U.S. patent application number 13/935974 was filed with the patent office on 2015-01-08 for multi-layer golf ball.
This patent application is currently assigned to NIKE, INC.. The applicant listed for this patent is NIKE, INC.. Invention is credited to Chien-Hsin Chou, Jun Ichinose, Hideyuki Ishii, Chen-Tai Liu, Nicholas Yontz.
Application Number | 20150011332 13/935974 |
Document ID | / |
Family ID | 52133187 |
Filed Date | 2015-01-08 |
United States Patent
Application |
20150011332 |
Kind Code |
A1 |
Ishii; Hideyuki ; et
al. |
January 8, 2015 |
MULTI-LAYER GOLF BALL
Abstract
A multi-layer golf ball includes a core, and intermediate layer,
and a cover. The core has an outer surface that includes a
plurality of protrusions extending from a spherical land portion.
Each protrusion has a maximum height relative to the spherical land
portion of between 0.15 mm and 2.0 mm. The intermediate layer
surrounds the core and has a radially outward surface that is flush
with the outer surface of the core. The cover layer surrounds the
intermediate layer and defines an outermost portion of ball.
Inventors: |
Ishii; Hideyuki; (Portland,
OR) ; Yontz; Nicholas; (Portland, OR) ;
Ichinose; Jun; (Kodaira Tokoyo, JP) ; Chou;
Chien-Hsin; (Yun-lin Hsien, TW) ; Liu; Chen-Tai;
(Yun-lin Hsien, TW) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
NIKE, INC. |
Beaverton |
OR |
US |
|
|
Assignee: |
NIKE, INC.
Beaverton
OR
|
Family ID: |
52133187 |
Appl. No.: |
13/935974 |
Filed: |
July 5, 2013 |
Current U.S.
Class: |
473/373 |
Current CPC
Class: |
A63B 37/0037 20130101;
A63B 37/0065 20130101; A63B 37/0018 20130101; A63B 37/0045
20130101; A63B 37/0043 20130101; A63B 37/0069 20130101; A63B
37/0031 20130101; A63B 37/0064 20130101; A63B 2037/0079 20130101;
A63B 37/0087 20130101; A63B 37/0076 20130101; A63B 37/0039
20130101; A63B 37/0062 20130101; A63B 37/0097 20130101 |
Class at
Publication: |
473/373 |
International
Class: |
A63B 37/00 20060101
A63B037/00 |
Claims
1. A multi-layer golf ball comprising: a core having an outer
surface that includes: a plurality of protrusions extending
radially outward from a spherical land portion; wherein each
protrusion has a maximum height relative to the spherical core of
between 0.15 mm and 2.0 mm; and wherein the spherical land portion
has a diameter of between 24 mm and 32 mm; an intermediate layer
surrounding the core and having a radially inward surface that is
bonded to the outer surface of the core across the entire outer
surface, the intermediate layer having a minimum radial thickness
of between 4 mm and 9 mm; a cover layer surrounding the
intermediate layer and defining an outermost portion of ball.
2. The golf ball of claim 1, wherein the core is formed from an
ionomeric material and has a hardness measured on the JIS-C scale
of between 34 and 70; and wherein the intermediate layer is formed
from a rubber, and has a hardness measured on the Shore D scale of
between 56 and 64.
3. The golf ball of claim 1, wherein each protrusion has a width
measured at the spherical land portion; and wherein each protrusion
has a width/maximum height ratio of between 2 and 8.
4. The golf ball of claim 1, wherein the cover layer includes one
or more of an ionomer resin, a polyethylene, and a polyester
resin.
5. The golf ball of claim 1, wherein the cover layer is formed from
a thermoplastic material having a hardness measured on the Shore-D
scale of up to about 72.
6. The golf ball of claim 5, wherein the thermoplastic material is
a thermoplastic polyurethane having a flexural modulus of up to
about 1000 psi.
7. The golf ball of claim 1, wherein the intermediate layer is a
first intermediate layer; and further comprising a second
intermediate layer disposed between the first intermediate layer
and the cover layer.
8. The golf ball of claim 7, wherein the second intermediate layer
has a hardness measured on the Shore-D scale of greater than 63 and
greater than a hardness of the cover layer.
9. The golf ball of claim 1, wherein the core has a 10-130 kg
compression deformation of between 3.5 mm and 5.5 mm.; wherein the
core and the intermediate layer define an intermediate ball; and
wherein the intermediate ball has a 10-130 kg compression
deformation of between 2.7 and 5.5 mm, and less than the 10-130 kg
compression deformation of the core.
10. The golf ball of claim 1, wherein the intermediate layer is
bonded to the core through an adhesive layer.
11. The golf ball of claim 10, wherein the adhesive layer includes
an ethylene vinyl acetate copolymer-based adhesive.
12. The golf ball of claim 2, wherein the ionomeric material has a
flexural modulus of less than 10,000 psi.
13. The golf ball of claim 1, wherein the intermediate layer is
formed from a rubber material that includes: a main rubber
containing a polybutadiene; an unsaturated carboxylic acid and/or a
metal salt thereof; and an organic peroxide.
14. The golf ball of claim 1, wherein the plurality of protrusions
includes between 50 and 80 protrusions that are symmetrically
disposed about the core.
15. A multi-layer golf ball comprising: a core formed from an
ionomeric material and has a hardness measured on the JIS-C scale
of between 34 and 70, the core having an outer surface that
includes: between 50 and 80 of protrusions extending radially
outward from a spherical land portion; wherein each protrusion has
a maximum height relative to the spherical core of between 0.15 mm
and 2.0 mm; and wherein the spherical land portion has a diameter
of between 24 mm and 32 mm; an intermediate layer formed from a
rubber, and having a hardness measured on the Shore D scale of
between 56 and 64, the intermediate layer surrounding the core and
having a radially inward surface that is bonded to the outer
surface of the core across the entire outer surface, the
intermediate layer having a minimum radial thickness of between 4
mm and 9 mm; a cover layer surrounding the intermediate layer and
defining an outermost portion of ball.
16. The golf ball of claim 15, wherein each protrusion has a width
measured at the spherical land portion; and wherein each protrusion
has a width/maximum height ratio of between 2 and 8.
17. The golf ball of claim 15, wherein the cover layer includes one
or more of an ionomer resin, a polyethylene, and a polyester
resin.
18. The golf ball of claim 15, wherein the cover layer is formed
from a thermoplastic material having a hardness measured on the
Shore-D scale of up to about 72.
19. The golf ball of claim 18, wherein the thermoplastic material
is a thermoplastic polyurethane having a flexural modulus of up to
about 1000 psi.
20. The golf ball of claim 15, wherein the intermediate layer is a
first intermediate layer; and further comprising a second
intermediate layer disposed between the first intermediate layer
and the cover layer.
21. The golf ball of claim 20, wherein the second intermediate
layer has a hardness measured on the Shore-D scale of greater than
63 and greater than a hardness of the cover layer.
22. The golf ball of claim 15, wherein the core has a 10-130 kg
compression deformation of between 3.5 mm and 5.5 mm; wherein the
core and the intermediate layer define an intermediate ball; and
wherein the intermediate ball has a 10-130 kg compression
deformation of between 2.7 and 5.5 mm, and less than the 10-130 kg
compression deformation of the core.
23. The golf ball of claim 15, wherein the intermediate layer is
bonded to the core through an adhesive layer.
24. The golf ball of claim 23, wherein the adhesive layer includes
an ethylene vinyl acetate copolymer-based adhesive.
25. The golf ball of claim 15, wherein the ionomeric material has a
flexural modulus of less than 10,000 psi.
26. The golf ball of claim 15, wherein rubber material includes: a
main rubber containing a polybutadiene; an unsaturated carboxylic
acid and/or a metal salt thereof; and an organic peroxide.
Description
TECHNICAL FIELD
[0001] The present invention relates generally to a multi-layer
golf ball.
BACKGROUND
[0002] The game of golf is an increasingly popular sport at both
the amateur and professional levels. To account for the wide
variety of play styles and abilities, it is desirable to produce
golf balls having different play characteristics.
[0003] Attempts have been made to balance a soft "feel" with good
resilience in a multi-layer golf ball by giving the ball a hardness
distribution across its respective layers (core, intermediate layer
or layers, and cover) in such a way as to retain both properties. A
harder golf ball will generally achieve greater distances, but less
spin, and so will be better for drives but more difficult to
control on shorter shots. On the other hand, a softer ball will
generally experience more spin, thus being easier to control, but
will lack distance. Additionally, certain design characteristics
may affect the "feel" of the ball when hit, as well as the
durability of the ball.
SUMMARY
[0004] A multi-layer golf ball includes a core, and intermediate
layer, and a cover. The core has an outer surface that includes a
plurality of protrusions extending from a spherical land portion.
Each protrusion has a maximum height relative to the spherical land
portion of between 0.15 mm and 2.0 mm. The intermediate layer
surrounds the core and has a radially outward surface that is flush
with the outer surface of the core. The cover layer surrounds the
intermediate layer and defines an outermost portion of ball.
[0005] In one configuration, the plurality of protrusions may
include between 50 and 80 protrusions that are symmetrically
disposed about the surface. Each protrusion has a maximum height
relative to the spherical land portion of between 0.15 mm and 2.0
mm. In more specific configurations, each protrusion may have a
height of between 0.15 mm and 1.0 mm, or between 0.15 mm and 0.6
mm. Each protrusion may have a maximum height that is substantially
the same. Additionally, each protrusion may have a circular outer
profile where the respective protrusion meets the spherical land
portion. The circular outer profile may have a diameter of greater
than 5 mm. In one configuration, one or more protrusions may have a
central portion that is substantially flat, or which may lie on a
sphere that is concentric with the spherical land portion.
[0006] The core may have a geometric center and a center of mass
that are coincident. The spherical land portion may have a diameter
of between 24 mm and 32 mm. Additionally the intermediate layer may
have a minimum radial thickness of between 4.0 mm and 9.0 mm.
[0007] In one example, the core may be formed from an ionomeric
material that has a flexural modulus of up to about 10,000 psi. The
intermediate layer may be formed from a rubber material including:
polybutadiene; an unsaturated carboxylic acid or a metal salt
thereof; and an organic peroxide. The cover layer may be formed
from a thermoplastic material having a hardness measured on the
Shore-D scale of up to about 72. The thermoplastic material may be
a thermoplastic polyurethane having a flexural modulus of up to
about 1000 psi.
[0008] In one configuration, the intermediate layer is a first
intermediate layer; and the ball may further include a second
intermediate layer disposed between the first intermediate layer
and the cover layer. The second intermediate layer may have a
hardness measured on the Shore-D scale of greater than 63 and
greater than a hardness of the cover layer. Additionally, the
second intermediate layer and the cover layer may have a total
radial thickness of less than 2.5 mm.
[0009] The above features and advantages and other features and
advantages of the present invention are readily apparent from the
following detailed description of the best modes for carrying out
the invention when taken in connection with the accompanying
drawings.
[0010] "A," "an," "the," "at least one," and "one or more" are used
interchangeably to indicate that at least one of the item is
present; a plurality of such items may be present unless the
context clearly indicates otherwise. All numerical values of
parameters (e.g., of quantities or conditions) in this
specification, including the appended claims, are to be understood
as being modified in all instances by the term "about" whether or
not "about" actually appears before the numerical value. "About"
indicates that the stated numerical value allows some slight
imprecision (with some approach to exactness in the value; about or
reasonably close to the value; nearly). If the imprecision provided
by "about" is not otherwise understood in the art with this
ordinary meaning, then "about" as used herein indicates at least
variations that may arise from ordinary methods of measuring and
using such parameters. In addition, disclosure of ranges includes
disclosure of all values and further divided ranges within the
entire range. Each value within a range and the endpoints of a
range are hereby all disclosed as separate embodiment. In this
description of the invention, for convenience, "polymer" and
"resin" are used interchangeably to encompass resins, oligomers,
and polymers. The terms "comprises," "comprising," "including," and
"having," are inclusive and therefore specify the presence of
stated items, but do not preclude the presence of other items. As
used in this specification, the term "or" includes any and all
combinations of one or more of the listed items. When the terms
first, second, third, etc. are used to differentiate various items
from each other, these designations are merely for convenience and
do not limit the items.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a partially exploded, schematic partial
cross-sectional view of a multi-layer golf ball.
[0012] FIG. 2 is a side view of an embodiment of a core of a golf
ball.
[0013] FIG. 3 is a schematic cross-sectional view of a first
configuration of a protrusion.
[0014] FIG. 4 is a schematic cross-sectional view of a second
configuration of a protrusion.
[0015] FIG. 5 is a schematic cross-sectional view of a third
configuration of a protrusion.
[0016] FIG. 6 is a schematic cross-sectional view of a fourth
configuration of a protrusion.
[0017] FIG. 7 is a schematic cross-sectional view of a fifth
configuration of a protrusion.
[0018] FIG. 8 is a schematic cross-sectional view of a sixth
configuration of a protrusion.
[0019] FIG. 9 is a schematic cross-sectional view of a multi-layer
golf ball.
[0020] FIG. 10A is a schematic cross-sectional view of a pair of
injection molding dies for forming a core of a golf ball.
[0021] FIG. 10B is a schematic cross-sectional view of a pair of
injection molding dies having a thermoplastic core of a golf ball
formed therein.
[0022] FIG. 11A is a schematic cross-sectional view of piece of
rubber stock.
[0023] FIG. 11B is a schematic cross-sectional view of an
intermediate layer cold-formed blank.
[0024] FIG. 11C is a schematic cross-sectional view of a pair of
compression molding dies being used to form a pair of cold-formed
blanks about a metallic spherical core.
[0025] FIG. 11D is a schematic cross-sectional view of a pair of
compression molding dies being used to compression mold an
intermediate layer of a golf ball about a polymeric core.
DETAILED DESCRIPTION
Golf Ball Design
[0026] Referring to the drawings, wherein like reference numerals
are used to identify like or identical components in the various
views, FIG. 1 schematically illustrates a schematic, exploded,
partial cross-sectional view of a golf ball 10. As shown, the golf
ball 10 may have a multi-layer construction that includes a core 12
surrounded by one or more intermediate layers 14, 16, and a cover
18 (i.e., where the cover 18 surrounds the one or more intermediate
layers 14, 16). While FIG. 1 generally illustrates a ball 10 with a
four-piece construction, the presently described structure and
techniques may be equally applicable to three-piece balls, as well
as five or more piece balls. In general, the cover 18 may define an
outermost portion 20 of the ball 10, and may include any desired
number of dimples 22, including, for example, between 280 and 432
total dimples, and in some examples, between 300 and 392 total
dimples, and typically between 298 to 360 total dimples. As known
in the art, the inclusion of dimples generally decreases the
aerodynamic drag of the ball, which may provide for greater flight
distances when the ball is properly struck.
[0027] In a completely assembled ball 10, each layer (including the
core 12, cover 18, and one or more intermediate layers 14, 16) may
be substantially concentric with every other layer such that every
layer shares a common geometric center. Additionally, the mass
distribution of each layer may be uniform such that the center of
mass for each layer, and the ball as a whole, is coincident with
the geometric center.
[0028] As generally shown in FIG. 1, and again in FIG. 2, the core
12 may have an outer surface 30 that has a varying radial
dimension. For example, in one configuration as shown, the outer
surface 30 may include a plurality of protrusions 32 that each
extend radially outward from a spherical land portion 34. Each
protrusion 32 may generally extend from the surface of the
spherical land portion 34, though may have local portions that may
be flat or even concave relative to the core 12.
[0029] FIGS. 3-8 generally illustrate six schematic cross-sectional
profiles of various protrusion types. Each protrusion may generally
be characterized by a width 36, measured at the spherical land
portion 34, and a maximum height 38, measured from the spherical
land portion 34 (or a spherical datum aligned with the spherical
land portion) to the most radially outward point of the protrusion
32 along a radial direction relative to the core 12. In one
configuration, the maximum height 38 may be in the range of 0.15 mm
to 2.0 mm. In other embodiments, the maximum height 38 may be in
the range of 0.15 mm to 1.0 mm, or even 0.15 mm to 0.6 mm. In one
configuration, each of the plurality of protrusions 32 may be
identical to every other protrusion 32 and/or each protrusion 32
may each extend from the spherical land portion 34 by some common
maximum height 38. In yet another configuration, the plurality of
protrusions may include two or more, three or more, or four or more
different types/sizes of protrusions across the core 12.
[0030] As generally illustrated in FIG. 3, in a first configuration
40, a protrusion 32 may include linearly sloping sidewalls 42 that
meet at a central point 44. In one configuration, the sidewalls 42
may be disposed at an oblique angle relative to the radial axis
and/or to the spherical land portion 34. For example, the linearly
sloping sidewalls 42 may be disposed at an angle 43 between about
40.degree. and about 80.degree. or between about 55.degree. and
about 65.degree. away from a radial axis. In a second configuration
46 (FIG. 4), similar linearly sloping sidewalls 42 may meet at a
substantially planar central portion 48.
[0031] In a third configuration 50 (FIG. 5), the entire
cross-section of the protrusion 32 may have a continuous
(potentially varying) curvature 52. In one configuration, the
radius of curvature at a central point on the protrusion 32 may be
in the range of 1.0 mm to about 8.0 mm. In a fourth configuration
54 (FIG. 6), each sidewall 56 may include a radius 58 that may
transition from the sidewall 56 to a central portion 60. The radius
58 may be, for example, between about 0.25 mm and about 2.0 mm or
between about 0.4 mm and about 0.8 mm. In a fifth configuration 62
(FIG. 7), each sidewall 64 may include two radiuses 66, 68 that may
respectively transition from the spherical land portion 34 to the
sidewall 64, and from the sidewall 64 to a central portion 60. In
one configuration, each radius 66, 68 may be, for example, between
about 0.25 mm and about 2.0 mm or between about 0.4 mm and about
0.8 mm.
[0032] Finally, in a sixth configuration 70 (FIG. 8), linearly
sloping sidewalls 42 may meet at a central portion 72 that has a
curvature. As generally shown in FIG. 8, the central portion 72 may
substantially lie on the surface of a sphere 74 that is concentric
with the spherical land portion 34. It should be appreciated that
these six protrusion configurations are provided for illustrative
purposes. In addition to those explicitly provided in the figures,
combinations of one or more of the configurations may also be
used.
[0033] Referring again to FIG. 2, in one configuration, the outer
surface 30 may have between 40 and 120 protrusions 32 that are
spaced around the surface 30. In another configuration, the outer
surface 30 may have between 50 and 80 protrusions 32 that are
spaced around the surface 30. In still another configuration, the
outer surface 30 may have between about 100 and about 300
protrusions. The protrusions 32 may generally be arranged about the
core 12 in a symmetric manner to maintain balance. For example, in
one configuration, the arrangement of the protrusions 32 may
establish at least two orthogonal planes of symmetry 80, 82. In a
more specific embodiment, the protrusions 32 may further establish
a third plane of symmetry 84 that is orthogonal to each of the
first two planes 80, 82, and where all three planes intersect at
the geometric center of the core 12.
[0034] Each protrusion 32 may have a perimeter or outer profile 86
that is formed where the protrusion 32 intersects with the
spherical land portion 34. The outer profile 86 for each protrusion
32 may be generally circular, and in one configuration, may have a
diameter of at least 5 mm. In other configurations, the outer
profile 86 for each protrusion 32 may be generally of a regular
geometric shape, for example generally a triangle, a quadrilateral,
a pentagon, a hexagon, or an octagon, or it may have a symmetric
complex shape (e.g., a plurality of lobes or other such
contours).
[0035] FIG. 9 generally illustrates a cross-sectional view 90 of a
multi-layer golf ball 10. As shown, an intermediate layer 14
surrounds a core 12, and includes a radially inward-facing surface
92 that is bonded to the outer surface 30 of the core 12 across the
entire outer surface 30. In this manner, the intermediate layer 14
completely surrounds the core 12 without leaving any voids between
the intermediate layer 14 and the core 12. The bonding may occur
either through direct material contact between the materials (i.e.,
physical bonding) or through one or more thin adhesive or
adhesion-promoting layers (i.e., chemical bonding) that may be
disposed between the core 12 and the intermediate layer 14. In one
configuration, a thin, adhesion layer may be formed from a
polymeric material disposed about the core 12, which may have a
maximum radial thickness of less than about 1.0 mm.
[0036] As further illustrated in FIG. 9, the core may generally
have a diameter 94 (measured via the spherical land portion 34) of
between about 24 mm and about 32 mm. Additionally, the intermediate
layer 14 may have a minimum radial thickness 96 of between about
4.0 mm and 9.0 mm. Finally, the cover layer 18 may have a minimum
thickness 98 (i.e., thickness at its narrowest portion) of between
about 0.5 mm and about 2.5 mm. In some configurations, a second
intermediate layer 16 may be included in the multi-layer ball 10
between the first intermediate layer 14 and the cover layer 18. In
such a construction, the second intermediate layer 16 and cover
layer 18 may have a combined thickness 98 at the narrowest portion
of between about 0.5 mm and about 2.5 mm.
Golf Ball Manufacturing and Material Parameters
[0037] In general, the golf ball 10 may be formed through one or
more injection molding or compression molding steps. For example,
in one configuration, the fabrication of a multi-layer golf ball 10
may include: forming a core 12 through injection molding;
compression molding one or more cold formed or pre-cured
intermediate layers 14, 16 about the core 12; and forming a cover
layer 18 about the intermediate layer 14 though injection molding
or compression molding.
[0038] As schematically illustrated in FIGS. 10A & 10B, during
the injection molding process used to form the core 12, two
hemispherical dies 150, 152 may cooperate to form a mold cavity 154
that may be filled with a thermoplastic material 156 in a softened
state. The hemispherical molding dies 150, 152 may meet at a
parting line 158 that, in one configuration, may be aligned along a
plane of symmetry 80, 82, or 84 of the core 12. In one
configuration, a thermoplastic ionomer may be used to form the core
12, such as one that may have a Vicat softening temperature,
measured according to ASTM D1525, of between about 50.degree. C.
and about 60.degree. C., or alternatively between about 52.degree.
C. and about 55.degree. C. Suitable thermoplastic ionomeric
materials are commercially available, for example, from the E. I.
du Pont de Nemours and Company under the tradename Surlyn.RTM..
More specific examples of suitable thermoplastic materials are
described below.
[0039] Once the material 156 is cooled to ambient temperature, it
may harden and be removed from the molding dies. The ease with
which the solidified core 12 may be ejected from the dies may vary
inversely with the degree to which the outer surface 30 is
contoured. For example, as the height of the protrusions 32
increase, the mold, itself, may restrict the ejection of the core
(i.e., referred to as undercut). While the inherent compliance
and/or flexibility of the thermoplastic material, along with
natural shrinkage of the core 12, may permit some amount of
undercut, a protrusion height of greater than about 2.0 mm may
restrict the ability to use a solid hemispherical mold to fabricate
the core and may considerably increase manufacturing cost and
complexity. Incorporating sloped sidewalls 42 with the plurality of
protrusions 32 may serve to reduce the amount of undercut, and may
allow for a greater maximum protrusion height.
[0040] Once the core 12 is formed and removed from the mold, any
molding flash may be removed using any combination of cutting,
grinding, sanding, tumbling with an abrasive media, and/or
cryogenic deflashing. Following the deflashing, an adhesive or
bonding agent may be applied to the outer surface 30, such as
through spraying, tumbling, and/or dipping. Additionally, one or
more surface treatments may also be employed at this stage, such as
mechanical surface roughening, plasma treatment, corona discharge
treatment, or chemical treatment to increase subsequent adhesion.
Nonlimiting, suitable examples of adhesives and bonding agents that
may be used include polymeric adhesives such as ethylene vinyl
acetate copolymers, two-component adhesives such as epoxy resins,
polyurethane resins, acrylic resins, polyester resins, and
cellulose resins and crosslinkers therefor, e.g., with polyamine or
polycarboxylic acid crosslinkers for polyepoxides resins,
polyisocyanate crosslinkers for polyalcohol-functional resins, and
so on; or siliane coupling agents or silane adhesives. The adhesive
or bonding agent may be used with or without a surface treatment
such as mechanical surface roughening, plasma treatment, corona
discharge treatment, or chemical treatment.
[0041] Once any surface coatings/preparations are applied/performed
(if any), the intermediate layer 14 may then be formed around the
core 12, for example, through a compression molding process or a
subsequent injection molding process. During compression molding,
two cold formed and/or pre-cured hemispherical blanks may be
press-fit around the core 12. Once positioned, a suitable die may
apply heat and/or pressure to the exterior of the blanks to
crosslink the blanks while fusing/curing them together. During the
curing process, the application of heat may cause the hemispherical
blanks to initially soften and/or melt prior to the start of any
crosslinking. The applied pressure may then cause the molten
material to form to the outer surface 30 of the core 12. The curing
process may be accelerated and/or initiated when as the material
temperature approaches or exceeds about 200.degree. C. In one
configuration, the intermediate layer 14 may be formed from a
rubber material, which may include a main rubber (e.g., a
polybutadiene), an unsaturated carboxylic acid or metal salt
thereof, and an organic peroxide. Other examples of suitable
rubbers and specific formulations are provided below.
[0042] FIGS. 11A-11D schematically illustrate one embodiment of a
process that may be used to compression mold an intermediate layer
14 about the core 12. As shown in FIG. 11A, the intermediate layer
may begin as piece of rubber stock 160 that may include one or more
crosslinking agents and/or fillers that may be homogeneously or
heterogeneously mixed throughout the stock 160. The stock 160 may
be cold-formed into a substantially hemispherical blank 162 (shown
in FIG. 11B) through one or more cutting, stamping, or pressing
processes.
[0043] As schematically shown in FIG. 11C, two compression molding
dies 164, 166 may form a pair of opposing blanks 168, 170 about a
spherical metal core 172. At this stage, the blanks 168, 170 may be
either cold-formed or partially cured through the application of
heat so that they may retain a true hemispherical shape (within
applicable tolerances). Finally, as shown in FIG. 11D, the
spherical metal core 172 may be replaced by the contoured
thermoplastic core 12, and the blanks 168, 170 may be compression
molded a second time by a second pair of opposing molding dies 172,
174 (which may or may not be the same dies 164, 166 used in the
prior step). During this stage, the dies 172, 174 may apply a
sufficient amount of heat and pressure to cause the blanks 168, 170
to flow within the mold cavity, and both internally crosslink and
fuse to each other. Once set, the intermediate ball (i.e., the
joined core 12 and intermediate layer 14) may be removed from the
mold.
[0044] The cover layer 18 may generally surround the one or more
intermediate layers 14, 16, and may define the outermost surface of
the ball 10. The cover may generally be formed from a thermoplastic
material, such as a thermoplastic polyurethane that may have a
flexural modulus of up to about 1000 psi. In other embodiments, the
cover may be formed from a ionomer, such as commercially available
from the E. I. du Pont de Nemours and Company under the tradename
Surlyn.RTM.. When a thermoplastic polyurethane is used, the cover
may have a hardness measured on the Shore-D hardness scale of up to
about 65, measured on the ball. In other embodiments, the
thermoplastic polyurethane cover may have a hardness measured on
the Shore-D hardness scale of up to about 60, measured on the ball.
If other ionomers are used to form the cover layer, the cover may
have a hardness measured on the Shore-D hardness scale of up to
about 72.
[0045] If a second intermediate layer 16 is utilized in the
construction of the multi-layer ball 10, the second intermediate
layer 16 may have a hardness measured on the Shore-D scale of at
least about 63, and also greater than the hardness of the cover
layer.
[0046] In one configuration, the thermoplastic material used for
the core 12 may have a flexural modulus of up to about 10,000 psi
(flexural modulus being measured according to ASTM D790), such as
the Surlyn.RTM. grades 8120, 8320, 9320, available from E. I. du
Pont de Nemours and Company, or such as those that may have a
flexural modulus of between about 6000 psi and about 7000 psi, or
even between about 6300 psi and about 6700 psi. In addition to
being specified by the flexural modulus (or alternatively), the
ionomeric material used for the core 12 may have a hardness
measured on the Shore D scale of up to about 40, measured on the
ball. In alternative embodiments, the material may have a hardness
measured on the Shore D scale of between about 30 and about 40, or
between about 32 and about 36. Hardness on the Shore-D hardness
scale is measured according to ASTM D2240, but in this specific
application, it is measured on a land area of a curved surface of
the ball or sub-layer of the ball (i.e., generally referred to as
"on the ball"). It is understood in this technical field of art
that the hardness measured in this way often varies from the
hardness of a flat slab or button of material in a non-linear way
that cannot be correlated, for example because of effects of
underlying layers. Because of the curved surface, care must be
taken to center the golf ball or golf ball subassembly under the
durometer indentor before a surface hardness reading is obtained
and to measure an even area, e.g. on the dimpled surface cover
measurements are taken on a land (fret) area between dimples. In
addition to Shore-D hardness, the core 12 may have a hardness
measured on the JIS-C scale of between 34 and 70, which may be
measured on the ball using a standard JIS-C hardness meter.
[0047] "Compression deformation" refers to the deformation amount
under a compressive load of 130 kg minus the deformation amount
under a compressive load of 10 kg. To determine a "10-130 kg
compression deformation," the amount of deformation of the ball
under a force of 10 kg is measured, then the force is increased to
130 kg and the amount of deformation under the new force of 130 kg
is measured. The deformation amount at 10 kg is subtracted from the
deformation amount at 130 kg to give the "10-130 kg compression
deformation."
[0048] In the present multi-layer golf ball, the core 12 may have a
10-130 kg compression deformation (C1) of between about 3.5 mm and
about 5.5 mm. When the core 12 and the intermediate layer 14 are
combined to form an inner ball, the inner ball may have a 10-130 kg
compression deformation (C2) of at least about 2.7 mm, though less
than C1. In one configuration, C2 may be from about 2.7 mm to about
3.5 mm. When the ball is tested as a whole (i.e., core,
intermediate layer(s), and cover), the ball may have a 10-130 kg
compression deformation (C3) of at least about 2.3 mm or between
about 2.5 mm and about 3.5 mm. In one configuration, the ratio of
C2/C1 may be between about 0.6 and 0.8.
[0049] In one configuration, the above-described golf ball may be
designed to have a coefficient of restitution at 40 m/s of up to
about 0.8 or between about 0.77 and about 0.80. Coefficient of
restitution or COR in the present invention may be measured
generally according to the following procedure: a golf ball is
fired by an air cannon at an initial velocity of 40 m/s, and a
speed monitoring device is located over a distance of 0.6 to 0.9
meters from the cannon. After striking a steel plate positioned
about 1.2 meters away from the air cannon, the test object rebounds
through the speed-monitoring device. The return velocity divided by
the initial velocity is the COR.
[0050] As described above, in some embodiments, the above-described
contoured core 12, may result in an increase in the surface area of
the core 12 by about 5% to about 25% above that of a generic
sphere. It has generally been found that, an increase in core
surface area 152 may result in an increase in ultimate adhesion
strength 154 between the core 12 and the intermediate layer 14.
Such an increase in adhesion may corresponding increase the load
transfer efficiency between the respective layers.
[0051] In addition to increasing ultimate adhesion strength 154
between layers, ball strike data shows that a contoured core with a
maximum protrusion height of between about 0.2 mm and about 0.6 mm
produces faster resultant launch speeds, at higher launch angles,
with less spin, across a range of club types. These are all
advantageous qualities when attempting to maximize the travel
distance for a particular ball strike.
Golf Ball Materials
[0052] Each of the center and intermediate layer or layers may be
made of one or more elastomeric materials and may also include one
or more non-elastomeric materials. The elastomeric materials
include thermoplastic elastomers and thermoset elastomers including
rubbers and crosslinked block copolymer elastomers. Nonlimiting
examples of suitable thermoplastic elastomers that can be used in
making the golf ball center, each intermediate layer, and cover
include metal cation ionomers of addition copolymers ("ionomer
resins"), metallocene-catalyzed block copolymers of ethylene and
.alpha.-olefins having 4 to about 8 carbon atoms, thermoplastic
polyamide elastomers (polyether block polyamides), thermoplastic
polyester elastomers, thermoplastic styrene block copolymer
elastomers such as poly(styrene-butadiene-styrene),
poly(styrene-ethylene-co-butylene-styrene), and
poly(styrene-isoprene-styrene), thermoplastic polyurethane
elastomers, thermoplastic polyurea elastomers, and dynamic
vulcanizates of rubbers in these thermoplastic elastomers and in
other thermoplastic matrix polymers. The center, each intermediate
layer, and cover may also be made of thermoset materials,
particularly crosslinked elastomers. The center and each
intermediate layer in particular may also be made from a
rubber.
[0053] Ionomer resins are metal cation ionomers of addition
copolymers of ethylenically unsaturated acids. Preferred ionomers
are copolymers of at least one alpha olefin, at least one C.sub.3-8
.alpha.,.beta.-ethylenically unsaturated carboxylic acid, and
optionally other comonomers. The copolymers may contain as a
comonomer at least one softening monomer such as an ethylenically
unsaturated ester, for example vinyl acetate or an alkyl acrylate
or methacrylate such as a C.sub.1 to C.sub.8 alkyl acrylate or
methacrylate ester.
[0054] The weight percentage of acid monomer units in the ionomer
copolymer may be in a range having a lower limit of about 1 or
about 4 or about 6 or about 8 or about 10 or about 12 or about 15
or about 20 weight percent and an upper limit of about 20 (when the
lower limit is not 20) or about 25 or about 30 or about 35 or about
40 weight percent based on the total weight of the acid copolymer.
The .alpha.,.beta.-ethylenically unsaturated acid is preferably
selected from acrylic acid, methacrylic acid, ethacrylic acid,
maleic acid, crotonic acid, fumaric acid, itaconic acid, and
combinations of these. In various embodiments, acrylic acid and
methacrylic acid may be particularly preferred.
[0055] The acid monomer is preferably copolymerized with an
alpha-olefin selected from ethylene and propylene. The weight
percentage of alpha-olefin units in the ionomer copolymer may be at
least about 15 or about 20 or about 25 or about 30 or about 40 or
about 50 or about 60 weight based on the total weight of the acid
copolymer.
[0056] In certain preferred embodiments, particularly for the
cover, the ionomer includes no other comonomer besides the
alpha-olefin and the ethylenically unsaturated carboxylic acid. In
other embodiments, a softening comonomer is copolymerized.
Nonlimiting examples of suitable softening comonomers are alkyl
esters of C.sub.3-8 .alpha.,.beta.-ethylenically unsaturated
carboxylic acids, particularly those in which the alkyl group has 1
to 8 carbon atoms, for instance methyl methacrylate, ethyl
acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate,
butyl acrylate, butyl methacrylate, isobutyl acrylate, tert-butyl
methacrylate, hexyl acrylate, 2-ethylhexyl methacrylate, and
combinations of these. When the ionomer includes a softening
comonomer, the softening comonomer monomer units may be present in
a weight percentage of the copolymer in a range with a lower limit
of a finite amount more than zero, or about 1 or about 3 or about 5
or about 11 or about 15 or about 20 weight percent of the copolymer
and an upper limit of about 23 or about 25 or about 30 or about 35
or about 50 weight percent of the copolymer.
[0057] Nonlimiting specific examples of acid-containing ethylene
copolymers include copolymers of ethylene/acrylic acid/n-butyl
acrylate, ethylene/methacrylic acid/n-butyl acrylate,
ethylene/methacrylic acid/isobutyl acrylate, ethylene/acrylic
acid/isobutyl 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 copolymers of
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. In
various embodiments the most preferred acid-containing ethylene
copolymers include ethylene/(meth)acrylic acid/n-butyl acrylate,
ethylene/(meth)acrylic acid/ethyl acrylate, and
ethylene/(meth)acrylic acid/methyl acrylate copolymers.
[0058] The acid moiety in the ethylene-acid copolymer may be
neutralized by any metal cation. Suitable cations include lithium,
sodium, potassium, magnesium, calcium, barium, lead, tin, zinc,
aluminum, bismuth, chromium, cobalt, copper, strontium, titanium,
tungsten, or a combination of these cations; in various embodiments
alkali, alkaline earth, or zinc metal cations are preferred. In
various embodiments, the acid groups of the ionomer may be
neutralized from about 10% or from about 20% or from about 30% or
from about 40% to about 60% or to about 70% or to about 75% or to
about 80% or to about 90% or to 100%.
[0059] The ionomer resin may be a high acid ionomer resin. In
general, ionomers prepared by neutralizing acid copolymers
including at least about 16 weight % of copolymerized acid residues
based on the total weight of the unneutralized ethylene acid
copolymer are considered "high acid" ionomers. In these high
modulus ionomers, the acid monomer, particularly acrylic or
methacrylic acid, is present in about 16 to about 35 weight %. In
various embodiments, the copolymerized carboxylic acid may be from
about 16 weight %, or about 17 weight % or about 18.5 weight % or
about 20 weight % up to about 21.5 weight % or up to about 25
weight % or up to about 30 weight % or up to about 35 weight % of
the unneutralized copolymer. A high acid ionomer resin may be
combined with a "low acid" ionomer resin in which the copolymerized
carboxylic acid is less than 16 weight % of the unneutralized
copolymer.
[0060] In various preferred embodiments, the ionomer resin is
formed by adding a sufficiently high molecular weight, monomeric,
mono-functional organic acid or salt of organic acid to the acid
copolymer or ionomer so that the acid copolymer or ionomer can be
neutralized, without losing processability, to a level above the
level that would cause the ionomer alone to become
non-melt-processable. The monomeric, mono-functional organic acid
its salt may be added to the ethylene-unsaturated acid copolymers
before they are neutralized or after they are optionally partially
neutralized to a level between about 1 and about 100%, provided
that the level of neutralization is such that the resulting ionomer
remains melt-processable. In generally, when the monomeric,
mono-functional organic acid is included the acid groups of the
copolymer may be neutralized from at least about 40 to about 100%,
preferably at least about 80% to about 100%, more preferably at
least about 90% to about 100%, still more preferably at least about
95% to about 100%, and most preferably about 100% without losing
processability. Such high neutralization, particularly to levels of
at least about 80% or at least about 90% or at least about 95% or
most preferably 100%, without loss of processability can be done by
(a) melt-blending the ethylene .alpha.,.beta.-ethylenically
unsaturated carboxylic acid copolymer or a melt-processable salt of
the copolymer with the organic acid or the salt of the organic
acid, and (b) adding a sufficient amount of a cation source up to
110% of the amount needed to neutralize the total acid in the
copolymer or ionomer and organic acid or salt to the desired level
to increase the level of neutralization of all the acid moieties in
the mixture preferably at least about 80%, at least about 90%, at
least about 95%, or preferably to about 100%. To obtain 100%
neutralization, it is preferred to add a slight excess of up to
110% of cation source over the amount stoichiometrically required
to obtain the 100% neutralization.
[0061] The preferred monomeric, monofunctional organic acids are
aliphatic or aromatic saturated or unsaturated acids that may have
from 6 or from about 8 or from about 12 or from about 18 carbon
atoms up to about 36 carbon atoms or up to 35 carbon atoms.
Nonlimiting suitable examples of the monomeric, monofunctional
organic acid includes caproic acid, caprylic acid, capric acid,
lauric acid, stearic acid, behenic acid, erucic acid, oleic acid,
linoleic acid, myristic acid, benzoic acid, palmitic acid,
phenylacetic acid, naphthalenic acid, dimerized derivatives of
these, and their salts, particularly the barium, lithium, sodium,
zinc, bismuth, chromium, cobalt, copper, potassium, strontium,
titanium, tungsten, magnesium or calcium salts. These may be used
in any combination.
[0062] Many grades of ionomer resins are commercially available,
for example from E.I. du Pont de Nemours and Company, Inc. under
the trademark Surlyn.RTM. or the designation "HPF," from ExxonMobil
Chemical under the trademarks Iotek.TM. and Escor.TM., or from
Honeywell International Inc. under the trademark AClyn.RTM.. The
various grades may be used in combination. In various preferred
embodiments, the inomer resin may be a highly neutralized ionomer
resin of the acrylic or methacrylic acid type, such as DuPont.TM.
HPF 2000 or AD-1035 made by E.I. du Pont de Nemours and Company,
Inc.
[0063] Thermoplastic polyolefin elastomers may also be used in in
making the golf ball. These are metallocene-catalyzed block
copolymers of ethylene and .alpha.-olefins having 4 to about 8
carbon atoms that are prepared by single-site metallocene
catalysis, for example in a high pressure process in the presence
of a catalyst system comprising a cyclopentadienyl-transition metal
compound and an alumoxane. Nonlimiting examples of the
.alpha.-olefin softening comonomer include hexane-1 or octene-1;
octene-1 is a preferred comonomer to use. These materials are
commercially available, for example, from ExxonMobil under the
tradename Exact.TM. and from the Dow Chemical Company under the
tradename Engage.TM..
[0064] In various preferred embodiments, the golf ball includes a
polyolefin elastomer, especially one of the thermoplastic
polyolefin elastomers just described. The core center may include
from about 5 percent by weight to about 50 percent by weight,
preferably from about 10 percent by weight to about 30 percent by
weight polyolefin elastomer based on the combined weights of
polyolefin elastomer and ionomer resin.
[0065] In one embodiment, the core center or an intermediate layer
is made of a combination of a metal ionomer of a copolymer of
ethylene and at least one of acrylic acid and methacrylic acid, a
metallocene-catalyzed copolymer of ethylene and an .alpha.-olefin
having 4 to about 8 carbon atoms, and a metal salt of an
unsaturated fatty acid. that may be prepared as described in Statz
et al., U.S. Pat. No. 7,375,151 or as described in Kennedy,
"Process for Making Thermoplastic Golf Ball Material and Golf Ball
with Thermoplastic Material, U.S. patent application Ser. No.
13/825,112, filed 15 Mar. 2013, the entire contents of both being
incorporated herein by reference.
[0066] Suitable thermoplastic styrene block copolymer elastomers
that may be used in the center, intermediate layer, or cover of the
golf ball include poly(styrene-butadiene-styrene),
poly(styrene-ethylene-co-butylene-styrene),
poly(styrene-isoprene-styrene), and
poly(styrene-ethylene-co-propylene) copolymers. These styrenic
block copolymers may be prepared by living anionic polymerization
with sequential addition of styrene and the diene forming the soft
block, for example using butyl lithium as initiator. Thermoplastic
styrene block copolymer elastomers are commercially available, for
example, under the trademark Kraton.TM. sold by Kraton Polymers
U.S. LLC, Houston, Tex. Other such elastomers may be made as block
copolymers by using other polymerizable, hard, non-rubber monomers
in place of the styrene, including meth(acrylate) esters such as
methyl methacrylate and cyclohexyl methacrylate, and other vinyl
arylenes, such as alkyl styrenes.
[0067] Thermoplastic polyurethane elastomers such as thermoplastic
polyester-polyurethanes, polyether-polyurethanes, and
polycarbonate-polyurethanes may be used as a core or cover
thermoplastic material. The thermoplastic polyurethane elastomers
include polyurethanes polymerized using as polymeric diol reactants
polyethers and polyesters including polycaprolactone polyesters.
These polymeric diol-based polyurethanes are prepared by reaction
of the polymeric diol (polyester diol, polyether diol,
polycaprolactone diol, polytetrahydrofuran diol, or polycarbonate
diol), one or more polyisocyanates, and, optionally, one or more
chain extension compounds. Chain extension compounds, as the term
is being used, are compounds having two or more functional groups
reactive with isocyanate groups, such as the diols, amino alcohols,
and diamines. Preferably the polymeric diol-based polyurethane is
substantially linear (i.e., substantially all of the reactants are
difunctional).
[0068] Diisocyanates used in making the polyurethane elastomers may
be aromatic or aliphatic. Useful diisocyanate compounds used to
prepare thermoplastic polyurethanes include, without limitation,
isophorone diisocyanate (IPDI), methylene bis-4-cyclohexyl
isocyanate (H.sub.12MDI), cyclohexyl diisocyanate (CHDI),
m-tetramethyl xylene diisocyanate (m-TMXDI), p-tetramethyl xylene
diisocyanate (p-TMXDI), 4,4'-methylene diphenyl diisocyanate (MDI,
also known as 4,4'-diphenylmethane diisocyanate), 2,4- or
2,6-toluene diisocyanate (TDI), ethylene diisocyanate,
1,2-diisocyanatopropane, 1,3-diisocyanatopropane,
1,6-diisocyanatohexane (hexamethylene diisocyanate or HDI),
1,4-butylene diisocyanate, lysine diisocyanate,
meta-xylylenediioscyanate and para-xylylenediisocyanate,
4-chloro-1,3-phenylene diisocyanate, 1,5-tetrahydro-naphthalene
diisocyanate, 4,4'-dibenzyl diisocyanate, and xylylene diisocyanate
(XDI), and combinations of these. Nonlimiting examples of
higher-functionality polyisocyanates that may be used in limited
amounts to produce branched thermoplastic polyurethanes (optionally
along with monofunctional alcohols or monofunctional isocyanates)
include 1,2,4-benzene triisocyanate, 1,3,6-hexamethylene
triisocyanate, 1,6,11-undecane triisocyanate, bicycloheptane
triisocyanate, triphenylmethane-4,4',4''-triisocyanate,
isocyanurates of diisocyanates, biurets of diisocyanates,
allophanates of diisocyanates, and the like.
[0069] Nonlimiting examples of suitable diols that may be used as
extenders include ethylene glycol and lower oligomers of ethylene
glycol including diethylene glycol, triethylene glycol and
tetraethylene glycol; propylene glycol and lower oligomers of
propylene glycol including dipropylene glycol, tripropylene glycol
and tetrapropylene glycol; cyclohexanedimethanol, 1,6-hexanediol,
2-ethyl-1,6-hexanediol, 1,4-butanediol, 2,3-butanediol,
1,5-pentanediol, 1,3-propanediol, butylene glycol, neopentyl
glycol, dihydroxyalkylated aromatic compounds such as the
bis(2-hydroxyethyl)ethers of hydroquinone and resorcinol;
p-xylene-.alpha.,.alpha.'-diol; the bis(2-hydroxyethyl)ether of
p-xylene-.alpha.,.alpha.'-diol; m-xylene-.alpha.,.alpha.'-diol, and
combinations of these. Other active hydrogen-containing chain
extenders that contain at least two active hydrogen groups may be
used, for example, dithiols, diamines, or compounds having a
mixture of hydroxyl, thiol, and amine groups, such as
alkanolamines, aminoalkyl mercaptans, and hydroxyalkyl mercaptans,
among others. Suitable diamine extenders include, without
limitation, ethylene diamine, diethylene triamine, triethylene
tetraamine, and combinations of these. Other typical chain
extenders are amino alcohols such as ethanolamine, propanolamine,
butanolamine, and combinations of these. The molecular weights of
the chain extenders preferably range from about 60 to about 400.
Alcohols and amines are preferred.
[0070] In addition to difunctional extenders, a small amount of a
trifunctional extender such as trimethylolpropane,
1,2,6-hexanetriol and glycerol, or monofunctional active hydrogen
compounds such as butanol or dimethyl amine, may also be present.
The amount of trifunctional extender or monofunctional compound
employed may be, for example, 5.0 equivalent percent or less based
on the total weight of the reaction product and active hydrogen
containing groups used.
[0071] The polyester diols used in forming a thermoplastic
polyurethane elastomer are in general prepared by the condensation
polymerization of one or more polyacid compounds and one or more
polyol compounds. Preferably, the polyacid compounds and polyol
compounds are di-functional, i.e., diacid compounds and diols are
used to prepare substantially linear polyester diols, although
minor amounts of mono-functional, tri-functional, and higher
functionality materials can be included to provide a slightly
branched, but uncrosslinked polyester polyol component. Suitable
dicarboxylic acids include, without limitation, glutaric acid,
succinic acid, malonic acid, oxalic acid, phthalic acid,
hexahydrophthalic acid, adipic acid, maleic acid, suberic acid,
azelaic acid, dodecanedioic acid, their anhydrides and
polymerizable esters (e.g., methyl esters) and acid halides (e.g.,
acid chlorides), and mixtures of these. Suitable polyols include
those already mentioned, especially the diols. Typical catalysts
for the esterification polymerization are protonic acids, Lewis
acids, titanium alkoxides, and dialkyltin oxides.
[0072] A polymeric polyether or polycaprolactone diol reactant for
preparing thermoplastic polyurethane elastomers may be obtained by
reacting a diol initiator, e.g., 1,3-propanediol or ethylene or
propylene glycol, with a lactone or alkylene oxide chain-extension
reagent. Lactones that can be ring opened by an active hydrogen are
well-known in the art. Examples of suitable lactones include,
without limitation, .epsilon.-caprolactone, .gamma.-caprolactone,
.beta.-butyrolactone, .beta.-propriolactone, .gamma.-butyrolactone,
.alpha.-methyl-.gamma.-butyrolactone,
.beta.-methyl-.gamma.-butyrolactone, .gamma.-valerolactone,
.delta.-valerolactone, .gamma.-decanolactone,
.delta.-decanolactone, .gamma.-nonanoic lactone, .gamma.-octanoic
lactone, and combinations of these. In one preferred embodiment,
the lactone is .epsilon.-caprolactone. Useful catalysts include
those mentioned above for polyester synthesis. Alternatively, the
reaction can be initiated by forming a sodium salt of the hydroxyl
group on the molecules that will react with the lactone ring. In
other embodiments, a diol initiator may be reacted with an
oxirane-containing compound to produce a polyether diol to be used
in the polyurethane elastomer polymerization. Alkylene oxide
polymer segments include, without limitation, the polymerization
products of ethylene oxide, propylene oxide, 1,2-cyclohexene oxide,
1-butene oxide, 2-butene oxide, 1-hexene oxide, tert-butylethylene
oxide, phenyl glycidyl ether, 1-decene oxide, isobutylene oxide,
cyclopentene oxide, 1-pentene oxide, and combinations of these. The
oxirane-containing compound is preferably selected from ethylene
oxide, propylene oxide, butylene oxide, tetrahydrofuran, and
combinations of these. The alkylene oxide polymerization is
typically base-catalyzed. The polymerization may be carried out,
for example, by charging the hydroxyl-functional initiator compound
and a catalytic amount of caustic, such as potassium hydroxide,
sodium methoxide, or potassium tert-butoxide, and adding the
alkylene oxide at a sufficient rate to keep the monomer available
for reaction. Two or more different alkylene oxide monomers may be
randomly copolymerized by coincidental addition or polymerized in
blocks by sequential addition. Homopolymers or copolymers of
ethylene oxide or propylene oxide are preferred. Tetrahydrofuran
may be polymerized by a cationic ring-opening reaction using such
counterions as SbF.sub.6.sup.-, AsF.sub.6.sup.-, PF.sub.6.sup.-,
SbCl.sub.6.sup.-, BF.sub.4.sup.-, CF.sub.3SO.sub.3.sup.-,
FSO.sub.3.sup.-, and ClO.sub.4.sup.-. Initiation is by formation of
a tertiary oxonium ion. The polytetrahydrofuran segment can be
prepared as a "living polymer" and terminated by reaction with the
hydroxyl group of a diol such as any of those mentioned above.
Polytetrahydrofuran is also known as polytetramethylene ether
glycol (PTMEG).
[0073] Aliphatic polycarbonate diols that may be used in making a
thermoplastic polyurethane elastomer may be prepared by the
reaction of diols with dialkyl carbonates (such as diethyl
carbonate), diphenyl carbonate, or dioxolanones (such as cyclic
carbonates having five- and six-member rings) in the presence of
catalysts like alkali metal, tin catalysts, or titanium compounds.
Useful diols include, without limitation, any of those already
mentioned. Aromatic polycarbonates are usually prepared from
reaction of bisphenols, e.g., bisphenol A, with phosgene or
diphenyl carbonate.
[0074] In various embodiments, the polymeric diol preferably has a
weight average molecular weight of at least about 500, more
preferably at least about 1000, and even more preferably at least
about 1800 and a weight average molecular weight of up to about
10,000, but polymeric diols having weight average molecular weights
of up to about 5000, especially up to about 4000, may also be
preferred. The polymeric diol advantageously has a weight average
molecular weight in the range from about 500 to about 10,000,
preferably from about 1000 to about 5000, and more preferably from
about 1500 to about 4000. The weight average molecular weights may
be determined by ASTM D4274.
[0075] The reaction of the polyisocyanate, polymeric diol, and diol
or other chain extension agent is typically carried out at an
elevated temperature in the presence of a catalyst. Typical
catalysts for this reaction include organotin catalysts such as
stannous octoate, dibutyl tin dilaurate, dibutyl tin diacetate,
dibutyl tin oxide, tertiary amines, zinc salts, and manganese
salts. Generally, for elastomeric polyurethanes, the ratio of
polymeric diol, such as polyester diol, to extender can be varied
within a relatively wide range depending largely on the desired
flexural modulus of the final polyurethane elastomer. For example,
the equivalent proportion of polyester diol to extender may be
within the range of 1:0 to 1:12 and, more preferably, from 1:1 to
1:8. Preferably, the diisocyanate(s) employed are proportioned such
that the overall ratio of equivalents of isocyanate to equivalents
of active hydrogen containing materials is within the range of 1:1
to 1:1.05, and more preferably, 1:1 to 1:1.02. The polymeric diol
segments typically are from about 35% to about 65% by weight of the
polyurethane polymer, and preferably from about 35% to about 50% by
weight of the polyurethane polymer.
[0076] Suitable thermoplastic polyurea elastomers may be prepared
by reaction of one or more polymeric diamines or polyols with one
or more of the polyisocyanates already mentioned and one or more
diamine extenders. Nonlimiting examples of suitable diamine
extenders include ethylene diamine, 1,3-propylene diamine,
2-methyl-pentamethylene diamine, hexamethylene diamine, 2,2,4- and
2,4,4-trimethyl-1,6-hexane diamine, imino-bis(propylamine),
imido-bis(propylamine),
N-(3-aminopropyl)-N-methyl-1,3-propanediamine),
1,4-bis(3-aminopropoxy)butane,
diethyleneglycol-di(aminopropyl)ether),
1-methyl-2,6-diamino-cyclohexane, 1,4-diamino-cyclohexane, 1,3- or
1,4-bis(methylamino)-cyclohexane, isophorone diamine, 1,2- or
1,4-bis(sec-butylamino)-cyclohexane, N,N'-diisopropyl-isophorone
diamine, 4,4'-diamino-dicyclohexylmethane,
3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane,
N,N'-dialkylamino-dicyclohexylmethane, and
3,3'-diethyl-5,5'-dimethyl-4,4'-diamino-dicyclohexylmethane.
Polymeric diamines include polyoxyethylene diamines,
polyoxypropylene diamines, poly(oxyethylene-oxypropylene)diamines,
and poly(tetramethylene ether)diamines. The amine- and
hydroxyl-functional extenders already mentioned may be used as
well. Generally, as before, trifunctional reactants are limited and
may be used in conjunction with monofunctional reactants to prevent
crosslinking.
[0077] Suitable thermoplastic polyamide elastomers may be obtained
by: (1) polycondensation of (a) a dicarboxylic acid, such as oxalic
acid, adipic acid, sebacic acid, terephthalic acid, isophthalic
acid, 1,4-cyclohexanedicarboxylic acid, or any of the other
dicarboxylic acids already mentioned with (b) a diamine, such as
ethylenediamine, tetramethylenediamine, pentamethylenediamine,
hexamethylenediamine, or decamethylenediamine,
1,4-cyclohexanediamine, m-xylylenediamine, or any of the other
diamines already mentioned; (2) a ring-opening polymerization of a
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 to prepare a carboxylic acid-functional polyamide block,
followed by reaction with a polymeric ether diol (polyoxyalkylene
glycol) such as any of those already mentioned. Polymerization may
be carried out, for example, at temperatures of from about
180.degree. C. to about 300.degree. C. Specific examples of
suitable polyamide block copolymers include NYLON 6, NYLON 66,
NYLON 610, NYLON 11, NYLON 12, copolymerized NYLON MXD6, and NYLON
46 block copolymer elastomers.
[0078] Thermoplastic polyester elastomers have blocks of monomer
units with low chain length that form the crystalline regions and
blocks of softening segments with monomer units having relatively
higher chain lengths. Thermoplastic polyester elastomers are
commercially available under the trademark Hytrel.RTM. from DuPont
and under the trademark Pebax.RTM. from Arkema.
[0079] Another suitable example of thermoplastic elastomers are
those having dispersed domains of cured rubbers incorporated in a
thermoplastic matrix via dynamic vulcanization of rubbers. The
thermoplastic matrix may be any of these thermoplastic elastomers
or other thermoplastic polymers. One such composition is described
in Voorheis et al, U.S. Pat. No. 7,148,279, which is incorporated
herein by reference. In various embodiments, the core center may
include a thermoplastic dynamic vulcanizate of a rubber in a
non-elastomeric matrix resin such as polypropylene. Thermoplastic
vulcanizates commercially available from ExxonMobil under the
tradename Santoprene.TM. are believed to be vulcanized domains of
EPDM in polypropylene.
[0080] Plasticizers or softening polymers may be incorporated. One
example of such a plasticizer is the high molecular weight,
monomeric organic acid or its salt that may be incorporated, for
example, with an ionomer polymer as already described, including
metal stearates such as zinc stearate, calcium stearate, barium
stearate, lithium stearate and magnesium stearate. For most
thermoplastic elastomers, the percentage of hard-to-soft segments
is adjusted if lower hardness is desired rather than by adding a
plasticizer.
[0081] Thermoset elastomers may also be used. In particular, cured
rubbers may be used in the core and crosslinked thermoplastic
elastomers may be used for the cover.
[0082] Suitable nonlimiting examples of base rubbers include
butadiene, such as high cis-1,4 polybutadiene, natural rubber,
polyisoprene rubber, styrene polybutadiene rubber, and
ethylene-propylene-diene rubber (EPDM).
[0083] In various embodiments, the center or an intermediate layer
many include a cured product of a rubber composition comprising a
polybutadiene, an unsaturated carboxylic acid or metal salt of an
unsaturated carboxylic acid, and an organic peroxide. In certain
embodiments, the polybutadiene may have a Mooney viscosity
(ML.sub.1+4(100.degree. C.)) of at least about 40, preferably from
about 40 to about 85, and more preferably from about 50 to about
85. "Mooney viscosity (ML.sub.1+4(100.degree. C.))" is measured
according to JIS K6300 using a Mooney viscometer, which is a type
of rotary plastomer. In the term ML.sub.1+4(100.degree. C.), "M"
indicates Mooney viscosity, "L" stands for large rotor (L-type),
and "1+4" indicates a pre-heating time of 1 minute and a rotor
rotation time of 4 minutes. The "(100.degree. C.)" indicates that
the measurement is carried out at a temperature of 100.degree.
C.
[0084] In certain embodiments, the polybutadiene may have at least
about 70%, preferably at least about 80%, more preferably at least
about 90%, and still more preferably at least about 95%, and most
preferably at least about 98% of the monomer units joined via
cis-1,4 bonds based on the total number of butadiene monomer units.
Higher cis-1,4-bond content in the polybutadiene generally
increases resilience. Moreover, it may be preferred that the
polybutadiene have a 1,2-vinyl bond content of preferably not more
than 2%, more preferably not more than 1.7%, and even more
preferably not more than 1.5%. Such high cis-1,4 polybutadienes are
commercially available or can be polymerized using a rare-earth
catalyst or a Group VIII metal compound catalyst, preferably a
rare-earth catalyst. Nonlimiting examples of rare-earth catalysts
that may be used include those made by a combination of a
lanthanide series rare-earth compound with an organoaluminum
compound, an alumoxane, a halogen-bearing compound, and an optional
Lewis base. Examples of suitable lanthanide series rare-earth
compounds include halides, carboxylates, alcoholates,
thioalcoholates and amides of atomic number 57 to 71 metals. A
neodymium catalyst is particularly advantageous because it results
in a polybutadiene rubber having a high cis-1,4 bond content and a
low 1,2-vinyl bond content. When other rubbers are included, the
high cis-1,4 polybutadiene should be at least about 50% by weight,
preferably at least about 80% by weight based on the total weight
of base rubber.
[0085] The rubber composition may include an unsaturated carboxylic
acid or metal salt of an unsaturated carboxylic acid which acts as
a crosslinker or co-crosslinking agent. Such unsaturated carboxylic
acids or salts may, in general, be .alpha.,.beta.-ethylenically
unsaturated acids having 3 to 8 carbon atoms such as acrylic acid,
methacrylic acid, crotonic acid, maleic acid, and fumaric acid that
may be used as their magnesium and zinc salts. Specific examples of
preferable co-crosslinking agents include zinc diacrylate,
magnesium diacrylate, zinc dimethacrylate and magnesium
dimethacrylate. The amount of the unsaturated carboxylic acid or
its salt is typically at least about 10 parts by weight, preferably
at least about 15 parts by weight and up to about 50 parts by
weight, preferably up to about 45 parts by weight per 100 parts by
weight of the base rubber.
[0086] The rubber composition includes a free radical initiator or
sulfur compound. Suitable initiators include organic peroxide
compounds such as dicumyl peroxide, 1,1-di(t-butylperoxy)
3,3,5-trimethyl cyclohexane,
.alpha.,.alpha.-bis(t-butylperoxy)diisopropylbenzene,
2,5-dimethyl-2,5 di(t-butylperoxy)hexane, di-t-butyl peroxide. The
amount of the organic peroxide is typically at least about 0.1 part
by weight, preferably at least about 0.3 part by weight, more
preferably equal at least about 0.5 part by weight up to about 3.0
parts by weight, preferably up to about 2.5 parts by weight, based
on 100 parts by weight of the base rubber. Nonlimiting examples of
suitable sulfur compounds include thiophenols, thionaphthols,
halogenated thiophenols, and metal salts of these, for example
pentachlorothiophenol, pentafluorothiophenol, pentabromothiophenol,
p-chlorothiophenol, and zinc salts thereof; diphenylpolysulfides,
dibenzylpolysulfides, dibenzoylpolysulfides,
dibenzothiazoylpolysulfides and dithiobenzoylpolysulfides having 2
to 4 sulfur atoms; alkylphenyldisulfides; and furan ring-containing
sulfur compounds and thiophene ring-containing sulfur compounds,
particularly diphenyldisulfide or the zinc salt of
pentachlorothiophenol. The amount of the sulfur compound is
typically at least about 0.05 part by weight, preferably at least
about 0.2 part by weight, more preferably at least about 0.4 part
by weight or at least about 0.7 part by weight up to about 5.0
parts by weight, preferably up to about 4 parts by weight, more
preferably up to about 3 parts by weight or up to about 1.5 parts
by weight, based on 100 parts by weight of the base rubber.
[0087] The cover may also be include a crosslinked thermoplastic
elastomer, such as a crosslinked polyurethane, polyurea, or
polyamide elastomer. Crosslinked polyurethane and polyurea covers
may be formed by crosslinking a polyester or polymeric polyamine,
for examples one of those described above in making thermoplastic
polyurethanes and polyureas, with a polyisocyanate crosslinker or
by crosslinking a hydroxyl-functional thermoplastic polyurethane
elastomer or amine-functional thermoplastic polyurea elastomer, or
amine-functional thermoplastic polyamide with a polyisocyanate
crosslinker. Nonlimiting examples of polyisocyanate crosslinkers
that may be used include 1,2,4-benzene triisocyanate,
1,3,6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate,
bicycloheptane triisocyanate,
triphenylmethane-4,4',4''-triisocyanate, isocyanurates of
diisocyanates, biurets of diisocyanates, allophanates of
diisocyanates, such as any of the diisocyanates already mentioned
above.
[0088] In another embodiment, the cover includes a crosslinked
thermoplastic polyurethane elastomer prepared by crosslinking
ethylencially unsaturated bonds located in the hard segments that
may be crosslinked by free radical initiation, for example using
heat or actinic radiation. The crosslinks may be made through allyl
ether side groups provided by forming the thermoplastic
polyurethane using an unsaturated diol having two
isocyanate-reactive groups, for example primary hydroxyl groups,
and at least one allyl ether side group. Nonlimiting examples of
such unsaturated diols include those of the formula
##STR00001##
in which R is a substituted or unsubstituted alkyl group and x and
y are independently integers of 1 to 4. In one particular
embodiment, the unsaturated diol may be trimethylolpropane
monoallylether ("TMPME") (CAS no. 682-11-1). TMPME is commercially
available, for example from Perstorp Specialty Chemicals AB. Other
suitable compounds that may be used as the unsaturated diol may
include: 1,3-propanediol,
2-(2-propen-1-yl)-2-[(2-propen-1-yloxy)methyl]; 1,3-propanediol,
2-methyl-2-[(2-propen-1-yloxy)methyl]; 1,3-propanediol,
2,2-bis[(2-propen-1-yloxy)methyl; and 1,3-propanediol,
2-[(2,3-dibromopropoxy)methyl]-2-[(2-propen-1-yloxy)methyl]. The
crosslinked polyurethane is prepared by reacting the unsaturated
diol, at least one diisocyanate, at least one polymeric polyol
having a number average molecular weight of from about 500 and to
about 4,000, optionally at least one nonpolymeric reactant with two
or more isocyanate-reactive groups (an "extender") that typically
has a molecular weight of less than about 450, and a sufficient
amount of free radical initiator to generate free radicals that
induce crosslinking through addition polymerization of the
ethylenically unsaturated groups.
[0089] Ethylenic unsaturation may also be introduced after the
polyurethane is made, for example by copolymerizing
dimethylolpropionic acid then reacting the pendent carboxyl groups
with isocyanatoethyl methacrylate, glycidyl methacrylate, glycidyl
acrylate, or allyl glycidyl ether.
[0090] The amount of unsaturated diol monomer units in the
crosslinked thermoplastic polyurethane elastomer may generally be
from about 0.1 wt. % to about 25 wt. %. In particular embodiments,
the amount of unsaturated diol monomer units in the crosslinked
thermoplastic polyurethane elastomer may be about 10 wt. %.
Furthermore, the NCO index of the reactants making up the
crosslinked thermoplastic polyurethane elastomer may be from about
0.9 to about 1.3. As is generally known, the NCO index is the molar
ratio of isocyanate functional groups to active hydrogen containing
groups. In particular embodiments, the NCO index may be about
1.0.
[0091] Once reacted, the portions of the polymer chain made up of
the chain extender and diisocyanate generally align themselves into
crystalline domains through weak (i.e., non-covalent) association,
such as through Van der Waals forces, dipole-dipole interactions or
hydrogen bonding. These portions are commonly referred to as the
hard segments because the crystalline structure is harder than the
amorphous portions made up of the polymeric polyol segments. The
crosslinks formed from addition polymerization of the allyl ether
or other ethylenically unsaturated side groups are understood to be
in such crystalline domains.
[0092] The physical properties of the golf ball materials can be
modified by including a filler. Nonlimiting examples of suitable
fillers include clay, talc, asbestos, graphite, glass, mica,
calcium metasilicate, barium sulfate, zinc sulfide, aluminum
hydroxide, silicates, diatomaceous earth, carbonates (such as
calcium carbonate, magnesium carbonate and the like), metals (such
as titanium, tungsten, aluminum, bismuth, nickel, molybdenum, iron,
copper, brass, boron, bronze, cobalt, beryllium and alloys of
these), metal oxides (such as zinc oxide, iron oxide, aluminum
oxide, titanium oxide, magnesium oxide, zirconium oxide and the
like), particulate synthetic plastics (such as high molecular
weight polyethylene, polystyrene, polyethylene ionomeric resins and
the like), particulate carbonaceous materials (such as carbon
black, natural bitumen and the like), as well as cotton flock,
cellulose flock and/or leather fiber. Nonlimiting examples of
heavy-weight fillers that may be used to increase specific gravity
include titanium, tungsten, aluminum, bismuth, nickel, molybdenum,
iron, steel, lead, copper, brass, boron, boron carbide whiskers,
bronze, cobalt, beryllium, zinc, tin, and metal oxides (such as
zinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium
oxide, zirconium oxide). Nonlimiting examples of light-weight
fillers that may be used to decrease specific gravity include
particulate plastics, glass, ceramics, and hollow spheres,
regrinds, or foams of these. Fillers that may be used in the core
center and core layers of a golf ball are typically in a finely
divided form.
[0093] The cover may be formulated with a pigment, such as a yellow
or white pigment, and in particular a white pigment such as
titanium dioxide or zinc oxide. Generally titanium dioxide is used
as a white pigment, for example in amounts of from about 0.5 parts
by weight or 1 part by weight to about 8 parts by weight or 10
parts by weight passed on 100 parts by weight of polymer. In
various embodiments, a white-colored cover may be tinted with a
small amount of blue pigment or brightener.
[0094] Customary additives can also be included in the golf ball
materials, for example dispersants, antioxidants such as phenols,
phosphites, and hydrazides, processing aids, surfactants,
stabilizers, and so on. The cover may also contain additives such
as hindered amine light stabilizers such as piperidines and
oxanalides, ultraviolet light absorbers such as benzotriazoles,
triazines, and hindered phenols, fluorescent materials and
fluorescent brighteners, dyes such as blue dye, and antistatic
agents.
[0095] The materials may be compounded by conventional methods,
such as melt mixing in a single- or twin-screw extruder, a Banbury
mixer, an internal mixer, a two-roll mill, or a ribbon mixer. The
core or, in the case of a multilayer core, the center and
intermediate layer or layers may be formed by usual methods, for
example by injection molding and compression molding. The core may
be ground to a desired diameter. Grinding can also be used to
remove flash, pin marks, and gate marks due to the molding
process.
[0096] A cover layer is molded over the core. In various
embodiments, the third thermoplastic material used to make the
cover may preferably include thermoplastic polyurethane elastomers,
thermoplastic polyurea elastomers, and the metal cation salts of
copolymers of ethylene with ethylenically unsaturated carboxylic
acids.
[0097] The cover may be formed on the core by injection molding,
compression molding, casting, and so on. For example, when the
cover is formed by injection molding, a core fabricated beforehand
may be set inside a mold, and the cover material may be injected
into the mold. The cover is typically molded on the core by
injection molding or compression molding. Alternatively, another
method that may be used involves pre-molding a pair of half-covers
from the cover material by die casting or another molding method,
enclosing the core in the half-covers, and compression molding at,
for example, between 120.degree. C. and 170.degree. C. for a period
of 1 to 5 minutes to attach the cover halves around the core. The
core may be surface-treated before the cover is formed over it to
increase the adhesion between the core and the cover. Nonlimiting
examples of suitable surface preparations include mechanically or
chemically abrasion, corona discharge, plasma treatment, or
application of an adhesion promoter such as a silane or of an
adhesive. The cover typically has a dimple pattern and profile to
provide desirable aerodynamic characteristics to the golf ball.
[0098] In various embodiments, the material used to make the cover
may preferably include thermoplastic polyurethane elastomer,
thermoplastic polyurea elastomer, ionomer resin, or combinations of
these or thermoset polyurethane elastomer or polyurea
elastomer.
[0099] The golf balls can be of any size, although the USGA
requires that golf balls used in competition have a diameter of at
least 1.68 inches (42.672 mm) and a weight of no greater than 1.62
ounces (45.926 g). For play outside of USGA competition, the golf
balls can have smaller diameters and be heavier.
[0100] After a golf ball has been molded, it may undergo various
further processing steps such as buffing, painting and marking. In
a particularly preferred embodiment of the invention, the golf ball
has a dimple pattern that coverage of 65% or more of the surface.
The golf ball typically is coated with a durable,
abrasion-resistant and relatively non-yellowing finish coat.
[0101] While the best modes for carrying out the invention have
been described in detail, those familiar with the art to which this
invention relates will recognize various alternative designs and
embodiments for practicing the invention within the scope of the
appended claims. It is intended that all matter contained in the
above description or shown in the accompanying drawings shall be
interpreted as illustrative only and not as limiting.
* * * * *