U.S. patent application number 14/968587 was filed with the patent office on 2016-04-07 for golf balls containing multi-layered cores with foam center and thermoplastic outer layers.
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, Derek A. Ladd, Michael Michalewich, Shawn Ricci, Michael J. Sullivan.
Application Number | 20160096077 14/968587 |
Document ID | / |
Family ID | 55632066 |
Filed Date | 2016-04-07 |
United States Patent
Application |
20160096077 |
Kind Code |
A1 |
Sullivan; Michael J. ; et
al. |
April 7, 2016 |
Golf Balls Containing Multi-Layered Cores With Foam Center and
Thermoplastic Outer Layers
Abstract
Golf ball multi-layered core sub-assemblies and the resulting
golf balls are provided. The core structure includes a foam inner
core (center); and intermediate and outer core layers. Foamed
polyurethane is preferably used to make the inner core. The
intermediate and outer core layers are preferably made from
non-foamed thermoplastic compositions such as ethylene acid
copolymer ionomers that are partially or highly neutralized,
polyester-polyether block copolymers, polyether-amide block
copolymers, and blends thereof. The core layers have different
hardness and specific gravity levels. The ball further includes a
cover having at least one layer. The core structure and resulting
ball have relatively good resiliency.
Inventors: |
Sullivan; Michael J.; (Old
Lyme, CT) ; Ladd; Derek A.; (Acushnet, MA) ;
Binette; Mark L.; (Mattapoisett, MA) ; Comeau;
Brian; (Berkley, MA) ; Michalewich; Michael;
(Norton, MA) ; Ricci; Shawn; (New Bedford,
MA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Acushnet Company |
Fairhaven |
MA |
US |
|
|
Assignee: |
Acushnet Company
Fairhaven
MA
|
Family ID: |
55632066 |
Appl. No.: |
14/968587 |
Filed: |
December 14, 2015 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
14947141 |
Nov 20, 2015 |
|
|
|
14968587 |
|
|
|
|
13911344 |
Jun 6, 2013 |
9192820 |
|
|
14947141 |
|
|
|
|
Current U.S.
Class: |
473/376 |
Current CPC
Class: |
A63B 37/0043 20130101;
A63B 37/0058 20130101; C08G 18/7664 20130101; A63B 37/0033
20130101; A63B 37/0045 20130101; A63B 37/0064 20130101; A63B
37/0031 20130101; A63B 37/0047 20130101; A63B 37/0066 20130101;
C08G 18/3206 20130101; A63B 37/0092 20130101; C08G 18/792 20130101;
A63B 37/0091 20130101; C08G 18/6685 20130101; A63B 37/0063
20130101; A63B 37/0062 20130101; C08G 18/7671 20130101; A63B
37/0024 20130101; A63B 37/0051 20130101; C08G 18/725 20130101; A63B
37/0044 20130101; A63B 37/0035 20130101; A63B 37/0039 20130101;
C08G 18/324 20130101; C08G 18/4854 20130101; C08G 18/6677 20130101;
C08G 2101/0083 20130101; C08G 18/246 20130101; A63B 37/0076
20130101; A63B 37/0032 20130101 |
International
Class: |
A63B 37/00 20060101
A63B037/00 |
Claims
1. A core assembly for a golf ball, comprising: i) an inner core
layer comprising a foamed composition, the inner core layer having
a diameter in the range of about 0.100 to about 1.100 inches, a
specific gravity (SG.sub.inner), and an outer surface hardness
(H.sub.inner core surface) and a center hardness (H.sub.inner core
center), the H.sub.inner core surface being greater than the
H.sub.inner core center to provide a positive hardness gradient;
ii) an intermediate core layer comprising a first non-foamed
thermoplastic composition, the composition comprising an elastomer
selected from the group consisting of polyester-polyether block
copolymers, polyether-amide block copolymers, and blends thereof,
the intermediate layer being disposed about the inner core and
having a thickness in the range of about 0.050 to about 0.400
inches, a specific gravity (SG.sub.intermediate), and an outer
surface hardness (H.sub.outer surface of IC) and an inner surface
hardness (H.sub.inner surface of IC), the H.sub.outer surface of IC
being the same or less than the H.sub.inner surface of IC to
provide a zero or negative hardness gradient; and iii) an outer
core layer comprising a second non-foamed thermoplastic
composition, the composition comprising an ethylene acid copolymer
containing acid groups such that at least 70% of the acid groups
are neutralized, the outer core layer being disposed about the
intermediate core layer and having a thickness in the range of
about 0.100 to about 0.750 inches, a specific gravity
(SG.sub.outer), and an outer surface hardness (H.sub.outer surface
of OC) and an inner surface hardness (H.sub.inner surface of OC),
the H.sub.outer surface of OC being greater than the H.sub.inner
surface of OC to provide a positive hardness gradient, wherein the
SG.sub.outer, is greater than the SG.sub.inner, and the
SG.sub.intermediate is greater than the SG.sub.inner.
2. The core assembly of claim 1, wherein the inner core comprises a
foamed polyurethane composition.
3. The core assembly of claim 2, wherein the foamed polyurethane
composition is prepared by adding water to a mixture of
polyisocyanate, polyol, and curing agent compounds, surfactant and
catalyst, the water being added in a sufficient amount to cause the
mixture to foam.
4. The core assembly of claim 1, wherein the ethylene acid
copolymer is an E/X/Y-type copolymer, wherein E is ethylene, X is a
C.sub.3-C.sub.8 .alpha.,.beta.-ethylenically unsaturated carboxylic
acid present in an amount of 10 to 20 wt. %, based on total weight
of the copolymer, and Y is an acrylate selected from alkyl
acrylates and aryl acrylates present in an amount of 0 to 50 wt. %,
based on total weight of the copolymer, and wherein greater than
70% of the acid groups present in the composition are neutralized
with a metal ion.
5. The core assembly of claim 1, wherein the inner core has a
diameter in the range of about 0.100 to about 0.500 inches and
specific gravity in the range of about 0.25 to about 0.95 g/cc.
6. The core assembly of claim 1, wherein the inner core has a
diameter in the range of about 0.40 to about 0.80 inches and
specific gravity in the range of about 0.30 to about 0.80 g/cc.
7. The core assembly of claim 1, wherein the H.sub.inner core
center is in the range of about 10 Shore C or less to about 50
Shore C and the H.sub.inner core surface is in the range of about
15 Shore C to about 60 Shore C.
8. The core assembly of claim 1, wherein the inner surface hardness
of the intermediate core (H.sub.inner surface of IC) is in the
range of about 35 Shore C to about 96 Shore C, and the outer
surface hardness of the intermediate core (H.sub.outer surface of
IC) is in the range of about 32 Shore C to and about 93 Shore
C.
9. The core assembly of claim 1, wherein the outer core layer has a
thickness in the range of about 0.150 to about 0.650 inches and
specific gravity in the range of about 0.90 to about 2.90 g/cc.
10. The core assembly of claim 1, wherein the H.sub.inner surface
of OC is in the range of about 40 Shore C to about 87 Shore C and
the H.sub.outer surface of OC is in the range of about 43 Shore C
to about 90 Shore C.
11. A core assembly for a golf ball, comprising: i) an inner core
layer comprising a foamed composition, the inner core layer having
a diameter in the range of about 0.100 to about 1.100 inches, a
specific gravity (SG.sub.inner), and an outer surface hardness
(H.sub.inner core surface) and a center hardness (H.sub.inner core
center), the H.sub.inner core surface being greater than the
H.sub.inner core center to provide a positive hardness gradient;
ii) an intermediate core layer comprising a first non-foamed
thermoplastic composition, the composition comprising an elastomer
selected from the group consisting of polyester-polyether block
copolymers, polyether-amide block copolymers, and blends thereof,
the intermediate layer being disposed about the inner core and
having a thickness in the range of about 0.050 to about 0.400
inches, a specific gravity (SG.sub.intermediate), and an outer
surface hardness (H.sub.outer surface of IC) and an inner surface
hardness (H.sub.inner surface of IC), the H.sub.outer surface of IC
being greater than the H.sub.inner surface of IC to provide a
positive hardness gradient; and iii) an outer core layer comprising
a second non-foamed thermoplastic composition, the composition
comprising an ethylene acid copolymer containing acid groups such
that at least 70% of the acid groups are neutralized, the outer
core layer being disposed about the intermediate core layer and
having a thickness in the range of about 0.100 to about 0.750
inches, a specific gravity (SG.sub.outer), and an outer surface
hardness (H.sub.outer surface of OC) and an inner surface hardness
(H.sub.inner surface of OC), the H.sub.outer surface of OC being
the same or less than the H.sub.inner surface of OC to provide a
zero or negative hardness gradient, wherein the SG.sub.outer, is
greater than the SG .sub.inner, and the SG.sub.intermediate is
greater than the SG.sub.inner.
12. The core assembly of claim 11, wherein the inner core comprises
a foamed polyurethane composition.
13. The core assembly of claim 11, wherein the H.sub.inner core
center is in the range of about 10 Shore C to about 50 Shore C and
the H.sub.inner core surface is in the range of about 13 Shore C to
about 60 Shore C.
14. The core assembly of claim 11, wherein the inner surface
hardness of the intermediate core (H.sub.inner surface of IC) is in
the range of about 34 Shore C to about 93 Shore C, and the outer
surface hardness of the intermediate core (H.sub.outer surface of
IC) is in the range of about 37 Shore C to and about 96 Shore
C.
15. The of claim 11, wherein the H.sub.inner surface of OC is in
the range of about 42 Shore C to about 96 Shore C and the
H.sub.outer surface of OC is in the range of about 40 Shore C to
about 93 Shore C.
16. A core assembly for a golf ball, comprising: i) an inner core
layer comprising a foamed composition, the inner core layer having
a diameter in the range of about 0.100 to about 1.100 inches, a
specific gravity (SG.sub.inner), and an outer surface hardness
(H.sub.inner core surface) and a center hardness (H.sub.inner core
center), the H.sub.inner core surface being greater than the
H.sub.inner core center to provide a positive hardness gradient;
ii) an intermediate core layer comprising a first non-foamed
thermoplastic composition, the composition comprising an elastomer
selected from the group consisting of polyester-polyether block
copolymers, polyether-amide block copolymers, and blends thereof,
the intermediate layer being disposed about the inner core and
having a thickness in the range of about 0.050 to about 0.400
inches, a specific gravity (SG.sub.intermediate), and an outer
surface hardness (H.sub.outer surface of IC) and an inner surface
hardness (H.sub.inner surface of IC), the H.sub.outer surface of IC
being the same or less than the H.sub.inner surface of IC to
provide a zero or negative hardness gradient; and iii) an outer
core layer comprising a second non-foamed thermoplastic
composition, the composition comprising an ethylene acid copolymer
containing acid groups such that at least 70% of the acid groups
are neutralized, the outer core layer being disposed about the
intermediate core layer and having a thickness in the range of
about 0.100 to about 0.750 inches, a specific gravity
(SG.sub.outer), and an outer surface hardness (H.sub.outer surface
of OC).sub.and an inner surface hardness (H.sub.inner surface of
OC), the H.sub.outer surface of OC being the same or less than the
H.sub.inner surface of OC to provide a zero or negative hardness
gradient, p1 wherein the SG.sub.outer, is greater than the
SG.sub.inner, and the SG.sub.intermediate is greater than the
SG.sub.inner.
17. The core assembly of claim 16, wherein the inner core comprises
a foamed polyurethane composition.
18. The core assembly of claim 16, wherein the H.sub.inner core
center is in the range of about 10 Shore C to about 50 Shore C and
the H.sub.inner core surface is in the range of about 13 Shore C to
about 60 Shore C.
19. The core assembly of claim 16, wherein the inner surface
hardness of the intermediate core (H.sub.inner surface of IC) is in
the range of about 34 Shore C to about 96 Shore C, and the outer
surface hardness of the intermediate core (H.sub.outer surface of
IC) is in the range of about 30 Shore C to and about 93 Shore
C.
20. The core assembly of claim 16, wherein the H.sub.inner surface
of OC is in the range of about 42 Shore C to about 96 Shore C and
the H.sub.outer surface of OC is in the range of about 40 Shore C
to about 93 Shore C.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of co-pending,
co-assigned U.S. patent application Ser. No. 14/947,141 having a
filing date of Nov. 20, 2015, which is a divisional of co-assigned
U.S. patent application Ser. No. 13/911,344 having a filing date of
Jun. 6, 2013, now U.S. Pat. No. 9,192,820 issued on Nov. 24, 2015,
the entire disclosures of which are hereby incorporated by
reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates generally to multi-piece golf
balls containing a solid core comprising layers made of foam
compositions and non-foam thermoplastic compositions. Particularly,
the multi-layered core has a foam inner core (center) and outer
non-foam thermoplastic core layer. A non-foam thermoplastic
intermediate core layer may be disposed between the foam center and
outer thermoplastic layer. The core layers have different hardness
gradients and specific gravity values. The ball further includes a
cover having at least one layer.
[0004] 2. Brief Review of the Related Art
[0005] Professional and recreational golfers normally play with
multi-piece, solid golf balls. Such balls typically include an
inner core made of a natural or synthetic rubber such as
polybutadiene, styrene butadiene, or polyisoprene. The core may be
made of one or more material layers. The ball further includes a
cover disposed about the core. The cover protects the inner core
and makes the ball more durable. The cover also may be
multi-layered and may be made from a variety of materials including
ethylene acid copolymer ionomers, polyamides, polyesters,
polyurethanes, and polyureas. The ball may further include one or
more casing or mantle layers disposed between the core and
cover.
[0006] Manufacturers of golf balls use different materials to
impart specific features to the ball. For example, the resiliency
and rebounding performance of the golf ball are important
properties and are based primarily on the composition and
construction of the core. The core acts as an engine or spring for
the ball. In general, the rebounding performance of the ball is
determined by calculating its initial velocity after being struck
by the face of the golf club and its outgoing velocity after making
impact with a hard surface. More particularly, the "Coefficient of
Restitution" or "COR" of a golf ball refers to the ratio of a
ball's rebound velocity to its initial incoming velocity when the
ball is fired out of an air cannon into a rigid vertical plate. The
COR for a golf ball is written as a decimal value between zero and
one. A golf ball may have different COR values at different initial
velocities. The United States Golf Association (USGA) sets limits
on the initial velocity of the ball so one objective of golf ball
manufacturers is to maximize COR under such conditions. Balls with
a higher rebound velocity have a higher COR value. Such golf balls
rebound faster, retain more total energy when struck with a club,
and have longer flight distance.
[0007] The durability, spin rate, and feel of the ball also are
important properties. In general, the durability of the ball refers
to the impact-resistance of the ball. Balls having low durability
appear worn and damaged even when such balls are used only for
brief time periods. In some instances, the cover may be cracked or
torn. The spin rate refers to the ball's rate of rotation after it
is hit by a club. Balls having a relatively high spin rate are
advantageous for short distance shots made with irons and wedges.
Professional and highly skilled amateur golfers can place a back
spin more easily on such balls. This helps a player better control
the ball and improves shot accuracy and placement. By placing the
right amount of spin on the ball, the player can get the ball to
stop precisely on the green or place a fade on the ball during
approach shots. On the other hand, recreational players who cannot
intentionally control the spin of the ball when hitting it with a
club are less likely to use high spin balls. For such players, the
ball can spin sideways more easily and drift far-off the course,
especially if it is hooked or sliced. Meanwhile, the "feel" of the
ball generally refers to the sensation that a player experiences
when striking the ball with the club and it is a difficult property
to quantify. Most players prefer balls having a soft feel, because
the player experience a more natural and comfortable sensation when
their club face makes contact with these balls. Balls having a
softer feel are particularly desirable when making short shots
around the green, because the player senses more with such balls.
The feel of the ball primarily depends upon the hardness and
compression of the ball.
[0008] Manufacturers of golf balls are constantly looking to new
materials for improving the playing performance properties of the
ball. For example, Puckett and Cadorniga, U.S. Pat. Nos. 4,836,552
and 4,839,116 disclose one-piece, short distance golf balls made of
a foam composition comprising a thermoplastic polymer (ethylene
acid copolymer ionomer such as Surlyn.RTM.) and filler material
(microscopic glass bubbles). The density of the composition
increases from the center to the surface of the ball. Thus, the
ball has relatively dense outer skin and a cellular inner core.
According to the '552 and '116 Patents, by providing a short
distance golf ball, which will play approximately 50% of the
distance of a conventional golf ball, the land requirements for a
golf course can be reduced 67% to 50%.
[0009] Gentiluomo, U.S. Pat. No. 5,104,126 discloses a three-piece
golf ball (FIG. 2) containing a high density center (3) made of
steel, surrounded by an outer core (4) of low density resilient
syntactic foam composition, and encapsulated by an ethylene acid
copolymer ionomer (Surlyn.RTM.) cover (5). The '126 Patent defines
the syntactic foam as being a low density composition consisting of
granulated cork or hollow spheres of either phenolic, epoxy,
ceramic or glass, dispersed within a resilient elastomer.
[0010] Aoyama, U.S. Pat. Nos. 5,688,192 and 5,823,889 disclose a
golf ball containing a core, wherein the core comprising an inner
and outer portion, and a cover made of a material such as balata
rubber or ethylene acid copolymer ionomer. The core is made by
foaming, injecting a compressible material, gasses, blowing agents,
or gas-containing microspheres into polybutadiene or other core
material. According to the '889 Patent, polyurethane compositions
may be used. The compressible material, for example, gas-containing
compressible cells may be dispersed in a limited part of the core
so that the portion containing the compressible material has a
specific gravity of greater than 1.00. Alternatively, the
compressible material may be dispersed throughout the entire core.
In one embodiment, the core comprises an inner and outer portion.
In another embodiment, the core comprises inner and outer
layers.
[0011] Sullivan and Binette, U.S. Pat. No. 5,833,553 discloses a
golf ball having core with a coefficient of restitution of at least
0.650 and a cover with a thickness of at least 3.6 mm (0.142
inches) and a Shore D hardness of at least 60. According to the
'553 Patent, the combination of a soft core with a thick, hard
cover results in a ball having better distance. The '553 Patent
discloses that the core may be formed from a uniform composition or
may be a dual or multi-layer core, and it may be foamed or
unfoamed. Polybutadiene rubber, natural rubber, metallocene
catalyzed polyolefins, and polyurethanes are described as being
suitable materials for making the core.
[0012] Sullivan and Ladd, U.S. Pat. No. 6,688,991 discloses a golf
ball containing a low specific gravity core and an optional
intermediate layer. This sub-assembly is encased within a high
specific gravity cover with Shore D hardness in the range of about
40 to about 80. The core is preferably made from a highly
neutralized thermoplastic polymer such as ethylene acid copolymer
which has been foamed. The cover preferably has high specific
gravity fillers dispersed therein.
[0013] Nesbitt, U.S. Pat. No. 6,767,294 discloses a golf ball
comprising: i) a pressurized foamed inner center formed from a
thermoset material, a thermoplastic material, or combinations
thereof, a blowing agent and a cross-linking agent and, ii) an
outer core layer formed from a second thermoset material, a
thermoplastic material, or combinations thereof. Additionally, a
barrier resin or film can be applied over the outer core layer to
reduce the diffusion of the internal gas and pressure from the
nucleus (center and outer core layer). Preferred polymers for the
barrier layer have low permeability such as Saran.RTM. film (poly
(vinylidene chloride), Barex.RTM. resin (acyrlonitrile-co-methyl
acrylate), poly (vinyl alcohol), and PET film (polyethylene
terephthalate). The '294 Patent does not disclose core layers
having different hardness gradients.
[0014] Sullivan, Ladd, and Hebert, U.S. Pat. No. 7,708,654
discloses a golf ball having a foamed intermediate layer. Referring
to FIG. 1 in the '654 Patent, the golf ball includes a core (12),
an intermediate layer (14) made of a highly neutralized polymer
having a reduced specific gravity (less than 0.95), and a cover
(16). According to the '654 Patent, the intermediate layer can be
an outer core, a mantle layer, or an inner cover. The reduction in
specific gravity of the intermediate layer is caused by foaming the
composition of the layer and this reduction can be as high as 30%.
The '654 Patent discloses that other foamed compositions such as
foamed polyurethanes and polyureas may be used to form the
intermediate layer.
[0015] Tutmark, U.S. Pat. No. 8,272, 971 is directed to golf balls
containing an element that reduces the distance of the ball's
flight path. In one embodiment, the ball includes a core and cover.
A cavity is formed between core and cover and this may be filled by
a foamed polyurethane "middle layer" in order to dampen the ball's
flight properties. The foam of the middle layer is relatively light
in weight; and the core is relatively heavy and dense. According to
the '971 Patent, when a golfer strikes the ball with a club, the
foam in the middle layer actuates and compresses, thereby absorbing
much of the impact from the impact of the ball.
[0016] One disadvantage with golf balls having a foam core is the
ball tends to have low resiliency. That is, the velocity of the
ball tends to be low after being hit by a club and the ball
generally travels short distances. Golf balls having foam inner
cores are often referred to as reduced distance balls. There is a
need for new balls having a foam core with improved resiliency that
will allow players to generate higher initial ball speed. This will
allow players to make longer distance shots. The present invention
provides new foam core constructions having improved resiliency as
well as other advantageous properties, features, and benefits. The
invention also encompasses golf balls containing the improved core
constructions.
SUMMARY OF THE INVENTION
[0017] The present invention provides a multi-piece golf ball
comprising a solid core having two layers and a cover having at
least one layer. The golf ball may have different constructions.
For example, in one version, the multi-layered core includes: i) an
inner core (center) comprising a foamed composition, wherein the
inner core has a diameter in the range of about 0.100 to about
1.100 inches and a specific gravity (SG.sub.inner): ii) an
intermediate layer comprising a first non-foamed thermoplastic
material, wherein the intermediate layer is disposed about the
inner core and has a thickness in the range of about 0.050 to about
0.400 inches and a specific gravity (SG.sub.intermediate); and iii)
an outer core layer comprising a second non-foamed thermoplastic
material, wherein the outer cover layer is disposed about the
intermediate core layer and has a thickness in the range of about
0.100 to about 0.750 inches and a specific gravity (SG.sub.outer).
Preferably, the SG.sub.inner is less than the SG.sub.intermediate
and SG.sub.outer. That is, each of the SG.sub.outer and
SG.sub.intermediate values is greater than the SG.sub.inner
value.
[0018] Preferably, the inner core comprises a foam polyurethane
composition prepared from a mixture comprising polyisocyanate,
polyol, and curing agent compounds, and blowing agent. Aromatic and
aliphatic polyisocyanates may be used. The foamed polyurethane
composition may be prepared by using water as a blowing agent. The
water is added to the mixture in a sufficient amount to cause the
mixture to foam. Surfactants and catalysts, such as zinc and
tin-based catalysts, may be included in the mixture.
[0019] Different thermoplastic materials may be used to form the
intermediate and outer core layers. For example, the thermoplastic
material used to make the intermediate core layer may be an
elastomer selected from the group consisting of polyester-polyether
block copolymers, polyether-amide block copolymers, and blends
thereof. An ethylene acid copolymer containing acid groups such
that at least 70% of the acid groups are neutralized, preferably
greater than 90%, may be used to make the outer core layer in one
example. In another example, the above thermoplastic elastomers may
be used to make the outer core and the ethylene acid copolymer may
be used to make the intermediate core layer.
[0020] The intermediate and outer core layers may have different
thicknesses and properties. For example, the intermediate core
layer may have a thickness in the range of about 0.070 to about
0.130 inches and a specific gravity in the range of about 0.85 to
about 3.10 g/cc. In another example, the outer core layer may have
a thickness in the range of about 0.250 to about 0.750 inches and a
specific gravity in the range of about 0.60 to about 2.90 g/cc.
[0021] Also, the core layers may have different hardness gradients.
For example, each core layer may have a positive, zero, or negative
hardness gradient. In one embodiment, the inner core has a positive
hardness gradient; the intermediate core layer has a zero or
negative hardness gradient; and the outer core layer has a positive
hardness gradient. In a second embodiment, each of the core layers
has a positive hardness gradient. In yet another embodiment, the
inner core has a positive hardness gradient; the intermediate core
layer has a positive hardness gradient; and the outer core layer
has a zero or negative hardness gradient. In another alternative
version, each of the inner; intermediate; and outer core layers has
a positive hardness gradient.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] The novel features that are characteristic of the present
invention are set forth in the appended claims. However, the
preferred embodiments of the invention, together with further
objects and attendant advantages, are best understood by reference
to the following detailed description in connection with the
accompanying drawings in which:
[0023] FIG. 1 is a perspective view of a spherical inner core made
of a foamed composition in accordance with the present
invention;
[0024] FIG. 2 is a perspective view of one embodiment of upper and
lower mold cavities used to make the multi-layered cores of the
present invention;
[0025] FIG. 3 is a partial cut-away perspective view of a
multi-layered core having inner, intermediate, and outer core
layers made in accordance with the present invention;
[0026] FIG. 4 is a cross-sectional view of a four-piece golf ball
having a multi-layered core made in accordance with the present
invention;
[0027] FIG. 5 is a cross-sectional view of a five-piece golf ball
having a multi-layered core made in accordance with the present
invention;
[0028] FIG. 6 is a cross-sectional view of a six-piece golf ball
having a multi-layered core made in accordance with the present
invention;
[0029] FIG. 7A is a graph showing the hardness of a three-layered
core having a diameter of 0.5 inches (foam center; thermoplastic
intermediate layer; and thermoplastic outer layer) at different
points in the core structure per one example of this invention;
[0030] FIG. 7B is a graph showing the hardness of a three-layered
core having a diameter of 0.5 inches (foam center; thermoplastic
intermediate layer; and thermoplastic outer layer) at different
points in the core structure per a second example of this
invention;
[0031] FIG. 7C is a graph showing the hardness of a three-layered
core having a diameter of 0.5 inches (foam center; thermoplastic
intermediate layer; and thermoplastic outer layer) at different
points in the core structure per a third example of this invention;
and
[0032] FIG. 7D is a graph showing the hardness of a three-layered
core having a diameter of 0.75 inches (foam center; thermoplastic
intermediate layer; and thermoplastic outer layer) at different
points in the core structure per a fourth example of this
invention.
DETAILED DESCRIPTION OF THE INVENTION
[0033] Golf Ball Constructions
[0034] Golf balls having various constructions may be made in
accordance with this invention. For example, golf balls having
one-piece, two-piece, three-piece, four-piece, and five or
more-piece constructions with the term "piece" referring to any
core, cover or intermediate layer of a golf ball construction.
Representative illustrations of such golf ball constructions are
provided and discussed further below. The term, "layer" as used
herein means generally any spherical portion of the golf ball. In
one version, a three-piece golf ball containing a dual-layered core
and single-layered cover is made. The dual-core includes an inner
core (center) made of a foam composition and a surrounding outer
core layer made of a non-foamed thermoplastic composition. In
another version, a four-piece golf ball containing a dual-core
including an inner core (center) made of a foam composition and a
surrounding outer core layer made of a non-foamed thermoplastic
composition and a dual-cover (inner cover and outer cover layers)
is made. In another four-piece golf ball embodiment, a four-piece
ball containing a three-layered core (including a foam center and
non-foamed thermoplastic intermediate and outer core layers) and a
single-layered cover is made. In still another construction, a
five-piece ball containing a three-layered core (including a foam
center, and non-foamed thermoplastic intermediate and outer core
layers) may be made. In the five-piece ball, the cover includes
inner and outer cover layers. The diameter and thickness of the
different layers along with properties such as hardness and
compression may vary depending upon the construction and desired
playing performance properties of the golf ball. The
above-described examples refer to the inner core as being made of
the foam composition; however, it should be understood that any one
or more of the layers of any of the one, two, three, four, or five,
or more-piece (layered) balls described herein may comprise the
foam composition. That is, any of the inner (center) core and/or
intermediate core layers and/or outer core layers, and/or cover
layers may comprise the foam composition of this invention.
[0035] Also, when more than one thermoplastic layer is used in the
golf ball, the thermoplastic composition in the respective layers
may be the same or different, and the composition may have the same
or different hardness values. For example, a three-layered core
assembly may be made with a foam inner core and an intermediate
core comprising a first non-foamed thermoplastic composition and
outer core layer comprising a second non-foamed thermoplastic
composition. The first and second thermoplastic compositions may be
the same, or the respective compositions may be different.
Furthermore, in some examples, the thermoplastic material in a
particular thermoplastic layer may constitute two, three, or more
"sub-layers" of the same or different thermoplastic composition.
That is, each thermoplastic layer can be formed from one or more
sub-layers of the same or different thermoplastic material. In such
instances, the thermoplastic layer can be considered a composite
layer made of multiple independent and distinct component
layers.
[0036] Foam Inner Core
[0037] In general, foam compositions are made by forming gas
bubbles in a polymer mixture using a foaming (blowing) agent. As
the bubbles form, the mixture expands and forms a foam composition
that can be molded into an end-use product having either an open or
closed cellular structure. Flexible foams generally have an open
cell structure, where the cells walls are incomplete and contain
small holes through which liquid and air can permeate. Such
flexible foams are used for automobile seats, cushioning,
mattresses, and the like. Rigid foams generally have a closed cell
structure, where the cell walls are continuous and complete, and
are used for used for automobile panels and parts, building
insulation and the like.
[0038] In the present invention, the inner core (center) comprises
a lightweight foam thermoplastic or thermoset polymer composition
that may range from a relatively rigid foam to a very flexible
foam. Referring to FIG. 1, a foamed inner core (4) having a
geometric center (6) and outer skin (8) may be prepared in
accordance with this invention.
[0039] A wide variety of thermoplastic and thermoset materials may
be used in forming the foam composition of this invention
including, for example, polyurethanes; polyureas; copolymers,
blends and hybrids of polyurethane and polyurea; olefin-based
copolymer ionomer resins (for example, Surlyn.RTM. ionomer resins
and DuPont HPF.RTM. 1000 and HPF.RTM. 2000, commercially available
from DuPont; Iotek.RTM. ionomers, commercially available from
ExxonMobil Chemical Company; Amplify.RTM. IO ionomers onomers of
ethylene acrylic acid copolymers, commercially available from Dow
Chemical Company; and Clarix.RTM. ionomer resins, commercially
available from A. Schulman Inc.); polyethylene, including, for
example, low density polyethylene, linear low density polyethylene,
and high density polyethylene; polypropylene; rubber-toughened
olefin polymers; acid copolymers, for example, poly(meth)acrylic
acid, which do not become part of an ionomeric copolymer;
plastomers; flexomers; styrene/butadiene/styrene block copolymers;
styrene/ethylene-butylene/styrene block copolymers; dynamically
vulcanized elastomers; copolymers of ethylene and vinyl acetates;
copolymers of ethylene and methyl acrylates; polyvinyl chloride
resins; polyamides, poly(amide-ester) elastomers, and graft
copolymers of ionomer and polyamide including, for example,
Pebax.RTM. thermoplastic polyether block amides, commercially
available from Arkema Inc; cross-linked trans-polyisoprene and
blends thereof; polyester-based thermoplastic elastomers, such as
Hytrel.RTM., commercially available from DuPont or RiteFlex.RTM.,
commercially available from Ticona Engineering Polymers;
polyurethane-based thermoplastic elastomers, such as
Elastollan.RTM., commercially available from BASF; synthetic or
natural vulcanized rubber; and combinations thereof. Castable
polyurethanes, polyureas, and hybrids of polyurethanes-polyureas
are particularly desirable because these materials can be used to
make a golf ball having good playing performance properties as
discussed further below. By the term, "hybrids of polyurethane and
polyurea," it is meant to include copolymers and blends
thereof.
[0040] Basically, polyurethane compositions contain urethane
linkages formed by the reaction of a multi-functional isocyanate
containing two or more NCO groups with a polyol having two or more
hydroxyl groups (OH--OH) sometimes in the presence of a catalyst
and other additives. Generally, polyurethanes can be produced in a
single-step reaction (one-shot) or in a two-step reaction via a
prepolymer or quasi-prepolymer. In the one-shot method, all of the
components are combined at once, that is, all of the raw
ingredients are added to a reaction vessel, and the reaction is
allowed to take place. In the prepolymer method, an excess of
polyisocyanate is first reacted with some amount of a polyol to
form the prepolymer which contains reactive NCO groups. This
prepolymer is then reacted again with a chain extender or curing
agent polyol to form the final polyurethane. Polyurea compositions,
which are distinct from the above-described polyurethanes, also can
be formed. In general, polyurea compositions contain urea linkages
formed by reacting an isocyanate group (--N.dbd.C.dbd.O) with an
amine group (NH or NH.sub.2). Polyureas can be produced in similar
fashion to polyurethanes by either a one shot or prepolymer method.
In forming a polyurea polymer, the polyol would be substituted with
a suitable polyamine. Hybrid compositions containing urethane and
urea linkages also may be produced. For example, when polyurethane
prepolymer is reacted with amine-terminated curing agents during
the chain-extending step, any excess isocyanate groups in the
prepolymer will react with the amine groups in the curing agent.
The resulting polyurethane-urea composition contains urethane and
urea linkages and may be referred to as a hybrid. In another
example, a hybrid composition may be produced when a polyurea
prepolymer is reacted with a hydroxyl-terminated curing agent. A
wide variety of isocyanates, polyols, polyamines, and curing agents
can be used to form the polyurethane and polyurea compositions as
discussed further below.
[0041] To prepare the foamed polyurethane, polyurea, or other
polymer composition, a foaming agent is introduced into the polymer
formulation. In general, there are two types of foaming agents:
physical foaming agents and chemical foaming agents.
[0042] Physical foaming agents. These foaming agents typically are
gasses that are introduced under high pressure directly into the
polymer composition. Chlorofluorocarbons (CFCs) and partially
halogenated chlorofluorocarbons are effective, but these compounds
are banned in many countries because of their environmental side
effects. Alternatively, aliphatic and cyclic hydrocarbon gasses
such as isobutene and pentane may be used. Inert gasses, such as
carbon dioxide and nitrogen, also are suitable.
[0043] Chemical foaming agents. These foaming agents typically are
in the form of powder, pellets, or liquids and they are added to
the composition, where they decompose or react during heating and
generate gaseous by-products (for example, nitrogen or carbon
dioxide). The gas is dispersed and trapped throughout the
composition and foams it.
[0044] Preferably, a chemical foaming agent is used to prepare the
foam compositions of this invention. Chemical blowing agents may be
inorganic, such as ammonium carbonate and carbonates of alkalai
metals, or may be organic, such as azo and diazo compounds, such as
nitrogen-based azo compounds. Suitable azo compounds include, but
are not limited to, 2,2'-azobis(2-cyanobutane),
2,2'-azobis(methylbutyronitrile), azodicarbonamide,
p,p'-oxybis(benzene sulfonyl hydrazide), p-toluene sulfonyl
semicarbazide, p-toluene sulfonyl hydrazide. Other foaming agents
include any of the Celogens.RTM. sold by Crompton Chemical
Corporation, and nitroso compounds, sulfonylhydrazides, azides of
organic acids and their analogs, triazines, tri- and tetrazole
derivatives, sulfonyl semicarbazides, urea derivatives, guanidine
derivatives, and esters such as alkoxyboroxines. Also, foaming
agents that liberate gasses as a result of chemical interaction
between components such as mixtures of acids and metals, mixtures
of organic acids and inorganic carbonates, mixtures of nitriles and
ammonium salts, and the hydrolytic decomposition of urea may be
used. Water is a preferred foaming agent. When added to the
polyurethane formulation, water will react with the isocyanate
groups and form carbamic acid intermediates. The carbamic acids
readily decarboxylate to form an amine and carbon dioxide. The
newly formed amine can then further react with other isocyanate
groups to form urea linkages and the carbon dioxide forms the
bubbles to produce the foam.
[0045] During the decomposition reaction of certain chemical
foaming agents, more heat and energy is released than is needed for
the reaction. Once the decomposition has started, it continues for
a relatively long time period. If these foaming agents are used,
longer cooling periods are generally required. Hydrazide and
azo-based compounds often are used as exothermic foaming agents. On
the other hand, endothermic foaming agents need energy for
decomposition. Thus, the release of the gasses quickly stops after
the supply of heat to the composition has been terminated. If the
composition is produced using these foaming agents, shorter cooling
periods are needed. Bicarbonate and citric acid-based foaming
agents can be used as exothermic foaming agents.
[0046] Other suitable foaming agents include expandable
gas-containing microspheres. Exemplary microspheres consist of an
acrylonitrile polymer shell encapsulating a volatile gas, such as
isopentane gas. This gas is contained within the sphere as a
blowing agent. In their unexpanded state, the diameter of these
hollow spheres range from 10 to 17 .mu.m and have a true density of
1000 to 1300 kg/m.sup.3. When heated, the gas inside the shell
increases its pressure and the thermoplastic shell softens,
resulting in a dramatic increase of the volume of the microspheres.
Fully expanded, the volume of the microspheres will increase more
than 40 times (typical diameter values would be an increase from 10
to 40 .mu.m), resulting in a true density below 30 kg/m.sup.3 (0.25
lbs/gallon). Typical expansion temperatures range from
80-190.degree. C. (176-374.degree. F.). Such expandable
microspheres are commercially available as Expancel.RTM. from
Expancel of Sweden or Akzo Nobel.
[0047] As an alternative to chemical and physical foaming agents or
in addition to such foaming agents, as described above, other types
of fillers that lower the specific gravity of the composition can
be used in accordance with this invention. For example, polymeric,
ceramic, and glass unfilled microspheres having a density of 0.1 to
1.0 g/cc and an average particle size of 10 to 250 microns can be
used to help lower specific gravity of the composition and achieve
the desired density and physical properties.
[0048] Additionally, BASF polyurethane materials sold under the
trade name Cellasto.RTM. and Elastocell.RTM., microcellular
polyurethanes, Elastopor.RTM. H that is a closed-cell polyurethane
rigid foam, Elastoflex.RTM. W flexible foam systems,
Elastoflex.RTM. E semiflexible foam systems, Elastofoam.RTM.
flexible integrally-skinning systems, Elastolit.RTM. D/K/R integral
rigid foams, Elastopan.RTM. S, Elastollan.RTM. thermoplastic
polyurethane elastomers (TPUs), and the like may be used in
accordance with the present invention. Bayer also produces a
variety of materials sold as Texin.RTM. TPUs, Baytec.RTM. and
Vulkollan.RTM. elastomers, Baymer.RTM. rigid foams, Baydur.RTM.
integral skinning foams, Bayfit.RTM. flexible foams available as
castable, RIM grades, sprayable, and the like that may be used.
Additional foam materials that may be used herein include
polyisocyanurate foams and a variety of "thermoplastic" foams,
which may be cross-linked to varying extents using free-radical
(for example, peroxide) or radiation cross-linking (for example,
UV, IR, Gamma, EB irradiation). Also, foams may be prepared from
polybutadiene, polystyrene, polyolefin (including metallocene and
other single site catalyzed polymers), ethylene vinyl acetate
(EVA), acrylate copolymers, such as EMA, EBA, Nucrel.RTM.-type acid
co and terpolymers, ethylene propylene rubber (such as EPR, EPDM,
and any ethylene copolymers), styrene-butadiene, and SEBS (any
Kraton-type), PVC, PVDC, CPE (chlorinated polyethylene). Epoxy
foams, urea-formaldehyde foams, latex foams and sponge, silicone
foams, fluoropolymer foams and syntactic foams (hollow sphere
filled) also may be used.
[0049] In addition to the polymer and foaming agent, the foam
composition also may include other ingredients such as, for
example, cross-linking agents, chain extenders, surfactants, dyes
and pigments, coloring agents, fluorescent agents, adsorbents,
stabilizers, softening agents, impact modifiers, antioxidants,
antiozonants, and the like. The formulations used to prepare the
polyurethane foam compositions of this invention preferably contain
a polyol, polyisocyanate, water, an amine or hydroxyl curing agent,
surfactant, and a catalyst as described further below.
[0050] Properties of Polyurethane Foams
[0051] The polyurethane foam compositions of this invention have
numerous chemical and physical properties making them suitable for
core assemblies in golf balls. For example, there are properties
relating to the reaction of the isocyanate and polyol components
and blowing agent, particularly "cream time," "gel time," "rise
time," "tack-free time," and "free-rise density." In general, cream
time refers to the time period from the point of mixing the raw
ingredients together to the point where the mixture turns cloudy in
appearance or changes color and begins to rise from its initial
stable state. Normally, the cream time of the foam compositions of
this invention is within the range of about 20 to about 240
seconds. In general, gel time refers to the time period from the
point of mixing the raw ingredients together to the point where the
expanded foam starts polymerizing/gelling. Rise time generally
refers to the time period from the point of mixing the raw
ingredients together to the point where the reacted foam has
reached its largest volume or maximum height. The rise time of the
foam compositions of this invention typically is in the range of
about 60 to about 360 seconds. Tack-free time generally refers to
the time it takes for the reacted foam to lose its tackiness, and
the foam compositions of this invention normally have a tack-free
time of about 60 to about 3600 seconds. Free-rise density refers to
the density of the resulting foam when it is allowed to rise
unrestricted without a cover or top being placed on the mold.
[0052] The density of the foam is an important property and is
defines as the weight per unit volume (typically, kg/m.sup.3 or
lb/ft.sup.3 or g/cm.sup.3) and can be measured per ASTM D-1622. The
hardness, stiffness, and load-bearing capacity of the foam are
independent of the foam's density, although foams having a high
density typically have high hardness and stiffness. Normally, foams
having higher densities have higher compression strength.
Surprisingly, the foam compositions used to produce the inner core
of the golf balls per this invention have a relatively low density;
however, the foams are not necessarily soft and flexible, rather,
they may be relatively firm, rigid, or semi-rigid, depending upon
the desired golf ball properties. Tensile strength,
tear-resistance, and elongation generally refer to the foam's
ability to resist breaking or tearing, and these properties can be
measured per ASTM D-1623. The durability of foams is important,
because introducing fillers and other additives into the foam
composition can increase the tendency of the foam to break or tear
apart. In general, the tensile strength of the foam compositions of
this invention is in the range of about 20 to about 1000 psi
(parallel to the foam rise) and about 50 to about 1000 psi
(perpendicular to the foam rise) as measured per ASTM D-1623 at
23.degree. C. and 50% relative humidity (RH). Meanwhile, the flex
modulus of the foams of this invention is generally in the range of
about 5 to about 45 kPa as measured per ASTM D-790, and the foams
generally have a compressive modulus of 200 to 50,000 psi.
[0053] In another test, compression strength is measured on an
Instron machine according to ASTM D-1621. The foam is cut into
blocks and the compression strength is measured as the force
required to compress the block by 10%. In general, the compressive
strength of the foam compositions of this invention is in the range
of about 100 to about 1800 psi (parallel and perpendicular to the
foam rise) as measured per ASTM D-1621 at 23.degree. C. and 50%
relative humidity (RH). The test is conducted perpendicular to the
rise of the foam or parallel to the rise of the foam. The
Percentage (%) of Compression Set also can be used. This is a
measure of the permanent deformation of a foam sample after it has
been compressed between two metal plates under controlled time and
temperature condition (standard-22 hours at 70.degree. C.
(158.degree. F.)). The foam is compressed to a thickness given as a
percentage of its original thickness that remained "set."
Preferably, the Compression Set of the foam is less than ten
percent (10%), that is, the foam recovers to a point of 90% or
greater of its original thickness.
[0054] Methods of Preparing Foam Composition
[0055] The foam compositions of this invention may be prepared
using different methods. In one preferred embodiment, the method
involves preparing a castable composition comprising a reactive
mixture of a polyisocyanate, polyol, water, curing agent,
surfactant, and catalyst. A motorized mixer can be used to mix the
starting ingredients together and form a reactive liquid mixture.
Alternatively, the ingredients can be manually mixed together. An
exothermic reaction occurs when the ingredients are mixed together
and this continues as the reactive mixture is dispensed into the
mold cavities (otherwise referred to as half-molds or mold cups).
The mold cavities may be referred to as first and second, or upper
and lower, mold cavities. The mold cavities preferably are made of
metal such as, for example, brass or silicon bronze.
[0056] Referring to FIG. 2, the mold cavities are generally
indicated at (9) and (10). The lower and upper mold cavities (9,
10) are placed in lower and upper mold frame plates (11, 12). The
frame plates (11, 12) contain guide pins and complementary
alignment holes (not shown in drawing). The guide pins are inserted
into the alignment holes to secure the lower plate (11) to the
upper plate (12). The lower and upper mold cavities (9, 10) are
mated together as the frame plates (11, 12) are fastened. When the
lower and upper mold cavities (9, 10) are joined together, they
define an interior spherical cavity that houses the spherical core.
The upper mold contains a vent or hole (14) to allow for the
expanding foam to fill the cavities uniformly. A secondary overflow
chamber (16), which is located above the vent (14), can be used to
adjust the amount of foam overflow and thus adjust the density of
the core structure being molded in the cavities. As the lower and
upper mold cavities (9, 10) are mated together and sufficient heat
and pressure is applied, the foamed composition cures and
solidifies to form a relatively rigid and lightweight spherical
core. The resulting cores are cooled and then removed from the
mold.
[0057] Hardness of the Inner Core
[0058] As shown in FIG. 1, a foamed inner core (4) having a
geometric center (6) and outer skin (8) may be prepared per the
molding method discussed above. The outer skin (8) is generally a
non-foamed region that forms the outer surface of the inner core
structure. The resulting inner core preferably has a diameter
within a range of about 0.100 to about 1.100 inches. In one
example, the inner core may have a diameter in the range of about
0.100 to about 0.500 inches. In another example, the inner core may
have a diameter in the range of about 0.250 to about 1.000 inches.
In yet another example, the inner core may have a diameter within a
range of about 0.300 to about 0.800 inches. More particularly, the
inner core preferably has a diameter size with a lower limit of
about 0.10 or 0.12 or 0.15 or 0.25 or 0.30 or 0.35 or 0.45 or 0.55
inches and an upper limit of about 0.60 or 0.65 or 0.70 or 0.80 or
0.90 or 1.00 or 1.10 inches. The outer skin (8) of the inner core
is relatively thin preferably having a thickness of less than about
0.020 inches and more preferably less than 0.010 inches. In one
preferred embodiment, the foamed core has a "positive" hardness
gradient (that is, the outer skin of the inner core is harder than
its geometric center.)
[0059] For example, the geometric center hardness of the inner core
(H.sub.inner core center), as measured in Shore C units, is about
10 Shore C or greater and preferably has a lower limit of about 10
or 16 or 20 or 25 or 30 or 32 or 34 or 36 or 40 Shore C and an
upper limit of about 42 or 44 or 48 or 50 or 52 or 56 or 60 or 62
or 65 or 68 or 70 or 74 or 78 or 80 Shore C. In one preferred
version, the geometric center hardness of the inner core
(H.sub.inner core center) is about 60 Shore C. When a flexible,
relatively soft foam is used, the foam may have a Shore A hardness
of about 10 or greater, and preferably has a lower limit of 15, 20,
25, 30, or 35 Shore A and an upper limit of about 60, 65, 70, 75,
80, 85, or 90 Shore A. In one preferred embodiment, the geometric
center hardness of the inner core is about 55 Shore A. The
H.sub.inner core center, as measured in Shore D units, is about 15
Shore D or greater and more preferably within a range having a
lower limit of about 15 or 18 or 20 or 22 or 25 or 28 or 30 or 32
or 36 or 40 or 44 Shore D and an upper limit of about 45 or 48 or
50 or 52 or 55 or 58 or 60 or 62 or 64 or 66 or 70 or 72 or 74 or
78 or 80 or 82 or 84 or 88 or 90 Shore D. Meanwhile, the outer
surface hardness of the inner core (H.sub.inner core surface), as
measured in Shore C, is about 10 Shore C or greater and preferably
has a lower limit of about 13 or 17 or 20 or 22 or 24 or 28 or 30
or 32 or 35 or 36 or 40 or 42 or 44 or 48 or 50 Shore C and an
upper limit of about 52 or 55 or 58 or 60 or 62 or 64 or 66 or 70
or 74 or 78 or 80 or 86 or 88 or 90 or 92 or 95 Shore C. The outer
surface hardness of the inner core ((H.sub.inner core surface), as
measured in Shore D units, preferably has a lower limit of about 25
or 28 or 30 or 32 or 36 or 40 or 44 Shore D and an upper limit of
about 45 or 48 or 50 or 52 or 55 or 58 or 60 or 62 or 64 or 66 or
70 or 74 or 78 or 80 or 82 or 84 or 88 or 90 or 94 or 96 Shore
D.
[0060] Density of the Inner Core
[0061] The foamed inner core preferably has a specific gravity of
about 0.25 to about 1.25 g/cc. That is, the density of the inner
core (as measured at any point of the inner core structure) is
preferably within the range of about 0.25 to about 1.25 g/cc. By
the term, "specific gravity of the inner core" ("SG.sub.inner"), it
is generally meant the specific gravity of the inner core as
measured at any point of the inner core structure. It should be
understood, however, that the specific gravity values, as taken at
different points of the inner core structure, may vary. For
example, the foamed inner core may have a "positive" density
gradient (that is, the outer surface (skin) of the inner core may
have a density greater than the geometric center of the inner
core.) In one preferred version, the specific gravity of the
geometric center of the inner core (SG.sub.center of inner core) is
less than 1.00 g/cc and more preferably 0.90 g/cc or less. More
particularly, in one version, the (SG.sub.center of inner core) is
in the range of about 0.10 to about 0.90 g/cc. For example, the
(SG.sub.center of inner core) may be within a range having a lower
limit of about 0.10 or 0.15 of 0.20 or 0.24 or 0.25 or 0.30 or 0.35
or 0.37 or 0.40 or 0.42 or 0.45 or 0.47 or 0.50 and an upper limit
of about 0.60 or 0.65 or 0.70 or 0.74 or 0.78 or 0.80, or 0.82 or
0.84 or 0.85 or 0.88 or 0.90 or 0.95 g/cc. Meanwhile, the specific
gravity of the outer surface (skin) of the inner core (SG.sub.skin
of inner core), in one preferred version, is greater than about
0.90 g/cc and more preferably greater than 1.00 g/cc. For example,
the (SG.sub.skin of inner core) may fall within the range of about
0.90 to about 2.00. More particularly, in one version, the
(SG.sub.skin of inner core) may have a specific gravity with a
lower limit of about 0.90 or 0.92 or 0.95 or 0.98 or 1.00 or 1.02
or 1.06 or 1.10 or 1.12 or 1.15 or 1.18 and an upper limit of about
1.20 or 1.24 or 1.30 or 1.32 or 1.35 or 1.38 or 1.40 or 1.44 or
1.50 or 1.60 or 1.65 or 1.70 or 1.76 or 1.80 or 1.90 or 1.92 or
2.00. In other instances, the outer skin may have a specific
gravity of less than 0.90 g/cc. For example, the specific gravity
of the outer skin (SG.sub.skin of inner core) may be about 0.75 or
0.80 or 0.82 or 0.85 or 0.88 g/cc. In such instances, wherein both
the (SG.sub.center of inner core) and (SG.sub.skin of inner core)
are less than 0.90 g/cc, it is still preferred that the
(SG.sub.center of inner core) is less than the (SG.sub.skin of
inner core).
[0062] Polyisocyanates and Polyols for Making the Polyurethane
Foams
[0063] As discussed above, in one preferred embodiment, a foamed
polyurethane composition is used to form the inner core. In
general, the polyurethane compositions contain urethane linkages
formed by reacting an isocyanate group (--N.dbd.C.dbd.O) with a
hydroxyl group (OH). The polyurethanes are produced by the reaction
of multi-functional isocyanates containing two or more isocyanate
groups with a polyol having two or more hydroxyl groups. The
formulation may also contain a catalyst, surfactant, and other
additives.
[0064] In particular, the foam inner core of this invention may be
prepared from a composition comprising an aromatic polyurethane,
which is preferably formed by reacting an aromatic diisocyanate
with a polyol. Suitable aromatic diisocyanates that may be used in
accordance with this invention include, for example, toluene
2,4-diisocyanate (TDI), toluene 2,6-diisocyanate (TDI),
4,4'-methylene diphenyl diisocyanate (MDI), 2,4'-methylene diphenyl
diisocyanate (MDI), polymeric methylene diphenyl diisocyanate
(PMDI), p-phenylene diisocyanate (PPDI), m-phenylene diisocyanate
(PDI), naphthalene 1,5-diisocyanate (NDI), naphthalene
2,4-diisocyanate (NDI), p-xylene diisocyanate (XDI), and
homopolymers and copolymers and blends thereof. The aromatic
isocyanates are able to react with the hydroxyl or amine compounds
and form a durable and tough polymer having a high melting point.
The resulting polyurethane generally has good mechanical strength
and tear-resistance.
[0065] Alternatively, the foamed composition of the inner core may
be prepared from a composition comprising aliphatic polyurethane,
which is preferably formed by reacting an aliphatic diisocyanate
with a polyol. Suitable aliphatic diisocyanates that may be used in
accordance with this invention include, for example, isophorone
diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HDI),
4,4'-dicyclohexylmethane diisocyanate ("H.sub.12 MDI"),
meta-tetramethylxylyene diisocyanate (TMXDI), trans-cyclohexane
diisocyanate (CHDI), 1,3-bis(isocyanatomethyl)cyclohexane;
1,4-bis(isocyanatomethyl)cyclohexane; and homopolymers and
copolymers and blends thereof. The resulting polyurethane generally
has good light and thermal stability. Preferred polyfunctional
isocyanates include 4,4'-methylene diphenyl diisocyanate (MDI),
2,4'-methylene diphenyl diisocyanate (MDI), and polymeric MDI
having a functionality in the range of 2.0 to 3.5 and more
preferably 2.2 to 2.5.
[0066] Any suitable polyol may be used to react with the
polyisocyanate in accordance with this 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.
[0067] As discussed further below, chain extenders (curing agents)
are added to the mixture to build-up the molecular weight of the
polyurethane polymer. In general, hydroxyl-terminated curing
agents, amine-terminated curing agents, and mixtures thereof are
used.
[0068] A catalyst may be employed to promote the reaction between
the isocyanate and polyol compounds. Suitable catalysts include,
but are not limited to, bismuth catalyst; zinc octoate; tin
catalysts such as bis-butyltin dilaurate, bis-butyltin diacetate,
stannous octoate; tin (II) chloride, tin (IV) chloride,
bis-butyltin dimethoxide, dimethyl-bis[1-oxonedecyl)oxy]stannane,
di-n-octyltin bis-isooctyl mercaptoacetate; amine catalysts such as
triethylenediamine, triethylamine, tributylamine,
1,4-diaza(2,2,2)bicyclooctane, tetramethylbutane diamine,
bis[2-dimethylaminoethyl]ether, N,N-dimethylaminopropylamine,
N,N-dimethylcyclohexylamine,
N,N,N',N',N''-pentamethyldiethylenetriamine, diethanolamine,
dimethtlethanolamine,
N-[2-(dimethylamino)ethyl]-N-methylethanolamine, N-ethylmorpholine,
3-dimethylamino-N,N-dimethylpropionamide, and
N,N',N''-dimethylaminopropylhexahydrotriazine; organic acids such
as oleic acid and acetic acid; delayed catalysts; and mixtures
thereof. Zirconium-based catalysts such as, for example,
bis(2-dimethyl aminoethyl)ether; mixtures of zinc complexes and
amine compounds such as KKAT.TM. XK 614, available from King
Industries; and amine catalysts such as Niax.TM. A-2 and A-33,
available from Momentive Specialty Chemicals, Inc. are particularly
preferred. The catalyst is preferably added in an amount sufficient
to catalyze the reaction of the components in the reactive mixture.
In one embodiment, the catalyst is present in an amount from about
0.001 percent to about 1 percent, and preferably 0.1 to 0.5
percent, by weight of the composition.
[0069] In one preferred embodiment, as described above, water is
used as the foaming agent--the water reacts with the polyisocyanate
compound(s) and forms carbon dioxide gas which induces foaming of
the mixture. The reaction rate of the water and polyisocyanate
compounds affects how quickly the foam is formed as measured per
reaction profile properties such as cream time, gel time, and rise
time of the foam.
[0070] The hydroxyl chain-extending (curing) agents are preferably
selected from the group consisting of ethylene glycol; diethylene
glycol; polyethylene glycol; propylene glycol;
2-methyl-1,3-propanediol; 2-methyl-1,4-butanediol;
monoethanolamine; diethanolamine; triethanolamine;
monoisopropanolamine; diisopropanolamine; dipropylene glycol;
polypropylene glycol; 1,2-butanediol; 1,3-butanediol;
1,4-butanediol; 2,3-butanediol; 2,3-dimethyl-2,3-butanediol;
trimethylolpropane; cyclohexyldimethylol; triisopropanolamine;
N,N,N',N'-tetra-(2-hydroxypropyl)-ethylene diamine; diethylene
glycol bis-(aminopropyl)ether; 1,5-pentanediol; 1,6-hexanediol;
1,3-bis-(2-hydroxyethoxy)cyclohexane; 1,4-cyclohexyldimethylol;
1,3-bis-[2-(2-hydroxyethoxy)ethoxy]cyclohexane;
1,3-bis-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}cyclohexane;
trimethylolpropane; polytetramethylene ether glycol (PTMEG),
preferably having a molecular weight from about 250 to about 3900;
and mixtures thereof. Suitable amine chain-extending (curing)
agents that can be used in chain-extending the polyurethane
prepolymer include, but are not limited to, unsaturated diamines
such as 4,4'-diamino-diphenylmethane (i.e.,
4,4'-methylene-dianiline or "MDA"), m-phenylenediamine,
p-phenylenediamine, 1,2- or 1,4-bis(sec-butylamino)benzene,
3,5-diethyl-(2,4- or 2,6-)toluenediamine or "DETDA",
3,5-dimethylthio-(2,4- or 2,6-)toluenediamine, and
3,5-diethylthio-(2,4- or 2,6-)toluenediamine. One suitable
amine-terminated chain-extending agent is Ethacure 300.TM.
(dimethylthiotoluenediamine or a mixture of
2,6-diamino-3,5-dimethylthiotoluene and
2,4-diamino-3,5-dimethylthiotoluene.) The amine curing agents used
as chain extenders normally have a cyclic structure and a low
molecular weight (250 or less).
[0071] When a hydroxyl-terminated curing agent is used, the
resulting polyurethane composition contains urethane linkages. On
the other hand, when an amine-terminated curing agent is used, any
excess isocyanate groups will react with the amine groups in the
curing agent. The resulting polyurethane composition contains
urethane and urea linkages and may be referred to as a
polyurethane/urea hybrid.
[0072] Thermoplastic Outer Core Layer
[0073] As discussed above, the inner core is made preferably from a
foamed composition. Meanwhile, the outer core layer is made
preferably from a non-foamed thermoplastic composition. Also, the
intermediate core layer, if present in the core construction, is
preferably made of a non-foamed thermoplastic composition.
[0074] The same thermoplastic composition used to form the outer
core layer also may be used to form the intermediate core.
Alternatively, different thermoplastic compositions may be used in
the outer and intermediate core layers. In one embodiment, the
intermediate and outer core layers have the same specific gravity
levels. In a second embodiment, the specific gravity of the
intermediate core is greater than the specific gravity of the outer
core layer. Finally, in a third embodiment, the specific gravity of
the intermediate core is less than the specific gravity of the
outer core layer. Thus, both the intermediate and outer core layers
may be formed from ethylene acid copolymer compositions as
described above. If, in one example, the objective is to make the
specific gravities of the intermediate and outer core layers
different, the concentration and/or type of fillers used in the
respective compositions may be adjusted to achieve this result. For
example, the intermediate core layer may contain a relatively small
concentration of metal fillers, while the outer core contains a
large concentration of metal fillers. In another embodiment, the
intermediate core layer may be formulated so that it does not
contain any metal fillers; and the outer core may contain a small
amount of metal fillers.
[0075] Thermoplastic Elastomers
[0076] As discussed above, thermoplastic elastomers may be used to
form any of the core layers of the golf balls of this invention.
Any single (or multiple) core layer(s) (for example, center,
intermediate, and/or outer core layers) may comprise a
thermoplastic elastomer composition in accordance with this
invention. In general, thermoplastic elastomers refer to a class of
polymers having thermoplastic-like (softens when exposed to heat
and returns to original condition when cooled) properties and
elastomeric-like (can be stretched and then returns to original
condition when released) properties. In thermoplastic elastomer
block copolymers, there are some blocks having thermoplastic-like
properties and these blocks may be referred to as "hard" segments.
Also, there are some blocks having elastomeric-like properties and
these blocks may be referred to as "soft" segments. The ratio of
hard to soft segments and the composition of the segments are
significant factors in determining the properties of the resulting
thermoplastic elastomer.
[0077] One example of a suitable thermoplastic elastomer that can
be used to form the compositions of this invention is
polyester-polyether block copolymers. In general, these block
copolymers contain hard and soft segments having various lengths
and sequences. The hard, crystalline polyester segments are
normally derived from reacting an aromatic-containing dicarboxylic
acid or diester such as, for example, terephthalic acid, dimethyl
terephthalate, and the like with a diol containing about 2 to about
10 carbon atoms. For example, the hard segments may constitute
butylene terephthalate, tetramethylene terephthalate, or ethylene
terephthalate units. The soft, elastomeric segments are normally
derived from long or short-chain poly(alkylene oxide) glycols
containing a total of about 3 to about 12 carbon atoms including up
to 3 or 4 oxygen atoms with the remaining atoms being hydrocarbon
atoms. Useful poly(alkylene oxide)glycols include, for example,
poly(oxyethylene)diol, poly(oxypropylene)diol, and
poly(oxytetramethylene)diols. More particularly, the polyether
polyols have been based on polymers derived from cyclic ethers such
as ethylene oxide, 1,2-propylene oxide and tetrahydrofuran. When
these cyclic ethers are subjected to ring opening polymerization,
they provide the corresponding polyether glycol, for example,
polyethylene ether glycol (PEG), poly(1,2-propylene)glycol (PPG),
and polytetramethylene ether glycol (PO4G, also referred to as
PTMEG).
[0078] A preferred polyester-polyether block copolymer is
commercially-available under the trademark, Hytrel.RTM., from
DuPont. These block copolymers are available in different grades
and contain hard (crystalline) segments of polybutylene
terephthalate and soft (amorphous) segments based on long-chain
polyether glycols. These and other examples of polyester-polyether
block copolymers which can be used in accordance with the present
invention are disclosed in U.S. Pat. Nos. 2,623,031; 3,651,014;
3,763,109; and 3,896,078, the disclosures of which are hereby
incorporated by reference. Different grades of Hytrel.RTM.
polyester-polyether block copolymers may be used in accordance with
this invention.
[0079] Other examples of suitable thermoplastic elastomers that can
be used to form the compositions of this invention are
polyether-amide block copolymers, which are commonly known as
Pebax.RTM. resins, and are available from Arkema, Inc. (Columbs,
France).
[0080] In general, polyether amide block copolymers may be prepared
by polycondensation of a polyamide with carboxyl end-groups with a
polyether glycol. These block copolymers have been prepared using
polyethylene glycol, polypropylene glycol, polytetramethylene
glycol, copolyethers derived therefrom, and copolymers of THF and
3-alkylTHF as shown by U.S. Pat. Nos. 4,230,838, 4,252,920,
4,349,661, 4,331,786 and 6,300,463, the disclosures of which are
hereby incorporated by reference. The general structure of the
polyether amide block copolymer may be represented by the following
formula (I):
##STR00001##
represents a polyamide segment containing terminal carboxyl groups
or acid equivalents thereof (for example, diacid anhydrides, diacid
chlorides or diesters) and
--O-G-O--
is a polyether segment.
[0081] Different grades of Pebax.RTM. polyether amide block
copolymers may be used in accordance with this invention.
[0082] Thermoplastic Ionomers and Highly-Neutralized Polymers
(HNPs)
[0083] As discussed above, thermoplastic partially and
highly-neutralized ionomers may be used to form any of the core
layers of the golf balls of this invention. Any single (or
multiple) core layer(s) (for example, center, intermediate, and/or
outer core layers) may comprise a thermoplastic ionomer composition
in accordance with this invention. Suitable ionomer compositions
include partially-neutralized ionomers and highly-neutralized
polymers (HNPs), including ionomers formed from blends of two or
more partially-neutralized ionomers, blends of two or more
highly-neutralized polymers, and blends of one or more
partially-neutralized ionomers with one or more highly-neutralized
polymers. For purposes of the present disclosure, "HNP" refers to
an acid copolymer after at least 70% of all acid groups present in
the composition are neutralized. Preferred ionomers are salts of
O/X- and O/X/Y-type acid copolymers, wherein O is an
.alpha.-olefin, X is a C.sub.3-C.sub.8 .alpha.,.beta.-ethylenically
unsaturated carboxylic acid, and Y is a softening monomer. O is
preferably selected from ethylene and propylene. X is preferably
selected from methacrylic acid, acrylic acid, ethacrylic acid,
crotonic acid, and itaconic acid. Methacrylic acid and acrylic acid
are particularly preferred. Y is preferably selected from
(meth)acrylate and alkyl(meth)acrylates wherein the alkyl groups
have from 1 to 8 carbon atoms, including, but not limited to,
n-butyl(meth)acrylate, isobutyl(meth)acrylate,
methyl(meth)acrylate, and ethyl(meth)acrylate.
[0084] Preferred O/X and O/XY-type copolymers include, without
limitation, ethylene acid copolymers, such as
ethylene/(meth)acrylic acid, ethylene/(meth)acrylic acid/maleic
anhydride, ethylene/(meth)acrylic acid/maleic acid mono-ester,
ethylene/maleic acid, ethylene/maleic acid mono-ester,
ethylene/(meth)acrylic acid/n-butyl (meth)acrylate,
ethylene/(meth)acrylic acid/iso-butyl (meth)acrylate,
ethylene/(meth)acrylic acid/methyl (meth)acrylate,
ethylene/(meth)acrylic acid/ethyl (meth)acrylate terpolymers, and
the like. The term, "copolymer," as used herein, includes polymers
having two types of monomers, those having three types of monomers,
and those having more than three types of monomers. Preferred
.alpha.,.beta.-ethylenically unsaturated mono- or dicarboxylic
acids are (meth) acrylic acid, ethacrylic acid, maleic acid,
crotonic acid, fumaric acid, itaconic acid. (Meth)acrylic acid is
most preferred. As used herein, "(meth)acrylic acid" means
methacrylic acid and/or acrylic acid. Likewise, "(meth)acrylate"
means methacrylate and/or acrylate.
[0085] The .alpha.-olefin is typically present in the O/X or
O/X/Y-type copolymer in an amount of 15 wt. % or greater, or 25 wt.
% or greater, or 40 wt. % or greater, or 60 wt. % or greater, based
on the total weight of the acid copolymer. The acid is typically
present in the acid copolymer in an amount of 6 wt. % or greater,
or 9 wt. % or greater, or 10 wt. % or greater, or 11 wt. % or
greater, or 15 wt. % or greater, or 16 wt. % or greater, or in an
amount within a range having a lower limit of 1 or 4 or 5 or 6 or 8
or 10 or 11 or 12 or 15 wt. % and an upper limit of 15 or 16 or 17
or 19 or 20 or 20.5 or 21 or 25 or 30 or 35 or 40 wt. %, based on
the total weight of the acid copolymer. The optional softening
monomer is typically present in the acid copolymer in an amount
within a range having a lower limit of 0 or 1 or 3 or 5 or 11 or 15
or 20 wt. % and an upper limit of 23 or 25 or 30 or 35 or 50 wt. %,
based on the total weight of the acid copolymer.
[0086] The O/X or O/X/Y-type copolymer is at least partially
neutralized with a cation source, optionally in the presence of a
high molecular weight organic acid, such as those disclosed in U.S.
Pat. No. 6,756,436, the entire disclosure of which is hereby
incorporated herein by reference. The acid copolymer can be reacted
with the optional high molecular weight organic acid and the cation
source simultaneously, or prior to the addition of the cation
source. Suitable cation sources include, but are not limited to,
metal ion sources, such as compounds of alkali metals, alkaline
earth metals, transition metals, and rare earth elements; ammonium
salts and monoamine salts; and combinations thereof. Preferred
cation sources are compounds of magnesium, sodium, potassium,
cesium, calcium, barium, manganese, copper, zinc, lead, tin,
aluminum, nickel, chromium, lithium, and rare earth metals.
[0087] Non-limiting examples of suitable commercially available
ionomers and other thermoplastic materials that can be used in
accordance with this invention are Surlyn.RTM. ionomers and
DuPont.RTM. HPF 1000 and HPF 2000 highly neutralized polymers,
commercially available from E. I. du Pont de Nemours and Company;
Clarix.RTM. ionomers, commercially available from A. Schulman,
Inc.; Iotek.RTM. ionomers, commercially available from ExxonMobil
Chemical Company; and Amplify.RTM. IO ionomers, commercially
available from The Dow Chemical Company; Amplify.RTM. GR functional
polymers and Amplify.RTM. TY functional polymers, commercially
available from The Dow Chemical Company; Fusabond.RTM.
functionalized polymers, commercially available from E. I. du Pont
de Nemours and Company; Exxelor.RTM. maleic anhydride grafted
polymers, commercially available from ExxonMobil Chemical Company;
ExxonMobil.RTM. PP series polypropylene impact copolymers,
commercially available from ExxonMobil Chemical Company;
Vistamaxx.RTM. propylene-based elastomers, commercially available
from ExxonMobil Chemical Company; Exact.RTM. plastomers,
commercially available from ExxonMobil Chemical Company;
Santoprene.RTM. thermoplastic vulcanized elastomers, commercially
available from ExxonMobil Chemical Company; Kraton.RTM. styrenic
block copolymers, commercially available from Kraton Performance
Polymers Inc.; Septon.RTM. styrenic block copolymers, commercially
available from Kuraray Co., Ltd.; Lotader.RTM. ethylene acrylate
based polymers, commercially available from Arkema Corporation;
Polybond.RTM. grafted polyethylenes and polypropylenes,
commercially available from Chemtura Corporation; Pebax.RTM.
polyether and polyester amides, commercially available from Arkema
Inc.; polyester-based thermoplastic elastomers, such as Hytrel.RTM.
polyester elastomers, commercially available from E. I. du Pont de
Nemours and Company, and Riteflex.RTM. polyester elastomers,
commercially available from Ticona; Estane.RTM. thermoplastic
polyurethanes, commercially available from The Lubrizol
Corporation; Grivory.RTM. polyamides and Grilamid.RTM. polyamides,
commercially available from EMS Grivory; Zytel.RTM. polyamide
resins and Elvamide.RTM. nylon multipolymer resins, commercially
available from E. I. du Pont de Nemours and Company; Elvaloy.RTM.
acrylate copolymer resins, commercially available from E. I. du
Pont de Nemours and Company; Elastollan.RTM. polyurethane-based
thermoplastic elastomers, commercially available from BASF;
Xylex.RTM. polycarbonate/polyester blends, commercially available
from SABIC Innovative Plastics; and combinations of two or more
thereof.
[0088] As discussed above, the acid is typically present in the O/X
or O/X/Y-type copolymer in an amount of 6 wt. % or greater. "Low
acid" and "high acid" ionomeric copolymers, as well as blends of
such ionomers, may be used. In general, low acid ionomers are
considered to be those containing 16 wt. % or less of acid
moieties, whereas high acid ionomers are considered to be those
containing greater than 16 wt. % of acid moieties. The acidic
groups in the acid copolymers are partially or totally-neutralized
with a cation source. Suitable cation sources include metal cations
and salts thereof, organic amine compounds, ammonium, and
combinations thereof. Suitable cation sources include, for example,
metal cations and salts thereof, wherein the metal is preferably
lithium, sodium, potassium, magnesium, calcium, barium, lead, tin,
zinc, aluminum, manganese, nickel, chromium, copper, or a
combination thereof. The metal cation salts provide the cations
capable of neutralizing (at varying levels) the carboxylic acids of
the ethylene acid copolymer and fatty acids, if present, as
discussed further below. These include, for example, the sulfate,
carbonate, acetate, oxide, or hydroxide salts of lithium, sodium,
potassium, magnesium, calcium, barium, lead, tin, zinc, aluminum,
manganese, nickel, chromium, copper, or a combination thereof.
Preferred metal cation salts are calcium and magnesium-based salts.
High surface area cation particles such as micro and nano-scale
cation particles are preferred. The amount of cation used in the
composition is readily determined based on desired level of
neutralization.
[0089] For example, olefin acid copolymer ionomer resins having
acid groups that are neutralized from about 10 percent or greater
may be used. In one ionomer composition, the acid groups are
partially-neutralized. That is, the neutralization level is from
about 10% to about 70%, more preferably 20% to 60%, and most
preferably 30 to 50%. These ionomer compositions, containing acid
groups neutralized to 70% or less, may be referred to ionomers
having relatively low neutralization levels or
partial-neutralization. On the other hand, the ionomer composition
may contain acid groups that are highly or fully-neutralized. In
these HNPs, the neutralization level is greater than 70%,
preferably at least 90%, and even more preferably at least 100%. In
another embodiment, an excess amount of neutralizing agent, that
is, an amount greater than the stoichiometric amount needed to
neutralize the acid groups, may be used. That is, the acid groups
may be neutralized to 100% or greater, for example 110% or 120% or
greater.
[0090] When the .alpha.-olefin monomer is ethylene, such copolymers
are referred to herein as E/X-type copolymers and when a softening
monomer is included, such copolymers are referred to herein as
E/X/Y-type copolymers, wherein E is ethylene; X is a C.sub.3 to
C.sub.8 .alpha.,.beta.-ethylenically unsaturated mono- or
dicarboxylic acid; and Y is a softening monomer. The softening
monomer is typically an alkyl(meth)acrylate, wherein the alkyl
groups have from 1 to 8 carbon atoms. Preferred E/X/Y-type
copolymers are those wherein X is (meth)acrylic acid and/or Y is
selected from (meth)acrylate, n-butyl(meth)acrylate,
isobutyl(meth)acrylate, methyl(meth)acrylate, and
ethyl(meth)acrylate. More preferred E/X/Y-type copolymers are
ethylene/(meth)acrylic acid/n-butyl acrylate,
ethylene/(meth)acrylic acid/methyl acrylate, and
ethylene/(meth)acrylic acid/ethyl acrylate.
[0091] The amount of ethylene in the E/X and E/X/Y-type copolymers
is typically at least 15 wt. %, preferably at least 25 wt. %, more
preferably least 40 wt. %, and even more preferably at least 60 wt.
%, based on total weight of the copolymer. The amount of C.sub.3 to
C.sub.8 .alpha.,.beta.-ethylenically unsaturated mono- or
dicarboxylic acid in the ethylene acid copolymer is typically from
1 wt. % to 35 wt. %, preferably from 5 wt. % to 30 wt. %, more
preferably from 5 wt. % to 25 wt. %, and even more preferably from
10 wt. % to 20 wt. %, based on total weight of the copolymer. The
amount of optional softening monomer in the ethylene acid copolymer
is typically from 0 wt. % to 50 wt. %, preferably from 5 wt. % to
40 wt. %, more preferably from 10 wt. % to 35 wt. %, and even more
preferably from 20 wt. % to 30 wt. %, based on total weight of the
copolymer. As discussed above, "low acid" and "high acid" ionomeric
polymers, as well as blends of such ionomers, may be used. In
general, low acid ionomers are considered to be those containing 16
wt. % or less of acid moieties, whereas high acid ionomers are
considered to be those containing greater than 16 wt. % of acid
moieties.
[0092] As discussed above, the acidic groups in the E/X and
E/X/Y-type copolymer ionomers are partially or totally neutralized
with a cation source. Suitable cation sources include metal cations
and salts thereof, organic amine compounds, ammonium, and
combinations thereof. Preferred cation sources are metal cations
and salts thereof, wherein the metal is preferably lithium, sodium,
potassium, magnesium, calcium, barium, lead, tin, zinc, aluminum,
manganese, nickel, chromium, copper, or a combination thereof. The
metal cation salts provide the cations capable of neutralizing (at
varying levels) the carboxylic acids of the ethylene acid copolymer
and fatty acids, if present, as discussed further below. These
include, for example, the sulfate, carbonate, acetate, oxide, or
hydroxide salts of lithium, sodium, potassium, magnesium, calcium,
barium, lead, tin, zinc, aluminum, manganese, nickel, chromium,
copper, or a combination thereof. Preferred metal cation salts are
calcium and magnesium-based salts. High surface area cation
particles such as micro and nano-scale cation particles are
preferred. The amount of cation used in the composition is readily
determined based on desired level of neutralization.
[0093] For example, ethylene acid copolymers having acid groups
that are neutralized from about 10 percent or greater may be used.
In one ethylene acid copolymer composition, the acid groups are
partially-neutralized. That is, the neutralization level is from
about 10% to about 70%, more preferably 20% to 60%, and most
preferably 30 to 50%. These ethylene acid copolymer compositions,
containing acid groups neutralized to 70% or less, may be referred
to ionomers having relatively low neutralization levels or
partial-neutralization. On the other hand, the ethylene acid
copolymer composition may contain acid groups that are highly or
fully-neutralized. In these HNPs, the neutralization level is
greater than 70%, preferably at least 90%, and even more preferably
at least 100%. In another embodiment, an excess amount of
neutralizing agent, that is, an amount greater than the
stoichiometric amount needed to neutralize the acid groups, may be
used. That is, the acid groups may be neutralized to 100% or
greater, for example 110% or 120% or greater. In one preferred
embodiment, a high acid ethylene acid copolymer containing about 19
to 20 wt. % methacrylic or acrylic acid is neutralized with zinc
and sodium cations to a 95% neutralization level.
[0094] "Ionic plasticizers" such as organic acids or salts of
organic acids, particularly fatty acids, may be added to any of the
ionomer resins if needed. Such ionic plasticizers are used to make
conventional ionomer composition more processable as described in
Rajagopalan et al., U.S. Pat. No. 6,756,436, the disclosure of
which is hereby incorporated by reference. In one preferred
embodiment, the thermoplastic ionomer composition, containing acid
groups neutralized to 70% or less, does not include a fatty acid or
salt thereof, or any other ionic plasticizer. On the other hand,
the thermoplastic ionomer composition, containing acid groups
neutralized to greater than 70%, includes an ionic plasticizer,
particularly a fatty acid or salt thereof. For example, the ionic
plasticizer may be added in an amount of 0.5 to 10 pph, more
preferably 1 to 5 pph. The organic acids may be aliphatic, mono- or
multi-functional (saturated, unsaturated, or multi-unsaturated)
organic acids. Salts of these organic acids may also be employed.
Suitable fatty acid salts include, for example, metal stearates,
laureates, oleates, palmitates, pelargonates, and the like. For
example, fatty acid salts such as zinc stearate, calcium stearate,
magnesium stearate, barium stearate, and the like can be used. The
salts of fatty acids are generally fatty acids neutralized with
metal ions. The metal cation salts provide the cations capable of
neutralizing (at varying levels) the carboxylic acid groups of the
fatty acids. Examples include the sulfate, carbonate, acetate and
hydroxide salts of metals such as barium, lithium, sodium, zinc,
bismuth, chromium, cobalt, copper, potassium, strontium, titanium,
tungsten, magnesium, cesium, iron, nickel, silver, aluminum, tin,
or calcium, and blends thereof. It is preferred the organic acids
and salts 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).
[0095] As noted above, the final ionomer compositions may contain
additional materials such as, for example, a small amount of ionic
plasticizer, which is particularly effective at improving the
processability of highly-neutralized ionomers. For example, the
ionic plasticizer may be added in an amount of 0.5 to 10 pph, more
preferably 1 to 5 pph. In addition to the fatty acids and salts of
fatty acids discussed above, other suitable ionic plasticizers
include, for example, polyethylene glycols, waxes, bis-stearamides,
minerals, and phthalates. In another embodiment, an amine or
pyridine compound is used, preferably in addition to a metal
cation. Suitable examples include, for example, ethylamine,
methylamine, diethylamine, tert-butylamine, dodecylamine, and the
like.
[0096] The ionomer compositions may contain a wide variety of
fillers and some of these fillers may be used to adjust the
specific gravity of the composition as needed. High surface-area
fillers that have an affinity for the acid groups in ionomer may be
used. In particular, fillers such as particulate, fibers, or flakes
having cationic nature such that they may also contribute to the
neutralization of the ionomer are suitable. For example, aluminum
oxide, zinc oxide, tin oxide, barium sulfate, zinc sulfate, calcium
oxide, calcium carbonate, zinc carbonate, barium carbonate,
tungsten, tungsten carbide, and lead silicate fillers may be used.
Also, silica, fumed silica, and precipitated silica, such as those
sold under the tradename, HISIL.TM., from PPG Industries, carbon
black, carbon fibers, and nano-scale materials such as nanotubes,
nanoflakes, nanofillers, and nanoclays may be used. Relatively
heavy-weight fillers also may be added to the ionomer compositions
including, but not limited to, particulate, powders, fibers and
flakes of heavy metals such as copper, nickel, tungsten, brass,
steel, magnesium, molybdenum, cobalt, lead, tin, silver, gold, and
platinum, and alloys thereof. Steel materials also can be added. In
other instances, it may be desirable to add relatively light-weight
metals such as titanium and aluminum alloys thereof. Other
additives and fillers include, but are not limited to, chemical
blowing and foaming agents, optical brighteners, coloring agents,
fluorescent agents, whitening agents, UV absorbers, light
stabilizers, defoaming agents, processing aids, antioxidants,
stabilizers, softening agents, fragrance components, plasticizers,
impact modifiers, titanium dioxide, acid copolymer wax,
surfactants, rubber regrind (recycled core material), clay, mica,
talc, glass flakes, milled glass, and mixtures thereof. Suitable
additives are more fully described in, for example, Rajagopalan et
al., U.S. Patent Application Publication No. 2003/0225197, the
entire disclosure of which is hereby incorporated herein by
reference. In a particular embodiment, the total amount of
additive(s) and filler(s) present in the final thermoplastic
ionomeric composition is 25 wt. % or less, or 20 wt. % or less, or
15 wt. % or less, or 12 wt. % or less, or 10 wt. % or less, or 9
wt. % or less, or 6 wt. % or less, or 5 wt. % or less, or 4 wt. %
or less, or 3 wt. % or less, based on total weight of the ionomeric
composition.
[0097] The acid copolymer ionomer is used in an amount of at least
about 5% by weight based on total weight of composition and is
generally present in an amount of about 5% to about 100%, or an
amount within a range having a lower limit of 5% or 10% or 20% or
30% or 40% or 50% and an upper limit of 55% or 60% or 70% or 80% or
90% or 95% or 100%. Preferably, the concentration of acid copolymer
is about 40 to about 95 weight percent.
[0098] Other suitable thermoplastic polymers that may be used to
form the intermediate and/or outer core layers in accordance with
this invention include, but are not limited to, the following
polymers (including homopolymers, copolymers, and derivatives
thereof.)
[0099] (a) polyesters, particularly those modified with a
compatibilizing group such as sulfonate or phosphonate, including
modified poly(ethylene terephthalate), modified poly(butylene
terephthalate), modified poly(propylene terephthalate), modified
poly(trimethylene terephthalate), modified poly(ethylene
naphthenate), and those disclosed in U.S. Pat. Nos. 6,353,050,
6,274,298, and 6,001,930, the entire disclosures of which are
hereby incorporated herein by reference, and blends of two or more
thereof;
[0100] (b) polyamides, polyamide-ethers, and polyamide-esters, and
those disclosed in U.S. Pat. Nos. 6,187,864, 6,001,930, and
5,981,654, the entire disclosures of which are hereby incorporated
herein by reference, and blends of two or more thereof;
[0101] (c) polyurethanes, polyureas, polyurethane-polyurea hybrids,
and blends of two or more thereof;
[0102] (d) fluoropolymers, such as those disclosed in U.S. Pat.
Nos. 5,691,066, 6,747,110 and 7,009,002, the entire disclosures of
which are hereby incorporated herein by reference, and blends of
two or more thereof;
[0103] (e) polystyrenes, such as poly(styrene-co-maleic anhydride),
acrylonitrile-butadiene-styrene, poly(styrene sulfonate),
polyethylene styrene, and blends of two or more thereof;
[0104] (f) polyvinyl chlorides and grafted polyvinyl chlorides, and
blends of two or more thereof;
[0105] (g) polycarbonates, blends of
polycarbonate/acrylonitrile-butadiene-styrene, blends of
polycarbonate/polyurethane, blends of polycarbonate/polyester, and
blends of two or more thereof;
[0106] (h) polyethers, such as polyarylene ethers, polyphenylene
oxides, block copolymers of alkenyl aromatics with vinyl aromatics
and polyamicesters, and blends of two or more thereof;
[0107] (i) polyimides, polyetherketones, polyamideimides, and
blends of two or more thereof; and
[0108] (j) polycarbonate/polyester copolymers and blends.
[0109] These thermoplastic polymers may be used by and in
themselves to form the intermediate and/or outer core layers, or
blends of thermoplastic polymers including the above-described
polymers and ethylene acid copolymer ionomers may be used. It also
is recognized that the ionomer compositions may contain a blend of
two or more ionomers. For example, the composition may contain a
50/50 wt. % blend of two different highly-neutralized
ethylene/methacrylic acid copolymers. In another version, the
composition may contain a blend of one or more ionomers and a
maleic anhydride-grafted non-ionomeric polymer. The non-ionomeric
polymer may be a metallocene-catalyzed polymer. In another version,
the composition contains a blend of a highly-neutralized
ethylene/methacrylic acid copolymer and a maleic anhydride-grafted
metallocene-catalyzed polyethylene. In yet another version, the
composition contains a material selected from the group consisting
of highly-neutralized ionomers optionally blended with a maleic
anhydride-grafted non-ionomeric polymer; polyester elastomers;
polyamide elastomers; and combinations of two or more thereof.
[0110] Core Structure
[0111] As discussed above, in one preferred embodiment, the core of
the golf ball of this invention has a dual-layered structure
comprising an inner core and outer core layer. Referring to FIG. 3,
one version of a golf ball that can be made in accordance with this
invention is generally indicated at (20). The ball (20) contains a
dual-layered core (22) having an inner core (center) (22a) and
outer core layer (22b) surrounded by a single-layered cover (24).
The inner core (22a) is relatively small in volume and generally
has a diameter within a range of about 0.10 to about 1.10 inches.
More particularly, the inner core (22a) preferably has a diameter
size with a lower limit of about 0.15 or 0.25 or 0.35 or 0.45 or
0.55 inches and an upper limit of about 0.60 or 0.70 or 0.80 or
0.90 inches. In one preferred version, the diameter of the inner
core (22a) is in the range of about 0.025 to about 0.080 inches,
more preferably about 0.030 to about 0.075 inches. Meanwhile, the
outer core layer (22b) generally has a thickness within a range of
about 0.010 to about 0.250 inches and preferably has a lower limit
of 0.010 or 0.020 or 0.025 or 0.030 inches and an upper limit of
0.070 or 0.080 or 0.100 or 0.200 inches. In one preferred version,
the outer core layer has a thickness in the range of about 0.040 to
about 0.170 inches, more preferably about 0.060 to about 0.150
inches.
[0112] Referring to FIG. 4, in another version, the golf ball (25)
contains a dual-core (26) having an inner core (center) (26a) and
outer core layer (26b). The dual-core (26) is surrounded by a
multi-layered cover (28) having an inner cover layer (28a) and
outer cover layer (28b).
[0113] As discussed above, the inner core is made preferably from a
foamed composition, and the outer core is made preferably from a
thermoplastic composition.
[0114] In another preferred embodiment, a golf ball The
intermediate core layer, meanwhile, is formed preferably from
non-foamed thermoplastic or thermoset compositions. Preferably,
each of the intermediate and outer core layers is formed from a
non-foamed thermoplastic composition. That is, the intermediate
core layer may be formed from a first thermoplastic composition;
and the outer core layer may be formed from a second thermoplastic
composition.
[0115] As discussed above, the core preferably has a multi-layered
structure comprising an inner core, intermediate core layer, and
outer core layer.
[0116] In FIG. 3, a partial cut-away view of one version of the
core (17) of this invention is shown. The core (17) includes an
inner core (18) comprising a foamed composition; an intermediate
core layer (20) comprising a first thermoplastic composition; and
an outer core layer (22) comprising a second thermoplastic
composition. As shown in FIG. 3, the intermediate core layer (20)
is disposed about the inner core (18), and the outer core layer
(22) surrounds the intermediate core layer. The first and second
thermoplastic materials are preferably non-foamed. The hardness of
the core sub-assembly (inner core, intermediate core layer, and
outer core layer) is an important property. In general, cores with
relatively high hardness values have higher compression and tend to
have good durability and resiliency. However, some high compression
balls are stiff and this may have a detrimental effect on shot
control and placement. Thus, the optimum balance of hardness in the
core sub-assembly needs to be attained.
[0117] Hardness Gradient
[0118] In one preferred golf ball, the inner core (center) has a
"positive" hardness gradient (that is, the outer surface of the
inner core is harder than its geometric center); the intermediate
core layer has a "positive" hardness gradient (that is, the outer
surface of the intermediate core layer is harder than the inner
surface of the intermediate core layer); and the outer core layer
has a "positive" hardness gradient (that is, the outer surface of
the outer core layer is harder than the inner surface of the outer
core layer.) In such cases where the inner core; intermediate; and
outer core layer each has a "positive" hardness gradient, the outer
surface hardness of the outer core layer is preferably greater than
the hardness of the geometric center of the inner core. In one
preferred version, the positive hardness gradient of the inner core
is in the range of about 2 to about 40 Shore C units and even more
preferably about 10 to about 25 Shore C units; while the positive
hardness gradient of the intermediate core is in the range of about
1 to about 5 Shore C; and the positive hardness gradient of the
outer core is in the range of about 2 to about 20 Shore C and even
more preferably about 3 to about 10 Shore C.
[0119] In an alternative version, the inner core may have a
positive hardness gradient; the intermediate core layer may have a
"zero" hardness gradient (that is, the hardness values of the outer
surface of the intermediate core layer and the inner surface of the
intermediate core layer are substantially the same) or a "negative"
hardness gradient (that is, the outer surface of the intermediate
core layer is softer than the inner surface of the intermediate
core layer.); and the outer core layer may have a "zero" hardness
gradient (that is, the hardness values of the outer surface of the
outer core layer and the inner surface of the outer core layer are
substantially the same) or a "negative" hardness gradient (that is,
the outer surface of the outer core layer is softer than the inner
surface of the outer core layer.) For example, in one version, the
inner core has a positive hardness gradient; the intermediate core
layer has a zero hardness gradient; and the outer core layer has a
negative hardness gradient in the range of about 2 to about 25
Shore C. Alternatively, the inner core may have a positive hardness
gradient; the intermediate core layer may have a zero or negative
hardness gradient; and the outer core layer may have a positive
hardness gradient. Still yet, in another preferred embodiment, both
the inner core and intermediate core layers have positive hardness
gradients (more preferably within the range of about 2 to about 40
Shore C), while the outer core layer has a zero or negative
hardness gradient.
[0120] In another version, the inner core (center) has a zero or
negative hardness gradient, while the intermediate core layer has a
positive hardness gradient, and the outer core has a zero or
negative hardness gradient. In yet another version, both the inner
core and intermediate core layers have a zero or negative hardness
gradient, while the outer core layer has a positive hardness
gradient. Alternatively, in a further version, the inner core has a
zero or negative hardness gradient, while both the intermediate and
outer core layers have positive hardness gradients. Finally, in
still yet another version, the inner core, intermediate core, and
outer core layer each has a zero or negative hardness gradient.
[0121] In general, hardness gradients are further described in
Bulpett et al., U.S. Pat. Nos. 7,537,529 and 7,410,429, the
disclosures of which are hereby incorporated by reference. Methods
for measuring the hardness of the inner core, intermediate core,
and outer core layers along with other layers in the golf ball and
determining the hardness gradients of the various layers are
described in further detail below. The core layers have positive,
negative, or zero hardness gradients defined by hardness
measurements made at the outer surface of the inner core (or outer
surface of the intermediate or outer core layer) and radially
inward towards the center of the inner core (or inner surface of
the intermediate or outer core layer). These measurements are made
typically at 2-mm increments as described in the test methods
below. In general, the hardness gradient is determined by
subtracting the hardness value at the innermost portion of the
component being measured (for example, the center of the inner core
or inner surface of the intermediate or outer core layer) from the
hardness value at the outer surface of the component being measured
(for example, the outer surface of the inner core or outer surface
of the intermediate or outer core layer).
[0122] Positive Hardness Gradient. For example, if the hardness
value of the outer surface of the inner core is greater than the
hardness value of the inner core's geometric center (that is, the
inner core has a surface harder than its geometric center), the
hardness gradient will be deemed "positive" (a larger number minus
a smaller number equals a positive number.) For example, if the
outer surface of the inner core has a hardness of 67 Shore C and
the geometric center of the inner core has a hardness of 60 Shore
C, then the inner core has a positive hardness gradient of 7.
Likewise, if the outer surface of the intermediate (or outer) core
layer has a greater hardness value than the inner surface of the
intermediate (or outer) core layer respectively, the given
intermediate (and/or outer) core layer will be considered to have a
positive hardness gradient.
[0123] Negative Hardness Gradient. On the other hand, if the
hardness value of the outer surface of the inner core is less than
the hardness value of the inner core's geometric center (that is,
the inner core has a surface softer than its geometric center), the
hardness gradient will be deemed "negative." For example, if the
outer surface of the inner core has a hardness of 68 Shore C and
the geometric center of the inner core has a hardness of 70 Shore
C, then the inner core has a negative hardness gradient of 2.
Likewise, if the outer surface of the intermediate (or outer) core
layer has a lesser hardness value than the inner surface of the
intermediate (or outer) core layer, the given intermediate (and/or
outer) core layer will be considered to have a negative hardness
gradient.
[0124] Zero Hardness Gradient. In another example, if the hardness
value of the outer surface of the inner core is substantially the
same as the hardness value of the inner core's geometric center
(that is, the surface of the inner core has about the same hardness
as the geometric center), the hardness gradient will be deemed
"zero." For example, if the outer surface of the inner core and the
geometric center of the inner core each has a hardness of 65 Shore
C, then the inner core has a zero hardness gradient. Likewise, if
the outer surface of the outer core layer has a hardness value
approximately the same as the inner surface of the outer core
layer, the outer core layer will be considered to have a zero
hardness gradient. Also, if the outer surface of the intermediate
core layer has a hardness value approximately the same as the inner
surface of the intermediate core layer, the intermediate core layer
will be considered to have a zero hardness gradient.
[0125] More particularly, the term, "positive hardness gradient" as
used herein means a hardness gradient of positive 3 Shore C or
greater, preferably 7 Shore C or greater, more preferably 10 Shore
C, and even more preferably 20 Shore C or greater. The term, "zero
hardness gradient" as used herein means a hardness gradient of less
than 3 Shore C, preferably less than 1 Shore C and may have a value
of zero or negative 1 to negative 10 Shore C. The term, "negative
hardness gradient" as used herein means a hardness value of less
than zero, for example, negative 3, negative 5, negative 7,
negative 10, negative 15, or negative 20 or negative 25. The terms,
"zero hardness gradient" and "negative hardness gradient" may be
used herein interchangeably to refer to hardness gradients of
negative 1 to negative 10.
[0126] The inner core preferably has a geometric center hardness
(H.sub.inner core center) of about 5 Shore D or greater. For
example, the (H.sub.inner core center) may be in the range of about
5 to about 88 Shore D and more particularly within a range having a
lower limit of about 5 or 10 or 18 or 20 or 26 or 30 or 34 or 36 or
38 or 42 or 48 of 50 or 52 Shore D and an upper limit of about 54
or 56 or 58 or 60 or 62 or 64 or 68 or 70 or 74 or 76 or 80 or 82
or 84 or 88 Shore D. In another example, the center hardness of the
inner core (H.sub.inner core center), as measured in Shore C units,
is preferably about 10 Shore C or greater; for example, the
H.sub.inner core center may have a lower limit of about 10 or 14 or
16 or 22 or 24 or 28 or 31 or 34 or 37 or 40 or 44 or 52 or 58
Shore C and an upper limit of about or 60 or 62 or 65 or 68 or 71
or 74 or 76 or 78 or 79 or 80 or 84 or 90 Shore C. Concerning the
outer surface hardness of the inner core (H.sub.inner core
surface), this hardness is preferably about 15 Shore D or greater;
for example, the H.sub.inner core surface may fall within a range
having a lower limit of about 15 or 18 or 20 or 23 or 26 or 30 or
34 or 36 or 38 or 42 or 48 of 50 or 52 Shore D and an upper limit
of about 54 or 56 or 58 or 60 or 62 or 70 or 72 or 75 or 78 or 80
or 82 or 84 or 86 or 90 Shore D. In one version, the outer surface
hardness of the inner core (H.sub.inner core surface), as measured
in Shore C units, has a lower limit of about 13 or 18 or 20 or 24
or 27 or 28 or 30 or 32 or 34 or 38 or 44 or 52 or 58 or 60 or 70
or 74 Shore C and an upper limit of about 76 or 78 or 80 or 84 or
86 or 88 or 90 or 92 Shore C. In another version, the geometric
center hardness (H.sub.inner core center) is in the range of about
10 Shore C to about 50 Shore C; and the outer surface hardness of
the inner core (H.sub.inner core surface) is in the range of about
5 Shore C to about 50 Shore C.
[0127] Meanwhile, the intermediate core layer preferably has an
outer surface hardness (H.sub.outer surface of IC) of about 30
Shore D or greater, and more preferably within a range having a
lower limit of about 30 or 35 or 40 or 42 or 44 or 46 or 48 or 50
or 52 or 54 or 56 or 58 and an upper limit of about 60 or 62 or 64
or 70 or 74 or 78 or 80 or 82 or 85 or 87 or 88 or 90 Shore D. The
outer surface hardness of the intermediate core layer (H.sub.outer
surface of IC), as measured in Shore C units, preferably has a
lower limit of about 30 or 33 or 35 40 or 42 or 46 or 50 or 56 or
60 or 63 or 65 or 67 or 70 or 73 or 75 or 76 or 78 Shore C, and an
upper limit of about 78 or 80 or 85 or 87 or 89 or 90 or 92 or 93
or 95 or 97 Shore C. While, the inner surface hardness of the
intermediate core (H.sub.inner surface of the IC) p referably is
about 25 Shore D or greater and more preferably is within a range
having a lower limit of about 26 or 30 or 34 or 36 or 38 or 42 or
48 of 50 or 52 Shore D and an upper limit of about 54 or 56 or 58
or 60 or 62 Shore D. As measured in Shore C units, the inner
surface hardness of the intermediate core (H.sub.inner surface of
the IC) preferably has a lower limit of about 38 or 44 or 52 or 58
or 60 or 70 or 74 Shore C and an upper limit of about 76 or 78 or
80 or 84 or 86 or 88 or 90 or 92 or 93 or 96 Shore C.
[0128] On the other hand, the outer core layer preferably has an
outer surface hardness (H.sub.outer surface of OC) of about 40
Shore D or greater, and more preferably within a range having a
lower limit of about 40 or 42 or 44 or 46 or 48 or 50 or 52 and an
upper limit of about 54 or 56 or 58 or 60 or 62 or 64 or 70 or 74
or 78 or 80 or 82 or 85 or 87 or 88 or 90 Shore D. The outer
surface hardness of the outer core layer (H.sub.outer surface of
OC), as measured in Shore C units, preferably has a lower limit of
about 40 or 43 or 45 or 48 or 50 or 54 or 58 or 60 or 63 or 65 or
67 or 70 or 73 or 76 Shore C, and an upper limit of about 78 or 80
or 84 or 85 or 87 or 89 or 90 or 92 or 95 Shore C. And, the inner
surface of the outer core layer (H.sub.inner surface of OC) p
referably has a hardness of about 40 Shore D or greater, and more
preferably within a range having a lower limit of about 40 or 42 or
44 or 46 or 48 or 50 or 52 and an upper limit of about 54 or 56 or
58 or 60 or 62 or 64 or 70 or 74 or 78 or 80 or 82 or 85 or 87 or
88 or 90 Shore D. The inner surface hardness of the outer core
layer (H.sub.inner surface of OC), as measured in Shore C units,
preferably has a lower limit of about 40 or 43 or 45 or 47 or 50 or
52 or 54 or 55 or 58 or 60 or 63 or 65 or 67 or 70 or 73 or 76
Shore C, and an upper limit of about 78 or 80 or 85 or 87 or 89 or
90 or 92 or 95 Shore C.
[0129] In one preferred embodiment, the outer surface hardness of
the intermediate core layer (H.sub.outer surface of IC), is less
than the outer surface hardness (H.sub.inner core surface) of the
inner core by at least 3 Shore C units and more preferably by at
least 5 Shore C.
[0130] In a second preferred embodiment, the outer surface hardness
of the intermediate core layer (H.sub.outer surface of IC), is
greater than the outer surface hardness (H.sub.inner core surface)
of the inner core by at least 3 Shore C units and more preferably
by at least 5 Shore C.
[0131] The core structure also has a hardness gradient across the
entire core assembly. In one embodiment, the (H.sub.inner core
center) is in the range of about 10 Shore C to about 60 Shore C,
preferably about 13 Shore C to about 55 Shore C; and the
(H.sub.outer surface of OC) is in the range of about 40 Shore C to
about 90 Shore C, preferably about 43 Shore C to about 87 Shore C
to provide a positive hardness gradient across the core
assembly.
[0132] Dimensions
[0133] The inner core preferably has a diameter in the range of
about 0.100 to about 1.100 inches, and the volume of the inner core
is preferably in the range of about 0.01 to about 11.4 cc. For
example, the inner core may have a diameter within a range of about
0.100 to about 0.500 inches. In another example, the inner core may
have a diameter within a range of about 0.300 to about 0.800
inches. More particularly, the inner core preferably has a diameter
size with a lower limit of about 0.10 or 0.12 or 0.15 or 0.25 or
0.30 or 0.35 or 0.45 or 0.55 inches and an upper limit of about
0.60 or 0.65 or 0.70 or 0.80 or 0.90 or 1.00 or 1.10 inches.
Concerning the volume, the inner core may have a volume with a
lower limit of 0.01 or 0.5 or 1.0 or 1.07 or 1.5 or 2.25 or 3.0 or
3.5 or 4.0 or 5.0 or 5.5 or 6.5 cc and an upper limit of 7.0 or 8.0
or 8.25 or 8.5 or 9.0 or 9.5 or 10.0 or 11.25 or 11.4 cc.
[0134] Meanwhile, the intermediate core layer preferably has a
thickness in the range of about 0.050 to about 0.400 inches. More
particularly, the thickness of the intermediate core layer
preferably has a lower limit of about 0.050 or 0.060 or 0.070 or
0.075 or 0.080 inches and an upper limit of about 0.090 or 0.100 or
0.130 or 0.150 or 0.200 or 0.250 or 0.300 or 0.400 inches. For
example, the intermediate core layer may have a volume with a lower
limit of 0.06 or 0.1 or 0.5 or 1.25 or 2.0 or 3.0 or 3.4 or 4.0 or
4.25 or 5.0 or 5.5 or 6.0 or 6.24 or 7.0 or 8.0 cc and an upper
limit of 9.0 or 10.0 or 10.5 or 11.0 or 12.0 or 12.1 or 12.7 or
13.0 or 14.0 or 14.5 or 15.0 or 16.0 or 16.5 or 17.0 or 17.8
cc.
[0135] As far as the outer core layer is concerned, it preferably
has a thickness in the range of about 0.100 to about 0.750 inches
and the volume of the outer core layer preferably is in the range
of about 1.78 to about 42.04 cc. For example, the lower limit of
thickness may be about 0.050 or 0.100 or 0.150 or 0.200 or 0.250 or
0.300 or 0.340 or 0.400 and the upper limit may be about 0.500 or
0.550 or 0.600 or 0.650 or 0.700 or 0.750 inches. For example, the
outer core layer may have a volume with a lower limit of 1.78 or
4.00 or 6.30 or 8.00 or 10.60 or 11.00 or 11.60 or 12.00 or 16.20
or 20.10 cc and an upper limit of 22.00 or 24.30 or 26.40 or 30.00
or 34.10 or 38.20 or 40.00 or 42.04 cc.
[0136] Multi-layered core structures containing layers with various
thickness and volume levels may be made in accordance with this
invention. For example, in one version, the total diameter of the
inner core and intermediate core is 0.2 inches and the total volume
of the inner and intermediate core is 0.07 cc. More particularly,
in this example, the volume of the intermediate core layer is 0.06
cc and the volume of the inner core is 0.01 cc. In one preferred
embodiment, the volume of the outer core layer is greater than the
volume of each of the inner and intermediate core layers. In
another preferred embodiment, the volume of the intermediate core
layer is greater than the volume of the inner core layer. Thus,
some core structure examples include an outer core layer having a
relatively large volume; an intermediate core layer having a
relatively mid-size volume, and an inner core having a relatively
small volume. That is, the volume of the outer core layer is
greater than the volume of the intermediate core layer; and the
volume of the intermediate core layer is greater than the volume of
the inner core. In one particular version, the volume of the outer
core layer is greater than the volume of the intermediate core
layer; and the volume of the intermediate core layer is greater
than the volume of the inner core.
[0137] As discussed above, the inner core is preferably formed from
a foamed thermoplastic or thermoset composition and more preferably
foamed polyurethanes. And, the intermediate and outer core layers
are formed preferably from a thermoplastic composition such as
ethylene acid copolymer. In another version, the intermediate core
layer may be formed from polybutadiene rubber; and the outer core
layer may be formed from an ethylene acid copolymer
composition.
[0138] Specific Gravities
[0139] In one preferred embodiment, the inner core has a specific
gravity in the range of about 0.25 to about 1.25 g/cc. Also, as
discussed above, the specific gravity of the inner core may vary at
different points of the inner core structure. That is, there may be
a specific gravity gradient in the inner core. For example, in one
preferred version, the geometric center of the inner core has a
density in the range of about 0.25 to about 0.75 g/cc; while the
outer skin of the inner core has a density in the range of about
0.75 to about 1.50 g/cc.
[0140] Meanwhile, the intermediate and outer core layers preferably
have relatively high specific gravities. Thus, the specific gravity
of the inner core layer (SG.sub.inner) is preferably less than the
specific gravity of the intermediate core layer
(SG.sub.intermediate) and outer core layer (SG.sub.outer). By the
term, "specific gravity of the intermediate core layer"
("SG.sub.intermediate "), it is generally meant the specific
gravity of the intermediate core layer as measured at any point of
the intermediate core layer. By the term, "specific gravity of the
outer core layer" ("SG.sub.outer"), it is generally meant the
specific gravity of the outer core layer as measured at any point
of the outer core layer in a manner similar to measuring the
specific gravity of the inner core as discussed above. The specific
gravity values at different points in the intermediate and outer
core layers may vary. That is, there may be specific gravity
gradients in the intermediate and outer core layers similar to the
inner core. For example, the intermediate and outer core layers
each may have a specific gravity within a range having a lower
limit of about 0.50 or 0.60 or 0.70 or 0.75 or 0.85 or 0.95 or 1.00
or 1.10 or 1.25 or 1.30 or 1.36 or 1.40 or 1.42 or 1.48 or 1.50 or
1.60 or 1.66 or 1.75 or 2.00 and an upper limit of 2.50 or 2.60 or
2.80 or 2.90 or 3.00 or 3.10 or 3.25 or 3.50 or 3.60 or 3.80 or
4.00, 4.25 or 5.00 or 5.10 or 5.20 or 5.30 or 5.40 or 6.00 or 6.20
or 6.25 or 6.30 or 6.40 or 6.50 or 7.00 or 7.10 or 7.25 or 7.50 or
7.60 or 7.65 or 7.80 or 8.00 or 8.20 or 8.50 or 9.00 or 9.75 or
10.00 g/cc.
[0141] In general, the specific gravities of the respective pieces
of an object affect the Moment of Inertia (MOI) of the object. The
Moment of Inertia of a ball (or other object) about a given axis
generally refers to how difficult it is to change the ball's
angular motion about that axis. If the ball's mass is concentrated
towards the center (the center piece (for example, inner core) has
a higher specific gravity than the outer piece(for example, outer
core layers), less force is required to change its rotational rate,
and the ball has a relatively low Moment of Inertia. In such balls,
most of the mass is located close to the ball's axis of rotation
and less force is needed to generate spin. Thus, the ball has a
generally high spin rate as the ball leaves the club's face after
making impact. Conversely, if the ball's mass is concentrated
towards the outer surface (the outer piece (for example, outer core
layers) has a higher specific gravity than the center piece (for
example, inner core), more force is required to change its
rotational rate, and the ball has a relatively high Moment of
Inertia. That is, in such balls, most of the mass is located away
from the ball's axis of rotation and more force is needed to
generate spin. Such balls have a generally low spin rate as the
ball leaves the club's face after making impact.
[0142] More particularly, as described in Sullivan, U.S. Pat. No.
6,494,795 and Ladd et al., U.S. Pat. No. 7,651,415, the formula for
the Moment of Inertia for a sphere through any diameter is given in
the CRC Standard Mathematical Tables, 24th Edition, 1976 at 20
(hereinafter CRC reference). The term, "specific gravity" as used
herein, has its ordinary and customary meaning, that is, the ratio
of the density of a substance to the density of water at 4.degree.
C., and the density of water at this temperature is 1
g/cm.sup.3.
[0143] In one embodiment, the golf balls of this invention are
relatively low spin and long distance. That is, the foam core
construction, as described above, wherein the inner core is made of
a foamed composition helps provide a relatively low spin ball
having good resiliency. The inner foam cores of this invention
preferably have a Coefficient of Restitution (COR) of about 0.300
or greater; more preferably about 0.400 or greater, and even more
preferably about 0.450 or greater. The resulting balls containing
the multi-layered core constructions of this invention and cover of
at least one layer preferably have a COR of about 0.700 or greater,
more preferably about 0.730 or greater; and even more preferably
about 0.750 to 0.810 or greater. The inner foam cores preferably
have a Soft Center Deflection Index ("SCDI") compression, as
described in the Test Methods below, in the range of about 50 to
about 190, and more preferably in the range of about 60 to about
170.
[0144] The USGA has established a maximum weight of 45.93 g (1.62
ounces) for golf balls. For play outside of USGA rules, the golf
balls can be heavier. In one preferred embodiment, the weight of
the multi-layered core is in the range of about 28 to about 38
grams. Also, golf balls made in accordance with this invention can
be of any size, although the USGA requires that golf balls used in
competition have a diameter of at least 1.68 inches. For play
outside of United States Golf Association (USGA) rules, the golf
balls can be of a smaller size. Normally, golf balls are
manufactured in accordance with USGA requirements and have a
diameter in the range of about 1.68 to about 1.80 inches. As
discussed further below, the golf ball contains a cover which may
be multi-layered and in addition may contain intermediate (casing)
layers, and the thickness levels of these layers also must be
considered. Thus, in general, the multi-layer core structure
normally has an overall diameter within a range having a lower
limit of about 1.00 or 1.20 or 1.30 or 1.40 inches and an upper
limit of about 1.58 or 1.60 or 1.62 or 1.66 inches, and more
preferably in the range of about 1.3 to 1.65 inches. In one
embodiment, the diameter of the core sub-assembly is in the range
of about 1.45 to about 1.62 inches.
[0145] Cover Structure
[0146] The golf ball sub-assemblies of this invention may be
enclosed with one or more cover layers. The golf ball sub-assembly
may comprise the multi-layered core structure as discussed above.
In other versions, the golf ball sub-assembly includes the core
structure and one or more casing (mantle) layers disposed about the
core. In one particularly preferred version, the golf ball includes
a multi-layered cover comprising inner and outer cover layers. The
inner cover layer is preferably formed from a composition
comprising an ionomer or a blend of two or more ionomers that helps
impart hardness to the ball. In a particular embodiment, the inner
cover layer is formed from a composition comprising a high acid
ionomer. A particularly suitable high acid ionomer is Surlyn
8150.RTM. (DuPont). Surlyn 8150.RTM. is a copolymer of ethylene and
methacrylic acid, having an acid content of 19 wt %, which is 45%
neutralized with sodium. In another particular embodiment, the
inner cover layer is formed from a composition comprising a high
acid ionomer and a maleic anhydride-grafted non-ionomeric polymer.
A particularly suitable maleic anhydride-grafted polymer is
Fusabond 525D.RTM. (DuPont). Fusabond 525D.RTM. is a maleic
anhydride-grafted, metallocene-catalyzed ethylene-butene copolymer
having about 0.9 wt % maleic anhydride grafted onto the copolymer.
A particularly preferred blend of high acid ionomer and maleic
anhydride-grafted polymer is an 84 wt %/16 wt % blend of Surlyn
8150.RTM. and Fusabond 525D.RTM.. Blends of high acid ionomers with
maleic anhydride-grafted polymers are further disclosed, for
example, in U.S. Pat. Nos. 6,992,135 and 6,677,401, the entire
disclosures of which are hereby incorporated herein by
reference.
[0147] The inner cover layer also may be formed from a composition
comprising a 50/45/5 blend of Surlyn.RTM. 8940/Surlyn.RTM.
9650/Nucrel.RTM. 960, and, in a particularly preferred embodiment,
the composition has a material hardness of from 80 to 85 Shore C.
In yet another version, the inner cover layer is formed from a
composition comprising a 50/25/25 blend of Surlyn.RTM.
8940/Surlyn.RTM. 9650/Surlyn.RTM. 9910, preferably having a
material hardness of about 90 Shore C. The inner cover layer also
may be formed from a composition comprising a 50/50 blend of
Surlyn.RTM. 8940/Surlyn.RTM. 9650, preferably having a material
hardness of about 86 Shore C. A composition comprising a 50/50
blend of Surlyn.RTM. 8940 and Surlyn.RTM. 7940 also may be used.
Surlyn.RTM. 8940 is an E/MAA copolymer in which the MAA acid groups
have been partially neutralized with sodium ions. Surlyn.RTM. 9650
and Surlyn.RTM. 9910 are two different grades of E/MAA copolymer in
which the MAA acid groups have been partially neutralized with zinc
ions. Nucrel.RTM. 960 is an E/MAA copolymer resin nominally made
with 15 wt % methacrylic acid.
[0148] A wide variety of materials may be used for forming the
outer cover including, for example, polyurethanes; polyureas;
copolymers, blends and hybrids of polyurethane and polyurea;
olefin-based copolymer ionomer resins (for example, Surlyn.RTM.
ionomer resins and DuPont HPF.RTM. 1000 and HPF.RTM. 2000,
commercially available from DuPont; Iotek.RTM. ionomers,
commercially available from ExxonMobil Chemical Company;
Amplify.RTM. IO ionomers of ethylene acrylic acid copolymers,
commercially available from The Dow Chemical Company; and
Clarix.RTM. ionomer resins, commercially available from A. Schulman
Inc.); polyethylene, including, for example, low density
polyethylene, linear low density polyethylene, and high density
polyethylene; polypropylene; rubber-toughened olefin polymers; acid
copolymers, for example, poly(meth)acrylic acid, which do not
become part of an ionomeric copolymer; plastomers; flexomers;
styrene/butadiene/styrene block copolymers;
styrene/ethylene-butylene/styrene block copolymers; dynamically
vulcanized elastomers; copolymers of ethylene and vinyl acetates;
copolymers of ethylene and methyl acrylates; polyvinyl chloride
resins; polyamides, poly(amide-ester) elastomers, and graft
copolymers of ionomer and polyamide including, for example,
Pebax.RTM. thermoplastic polyether block amides, commercially
available from Arkema Inc; cross-linked trans-polyisoprene and
blends thereof; polyester-based thermoplastic elastomers, such as
Hytrel.RTM., commercially available from DuPont or RiteFlex.RTM.,
commercially available from Ticona Engineering Polymers;
polyurethane-based thermoplastic elastomers, such as
Elastollan.RTM., commercially available from BASF; synthetic or
natural vulcanized rubber; and combinations thereof. Castable
polyurethanes, polyureas, and hybrids of polyurethanes-polyureas
are particularly desirable because these materials can be used to
make a golf ball having high resiliency and a soft feel. By the
term, "hybrids of polyurethane and polyurea," it is meant to
include copolymers and blends thereof.
[0149] Polyurethanes, polyureas, and blends, copolymers, and
hybrids of polyurethane/polyurea are also particularly suitable for
forming cover layers. When used as cover layer materials,
polyurethanes and polyureas can be thermoset or thermoplastic.
Thermoset materials can be formed into golf ball layers by
conventional casting or reaction injection molding techniques.
Thermoplastic materials can be formed into golf ball layers by
conventional compression or injection molding techniques.
[0150] The compositions used to make the casing (mantle) and cover
layers may contain a wide variety of fillers and additives to
impart specific properties to the ball. For example, relatively
heavy-weight and light-weight metal fillers such as, particulate;
powders; flakes; and fibers of copper, steel, brass, tungsten,
titanium, aluminum, magnesium, molybdenum, cobalt, nickel, iron,
lead, tin, zinc, barium, bismuth, bronze, silver, gold, and
platinum, and alloys and combinations thereof may be used to adjust
the specific gravity of the ball. Other additives and fillers
include, but are not limited to, optical brighteners, coloring
agents, fluorescent agents, whitening agents, UV absorbers, light
stabilizers, surfactants, processing aids, antioxidants,
stabilizers, softening agents, fragrance components, plasticizers,
impact modifiers, titanium dioxide, clay, mica, talc, glass flakes,
milled glass, and mixtures thereof.
[0151] The inner cover layer preferably has a material hardness
within a range having a lower limit of 70 or 75 or 80 or 82 Shore C
and an upper limit of 85 or 86 or 90 or 92 Shore C. The thickness
of the intermediate layer is preferably within a range having a
lower limit of 0.010 or 0.015 or 0.020 or 0.030 inches and an upper
limit of 0.035 or 0.045 or 0.080 or 0.120 inches. The outer cover
layer preferably has a material hardness of 85 Shore C or less. The
thickness of the outer cover layer is preferably within a range
having a lower limit of 0.010 or 0.015 or 0.025 inches and an upper
limit of 0.035 or 0.040 or 0.055 or 0.080 inches. Methods for
measuring hardness of the layers in the golf ball are described in
further detail below.
[0152] A single cover or, preferably, an inner cover layer is
formed around the outer core layer. When an inner cover layer is
present, an outer cover layer is formed over the inner cover layer.
Most preferably, the inner cover is formed from an ionomeric
material and the outer cover layer is formed from a polyurethane
material, and the outer cover layer has a hardness that is less
than that of the inner cover layer. Preferably, the inner cover has
a hardness of greater than about 60 Shore D and the outer cover
layer has a hardness of less than about 60 Shore D. In an
alternative embodiment, the inner cover layer is comprised of a
partially or fully neutralized ionomer, a thermoplastic polyester
elastomer such as Hytrel.TM., commercially available from DuPont, a
thermoplastic polyether block amide, such as Pebax.TM.,
commercially available from Arkema,Inc., or a thermoplastic or
thermosetting polyurethane or polyurea, and the outer cover layer
is comprised of an ionomeric material. In this alternative
embodiment, the inner cover layer has a hardness of less than about
60 Shore D and the outer cover layer has a hardness of greater than
about 55 Shore D and the inner cover layer hardness is less than
the outer cover layer hardness.
[0153] As discussed above, the core structure of this invention may
be enclosed with one or more cover layers. In one embodiment, a
multi-layered cover comprising inner and outer cover layers is
formed, 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. In this version, 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. The outer cover layer,
in this embodiment, preferably has 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, with a hardness of about Shore D 80 or less, more
preferably 70 or less, and most preferably about 60 or less. The
inner cover layer is harder than the outer cover layer in this
version. A preferred outer cover layer is a castable or reaction
injection molded polyurethane, polyurea or copolymer, blend, or
hybrid thereof having a Shore D hardness of about 40 to about 50.
In another multi-layer cover, dual-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. For this harder outer
cover/softer inner cover embodiment, the ionomer resins described
above would preferably be used as outer cover material.
[0154] Manufacturing of Golf Balls
[0155] As described above, the inner core preferably is formed by a
casting method. The intermediate and outer core layers, which
surround the inner core, are formed by molding compositions over
the inner core. Compression or injection molding techniques may be
used to form the other layers of the core sub-assembly. Then, the
casing and/or cover layers are applied over the core sub-assembly.
Prior to this step, the core structure may be surface-treated to
increase the adhesion between its outer surface and the next layer
that will be applied over the core. Such surface-treatment may
include mechanically or chemically-abrading the outer surface of
the core. For example, the core may be subjected to
corona-discharge, plasma-treatment, silane-dipping, or other
treatment methods known to those in the art.
[0156] The cover layers are formed over the core or ball
sub-assembly (the core structure and any casing layers disposed
about the core) using a suitable technique such as, for example,
compression-molding, flip-molding, injection-molding, retractable
pin injection-molding, reaction injection-molding (RIM), liquid
injection-molding, casting, spraying, powder-coating,
vacuum-forming, flow-coating, dipping, spin-coating, and the like.
Preferably, each cover layer is separately formed over the ball
subassembly. For example, an ethylene acid copolymer ionomer
composition may be injection-molded to produce half-shells.
Alternatively, the ionomer composition can be placed into a
compression mold and molded under sufficient pressure, temperature,
and time to produce the hemispherical shells. The smooth-surfaced
hemispherical shells are then placed around the core sub-assembly
in a compression mold. Under sufficient heating and pressure, the
shells fuse together to form an inner cover layer that surrounds
the sub-assembly. In another method, the ionomer composition is
injection-molded directly onto the core sub-assembly using
retractable pin injection molding. An outer cover layer comprising
a polyurethane or polyurea composition over the ball sub-assembly
may be formed by using a casting process.
[0157] After the golf balls have been removed from the mold, they
may be subjected to finishing steps such as flash-trimming,
surface-treatment, marking, coating, and the like using techniques
known in the art. For example, in traditional white-colored golf
balls, the white-pigmented cover may be surface-treated using a
suitable method such as, for example, corona, plasma, or
ultraviolet (UV) light-treatment. Then, indicia such as trademarks,
symbols, logos, letters, and the like may be printed on the ball's
cover using pad-printing, ink-jet printing, dye-sublimation, or
other suitable printing methods. Clear surface coatings (for
example, primer and top-coats), which may contain a fluorescent
whitening agent, are applied to the cover. The resulting golf ball
has a glossy and durable surface finish.
[0158] In another finishing process, the golf balls are painted
with one or more paint coatings. For example, white primer paint
may be applied first to the surface of the ball and then a white
top-coat of paint may be applied over the primer. Of course, the
golf ball may be painted with other colors, for example, red, blue,
orange, and yellow. As noted above, markings such as trademarks and
logos may be applied to the painted cover of the golf ball.
Finally, a clear surface coating may be applied to the cover to
provide a shiny appearance and protect any logos and other markings
printed on the ball.
[0159] In FIG. 4, a cross-sectional view of one version of a golf
ball that can be made in accordance with this invention is
generally indicated at (21). The ball (21) contains a multi-layered
core having a foam inner core (24), intermediate core layer (26),
and outer core layer (28) surrounded by a single-layered cover
(30).
[0160] In another version, as shown in FIG. 5, the golf ball (31)
contains a multi-layered core (32) having a foam inner core (32a),
intermediate core layer (32b), and outer core layer (32c). The
multi-layered core (32) is surrounded by a multi-layered cover (34)
having an inner cover layer (34a) and outer cover layer (34b).
Lastly, in FIG. 6, a six-piece ball (35) containing a multi-layered
core (36) comprising inner (36a), intermediate (36b), and outer
core (36c) layers is shown. The inner core (36a) is made of a
foamed composition. A casing or mantle layer (38) is disposed
between the core structure (36) and multi-layered cover (40). The
ball may include one or more casing layers (38). The multi-layered
cover (40) includes inner (40a) and outer (40b) cover layers.
[0161] Different ball constructions can be made using the core
construction of this invention as shown in FIGS. 1-6 discussed
above. Such golf ball constructions include, for example,
four-piece, five-piece, and six-piece constructions. It should be
understood that the golf balls shown in FIGS. 1-6 are for
illustrative purposes only, and they are not meant to be
restrictive. Other golf ball constructions can be made in
accordance with this invention.
[0162] For example, other constructions include a core sub-assembly
having a foam or non-foam inner core (center); a foam or non-foam
intermediate core layer; and a foam or non-foam outer core layer.
Dual-core sub-assemblies (inner core and outer core layer), wherein
the inner core and/or the outer core layer is foamed also may be
made. Furthermore, the inner cover layer, which surrounds the core
sub-assembly, may be foamed or non-foamed. As discussed above,
thermoplastic and thermoset foam compositions may be used to form
the different layers. Where more than one foam layer is used in a
single golf ball, the foamed composition may be the same or
different, and the composition may have the same or different
hardness or specific gravity values.
[0163] Test Methods
[0164] Hardness. The center hardness of a core is obtained
according to the following procedure. 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 is 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` surface is ground to a smooth, flat
surface, revealing the geometric center of the core, which can be
verified by measuring the height from 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. 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 according to
ASTM D-2240. Additional hardness measurements at any distance from
the center of the core can then be made by drawing a line radially
outward from the center mark, and measuring the hardness at any
given distance along the line, typically in 2 mm increments from
the center. The hardness at a particular distance from the center
should be measured along at least two, preferably four, radial arms
located 180.degree. apart, or 90.degree. apart, respectively, and
then averaged. All hardness measurements performed on a 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, and thus also parallel to the properly
aligned foot of the durometer.
[0165] The outer surface hardness of a golf ball layer is measured
on the actual outer surface of the layer and is obtained from the
average of a number of measurements taken from opposing
hemispheres, 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, care must be taken to
ensure that the golf ball or golf ball sub-assembly is centered
under the durometer indenter before a surface hardness reading is
obtained. A calibrated, digital durometer, capable of reading to
0.1 hardness units is used for the hardness measurements. The
digital durometer must be attached to, and its foot made parallel
to, the base of an automatic stand. The weight on the durometer and
attack rate conforms to ASTM D-2240.
[0166] In certain embodiments, a point or plurality of points
measured along the "positive" or "negative" gradients may be above
or below a line fit through the gradient and its outermost and
innermost hardness values. In an alternative preferred embodiment,
the hardest point along a particular steep "positive" or "negative"
gradient may be higher than the value at the innermost portion of
the inner core (the geometric center) or outer core layer (the
inner surface)--as long as the outermost point (i.e., the outer
surface of the inner core) is greater than (for "positive") or
lower than (for "negative") the innermost point (i.e., the
geometric center of the inner core or the inner surface of the
outer core layer), such that the "positive" and "negative"
gradients remain intact.
[0167] As discussed above, the direction of the hardness gradient
of a golf ball layer is defined by the difference in hardness
measurements taken at the outer and inner surfaces of a particular
layer. The center hardness of an inner core and hardness of the
outer surface of an inner core in a single-core ball or outer core
layer are readily determined according to the test procedures
provided above. The outer surface of the inner core layer (or other
optional intermediate core layers) in a dual-core ball are also
readily determined according to the procedures given herein for
measuring the outer surface hardness of a golf ball layer, if the
measurement is made prior to surrounding the layer with an
additional core layer. Once an additional core layer surrounds a
layer of interest, the hardness of the inner and outer surfaces of
any inner or intermediate layers can be difficult to determine.
Therefore, for purposes of the present invention, when the hardness
of the inner or outer surface of a core layer is needed after the
inner layer has been surrounded with another core layer, the test
procedure described above for measuring a point located 1 mm from
an interface is used.
[0168] Also, it should be understood that there is a fundamental
difference between "material hardness" and "hardness as measured
directly on a golf ball." For purposes of the present invention,
material hardness is measured according to ASTM D2240 and generally
involves measuring the hardness of a flat "slab" or "button" formed
of the material. Surface hardness as measured directly on a golf
ball (or other spherical surface) typically results in a different
hardness value. The difference in "surface hardness" and "material
hardness" values is due to several factors including, but not
limited to, ball construction (that is, core type, number of cores
and/or cover layers, and the like); ball (or sphere) diameter; and
the material composition of adjacent layers. It also should be
understood that the two measurement techniques are not linearly
related and, therefore, one hardness value cannot easily be
correlated to the other. Shore hardness (for example, Shore C or
Shore D hardness) was measured according to the test method ASTM
D-2240.
[0169] Compression. As disclosed in Jeff Dalton's Compression by
Any Other Name, Science and Golf IV, Proceedings of the World
Scientific Congress of Golf (Eric Thain ed., Routledge, 2002) ("J.
Dalton"), several different methods can be used to measure
compression, including Atti compression, Riehle compression,
load/deflection measurements at a variety of fixed loads and
offsets, and effective modulus. For purposes of the present
invention, compression refers to Soft Center Deflection Index
("SCDI"). 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. 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.
[0170] Drop Rebound. By "drop rebound," it is meant the number of
inches a sphere will rebound when dropped from a height of 72
inches in this case, measuring from the bottom of the sphere. A
scale, in inches is mounted directly behind the path of the dropped
sphere and the sphere is dropped onto a heavy, hard base such as a
slab of marble or granite (typically about 1 ft wide by 1 ft high
by 1 ft deep). The test is carried out at about 72-75.degree. F.
and about 50% RH
[0171] Coefficient of Restitution ("COR"). The COR is determined
according to a known procedure, wherein a golf ball or golf ball
sub-assembly (for example, a golf ball core) is fired from an air
cannon at two given velocities and a velocity of 125 ft/s is used
for the calculations. Ballistic light screens are located between
the air cannon and steel plate at a fixed distance to measure ball
velocity. As the ball travels toward the steel plate, it activates
each light screen and the ball's time period at each light screen
is measured. This provides an incoming transit time period which is
inversely proportional to the ball's incoming velocity. The ball
makes impact with the steel plate and rebounds so it passes again
through the light screens. As the rebounding ball activates each
light screen, the ball's time period at each screen is measured.
This provides an outgoing transit time period which is inversely
proportional to the ball's outgoing velocity. The COR is then
calculated as the ratio of the ball's outgoing transit time period
to the ball's incoming transit time period
(COR=V.sub.out/V.sub.in=T.sub.in/T.sub.out).
[0172] The present invention is illustrated further by the
following Examples, but these Examples should not be construed as
limiting the scope of the invention.
EXAMPLES
[0173] In the following Examples, different foam formulations were
used to prepare core samples using the above-described molding
methods. The different formulations are described in Tables 1 and 2
below.
TABLE-US-00001 TABLE 1 (Sample A) Ingredient Weight Percent 4,4
Methylene Diphenyl Diisocyanate (MDI) 14.65% Polyetratmethylene
ether glycol (PTMEG 34.92% 2000) *Mondur .TM. 582 (2.5 fn) 29.11%
Trifunctional caprolactone polyol (CAPA 3031) 20.22% (3.0 fn) Water
0.67% **Niax .TM. L-1500 surfactant 0.04% ***KKAT .TM. XK 614
catalyst 0.40% Dibutyl tin dilaurate (T-12) 0.03% *Mondur .TM. 582
(2.5 fn) - polymeric methylene diphenyl diisocyanate (p-MDI) with
2.5 functionality, available from Bayer Material Science. **Niax
.TM. L-1500 silicone-based surfactant, available from Momentive
Specialty Chemicals, Inc. ***KKAT .TM. XK 614 zinc-based catalyst,
available from King Industries.
The formulation described in above Table 1 was used to make a core
sample (Sample A) and the sample was evaluated and tested. The
spherical core Sample A (0.75 inch diameter) had a density of 0.45
g/cm.sup.3, a compression (SCDI) of 75, and drop rebound of 46%
based on average measurements using the test methods as described
above.
TABLE-US-00002 TABLE 2 (Sample B) Ingredient Weight Percent Mondur
.TM. 582 (2.5 fn) 30.35% *Desmodur .TM. 3900 aliphatic 30.35%
**Polymeg .TM. 650 19.43% ***Ethacure .TM. 300 19.43% Water 0.31%
Niax .TM. L-1500 surfactant 0.04% Dibutyl tin dilaurate (T-12)
0.09% *Desmodur .TM. 3900 - polyfunctional aliphatic polyisocyanate
resin based on hexamethylene diisocyanate (HDI), available from
Bayer Material Science. **Polymeg .TM. 650 - polyetratmethylene
ether glycol, available from Lyondell Chemical Company. ***Ethacure
.TM. 300 - aromatic diamine curing agent, available from Albemarle
Corp.
The formulation described in above Table 4 was used to make a core
sample (Sample B) and the sample was evaluated and tested. The
resulting spherical core Sample B (0.75 inch diameter) had a
density of 0.61 g/cm.sup.3, a compression (SCDI) of 160, and drop
rebound of 56% based on average measurements using the test methods
as described above.
[0174] Prophetic Examples
[0175] The following prophetic examples describe three-layered core
structures that may be made in accordance with this invention. The
foam center of the core may be made using a polyurethane foam
formulation as described above in Tables 1 and 2 or any other
suitable foam material as described above. The intermediate core
layer may be made of an ethylene acid copolymer ionomer,
thermoplastic elastomer, or any other suitable thermoplastic
material such as described above. The outer core layer also may be
made of a suitable thermoplastic.
Example 1
[0176] Three-layered core (foam center and non-foamed thermoplastic
intermediate and outer layers) having a center diameter of 0.5
inches and a hardness gradient across the core (as measured at
points in millimeters (mm) from the geometric center) in the range
of about 36 Shore C to about 78 Shore C. The hardness plot of this
core structure is shown in FIG. 7A.
Example 2
[0177] Three-layered core (foam center and non-foamed thermoplastic
intermediate and outer layers) having a center diameter of 0.5
inches and a hardness gradient across the core (as measured at mm
points from the geometric center) in the range of about 24 Shore C
to about 80 Shore C. The hardness plot of this core structure is
shown in FIG. 7B.
Example 3
[0178] Three-layered core (foam center and non-foamed thermoplastic
intermediate and outer layers) having a center diameter of 0.5
inches and a hardness gradient across the core (as measured at mm
points from the geometric center) in the range of about 53 Shore C
to about 74 Shore C. The hardness plot of this core structure is
shown in FIG. 7C.
Example 4
[0179] Three-layered core (foam center and non-foamed thermoplastic
intermediate and outer layers) having a center diameter of 0.75
inches and a hardness gradient across the core (as measured at mm
points from the geometric center) in the range of about 48 Shore C
to about 73 Shore C. The hardness plot of this core structure is
shown in FIG. 7D.
[0180] It is understood that the golf ball compositions, materials,
structures, products, and examples described and illustrated herein
represent only some embodiments of the invention. It is appreciated
by those skilled in the art that various changes and additions can
be made to compositions, materials, structures, products, and
examples without departing from the spirit and scope of this
invention. It is intended that all such embodiments be covered by
the appended claims.
[0181] When numerical lower limits and numerical upper limits are
set forth herein, it is contemplated that any combination of these
values may be used. 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.
[0182] All patents, publications, test procedures, and other
references cited herein, including priority documents, are fully
incorporated by reference to the extent such disclosure is not
inconsistent with this invention and for all jurisdictions in which
such incorporation is permitted.
* * * * *