blend thereof, or a copolymer or
hybrid thereof, having a hardness about 60 Shore D or less. In this
most preferred embodiment, the LOG core has a geometric center
hardness of about 70 to 80 Shore C, more preferably about 72 to 78
Shore C, and a surface hardness of about 71 to 88 Shore C, more
preferably about 73 to 80 Shore C, and most preferably, about 74 to
78 Shore C. The LOG core also preferably has a compression (Atti)
of about 50 to 90, more preferably about 60 to 80, and a surface
trans-polybutadiene content of about 10% or less and a
trans-polybutadiene content at the geometric center of about 8% or
less.
[0089] The optional intermediate layer may be either
relatively-hard (Shore C hardness of at least about 85, preferably
at least about 90; and a Shore D hardness of at least about 61,
preferably at least about 63) or relatively-soft (Shore C hardness
about 85 or less, preferably about 83 or less, and a Shore D
hardness of about 61 or less, preferably about 57 or less). The
intermediate layer may include either a thermoplastic or
thermosetting polymeric compositions. Thermosetting compositions
include diene rubber based compositions, such as a peroxide or
sulfur cured PBR, SBR, EPDM, NR, etc., or a polyurethane, polyurea,
epoxy, urethane-acrylate, etc. Thermoplastic materials include
ionomers, non-ionomers, polyesters, polyamides, PEBAX or HYTREL
TPE's, and styrene-block copolymers (SBS, SEBS,etc).
[0090] Cover materials may be any of the same materials disclosed
as suitable intermediate layer materials, and may even include a
LOG or zero- or low-hardness-gradient rubber formulation/cure, but
preferably include an ionomer, a polyurethane, or a polyurea. The
cover layer(s) may be either hard or soft, with hardness values as
described for the intermediate layers above.
[0091] The single (preferably), multi-layer, or multi-piece core
may have a diameter of about 0.80 to 1.62 inches, preferably about
1.1 to 1.62 inches, more preferably about 1.2 to 1.60 inches, and
most preferably about 1.3 to 1.58 inches. The combination of the
LOG core and the intermediate layer(s) preferably have an outer
diameter of about 1.0 to 1.66 inches, more preferably about 1.25 to
1.64 inches, and most preferably about 1.40 to 1.62 inches. The
cover layer preferably had a thickness of about 0.010 to 0.080
inches, more preferably about 0.015 to 0.060 inches, and most
preferably about 0.020 to 0.040 inches.
[0092] Generally when a harder cover is employed, it is typically
coupled with a relatively-soft intermediate layer to produce a
relatively low-spinning golf ball. When a softer cover is used, it
is typically coupled with a relatively hard intermediate layer to
produce a golf ball having higher spin rates than the same
construction using a hard cover. In alternative embodiments, a hard
cover can be used with a hard intermediate layer or a soft cover
can be used with a soft intermediate layer. It should be understood
that the term `hard` refers to a Shore D hardness of 55 or greater,
the term `soft` refers to a Shore D hardness of 45 or less; a
`typical` hardness would be 45 to 55 Shore D.
[0093] In another preferred embodiment the golf ball includes three
layers. A LOG core preferably has a shallow "positive" hardness
gradient of about 1 to 5 Shore C, a diameter of about 1.55 inches,
a compression of about 50 to 100, preferably 65 to 85, and a COR of
about 0.800-0.815, preferably 0.800-0.810. The intermediate layer
is formed from a thermoplastic ionomer-based composition having a
hardness of about 80 Shore C and an outer diameter of about 1.60
inches. A single cover layer is formed from an ionomer and has a
thickness of about 0.040 inches and a hardness of about 66 Shore D.
An alternative low-compression center embodiment may include a
center having a compression of about 1 to 50, more preferably about
10 to 40, most preferably about 15 to 35.
[0094] The core of the present invention may also have a Soft
Center Deflection Index ("SCDI") compression of less than about
160, more preferably, from about 40 and about 160, and most
preferably, from about 60 and about 120.
[0095] The SCDI is a program change for the Dynamic Compression
Machine ("DCM") that allows determination of the pounds required to
deflect a core 10% of its diameter. The DCM is an apparatus that
applies a load to a core or ball and measures the number of inches
the core or ball is deflected at measured loads. A crude
load/deflection curve is generated that is fit to the Atti
compression scale that results in a number being generated that
represents an Atti compression. The DCM does this via a load cell
attached to the bottom of a hydraulic cylinder that is triggered
pneumatically at a fixed rate (typically about 1.0 ft/s) towards a
stationary core. Attached to the cylinder is an LVDT that measures
the distance the cylinder travels during the testing timeframe. A
software-based logarithmic algorithm ensures that measurements are
not taken until at least five successive increases in load are
detected during the initial phase of the test.
[0096] The SCDI is a slight variation of this set up. The hardware
is the same, but the software and output has changed. With the
SCDI, the interest is in the pounds of force required to deflect a
core x amount of inches. That amount of deflection is 10% percent
of the core diameter. The DCM is triggered, the cylinder deflects
the core by 10% of its diameter, and the DCM reports back the
pounds of force required (as measured from the attached load cell)
to deflect the core by that amount. The value displayed is a single
number in units of pounds.
[0097] Alternatively, the LOG core of the previous embodiment has a
diameter of about 1.450 inches and is encased with an intermediate
layer formed from a non-ionomeric thermoplastic (i.e., a PEB
AX-type ester-amide block copolymer) having a of about 40 Shore D
and an outer diameter of about 1.580 inches. A preferred cover
layer is an ionomeric cover layer having a hardness of about 68
Shore D and a thickness of about 0.050 inches.
[0098] In still another preferred embodiment, the golf ball
includes four layers. The core is formed from a LOG formula as
described above and has an outer diameter of about 1.50 inches. The
golf ball includes two intermediate layers, each having a thickness
of about 0.060 inches. The innermost intermediate layer preferably
has a hardness of about 45 Shore D and the outermost intermediate
layer has a hardness of about 66 Shore D. The cover layer has a
thickness of about 0.030 inches and is formed from a thermosetting,
castable polyurethane or polyurea and has a hardness of about 53
Shore D.
[0099] In a fourth preferred embodiment, the golf ball includes
four layers. The core includes a LOG center having a diameter of
about 1.0 inch and an outer core layer. The outer core layer has an
outer diameter of about 1.540 inches and a surface hardness of
about 89 to 92 Shore C. The outer core layer is formed from a
"conventional" polybutadiene rubber formulation and not a LOG
formula. The intermediate layer is formed from an ionomer-based
material and has an outer diameter of about 1.62 inches and a
hardness of about 67 Shore D. The cover is formed from a cast
polyurethane or polyurea and has a hardness of about 45 Shore
D.
[0100] The hardness of the outer surface of the core may be lower
than a hardness of the geometric center to define a negative
hardness gradient of about -1 to about -15, more preferably about
-5 to -10. The outer surface of the core may have a hardness of
about 68 to about 80 Shore C and the geometric center has a
hardness of about 68 to 80 Shore C. A hardness measured at the
outer surface of the core may also be greater than a hardness of
the core center to define a positive hardness gradient of about 0
to 5, more preferably about 2 to 5. The core preferably has a
diameter of about 1.5 inches to 1.59 inches, more preferably about
1.51 to 1.57 inches, most preferably about 1.51 inches to 1.55
inches, including, specifically, 1.51 inches, 1.53 inches, or 1.55
inches.
[0101] The above embodiments may be tailored to meet predetermined
performance properties. For example, alternative embodiments
include those having an inner core having an outer diameter of
about 0.250 inches to about 1.550 inches, preferably about 0.500
inches to about 1.500 inches, and more preferably about 0.750
inches to about 1.400 inches. In preferred embodiments, the inner
core has an outer diameter of about 1.000 inch, 1.200 inches, or
1.300 inches, with a most preferred outer diameter being 1.130
inches. The outer core layer should have an outer diameter (the
entire dual core) of about 1.30 inches to about 1.620 inches,
preferably 1.400 inches to about 1.600 inches, and more preferably
about 1.500 inches to about 1.590 inches. In preferred embodiments,
the outer core layer has an outer diameter of about 1.510 inches,
1.530 inches, or most preferably 1.550 inches.
[0102] A number of cores were formed based on the formulation and
cure cycle described in TABLE 1 below and core hardness values are
reported in TABLE 2 below.
TABLE-US-00001 TABLE 1 Formulation (phr) Ex 1 Ex 2 Ex 3 Comp Ex 1
Comp Ex 2 Comp Ex 3 SR-526.sup.+ 34.0 34.0 31.2 29.0 29.0 29.0 ZnO
5 5 5 5 5 5 BaSO.sub.4 11.2 11.2 16.1 13.8 13.8 13.8 VANOX MBPC*
0.40 0.40 0.40 -- 0.50 -- TRIGONOX-265-50B** 1.4 1.4 1.6 -- -- 0.8
PERKADOX BC-FF*** -- -- -- 1.0 1.6 -- polybutadiene 100 100 100 100
100 100 ZnPCTP 2.35 2.35 2.60 2.35 2.35 2.35 regrind -- -- 17 17 --
-- antioxidant/initiator ratio 0.57 0.57 0.50 -- 0.31 -- Cure Temp.
(.degree. F.) 305 315 320 350 335 335 Cure Time (min) 14 11 16 11
11 11 Properties diameter (in) 1.530 1.530 1.530 1.530 1.530 1.530
Atti compression 69 63 70 69 47 -- COR @ 125 ft/s 0.808 0.806 0.804
0.804 -- -- *Vanox MBPC:
2,2'-methylene-bis-(4-methyl-6-t-butylphenol) available from R.T.
Vanderbilt Company Inc.; **Trigonox 265-50B: a mixture of
1,1-di(t-butylperoxy)-3,3,5-trimethycyclohexane and
di(2-t-butylperoxyisopropyl)benzene 50% active on an inert carrier
available from Akzo Nobel; ***Perkadox BC-FF: Dicumyl peroxide
(99%-100% active) available from Akzo Nobel; and .sup.+ SR-526: ZDA
available from Sartomer
TABLE-US-00002 TABLE 2 Shore C Hardness Comp Comp Comp Distance
from Center Ex 1 Ex 2 Ex 3 Ex 1 Ex 2 Ex 3 Center 73 70 71 61 52 61
2 74 71 72 67 57 62 4 74 72 73 70 62 65 6 75 73 73 72 64 67 8 75 73
73 73 64 69 10 75 73 74 73 64 71 12 74 74 73 72 66 72 14 74 74 72
73 70 73 16 70 71 70 77 71 73 18 60 60 63 80 72 73 Surface 63 70 66
85 73 74 Surface - Center -10 0 -5 24 21 13
[0103] A number of cores were prepared and hardness measurements
were made across the core. The cores, designated as Examples A-D in
Table 3 below, all had an outer diameter of 1.53 inches. The
hardness, in Shore C, was measured according to ASTM D-2240 at
various locations across a cross-section of the core. The hardness
results are tabulated below for the geometric center, outer
surface, and at locations 2-mm, 4-mm, 6-mm, 8-mm, 10-mm, 12-mm,
14-mm, 16-mm, and 18-mm radially-outward from the geometric center
of the core. The general core formulation included .gtoreq.85 phr
CB1221 polybutadiene rubber, .ltoreq.15 phr CB23 polybutadiene
rubber, about 35 phr zinc diacrylate, about 1 phr peroxide, about
0.5 phr VANOX MBPC, about 5 phr ZnO, about 0.5 phr ZnPCTP, about 1
phr AFLUX 16, about 13 phr POLYWATE 325, and about 15 phr regrind.
The cure cycles were adjusted, as necessary, to vary the hardness
gradient across the core. Temperature/time criteria varied between
about 330.degree. F./20 min, 335.degree. F./18 min, 340.degree.
F./16 min, and 345.degree. F./14 min.
TABLE-US-00003 TABLE 3 Ex A Ex B Ex C Ex D hardness hardness
hardness hardness Core Location (Shore C) (Shore C) (Shore C)
(Shore C) Center 73.1 73.1 72.1 73.9 2 mm 72.2 72.1 73.2 75.2 4 mm
72.9 73.9 75.3 75.9 6 mm 73.7 74.3 76.5 77.2 8 mm 74.0 74.3 76.5
77.1 10 mm 74.7 73.8 76.5 76.7 12 mm 73.9 73.9 77.1 76.8 14 mm 73.9
73.4 76.7 76.7 16 mm 74.3 73.7 76.1 76.5 18 mm 74.5 74.3 75.5 76.1
Surface 74.6 75.1 75.7 78.2 Hardness Gradient 1.5 2.0 3.6 4.3
[0104] The hardness gradients, as seen in Table 3 above, range from
1.5 to 4.3 Shore C. These are shallow positive gradients and are
determined by subtracting the hardness at the geometric center from
the hardness at the surface of the core.
[0105] Cores formed from the same general formula as described
above are also tested for the % cis-polybutadiene, %
trans-polybutadiene, and % vinyl-polybutadiene. The results are
presented below in Table 4.
TABLE-US-00004 TABLE 4 Core % Trans % Vinyl % Cis Ex E outer
surface 7.6 2.7 89.6 Ex E half radius 7.8 2.8 89.4 Ex E center 7.4
2.8 89.7 Ex F outer surface 9.2 2.7 88.4 Ex F half radius 13.2 2.6
85.4 Ex F center 8.5 2.9 88.6 Ex G outer surface 8.7 2.8 88.5 Ex G
half radius 12.6 2.6 85.7 Ex G center 7.3 2.6 90.1
[0106] The surface hardness of a core is obtained from the average
of a number of measurements taken from opposing hemispheres of a
core, taking care to avoid making measurements on the parting line
of the core or on surface defects, such as holes or protrusions.
Hardness measurements are made pursuant to ASTM D-2240 "Indentation
Hardness of Rubber and Plastic by Means of a Durometer." Because of
the curved surface of a core, care must be taken to insure that the
core is centered under the durometer indentor before a surface
hardness reading is obtained. A calibrated, digital durometer,
capable of reading to 0.1 hardness units is used for all hardness
measurements and is set to take hardness readings at 1 second after
the maximum reading is obtained. The digital durometer must be
attached to, and its foot made parallel to, the base of an
automatic stand, such that the weight on the durometer and attack
rate conform to ASTM D-2240.
[0107] To prepare a core for hardness gradient measurements, the
core is gently pressed into a hemispherical holder having an
internal diameter approximately slightly smaller than the diameter
of the core, such that the core is held in place in the
hemispherical portion of the holder while concurrently leaving the
geometric central plane of the core exposed. The core is secured in
the holder by friction, such that it will not move during the
cutting and grinding steps, but the friction is not so excessive
that distortion of the natural shape of the core would result. The
core is secured such that the parting line of the core is roughly
parallel to the top of the holder. The diameter of the core is
measured 90 degrees to this orientation prior to securing. A
measurement is also made from the bottom of the holder to the top
of the core to provide a reference point for future calculations. A
rough cut, made slightly above the exposed geometric center of the
core using a band saw or other appropriate cutting tool, making
sure that the core does not move in the holder during this step.
The remainder of the core, still in the holder, is secured to the
base plate of a surface grinding machine. The exposed `rough` core
surface is ground to a smooth, flat surface, revealing the
geometric center of the core, which can be verified by measuring
the height of the bottom of the holder to the exposed surface of
the core, making sure that exactly half of the original height of
the core, as measured above, has been removed to within .+-.0.004
inches.
[0108] Leaving the core in the holder, the center of the core is
found with a center square and carefully marked and the hardness is
measured at the center mark. Hardness measurements at any distance
from the center of the core may be measured by drawing a line
radially outward from the center mark, and measuring and marking
the distance from the center, typically in 2-mm increments. All
hardness measurements performed on the plane passing through the
geometric center are performed while the core is still in the
holder and without having disturbed its orientation, such that the
test surface is constantly parallel to the bottom of the holder.
The hardness difference from any predetermined location on the core
is calculated as the average surface hardness minus the hardness at
the appropriate reference point, e.g., at the center of the core
for single, solid core, such that a core surface softer than its
center will have a negative hardness gradient.
[0109] Referring to TABLES 1-2, in Example 1, the surface is 10
Shore C points lower than the center hardness and 12 Shore C points
lower than the hardest point in the core. In Example 3, the surface
is 5 Shore C points lower than the center hardness and 8 Shore C
points lower than the hardest point in the core. In Example 2, the
center and surface hardness values are equal and the softest point
in the core is 10 Shore C points lower than the surface.
[0110] In the examples of the invention presented in TABLE 1, the
cure temperatures are varied from 305.degree. F. to 320.degree. F.
and cure times are varied from 11 to 16 minutes. The core
compositions of examples 1 and 2 are identical, and only the cure
cycle is changed. In example 3 the amount of antioxidant is
identical to examples 1 and 2, but other ingredients are varied as
well the cure cycle. Additionally, the ratio of antioxidant to
initiator varies from 0.50 to 0.57 from example 1 and 2 to example
3.
[0111] The ratio of antioxidant to initiator is one factor to
control the surface hardness of the cores. The data shown in TABLE
2 shows that hardness gradient is at least, but not limited to, a
function of the amount of antioxidant and peroxide, their ratio,
and the cure cycle. It should be noted that higher antioxidant also
requires higher peroxide initiator to maintain the desired
compression.
[0112] The core of Comparative Example 1, whose composition is
shown in TABLE 1 was cured using a conventional cure cycle, with a
cure temperature of 350.degree. F. and a cure time of 11 minutes.
The inventive cores were produced using cure cycles of 305.degree.
F. for 14 minutes, 315.degree. F. for 11 minutes and 320.degree. F.
for 16 minutes. The hardness gradients of these cores were measured
and the following observations can be made. For the cores of the
Comparative Examples, as expected, a conventional hard surface to
soft center gradient can be clearly seen. The gradients for
inventive cores follow substantially the same shape as one
another.
[0113] In many preferred embodiments of invention, the hardness of
the core at the surface is at most about the same as or
substantially less than the hardness of the core at the center.
Furthermore, the center hardness of the core may not be the hardest
point in the core, but in all cases, it is preferred that it is at
least equal to or harder than the surface. Additionally, the lowest
hardness anywhere in the core does not have to occur at the
surface. In some embodiments, the lowest hardness value occurs
within about the outer 6 mm of the core surface. However, the
lowest hardness value within the core can occur at any point from
the surface, up to, but not including the center, as long as the
surface hardness is still equal to, or less than the hardness of
the center. It should be noted that in the present invention the
formulation is the same throughout the core, or core layer, and no
surface treatment is applied to the core to obtain the preferred
surface hardness.
[0114] The cores of the invention may have a volume weighted
average hardness ("VWAH") that preferably matches the hardness
gradient of the core. The VWAH of a core is determined by first
measuring the surface hardness of the core. Then the hardness
profile of the cross-sectioned core is measured from the center
radially outward in 1/16 inch increments.
[0115] The volume, V, at each radial point is calculated by the
formula:
V = 4 3 .pi. r 3 ##EQU00003##
where r is the radius. The curve of hardness as a function of
volume H(V) is numerically integrated using the trapezoid rule:
I V = 1 2 k = 1 N [ V k + 1 - V k ] [ H ( V k + 1 ) + H ( V k ) ] .
##EQU00004##
The integration value is divided by the total volume of the core,
V.sub.c, to give the volume weighted average hardness, H.sub.V:
H _ V = I V V c . ##EQU00005##
[0116] Tables 5-8 below show various examples both a single core
golf ball (Examples 1-2) and a dual core golf ball (Examples 3-4),
with hardness gradient (in Shore C) and VWAH tabulated from radius
(inches) and volume (in.sup.3)for all 4 examples.
TABLE-US-00005 TABLE 5 Example 1 r (in) Volume (in.sup.3) Hardness
(Shore C) 0.0000 0.00000 59.9 0.0625 0.00102 61.1 0.1250 0.00818
63.0 0.1875 0.02761 64.7 0.2500 0.06545 65.9 0.3125 0.12783 67.0
0.3750 0.22089 68.6 0.4375 0.35077 68.5 0.5000 0.52360 68.5 0.5625
0.74551 69.1 0.6250 1.02265 69.5 0.6875 1.36115 69.8 0.7500 1.76715
74.7 VWAH 73.5 hardness gradient 14.8 (Shore C)
TABLE-US-00006 TABLE 6 Example 2 r (in) Volume (in.sup.3) Hardness
(Shore C) 0.0000 0.00000 63.3 0.0625 0.00102 65.0 0.1250 0.00818
66.5 0.1875 0.02761 67.8 0.2500 0.06545 68.9 0.3125 0.12783 70.1
0.3750 0.22089 70.9 0.4375 0.35077 71.7 0.5000 0.52360 72.6 0.5625
0.74551 73.7 0.6250 1.02265 74.6 0.6875 1.36115 74.7 0.7500 1.76715
78.7 0.765 1.87531 81.1 VWAH 74.1 hardness gradient 15.4 (Shore
C)
TABLE-US-00007 TABLE 7 Example 3 r (in) Volume (in.sup.3) Hardness
(Shore C) 0.0000 0.00000 74.0 0.0625 0.00102 73.7 0.1250 0.00818
73.7 0.1875 0.02761 73.7 0.2500 0.06545 73.4 0.3125 0.12783 73.1
0.3750 0.22089 72.7 0.4375 0.35077 72.8 0.5000 0.52360 74.5 0.5625
0.74551 78.9 0.6250 1.02265 81.5 0.6875 1.36115 83.8 0.7500 1.76715
88.3 0.7750 1.94982 91.2 VWAH 80.5 hardness gradient 14.3 (Shore
C)
TABLE-US-00008 TABLE 8 Example 4 r (in) Volume (in.sup.3) Hardness
(Shore C) 0.0000 0.00000 64.2 0.0625 0.00102 65.5 0.1250 0.00818
64.7 0.1875 0.02761 64.5 0.2500 0.06545 65.7 0.3125 0.12783 66.7
0.3750 0.22089 69.1 0.4375 0.35077 71.4 0.5000 0.52360 73.4 0.5625
0.74551 75.6 0.6250 1.02265 78.9 0.6875 1.36115 80.8 0.7500 1.76715
81.4 VWAH 76.0 hardness gradient 17.2 (Shore C)
[0117] See examples 1-2 in Tables 5-6, respectively, for single
core hardness gradients (Shore C) and VWAH. Preferably, the VWAH is
about 70 to 80, more preferably the VWAH is about 70 to 75, and
most preferably the VWAH is about 73 to 75. See examples 3-4 in
Tables 7-8, respectively, for single core hardness gradients (Shore
C) and VWAH. Preferably, the VWAH is greater than about 75, more
preferably the VWAH is about 73 to 83, and most preferably the VWAH
is about 76 to 81. Hardness gradients are presented above, but are
preferably a medium hardness gradient of about 5 to 21 Shore C. In
a preferred embodiment, the hardness gradient of the core, single
or dual core, is about 10 to 20 Shore C, more preferably about 14
to 18 Shore C.
[0118] While the inventive golf ball may be formed from a variety
of differing and conventional cover materials (both intermediate
layer(s) and outer cover layer), preferred cover materials include,
but are not limited to: polyurethanes, such as those prepared from
polyols or polyamines and diisocyanates or polyisocyanates and/or
their prepolymers, and those disclosed in U.S. Pat. Nos. 5,334,673
and 6,506,851; polyureas, such as those disclosed in U.S. Pat. Nos.
5,484,870 and 6,835,794; and polyurethane-polyurea hybrids, blends
or copolymers comprising urethane or urea segments.
[0119] Suitable polyurethane compositions comprise a reaction
product of at least one polyisocyanate and at least one curing
agent. The curing agent can include, for example, one or more
polyamines, one or more polyols, or a combination thereof. The
polyisocyanate can be combined with one or more polyols to form a
prepolymer, which is then combined with the at least one curing
agent. Thus, the polyols described herein are suitable for use in
one or both components of the polyurethane material, i.e., as part
of a prepolymer and in the curing agent. Suitable polyurethanes are
described in U.S. Patent Application Publication No. 2005/0176523,
which is incorporated by reference in its entirety.
[0120] Any polyisocyanate available to one of ordinary skill in the
art is suitable for use according to the invention. Exemplary
polyisocyanates include, but are not limited to,
4,4'-diphenylmethane diisocyanate (MDI); polymeric MDI;
carbodiimide-modified liquid MDI; 4,4'-dicyclohexylmethane
diisocyanate (H.sub.12MDI); p-phenylene diisocyanate (PPDI);
m-phenylene diisocyanate (MPDI); toluene diisocyanate (TDI);
3,3'-dimethyl-4,4'-biphenylene diisocyanate;
isophoronediisocyanate; 1,6-hexamethylene diisocyanate (HDI);
naphthalene diisocyanate; xylene diisocyanate; p-tetramethylxylene
diisocyanate; m-tetramethylxylene diisocyanate; ethylene
diisocyanate; propylene-1,2-diisocyanate;
tetramethylene-1,4-diisocyanate; cyclohexyl diisocyanate;
dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate;
cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate;
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane; methyl
cyclohexylene diisocyanate; triisocyanate of HDI; triisocyanate of
2,4,4-trimethyl-1,6-hexane diisocyanate; tetracene diisocyanate;
napthalene diisocyanate; anthracene diisocyanate; isocyanurate of
toluene diisocyanate; uretdione of hexamethylene diisocyanate; and
mixtures thereof. Polyisocyanates are known to those of ordinary
skill in the art as having more than one isocyanate group, e.g.,
di-isocyanate, tri-isocyanate, and tetra-isocyanate. Preferably,
the polyisocyanate includes MDI, PPDI, TDI, or a mixture thereof,
and more preferably, the polyisocyanate includes MDI. It should be
understood that, as used herein, the term MDI includes
4,4'-diphenylmethane diisocyanate, polymeric MDI,
carbodiimide-modified liquid MDI, and mixtures thereof and,
additionally, that the diisocyanate employed may be "low free
monomer," understood by one of ordinary skill in the art to have
lower levels of "free" monomer isocyanate groups, typically less
than about 0.1% free monomer isocyanate groups. Examples of "low
free monomer" diisocyanates include, but are not limited to Low
Free Monomer MDI, Low Free Monomer TDI, and Low Free Monomer PPDI.
The at least one polyisocyanate should have less than about 14%
unreacted NCO groups. Preferably, the at least one polyisocyanate
has no greater than about 8.0% NCO, more preferably no greater than
about 7.8%, and most preferably no greater than about 7.5% NCO with
a level of NCO of about 7.2 or 7.0, or 6.5% NCO commonly used.
[0121] Any polyol available to one of ordinary skill in the art is
suitable for use according to the invention. Exemplary polyols
include, but are not limited to, polyether polyols,
hydroxy-terminated polybutadiene (including partially/fully
hydrogenated derivatives), polyester polyols, polycaprolactone
polyols, and polycarbonate polyols. In one preferred embodiment,
the polyol includes polyether polyol. Examples include, but are not
limited to, polytetramethylene ether glycol (PTMEG), polyethylene
propylene glycol, polyoxypropylene glycol, and mixtures thereof.
The hydrocarbon chain can have saturated or unsaturated bonds and
substituted or unsubstituted aromatic and cyclic groups.
Preferably, the polyol of the present invention includes PTMEG.
[0122] In another embodiment, polyester polyols are included in the
polyurethane material. Suitable polyester polyols include, but are
not limited to, polyethylene adipate glycol; polybutylene adipate
glycol; polyethylene propylene adipate glycol;
o-phthalate-1,6-hexanediol; poly(hexamethylene adipate) glycol; and
mixtures thereof. The hydrocarbon chain can have saturated or
unsaturated bonds, or substituted or unsubstituted aromatic and
cyclic groups.
[0123] In another embodiment, polycaprolactone polyols are included
in the materials of the invention. Suitable polycaprolactone
polyols include, but are not limited to, 1,6-hexanediol-initiated
polycaprolactone, diethylene glycol initiated polycaprolactone,
trimethylol propane initiated polycaprolactone, neopentyl glycol
initiated polycaprolactone, 1,4-butanediol-initiated
polycaprolactone, and mixtures thereof. The hydrocarbon chain can
have saturated or unsaturated bonds, or substituted or
unsubstituted aromatic and cyclic groups.
[0124] In yet another embodiment, polycarbonate polyols are
included in the polyurethane material of the invention. Suitable
polycarbonates include, but are not limited to, polyphthalate
carbonate and poly(hexamethylene carbonate) glycol. The hydrocarbon
chain can have saturated or unsaturated bonds, or substituted or
unsubstituted aromatic and cyclic groups. In one embodiment, the
molecular weight of the polyol is from about 200 to about 4000.
[0125] Polyamine curatives are also suitable for use in the
polyurethane composition of the invention and have been found to
improve cut, shear, and impact resistance of the resultant balls.
Preferred polyamine curatives include, but are not limited to,
3,5-dimethylthio-2,4-toluenediamine and isomers thereof;
3,5-diethyltoluene-2,4-diamine and isomers thereof, such as
3,5-diethyltoluene-2,6-diamine;
4,4'-bis-(sec-butylamino)-diphenylmethane;
1,4-bis-(sec-butylamino)-benzene,
4,4'-methylene-bis-(2-chloroaniline);
4,4'-methylene-bis-(3-chloro-2,6-diethylaniline);
polytetramethyleneoxide-di-p-aminobenzoate; N,N'-dialkyldiamino
diphenyl methane; p,p'-methylene dianiline; m-phenylenediamine;
4,4'-methylene-bis-(2-chloroaniline);
4,4'-methylene-bis-(2,6-diethylaniline);
4,4'-methylene-bis-(2,3-dichloroaniline);
4,4'-diamino-3,3'-diethyl-5,5'-dimethyl diphenylmethane;
2,2',3,3'-tetrachloro diamino diphenylmethane; trimethylene glycol
di-p-aminobenzoate; and mixtures thereof. Preferably, the curing
agent of the present invention includes
3,5-dimethylthio-2,4-toluenediamine and isomers thereof, such as
ETHACURE.RTM. 300, commercially available from Albermarle
Corporation of Baton Rouge, La. Suitable polyamine curatives, which
include both primary and secondary amines, preferably have
molecular weights ranging from about 64 to about 2000.
[0126] At least one of a diol, triol, tetraol, or
hydroxy-terminated curatives may be added to the aforementioned
polyurethane composition. Suitable diol, triol, and tetraol groups
include ethylene glycol; diethylene glycol; polyethylene glycol;
propylene glycol; polypropylene glycol; lower molecular weight
polytetramethylene ether glycol; 1,3-bis(2-hydroxyethoxy) benzene;
1,3-bis -[2-(2-hydroxyethoxy) ethoxy] benzene; 1,3-bis-{2-[2-(2-
hydroxyethoxy) ethoxy] ethoxy} benzene; 1,4-butanediol;
1,5-pentanediol; 1,6-hexanediol;
resorcinol-di-(.beta.-hydroxyethyl) ether;
hydroquinone-di-(.beta.-hydroxyethyl) ether; and mixtures thereof.
Preferred hydroxy-terminated curatives include
1,3-bis(2-hydroxyethoxy) benzene; 1,3-bis-[2-(2-hydroxyethoxy)
ethoxy] benzene; 1,3-bis-{2-[2-(2-hydroxyethoxy) ethoxy] ethoxy}
benzene; 1,4-butanediol, and mixtures thereof. Preferably, the
hydroxy-terminated curatives have molecular weights ranging from
about 48 to 2000. It should be understood that molecular weight, as
used herein, is the absolute weight average molecular weight and
would be understood as such by one of ordinary skill in the
art.
[0127] Both the hydroxy-terminated and amine curatives can include
one or more saturated, unsaturated, aromatic, and cyclic groups.
Additionally, the hydroxy-terminated and amine curatives can
include one or more halogen groups. The polyurethane composition
can be formed with a blend or mixture of curing agents. If desired,
however, the polyurethane composition may be formed with a single
curing agent.
[0128] In a preferred embodiment of the present invention,
saturated polyurethanes are used to form one or more of the cover
layers, preferably the outer cover layer, and may be selected from
among both castable thermoset and thermoplastic polyurethanes.
[0129] In this embodiment, the saturated polyurethanes of the
present invention are substantially free of aromatic groups or
moieties. Saturated polyurethanes suitable for use in the invention
are a product of a reaction between at least one polyurethane
prepolymer and at least one saturated curing agent. The
polyurethane prepolymer is a product formed by a reaction between
at least one saturated polyol and at least one saturated
diisocyanate. As is well known in the art, that a catalyst may be
employed to promote the reaction between the curing agent and the
isocyanate and polyol, or the curing agent and the prepolymer.
[0130] Saturated diisocyanates which can be used include, without
limitation, ethylene diisocyanate; propylene-1,2-diisocyanate;
tetramethylene-1,4-diisocyanate; 1,6-hexamethylene-diisocyanate;
2,2,4-trimethylhexamethylene diisocyanate;
2,4,4-trimethylhexamethylene diisocyanate;
dodecane-1,12-diisocyanate; dicyclohexylmethane diisocyanate;
cyclobutane-1,3-diisocyanate; cyclohexane-1,3-diisocyanate;
cyclohexane-1,4-diisocyanate;
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane;
isophorone diisocyanate; methyl cyclohexylene diisocyanate;
triisocyanate of HDI; triisocyanate of 2,2,4-trimethyl-1,6-hexane
diisocyanate. The most preferred saturated diisocyanates are
4,4'-dicyclohexylmethane diisocyanate and isophorone
diisocyanate.
[0131] Saturated polyols which are appropriate for use in this
invention include without limitation polyether polyols such as
polytetramethylene ether glycol and poly(oxypropylene) glycol.
Suitable saturated polyester polyols include polyethylene adipate
glycol, polyethylene propylene adipate glycol, polybutylene adipate
glycol, polycarbonate polyol and ethylene oxide-capped
polyoxypropylene diols. Saturated polycaprolactone polyols which
are useful in the invention include diethylene glycol-initiated
polycaprolactone, 1,4-butanediol-initiated polycaprolactone,
1,6-hexanediol-initiated polycaprolactone; trimethylol
propane-initiated polycaprolactone, neopentyl glycol initiated
polycaprolactone, and polytetramethylene ether glycol-initiated
polycaprolactone. The most preferred saturated polyols are
polytetramethylene ether glycol and PTMEG-initiated
polycaprolactone.
[0132] Suitable saturated curatives include 1,4-butanediol,
ethylene glycol, diethylene glycol, polytetramethylene ether
glycol, propylene glycol; trimethanolpropane;
tetra-(2-hydroxypropyl)-ethylenediamine; isomers and mixtures of
isomers of cyclohexyldimethylol, isomers and mixtures of isomers of
cyclohexane bis(methylamine); triisopropanolamine; ethylene
diamine; diethylene triamine; triethylene tetramine; tetraethylene
pentamine; 4,4'-dicyclohexylmethane diamine;
2,2,4-trimethyl-1,6-hexanediamine;
2,4,4-trimethyl-1,6-hexanediamine; diethyleneglycol
di-(aminopropyl)ether;
4,4'-bis-(sec-butylamino)-dicyclohexylmethane;
1,2-bis-(sec-butylamino)cyclohexane; 1,4-bis-(sec-butylamino)
cyclohexane; isophorone diamine; hexamethylene diamine; propylene
diamine; 1-methyl-2,4-cyclohexyl diamine; 1-methyl-2,6-cyclohexyl
diamine; 1,3-diaminopropane; dimethylamino propylamine;
diethylamino propylamine; imido-bis-propylamine; isomers and
mixtures of isomers of diaminocyclohexane; monoethanolamine;
diethanolamine; triethanolamine; monoisopropanolamine; and
diisopropanolamine. The most preferred saturated curatives are
1,4-butanediol, 1,4-cyclohexyldimethylol and
4,4'-bis-(sec-butylamino)-dicyclohexylmethane.
[0133] Alternatively, other suitable polymers include partially or
fully neutralized ionomer, metallocene, or other single-site
catalyzed polymer, polyester, polyamide, non-ionomeric
thermoplastic elastomer, copolyether-esters, copolyether-amides,
polycarbonate, polybutadiene, polyisoprene, polystryrene block
copolymers (such as styrene-butadiene-styrene),
styrene-ethylene-propylene-styrene,
styrene-ethylene-butylene-styrene, and the like, and blends
thereof. Thermosetting polyurethanes or polyureas are suitable for
the outer cover layers of the golf balls of the present
invention.
[0134] Additionally, polyurethane can be replaced with or blended
with a polyurea material. Polyureas are distinctly different from
polyurethane compositions, but also result in desirable aerodynamic
and aesthetic characteristics when used in golf ball components.
The polyurea-based compositions are preferably saturated in
nature.
[0135] Without being bound to any particular theory, it is now
believed that substitution of the long chain polyol segment in the
polyurethane prepolymer with a long chain polyamine oligomer soft
segment to form a polyurea prepolymer, improves shear, cut, and
resiliency, as well as adhesion to other components. Thus, the
polyurea compositions of this invention may be formed from the
reaction product of an isocyanate and polyamine prepolymer
crosslinked with a curing agent. For example, polyurea-based
compositions of the invention may be prepared from at least one
isocyanate, at least one polyether amine, and at least one diol
curing agent or at least one diamine curing agent.
[0136] Any polyamine available to one of ordinary skill in the art
is suitable for use in the polyurea prepolymer. Polyether amines
are particularly suitable for use in the prepolymer. As used
herein, "polyether amines" refer to at least polyoxyalkyleneamines
containing primary amino groups attached to the terminus of a
polyether backbone. Due to the rapid reaction of isocyanate and
amine, and the insolubility of many urea products, however, the
selection of diamines and polyether amines is limited to those
allowing the successful formation of the polyurea prepolymers. In
one embodiment, the polyether backbone is based on tetramethylene,
propylene, ethylene, trimethylolpropane, glycerin, and mixtures
thereof.
[0137] Suitable polyether amines include, but are not limited to,
methyldiethanolamine; polyoxyalkylenediamines such as,
polytetramethylene ether diamines, polyoxypropylenetriamine, and
polyoxypropylene diamines; poly(ethylene oxide capped oxypropylene)
ether diamines; propylene oxide-based triamines;
triethyleneglycoldiamines; trimethylolpropane-based triamines;
glycerin-based triamines; and mixtures thereof. In one embodiment,
the polyether amine used to form the prepolymer is JEFFAMINE.RTM.
D2000 (manufactured by Huntsman Chemical Co. of Austin, Tex.).
[0138] The molecular weight of the polyether amine for use in the
polyurea prepolymer may range from about 100 to about 5000. In one
embodiment, the polyether amine molecular weight is about 200 or
greater, preferably about 230 or greater. In another embodiment,
the molecular weight of the polyether amine is about 4000 or less.
In yet another embodiment, the molecular weight of the polyether
amine is about 600 or greater. In still another embodiment, the
molecular weight of the polyether amine is about 3000 or less. In
yet another embodiment, the molecular weight of the polyether amine
is between about 1000 and about 3000, and more preferably is
between about 1500 to about 2500. Because lower molecular weight
polyether amines may be prone to forming solid polyureas, a higher
molecular weight oligomer, such as JEFFAMINE.RTM. D2000, is
preferred.
[0139] As briefly discussed above, some amines may be unsuitable
for reaction with the isocyanate because of the rapid reaction
between the two components. In particular, shorter chain amines are
fast reacting. In one embodiment, however, a hindered secondary
diamine may be suitable for use in the prepolymer. Without being
bound to any particular theory, it is believed that an amine with a
high level of stearic hindrance, e.g., a tertiary butyl group on
the nitrogen atom, has a slower reaction rate than an amine with no
hindrance or a low level of hindrance. For example,
4,4'-bis-(sec-butylamino)-dicyclohexylmethane (CLEARLINK.RTM. 1000)
may be suitable for use in combination with an isocyanate to form
the polyurea prepolymer.
[0140] Any isocyanate available to one of ordinary skill in the art
is suitable for use in the polyurea prepolymer. Isocyanates for use
with the present invention include aliphatic, cycloaliphatic,
araliphatic, aromatic, any derivatives thereof, and combinations of
these compounds having two or more isocyanate (NCO) groups per
molecule. The isocyanates may be organic polyisocyanate-terminated
prepolymers. The isocyanate-containing reactable component may also
include any isocyanate-functional monomer, dimer, trimer, or
multimeric adduct thereof, prepolymer, quasi-prepolymer, or
mixtures thereof. Isocyanate-functional compounds may include
monoisocyanates or polyisocyanates that include any isocyanate
functionality of two or more.
[0141] Suitable isocyanate-containing components include
diisocyanates having the generic structure:
O.dbd.C.dbd.N--R--N.dbd.C.dbd.O, where R is preferably a cyclic,
aromatic, or linear or branched hydrocarbon moiety containing from
about 1 to about 20 carbon atoms. The diisocyanate may also contain
one or more cyclic groups or one or more phenyl groups. When
multiple cyclic or aromatic groups are present, linear and/or
branched hydrocarbons containing from about 1 to about 10 carbon
atoms can be present as spacers between the cyclic or aromatic
groups. In some cases, the cyclic or aromatic group(s) may be
substituted at the 2-, 3-, and/or 4-positions, or at the ortho-,
meta-, and/or para-positions, respectively. Substituted groups may
include, but are not limited to, halogens, primary, secondary, or
tertiary hydrocarbon groups, or a mixture thereof.
[0142] Examples of diisocyanates that can be used with the present
invention include, but are not limited to, substituted and isomeric
mixtures including 2,2'-, 2,4'-, and 4,4'-diphenylmethane
diisocyanate; 3,3'-dimethyl-4,4'-biphenylene diisocyanate; toluene
diisocyanate; polymeric MDI; carbodiimide-modified liquid
4,4'-diphenylmethane diisocyanate; para-phenylene diisocyanate;
meta-phenylene diisocyanate; triphenyl methane-4,4'- and triphenyl
methane-4,4'-triisocyanate; naphthylene-1,5-diisocyanate; 2,4'-,
4,4'-, and 2,2-biphenyl diisocyanate; polyphenyl polymethylene
polyisocyanate; mixtures of MDI and PMDI; mixtures of PMDI and TDI;
ethylene diisocyanate; propylene-1,2-diisocyanate;
tetramethylene-1,2-diisocyanate; tetramethylene-1,3-diisocyanate;
tetramethylene-1,4-diisocyanate; 1,6-hexamethylene-diisocyanate;
octamethylene diisocyanate; decamethylene diisocyanate;
2,2,4-trimethylhexamethylene diisocyanate;
2,4,4-trimethylhexamethylene diisocyanate;
dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate;
cyclohexane-1,2-diisocyanate; cyclohexane-1,3-diisocyanate;
cyclohexane-1,4-diisocyanate; methyl-cyclohexylene diisocyanate;
2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane
diisocyanate; 4,4'-dicyclohexyl diisocyanate; 2,4'-dicyclohexyl
diisocyanate; 1,3,5-cyclohexane triisocyanate;
isocyanatomethylcyclohexane isocyanate;
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane;
isocyanatoethylcyclohexane isocyanate;
bis(isocyanatomethyl)-cyclohexane diisocyanate;
4,4'-bis(isocyanatomethyl) dicyclohexane;
2,4'-bis(isocyanatomethyl) dicyclohexane; isophorone diisocyanate;
triisocyanate of HDI; triisocyanate of 2,2,4-trimethyl-1,6-hexane
diisocyanate; 4,4'-dicyclohexylmethane diisocyanate;
2,4-hexahydrotoluene diisocyanate; 2,6-hexahydrotoluene
diisocyanate; 1,2-, 1,3-, and 1,4-phenylene diisocyanate; aromatic
aliphatic isocyanate, such as 1,2-, 1,3-, and 1,4-xylene
diisocyanate; meta-tetramethylxylene diisocyanate;
para-tetramethylxylene diisocyanate; trimerized isocyanurate of any
polyisocyanate, such as isocyanurate of toluene diisocyanate,
trimer of diphenylmethane diisocyanate, trimer of tetramethylxylene
diisocyanate, isocyanurate of hexamethylene diisocyanate,
isocyanurate of isophorone diisocyanate, and mixtures thereof;
dimerized uredione of any polyisocyanate, such as uretdione of
toluene diisocyanate, uretdione of hexamethylene diisocyanate, and
mixtures thereof; modified polyisocyanate derived from the above
isocyanates and polyisocyanates; and mixtures thereof.
[0143] Examples of saturated diisocyanates that can be used with
the present invention include, but are not limited to, ethylene
diisocyanate; propylene-1,2-diisocyanate; tetramethylene
diisocyanate; tetramethylene-1,4-diisocyanate;
1,6-hexamethylene-diisocyanate; octamethylene diisocyanate;
decamethylene diisocyanate; 2,2,4-trimethylhexamethylene
diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate;
dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate;
cyclohexane-1,2-diisocyanate; cyclohexane-1,3-diisocyanate;
cyclohexane-1,4-diisocyanate; methyl-cyclohexylene diisocyanate;
2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane
diisocyanate; 4,4'-dicyclohexyl diisocyanate; 2,4'-dicyclohexyl
diisocyanate; 1,3,5-cyclohexane triisocyanate;
isocyanatomethylcyclohexane isocyanate;
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane;
isocyanatoethylcyclohexane isocyanate;
bis(isocyanatomethyl)-cyclohexane diisocyanate;
4,4'-bis(isocyanatomethyl) dicyclohexane;
2,4'-bis(isocyanatomethyl) dicyclohexane; isophorone diisocyanate;
triisocyanate of HDI; triisocyanate of 2,2,4-trimethyl-1,6-hexane
diisocyanate; 4,4'-dicyclohexylmethane diisocyanate;
2,4-hexahydrotoluene diisocyanate; 2,6-hexahydrotoluene
diisocyanate; and mixtures thereof. Aromatic aliphatic isocyanates
may also be used to form light stable materials. Examples of such
isocyanates include 1,2-, 1,3-, and 1,4-xylene diisocyanate;
m-tetramethylxylene diisocyanate; p-tetramethylxylene diisocyanate;
trimerized isocyanurate of any polyisocyanate, such as isocyanurate
of toluene diisocyanate, trimer of diphenylmethane diisocyanate,
trimer of tetramethylxylene diisocyanate, isocyanurate of
hexamethylene diisocyanate, isocyanurate of isophorone
diisocyanate, and mixtures thereof; dimerized uredione of any
polyisocyanate, such as uretdione of toluene diisocyanate,
uretdione of hexamethylene diisocyanate, and mixtures thereof;
modified polyisocyanate derived from the above isocyanates and
polyisocyanates; and mixtures thereof. In addition, the aromatic
aliphatic isocyanates may be mixed with any of the saturated
isocyanates listed above for the purposes of this invention.
[0144] The number of unreacted NCO groups in the polyurea
prepolymer of isocyanate and polyether amine may be varied to
control such factors as the speed of the reaction, the resultant
hardness of the composition, and the like. For instance, the number
of unreacted NCO groups in the polyurea prepolymer of isocyanate
and polyether amine may be less than about 14%. In one embodiment,
the polyurea prepolymer has from about 5% to about 11% unreacted
NCO groups, and even more preferably has from about 6 to about 9.5%
unreacted NCO groups. In one embodiment, the percentage of
unreacted NCO groups is about 3% to about 9%. Alternatively, the
percentage of unreacted NCO groups in the polyurea prepolymer may
be about 7.5% or less, and more preferably, about 7% or less. In
another embodiment, the unreacted NCO content is from about 2.5% to
about 7.5%, and more preferably from about 4% to about 6.5%.
[0145] When formed, polyurea prepolymers may contain about 10% to
about 20% by weight of the prepolymer of free isocyanate monomer.
Thus, in one embodiment, the polyurea prepolymer may be stripped of
the free isocyanate monomer. For example, after stripping, the
prepolymer may contain about 1% or less free isocyanate monomer. In
another embodiment, the prepolymer contains about 0.5% by weight or
less of free isocyanate monomer.
[0146] The polyether amine may be blended with additional polyols
to formulate copolymers that are reacted with excess isocyanate to
form the polyurea prepolymer. In one embodiment, less than about
30% polyol by weight of the copolymer is blended with the saturated
polyether amine. In another embodiment, less than about 20% polyol
by weight of the copolymer, preferably less than about 15% by
weight of the copolymer, is blended with the polyether amine. The
polyols listed above with respect to the polyurethane prepolymer,
e.g., polyether polyols, polycaprolactone polyols, polyester
polyols, polycarbonate polyols, hydrocarbon polyols, other polyols,
and mixtures thereof, are also suitable for blending with the
polyether amine. The molecular weight of these polymers may be from
about 200 to about 4000, but also may be from about 1000 to about
3000, and more preferably are from about 1500 to about 2500.
[0147] The polyurea composition can be formed by crosslinking the
polyurea prepolymer with a single curing agent or a blend of curing
agents. The curing agent of the invention is preferably an
amine-terminated curing agent, more preferably a secondary diamine
curing agent so that the composition contains only urea linkages.
In one embodiment, the amine-terminated curing agent may have a
molecular weight of about 64 or greater. In another embodiment, the
molecular weight of the amine-curing agent is about 2000 or less.
As discussed above, certain amine-terminated curing agents may be
modified with a compatible amine-terminated freezing point
depressing agent or mixture of compatible freezing point depressing
agents.
[0148] Suitable amine-terminated curing agents include, but are not
limited to, ethylene diamine; hexamethylene diamine;
1-methyl-2,6-cyclohexyl diamine; tetrahydroxypropylene ethylene
diamine; 2,2,4- and 2,4,4-trimethyl-1,6-hexanediamine;
4,4'-bis-(sec-butylamino)-dicyclohexylmethane;
1,4-bis-(sec-butylamino)-cyclohexane;
1,2-bis-(sec-butylamino)-cyclohexane; derivatives of
4,4'-bis-(sec-butylamino)-dicyclohexylmethane;
4,4'-dicyclohexylmethane diamine;
1,4-cyclohexane-bis-(methylamine);
1,3-cyclohexane-bis-(methylamine); diethylene glycol
di-(aminopropyl) ether; 2-methylpentamethylene-diamine;
diaminocyclohexane; diethylene triamine; triethylene tetramine;
tetraethylene pentamine; propylene diamine; 1,3-diaminopropane;
dimethylamino propylamine; diethylamino propylamine; dipropylene
triamine; imido-bis-propylamine; monoethanolamine, diethanolamine;
triethanolamine; monoisopropanolamine, diisopropanolamine;
isophoronediamine; 4,4'-methylenebis-(2-chloroaniline);
3,5;dimethylthio-2,4-toluenediamine;
3,5-dimethylthio-2,6-toluenediamine;
3,5-diethylthio-2,4-toluenediamine;
3,5;diethylthio-2,6-toluenediamine;
4,4'-bis-(sec-butylamino)-diphenylmethane and derivatives thereof;
1,4-bis-(sec-butylamino)-benzene; 1,2-bis-(sec-butylamino)-benzene;
N,N'-dialkylamino-diphenylmethane; N,N,N',N'-tetrakia
(2-hydroxypropyl) ethylene diamine;
trimethyleneglycol-di-p-aminobenzoate;
polytetramethyleneoxide-di-p-aminobenzoate;
4,4'-methylenebis-(3-chloro-2,6-diethyleneaniline);
4,4'-methylenebis-(2,6-diethylaniline); meta-phenylenediamine;
paraphenylenediamine; and mixtures thereof. In one embodiment, the
amine-terminated curing agent is
4,4'-bis-(sec-butylamino)-dicyclohexylmethane.
[0149] Suitable saturated amine-terminated curing agents include,
but are not limited to, ethylene diamine; hexamethylene diamine;
1-methyl-2,6-cyclohexyl diamine; tetrahydroxypropylene ethylene
diamine; 2,2,4- and 2,4,4-trimethyl-1,6-hexanediamine;
4,4'-bis-(sec-butylamino)-dicyclohexylmethane;
1,4-bis-(sec-butylamino)-cyclohexane;
1,2-bis-(sec-butylamino)-cyclohexane; derivatives of
4,4'-bis-(sec-butylamino)-dicyclohexylmethane;
4,4'-dicyclohexylmethane diamine;
4,4'-methylenebis-(2,6-diethylaminocyclohexane;
1,4-cyclohexane-bis-(methylamine);
1,3-cyclohexane-bis-(methylamine); diethylene glycol
di-(aminopropyl) ether; 2-methylpentamethylene-diamine;
diaminocyclohexane; diethylene triamine; triethylene tetramine;
tetraethylene pentamine; propylene diamine; 1,3-diaminopropane;
dimethylamino propylamine; diethylamino propylamine;
imido-bis-propylamine; monoethanolamine, diethanolamine;
triethanolamine; monoisopropanolamine, diisopropanolamine;
isophoronediamine; triisopropanolamine; and mixtures thereof. In
addition, any of the polyether amines listed above may be used as
curing agents to react with the polyurea prepolymers.
[0150] Cover layers of the inventive golf ball may also be formed
from ionomeric polymers, preferably highly-neutralized ionomers
(HNP). In a preferred embodiment, at least one intermediate layer
of the golf ball is formed from an HNP material or a blend of HNP
materials. The acid moieties of the HNP's, typically ethylene-based
ionomers, are preferably neutralized greater than about 70%, more
preferably greater than about 90%, and most preferably at least
about 100%. The HNP's can be also be blended with a second polymer
component, which, if containing an acid group, may be neutralized
in a conventional manner, by the organic fatty acids of the present
invention, or both. The second polymer component, which may be
partially or fully neutralized, preferably comprises ionomeric
copolymers and terpolymers, ionomer precursors, thermoplastics,
polyamides, polycarbonates, polyesters, polyurethanes, polyureas,
thermoplastic elastomers, polybutadiene rubber, balata,
metallocene-catalyzed polymers (grafted and non-grafted),
single-site polymers, high-crystalline acid polymers, cationic
ionomers, and the like. HNP polymers typically have a material
hardness of between about 20 and about 80 Shore D, and a flexural
modulus of between about 3,000 psi and about 200,000 psi.
[0151] A preferred medium-hardness-gradient golf ball includes a
core having an outer surface and a geometric center; an inner cover
layer, and an outer cover layer. The inner cover layer typically
includes an ionomeric material (including a fully-neutralized
ionomer) and has a material hardness of about 60 Shore D or
greater. The outer cover layer is formed from a polyurea or
polyurethane and has a material hardness of about 60 Shore M or
greater. In one embodiment, the outer cover layers has a material
hardness of about 50 Shore M or greater, more preferably about 55
Shore M or greater, and most preferably about 60 Shore M or
greater. Shore M hardness measurements can be made on a Shore.RTM.
51 Micro Hardness Model 719 Digital Durometer, or the equivalent,
according to ASTM procedure D2240 as it relates to measuring Shore
M hardness.
[0152] The outer surface of the core preferably has a hardness of
about 68 Shore C to about 92 Shore C, more preferably the outer
surface of the core has a hardness of about 74 Shore C to about 85
Shore C, and most preferably outer surface of the core preferably
has a hardness of about 80 Shore C to about 84 Shore C. In an
alternative embodiment, the outer surface of the core has a
hardness of about 45 Shore D to about 56 Shore D, preferably the
outer surface of the core has a hardness of about 48 Shore D to
about 54 Shore D.
[0153] The geometric center of the core may have a hardness of
about 45 Shore C to about 85 Shore C. Preferably, the geometric
center of the core has a hardness of about 60 Shore C to about 85
Shore C, more preferably the geometric center of the core has a
hardness of about 62 Shore C to about 80 Shore C, and most
preferably the geometric center of the core has a hardness of about
65 Shore C to about 72 Shore C. In an alternative embodiment, the
geometric center of the core has a hardness of about 35 Shore D to
about 45 Shore D, preferably the geometric center of the core has a
hardness of about 38 Shore D to about 43 Shore D.
[0154] While the core outer surface hardness may be greater than
the geometric center hardness by about 5 Shore C to about 55 Shore
C to define a positive hardness gradient, preferably the core outer
surface hardness is greater than the geometric center hardness by
about 5 Shore C to about 21 Shore C, more preferably the core outer
surface hardness is greater than the geometric center hardness by
about 11 Shore C to about 19 Shore C, and most preferably the core
outer surface hardness is greater than the geometric center
hardness by about 13 Shore C to about 18 Shore C. In an alternative
embodiment, the outer surface of the core has a hardness that is
greater than the hardness at the geometric center of the core by
about 3 Shore D to about 15 Shore D to define a positive hardness
gradient. More preferably, the positive hardness gradient is about
5 Shore D to about 13 Shore D, and most preferably, the positive
hardness gradient is about 7 Shore D to about 11 Shore D.
[0155] The outer surface of the core preferably has a trans content
of about 12% or less and the geometric center of the core
preferably has a trans content of about 10% or less. In one
alternative embodiment, the core has an outer diameter of about
1.45 to about 1.62 inches and, optionally, comprises an outer core
layer disposed between the core and the inner cover layer.
[0156] In one embodiment of the present invention the HNP's are
ionomers and/or their acid precursors that are preferably
neutralized, either fully or partially, with organic acid
copolymers or the salts thereof. The acid copolymers are preferably
a-olefin, such as ethylene, C.sub.3-8 .alpha.,.beta.-ethylenically
unsaturated carboxylic acid, such as acrylic and methacrylic acid,
copolymers. They may optionally contain a softening monomer, such
as alkyl acrylate and alkyl methacrylate, wherein the alkyl groups
have from 1 to 8 carbon atoms.
[0157] The acid copolymers can be described as E/X/Y copolymers
where E is ethylene, X is an .alpha.,.beta.-ethylenically
unsaturated carboxylic acid, and Y is a softening comonomer. In a
preferred embodiment, X is acrylic or methacrylic acid and Y is a C
.sub.1-8 alkyl acrylate or methacrylate ester. X is preferably
present in an amount from about 1 to about 35 weight percent of the
polymer, more preferably from about 5 to about 30 weight percent of
the polymer, and most preferably from about 10 to about 20 weight
percent of the polymer. Y is preferably present in an amount from
about 0 to about 50 weight percent of the polymer, more preferably
from about 5 to about 25 weight percent of the polymer, and most
preferably from about 10 to about 20 weight percent of the
polymer.
[0158] Specific acid-containing ethylene copolymers include, but
are not limited to, ethylene/acrylic acid/n-butyl acrylate,
ethylene/methacrylic acid/n-butyl acrylate, ethylene/methacrylic
acid/iso-butyl acrylate, ethylene/acrylic acid/iso-butyl acrylate,
ethylene/methacrylic acid/n-butyl methacrylate, ethylene/acrylic
acid/methyl methacrylate, ethylene/acrylic acid/methyl acrylate,
ethylene/methacrylic acid/methyl acrylate, ethylene/methacrylic
acid/methyl methacrylate, and ethylene/acrylic acid/n-butyl
methacrylate. Preferred acid-containing ethylene copolymers
include, ethylene/methacrylic acid/n-butyl acrylate,
ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic
acid/methyl acrylate, ethylene/acrylic acid/ethyl acrylate,
ethylene/methacrylic acid/ethyl acrylate, and ethylene/acrylic
acid/methyl acrylate copolymers. The most preferred acid-containing
ethylene copolymers are, ethylene/(meth) acrylic acid/n-butyl,
acrylate, ethylene/(meth)acrylic acid/ethyl acrylate, and
ethylene/(meth) acrylic acid/methyl acrylate copolymers.
[0159] Ionomers are typically neutralized with a metal cation, such
as Li, Na, Mg, K, Ca, or Zn. It has been found that by adding
sufficient organic acid or salt of organic acid, along with a
suitable base, to the acid copolymer or ionomer, however, the
ionomer can be neutralized, without losing processability, to a
level much greater than for a metal cation. Preferably, the acid
moieties are neutralized greater than about 80%, preferably from
90-100%, most preferably 100% without losing processability. This
accomplished by melt-blending an ethylene
.alpha.,.beta.-ethylenically unsaturated carboxylic acid copolymer,
for example, with an organic acid or a salt of organic acid, and
adding a sufficient amount of a cation source to increase the level
of neutralization of all the acid moieties (including those in the
acid copolymer and in the organic acid) to greater than 90%,
(preferably greater than 100%).
[0160] The organic acids of the present invention are aliphatic,
mono- or multi-functional (saturated, unsaturated, or
multi-unsaturated) organic acids. Salts of these organic acids may
also be employed. The salts of organic acids of the present
invention include the salts of barium, lithium, sodium, zinc,
bismuth, chromium, cobalt, copper, potassium, strontium, titanium,
tungsten, magnesium, cesium, iron, nickel, silver, aluminum, tin,
or calcium, salts of fatty acids, particularly stearic, behenic,
erucic, oleic, linoelic or dimerized derivatives thereof. It is
preferred that the organic acids and salts of the present invention
be relatively non-migratory (they do not bloom to the surface of
the polymer under ambient temperatures) and non-volatile (they do
not volatilize at temperatures required for melt-blending).
[0161] The ionomers of the invention may also be more conventional
ionomers, i.e., partially-neutralized with metal cations. The acid
moiety in the acid copolymer is neutralized about 1 to about 90%,
preferably at least about 20 to about 75%, and more preferably at
least about 40 to about 70%, to form an ionomer, by a cation such
as lithium, sodium, potassium, magnesium, calcium, barium, lead,
tin, zinc, aluminum, or a mixture thereof.
[0162] In a preferred embodiment, the inventive single-layer core
is enclosed with two cover layers, where the inner cover layer has
a thickness of about 0.01 inches to about 0.06 inches, more
preferably about 0.015 inches to about 0.040 inches, and most
preferably about 0.02 inches to about 0.035 inches, and the inner
cover layer is formed from a partially- or fully-neutralized
ionomer having a Shore D hardness of greater than about 55, more
preferably greater than about 60, and most preferably greater than
about 65. In this embodiment, the outer cover layer should have a
thickness of about 0.015 inches to about 0.055 inches, more
preferably about 0.02 inches to about 0.04 inches, and most
preferably about 0.025 inches to about 0.035 inches, and has a
hardness of about Shore D 60 or less, more preferably 55 or less,
and most preferably about 52 or less. The inner cover layer should
be harder than the outer cover layer. In this embodiment the outer
cover layer comprises a partially- or fully-neutralized iononomer,
a polyurethane, polyurea, or blend thereof. A most preferred outer
cover layer is a castable or reaction injection molded
polyurethane, polyurea or copolymer or hybrid thereof having a
Shore D hardness of about 40 to about 50. A most preferred inner
cover layer material is a partially-neutralized ionomer comprising
a zinc, sodium or lithium neutralized ionomer such as SURLYN.RTM.
8940, 8945, 9910, 7930, 7940, or blend thereof having a Shore D
hardness of about 63 to about 68.
[0163] In another multi-layer cover, single core embodiment, the
outer cover and inner cover layer materials and thickness are the
same but, the hardness range is reversed, that is, the outer cover
layer is harder than the inner cover layer.
[0164] In an alternative preferred embodiment, the golf ball is a
one-piece golf ball having a dimpled surface and having a surface
hardness equal to or less than the center hardness (i.e., a
negative hardness gradient). The one-piece ball preferably has a
diameter of about 1.680 inches to about 1.690 inches, a weight of
about 1.620 oz, an Atti compression of from about 40 to 120, and a
COR of about 0.750 to 0.825.
[0165] In a preferred two-piece ball embodiment, the single-layer
core having a negative hardness gradient is enclosed with a single
layer of cover material having a Shore D hardness of from about 20
to about 80, more preferably about 40 to about 75 and most
preferably about 45 to about 70, and comprises a thermoplastic or
thermosetting polyurethane, polyurea, polyamide, polyester,
polyester elastomer, polyether-amide or polyester-amide, partially
or fully neutralized ionomer, polyolefin such as polyethylene,
polypropylene, polyethylene copolymers such as ethylene-butyl
acrylate or ethylene-methyl acrylate, poly(ethylene methacrylic
acid) co-and terpolymers, metallocene-catalyzed polyolefins and
polar-group functionalized polyolefins and blends thereof. A
preferred cover material in the two-piece embodiment is an ionomer
(either conventional or HNP) having a hardness of about 50 to about
70 Shore D. Another preferred cover material in the two-piece
embodiment is a thermoplastic or thermosetting polyurethane or
polyurea. A preferred ionomer is a high acid ionomer comprising a
copolymer of ethylene and methacrylic or acrylic acid and having an
acid content of at least 16 to about 25 weight percent. In this
case the reduced spin contributed by the relatively rigid high acid
ionomer may be offset to some extent by the spin-increasing
negative gradient core. The core may have a diameter of about 1.0
inch to about 1.64 inches, preferably about 1.30 inches to about
1.620, and more preferably about 1.40 inches to about 1.60
inches.
[0166] Another preferred cover material comprises a castable or
reaction injection moldable polyurethane, polyurea, or copolymer or
hybrid of polyurethane/polyurea. Preferably, this cover is
thermosetting but may be a thermoplastic, having a Shore D hardness
of about 20 to about 70, more preferably about 30 to about 65 and
most preferably about 35 to about 60. A moisture vapor barrier
layer, such as disclosed in U.S. Pat. Nos. 6,632,147; 6,932,720;
7,004,854; and 7,182,702, all of which are incorporated by
reference herein in their entirety, are optionally employed between
the cover layer and the core.
[0167] The golf ball may include one or more coating layers
disposed about the outer cover layer. The one or more coating
layers preferably have a thickness of about 0.003 inches or less,
more preferably about 0.002 inches of less, and most preferably
about 0.001 inches or less. In a preferred embodiment, the golf
ball includes 3 coating layers, each layer having a thickness of
about 0.001 inches to about 0.003 inches. The one or more coating
layers preferably have a
[0168] Shore M hardness of about 60 Shore M or less, more
preferably about 55 Shore M or less, and most preferably about 50
Shore M or less.
[0169] The one or more coating layers preferably have an
instrumented hardness of about 1 MPa to about 23 MPa, more
preferably the one or more coating layers have an instrumented
hardness of about 1 MPa to about 10 MPa, and most preferably the
one or more coating layers have an instrumented hardness of about 4
MPa to about 7 MPa. In one alternative embodiment, the one or more
coating layers have an instrumented hardness of about 25 MPa to
about 26 MPa. The microhardness measurements were conducted with a
Modified Berkovich diamond indenter mounted on a TA
Instruments.RTM. Q800 DMA in force-controlled compression mode. The
measurement cycle used a 15-second load, 20-second hold, and a
15-second unload with a 100 mN maximum force. Instrumented Hardness
("HIT") was determined for each sample by a calculation using the
maximum force applied, the contact area, and depth of the indenter
at maximum deformation, and the slope of the unload curve as
described in ASTM procedure E2546-07, Standard Practice for
Instrumented Indentation Testing. Martens hardness was also
determined for each sample using the values obtained from the
force/indentation depth data at the end of the load cycle after
reaching maximum force in accordance with ISO 14577-1:2015(E) Annex
A.2.1. Samples for the analysis were prepared by gently pressing
the golf ball into a hemispherical holder and using a surface
grinding machine to remove any material above the equator of the
golf ball (leaving about half of the golf ball), exposing the
geometric center. The remaining golf ball hemisphere is removed
from the fixture, flipped, and ground with a surface grinder to
remove enough of the remaining half to form a 6-10 mm `puck` having
the center of the ball as one of the smooth, flat, and parallel
surfaces. Samples were held at 23.degree. C./50% relative humidity
("RH") for at least two days after preparation before hardness
measurements being taken at room temperature.
[0170] While any of the embodiments herein may have any known
dimple number and pattern, a preferred number of dimples is 252 to
456, and more preferably is 330 to 392. The dimples may comprise
any width, depth, and edge angle disclosed in the prior art and the
patterns may comprises multitudes of dimples having different
widths, depths and edge angles. The parting line configuration of
said pattern may be either a straight line or a staggered wave
parting line (SWPL). Most preferably the dimple number is 330, 332,
or 392 and comprises 5 to 7 dimples sizes and the parting line is a
SWPL.
[0171] In any of these embodiments the single-layer core may be
replaced with a 2 or more layer core wherein at least one core
layer has a negative hardness gradient.
[0172] Other than in the operating examples, or unless otherwise
expressly specified, all of the numerical ranges, amounts, values
and percentages such as those for amounts of materials and others
in the specification may be read as if prefaced by the word "about"
even though the term "about" may not expressly appear with the
value, amount or range. Accordingly, unless indicated to the
contrary, the numerical parameters set forth in the specification
and attached claims are approximations that may vary depending upon
the desired properties sought to be obtained by the present
invention. At the very least, and not as an attempt to limit the
application of the doctrine of equivalents to the scope of the
claims, each numerical parameter should at least be construed in
light of the number of reported significant digits and by applying
ordinary rounding techniques.
[0173] Notwithstanding that the numerical ranges and parameters
setting forth the broad scope of the invention are approximations,
the numerical values set forth in the specific examples are
reported as precisely as possible. Any numerical value, however,
inherently contain certain errors necessarily resulting from the
standard deviation found in their respective testing measurements.
Furthermore, when numerical ranges of varying scope are set forth
herein, it is contemplated that any combination of these values
inclusive of the recited values may be used.
[0174] While it is apparent that the illustrative embodiments of
the invention disclosed herein fulfill the objective stated above,
it is appreciated that numerous modifications and other embodiments
may be devised by those skilled in the art. Therefore, it will be
understood that the appended claims are intended to cover all such
modifications and embodiments, which would come within the spirit
and scope of the present invention.
* * * * *