U.S. patent application number 13/285474 was filed with the patent office on 2012-02-23 for golf balls containing visible decorative inserts enclosed in transparent layers.
Invention is credited to William E. Morgan, Michael J. Sullivan.
Application Number | 20120046124 13/285474 |
Document ID | / |
Family ID | 45594503 |
Filed Date | 2012-02-23 |
United States Patent
Application |
20120046124 |
Kind Code |
A1 |
Sullivan; Michael J. ; et
al. |
February 23, 2012 |
GOLF BALLS CONTAINING VISIBLE DECORATIVE INSERTS ENCLOSED IN
TRANSPARENT LAYERS
Abstract
Golf balls containing a composite layer comprising a
substantially transparent polymeric matrix with at least one
embedded decorative insert member (for example, charm or jewelry
piece) are provided. The ball further includes a core that may
comprise a reflective material such as white pigment. A cover
structure comprising a second substantially transparent polymeric
matrix surrounds the composite layer. The decorative insert can be
seen through the layers. Various light-reflective fillers, color
pigments, and dyes may be added to the layers to create different
optical effects. The resulting ball has an aesthetically pleasing
appearance while maintaining its good playing performance
properties.
Inventors: |
Sullivan; Michael J.;
(Barrington, RI) ; Morgan; William E.;
(Barrington, RI) |
Family ID: |
45594503 |
Appl. No.: |
13/285474 |
Filed: |
October 31, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12143879 |
Jun 23, 2008 |
8070626 |
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13285474 |
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11707493 |
Feb 16, 2007 |
7722483 |
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12143879 |
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Current U.S.
Class: |
473/372 ;
473/371; 473/377 |
Current CPC
Class: |
A63B 37/0039 20130101;
A63B 37/0097 20130101; A63B 37/0075 20130101; A63B 43/008 20130101;
A63B 37/0076 20130101 |
Class at
Publication: |
473/372 ;
473/371; 473/377 |
International
Class: |
A63B 37/12 20060101
A63B037/12; A63B 37/06 20060101 A63B037/06; A63B 37/00 20060101
A63B037/00 |
Claims
1. A multi-layered golf ball, comprising: a core having at least
one layer; a composite layer disposed about the core; the composite
layer comprising a decorative insert member fully embedded in a
first substantially transparent polymeric matrix; and a cover
having at least one layer, the cover being disposed about the
composite layer and comprising a second substantially transparent
polymeric matrix so that the decorative insert is visible from the
exterior of the ball.
2. The golf ball of claim 1, wherein the core is single-layered,
the core being formed from a rubber composition.
3. The golf ball of claim 1, wherein the core is dual-layered, the
core comprising an inner core and surrounding outer core layer, at
least one of the core layers being formed from a rubber
composition.
4. The golf ball of claim 1, wherein the core comprises a
reflective material.
5. The golf ball of claim 4, wherein the reflective material is
white pigment.
6. The golf ball of claim 1, wherein the insert member is a metal
material.
7. The golf ball of claim 1, wherein the insert member is a plastic
material.
8. The golf ball of claim 1, wherein the insert member has a
spherical shape.
9. The golf ball of claim 1, wherein the insert member has a
non-spherical shape.
10. The golf ball of claim 1, wherein the first substantially
transparent polymeric matrix comprises a polymer selected from the
group consisting of: ethylene acid copolymer ionomers; polyesters;
polyamides; polyurethanes, polyureas; fluoropolymers; polystyrenes;
polypropylenes, polyethylenes; polyvinyl chlorides; polyvinyl
acetates; polycarbonates; polyvinyl alcohols; polyethers;
polyimides, polyetherketones, polyamideimides; and mixtures
thereof.
11. The golf ball of claim 1, wherein the decorative insert member
comprises a reflective material.
12. The golf ball of claim 11, wherein the reflective material is
white pigment.
13. The golf ball of claim 1, wherein the decorative insert member
comprises light-reflective fillers selected from the group
consisting of pearlescent pigments, glitter, metalized films and
foils, and mixtures thereof.
14. The golf ball of claim 13, wherein the light-reflective fillers
are pearlescent pigments selected from the group consisting of
metalized pigments, mica-based pigments, borosilicate pigments,
titanium dioxide pigments, iron oxide pigments, and mixtures
thereof.
15. The golf ball of claim 1, wherein the decorative insert member
comprises a colorant selected from dyes, pigments, and mixtures
thereof.
16. The golf ball of claim 15, wherein the colorant is a
fluorescent dye.
17. The golf ball of claim 1, wherein the cover is a single layer
having a thickness of about 0.015 to about 0.090 inches.
18. The golf ball of claim 1, wherein the cover comprises two or
more layers and has an overall thickness of about 0.020 to about
0.210 inches.
19. The golf ball of claim 18, wherein the cover comprises an inner
cover layer formed of an ionomer resin comprising an ethylene acid
copolymer and an outer cover layer formed of a polyurethane
composition, each of the cover layers being optically
translucent.
20. The golf ball of claim 1, wherein the second substantially
transparent polymeric matrix comprises a polymer selected from the
group consisting of: ethylene acid copolymer ionomers; polyesters;
polyamides; polyurethanes, polyureas; fluoropolymers; polystyrenes;
polypropylenes and polyethylenes; polyvinyl chlorides; polyvinyl
acetates; polycarbonates; polyvinyl alcohols; polyethers;
polyimides, polyetherketones, polyamideimides; and mixtures
thereof.
21. The golf ball of claim 1, wherein the second substantially
transparent polymeric matrix comprises light-reflective fillers
selected from the group consisting of pearlescent pigments,
glitter, metalized films and foils, and mixtures thereof.
22. The golf ball of claim 21, wherein the light-reflective fillers
are pearlescent pigments selected from the group consisting of
metalized pigments, mica-based pigments, borosilicate pigments,
titanium dioxide pigments, iron oxide pigments, and mixtures
thereof.
23. The golf ball of claim 1, wherein the second substantially
transparent polymeric matrix comprises a colorant selected from
dyes, pigments, and mixtures thereof.
24. The golf ball of claim 23, wherein the colorant is a
fluorescent dye.
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. 12/143,879 filed Jun.
23, 2008, now allowed, which is a continuation-in-part of U.S.
patent application Ser. No. 11/707,493 filed Feb. 16, 2007, now
U.S. Pat. No. 7,722,483, the entire disclosures of which are hereby
incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention generally relates to multi-piece golf
balls and more particularly to golf balls having substantially
transparent layers. The ball contains a decorative insert member
that can be seen through the layers. Reflective fillers, pigments,
and dyes may be added to the layers to create different optical
effects. The resulting ball has an aesthetically pleasing
appearance and good playing performance properties.
[0004] 2. Brief Review of the Related Art
[0005] Golf ball manufacturers are interested in assembling
multi-piece solid golf balls today for various reasons including
cost-effective manufacturing technologies, raw material prices, and
demand. Both professional and amateur golfers enjoy playing with
multi-piece sold golf balls because of their playing performance
properties. Basically, a two-piece solid golf ball includes a solid
inner core protected by an outer cover. The inner core is made
commonly of a rubber material such as natural and synthetic
rubbers: styrene butadiene, polybutadiene, or polyisoprene. Highly
neutralized ethylene acid copolymer ionomer resins (HNPs) also may
be used to form the core. The outer cover is made commonly of
thermoplastic or thermoset resins such as ionomers, polyolefins,
polyamides, polyesters, polyurethanes, and polyureas. As new
materials and manufacturing processes have become more economically
feasible, three-piece, four-piece, and five-piece solid golf balls
have been introduced. Different materials are used in the golf ball
construction to impart specific properties and playing features to
the ball.
[0006] The cover may be formed around the golf ball sub-assembly by
dispensing polymeric material into the mold cavities and mating
them together under sufficient heat and pressure. By the term,
"sub-assembly" as used herein, it is meant the inner ball, that is
the core and any intermediate layer(s) disposed between the core
and outer cover layer. For example, one technique involves using a
white-pigmented material such as polyurethane, polyurea, or the
like to form the cover as described above. The cover is
surface-treated using a suitable method such as, for example,
corona treatment, plasma treatment, UV treatment, flame treatment,
or electron beam treatment. Trademarks, symbols, logos, letters,
numerals, and other indicia may be printed on the ball's cover
using pad-printing, ink-jet printing, dye sublimation, or other
suitable printing methods ,. Then, clear surface coatings (for
example, primer and top-coats), which may contain a fluorescent
whitening agent, are applied to the cover. Suitable materials that
can be used as such surface coatings include, for example,
urethanes, urethane hybrids, epoxies, polyesters and acrylics. The
resulting golf ball has a glossy and durable surface finish.
[0007] In another finishing process, the golf balls are painted
with one or more paint coatings. For example, 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. 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 finished appearance.
[0008] In recent years, there has been interest in manufacturing
and playing with golf balls having different aesthetics than
traditional white-colored balls. For example, Berard, U.S. Pat. No.
4,798,386 discloses golf balls having a cover with fluorescent
appearance. The cover material may be clear, and the core may be
white colored. The core may be stamped with a logo or trademark
that is visible through the clear cover. According to the '386
Patent, fluorescent dyes and pigments may be added to the cover
composition to make the cover brighter.
[0009] Meyer, U.S. Pat. No. 4,998,734 discloses a ball having a
core, an indicia-bearing liner, and a translucent or transparent
cover. According to the '734 Patent, the indicia-bearing liner is a
thin layer of plastic or paper material; where upon textual,
alphanumeric or graphic indicia can be printed thereon. The
indicia-bearing liner is sufficiently thin to permit substantial
transference of impact forces from the cover to the core without
substantially reducing the transferred force.
[0010] Proudfit et al., U.S. Pat. No. 5,542,680 discloses a golf
ball having a substantially clear cover so that the core of the
ball is visible through the cover. The cover is preferably formed
from a blend of ionomer resins. The core may be printed with
indicia such as a logo or stripes which are visible through the
clear cover. The core may include pigment or dye to provide color,
or a white core can be produced using titanium dioxide.
[0011] Welch, U.S. Pat. No. 5,989,135 discloses a golf ball having
a white core and a relatively thin, translucent cover made of
ionomer resin. The translucent cover contains a photostorage
material that stores radiant energy and re-emits a glow of light. A
brightly-colored fluorescent dye can be added to the ionomer cover
material to produce a golf ball that is brightly colored. For
example, when a bright yellow fluorescent dye is used, the ball can
be seen in daylight conditions. After the photostorage material is
charged by exposure to light, the yellow fluorescent ball emits a
bright glow for high visibility in the dark.
[0012] Yavitz, U.S. Pat. No. 6,012,992 discloses a golf ball having
a cover formed from a clear ionomer resin, and a distinct second
region formed from an opaque ionomer resin. Indicia such as a logo
may be printed on the surface of the core so that is disposed
beneath the first region 24. Because the first region of the cover
is transparent, the indicia are visible from the exterior of the
golf ball, and it is protected from wear and abrasion by the cover.
The second region of the cover is opaque, for example, it may be
colored to provide different visual effects.
[0013] Sullivan, U.S. Pat. No. 6,315,681 discloses a golf ball
containing core, a first cover layer, and a second cover layer.
There is a recessed region with a viewing window along the outer
surface of the ball. The first cover layer includes a particulate
weighting material such as heavy weight fillers or fibers, which
are added to increase the moment of inertia or the ball. The
viewing window in the recessed region is generally transparent and
enables at least a portion of the particulate weighting material in
the first cover layer to be seen from the outer surface of the
ball.
[0014] Sullivan et al., U.S. Pat. No. 7,435,192 discloses a golf
ball comprising: a non-spherical insert core; at least one
surrounding core layer; and at least one cover layer. The
non-spherical core insert (as shown in FIGS. 5-8), is viewable
through one or more translucent layers. The '301 Patent further
discloses that the cover/core layers may contain reflective or
optically active particulates such as pearlescent pigment.
[0015] Morgan et al., U.S. Pat. No. 7,722,483 discloses a golf ball
comprising a core, a cover and at least one intermediate layer
disposed between the core and cover. The intermediate layer
includes pigment which contributes to the color of the ball. The
cover is at least partially transparent such that the intermediate
layer is at least partially visible. The intermediate layer
preferably is formed from a composition containing thermoplastic
elastomer and florescent dye or optical brightener. The cover
preferably is formed from a substantially translucent composition
comprising polyisocyanate.
[0016] Morgan et al., U.S. Pat. No. 7,901,301 discloses a golf ball
having at least one core layer; at least one intermediate layer
encasing the core layer(s); and at least one cover layer encasing
the intermediate layer (s). The core, intermediate, and cover
layers may be translucent so that the non-spherical insert is
visible, and the layers may contain a visually enhancing means such
as metallics, fluorescents, phosphorescents, luminescents,
pearlescents, optical brighteners, edge-effect pigments, pigments,
dyes and/or tinting agents. The intermediate layer has a
non-uniform thickness, that is, its thickness varies around the
core layer and throughout the ball. The non-uniform thickness is
created by outer projections such as webs or ribs on the surface of
the intermediate layer as shown in FIGS. 1 and 1A. The intermediate
layer has a distinct geometric pattern which serves to orient the
golf ball in space, thereby indicating alignment of the golf
ball.
[0017] One drawback with golf balls using a pre-formed, selectively
weighted insert as the inner core, as described in the above patent
references, is that it must be over-molded with other materials to
form the final core structure. The cover structure then must be
molded over the core assembly and these layers are filled often
with additives. Thus, it can be generally difficult to see the
insert (inner core), because light must be transmitted through
multiple filled layers. Looking for the insert (inner core) through
these filled layers can be similar to looking at an object through
a frosted glass window. It can be difficult to see the detailed
features of the insert because of the overlapping filled layers.
Also, the resiliency and rebounding performance of the golf ball is
based primarily on the core. Balls with a higher rebound velocity
have a higher Coefficient of Restitution or "COR" value. Such balls
rebound faster, retain more total energy when struck by a club, and
have longer flight distance. It is important that an insert
incorporated in the golf ball does not negatively affect the ball's
playing performance properties of the ball.
[0018] There has been a recent demand for golf balls having more
appealing aesthetics. The present invention provides golf balls
containing one or more decorative insert members. In a preferred
version, a substantially transparent composite layer, which is
disposed between the core and cover, envelops the decorative
insert. The underlying core layers may be opaque and the cover
layers may be substantially transparent resulting in a golf ball
having unique optical effects along with other advantageous
properties and features.
SUMMARY OF THE INVENTION
[0019] The present invention relates to multi-layered golf balls
comprising a core having at least one layer; a composite layer that
is disposed about the core; and a cover having at least one layer
that is disposed about the composite layer. At least one decorative
insert member is enclosed in the composite layer. The composite and
cover layers are formed from first and second substantially
transparent polymeric matrices, respectively. The decorative
insert(s) is plainly visible to a human eye looking at the exterior
of the ball. In one embodiment, the core is single-layered and made
from a rubber composition. In another embodiment, the core has a
dual-layered construction. Different polymers may be used to form
the substantially transparent matrices, and these matrices also may
contain various reflective fillers, pigments, dyes, and the like;
provided, that the insert remains visible. In one embodiment, the
substantially transparent cover is single-layered and made from an
ionomer, polyurethane, or polyurea composition. In another
embodiment, the cover includes inner and outer cover layers, each
being substantially transparent.
[0020] The decorative insert is pre-formed prior to placing it in
the composite layer and may be molded, machined, cast, laser-cut,
or otherwise shaped into various geometries and dimensions. The
decorative insert may have a complex or simple geometry. For
example, the insert have a spherical or non-spherical shape such as
a polygonal structure. Particular examples of decorative inserts
include small figurines, charms, jewelry pieces, and other articles
that provide an ornamental effect to the ball. In accordance with
this invention, multiple decorative inserts of the same or
different geometries and dimensions are present preferably in the
golf ball layer(s). The decorative inserts may be made from metal,
plastic, rubber, or other suitable materials and are enclosed in
the golf ball to provide unique aesthetics and an appealing
appearance.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] 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:
[0022] FIG. 1 is a top view of a golf ball having a dimpled cover
and a visible decorative insert underlying the cover made in
accordance with the present invention;
[0023] FIG. 2 is a cut-away view of a the golf ball shown in FIG.
1;
[0024] FIG. 3 is a cross-sectional view of a three-piece golf ball
having an inner core; a composite layer, and an outer cover layer
made in accordance with the present invention; and
[0025] FIG. 4 is a cross-sectional view of a four-piece golf ball
having a dual-core comprising an inner core and outer core layer, a
composite layer, and an outer cover layer made in accordance with
the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0026] The present invention relates generally to golf balls
containing a composite layer comprising a substantially transparent
polymeric matrix. The composite layer contains a decorative insert
member embedded in the polymeric matrix, whereby the insert is
plainly visible to a human eye looking at the exterior of the ball.
Preferably, the composite layer containing the decorative insert is
disposed between the core and cover layers. That is, the composite
layer surrounds the core structure (for example, single or
dual-layered), and the cover structure (for example, single or
dual-layered) surrounds the composite layer. In this version, the
cover layer comprises a second substantially transparent polymeric
matrix, and the insert is visible through the cover layer. In an
alternative version, the composite layer containing the decorative
insert may be used as the innermost core (or center) of the ball
and outer core layers, intermediate or casing layers, and cover
structure may be disposed about the composite inner core layer. In
this version, the core comprises a substantially transparent
polymer matrix and contains the visible decorative insert. In a
further version, the composite layer containing the decorative
insert may be used as the outer core layer. In yet another version,
the composite layer containing the decorative insert may be used as
the inner or outer cover layer. Thus, there can be composite inner
and/or outer cover layers, whereby the insert is enclosed in the
cover but is relatively close to ball's surface. It also is
recognized that the golf ball may contain multiple decorative
inserts in the same layer or different layers. For example, the
composite layer, as described above, may contain a plurality of
decorative inserts. The inserts may have various geometries and
dimensions as described below. In another example, one decorative
insert may be incorporated in a core layer and a second decorative
insert may be incorporated in a cover layer. In yet another
example, each of the above-described layers (core, composite, and
cover) may enclose one or more decorative inserts.
[0027] Golf balls having various constructions may be made in
accordance with this invention. For example, golf balls having
three-piece, four-piece, and five-piece constructions may be made.
In a preferred embodiment, the balls include a core structure, a
composite layer disposed about the core structure, and a
surrounding cover structure. However, as discussed above, the
composite layer may be used to form any component or layer of the
golf ball so long as the insert is visible. For example, the
composite layer may be used in the core and cover structures of the
ball. The term, "layer" as used herein means generally any
spherical portion of the golf ball. The term, "composite layer" as
used herein means generally any layer containing the decorative
insert embedded therein. As noted above, the core may be single or
multi-layered. In one version, the core has a dual-layered
structure including an inner core (center) and surrounding outer
core layer. In another version, the core has a multi-layered
structure including a center, intermediate core layer, and outer
core layer. The cover also may be single or multi-layered. In one
version, the dual-cover includes inner cover and outer cover
layers. Cover structures having three separate layers also may be
made. In yet another construction, a five-piece golf ball having a
dual-core, composite layer, and dual-cover is made. The golf balls
also may include one or more intermediate layers disposed between
the core and composite layer and/or cover and composite layer. 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.
[0028] Core Structure
[0029] The golf ball may contain a single- or multi-layered core.
In one preferred embodiment, at least one of the core layers is
formed of a rubber composition comprising polybutadiene rubber
material. More particularly, in one version, the ball contains a
single inner core formed of the polybutadiene rubber composition.
In a second version, the ball contains a dual-core comprising an
inner core (center) and surrounding outer core layer. In yet
another version, the golf ball contains a multi-layered core
comprising an inner core, intermediate core layer, and outer core
layer.
[0030] In one version, the inner core (or at least one core layer
in a multi-layered core construction) is formed of a rubber
composition comprising a rubber material such as, for example,
polybutadiene, ethylene-propylene rubber, ethylene-propylene-diene
rubber, polyisoprene, styrene-butadiene rubber, polyalkenamers,
butyl rubber, halobutyl rubber, or polystyrene elastomers. In
another version, the inner core (or at least one core layer in a
multi-layered core construction) is formed from an ionomer
composition comprising an ethylene acid copolymer containing acid
groups such that greater than 70% of the acid groups are
neutralized. For example, a multi-layered core comprising an inner
core formed of a rubber composition; an intermediate core formed of
the highly neutralized ionomer composition; and outer core layer
formed of a rubber composition may be prepared. Such rubber and
ionomer compositions are discussed in further detail below.
[0031] In one preferred embodiment, the cores in the golf balls of
this invention have high-reflectance properties. Particularly, the
core layer(s) may comprise light-reflective fillers to effectively
scatter light rays that strike the outer surface of the core. For
example, these light-reflective fillers may be selected from the
group consisting of pearlescent pigments, glitter specks,
metallics, particularly metalized films and foils, and mixtures
thereof as discussed in further detail below. The light-reflective
fillers preferably comprise particles preferably have faces that
have an individual reflectance of over 75%, more preferably at
least 95%, and most preferably 99-100%. For example, flat particles
with two opposite faces can be used. The particle size preferably
is 0.1 mm-1.0 mm more preferably 0.2 mm-0.8 mm, and most preferably
0.25 mm-0.5 mm. In general, an aesthetically pleasing reflective
appearance can be obtained by using about 0.1-10, or more
preferably 1-4 parts by weight reflective particles based on the
weight of base rubber or other polymer in the composition. In other
instances, the core layer may be coated with a highly reflective
coating using vacuum-depositing techniques, spray, dipping, or
other suitable techniques. For example, a reflective layer of
vacuum-deposited aluminum or chrome, indium and the like may be
formed. Such a layer preferably has a thickness of between about
0.0001 and about 0.0010 inches. The core composition may comprise
white pigments such as, for example, zinc oxide, barium sulfate,
titanium dioxide, calcium oxide, or the like to provide the core
composition with high reflectance. Preferably, titanium dioxide is
used as the white pigment. The white pigments reflect the light
rays to provide a bright white opaque core. In this preferred
version, the core is substantially reflective and enhances the
appearance of the surrounding composite layer that contains the
decorative insert as discussed further below.
[0032] In a second preferred embodiment, the core composition may
contain colored pigments such as blue, green, red, or yellow
pigments or the like. These colored pigments absorb most of the
incident light as opposed to the white pigments that reflect most
of the light. Such a colored core can provide color vibrancy and
depth to the golf ball. The colored core material provides a richly
colored background for the substantially transparent surrounding
composite layer that contains the decorative insert as discussed
further below.
[0033] In one preferred embodiment, the entire core or at least one
core layer in a multi-layered structure is formed of a rubber
composition comprising a material selected from the group of
natural and synthetic rubbers including, but not limited to,
polybutadiene, polyisoprene, ethylene propylene rubber ("EPR"),
ethylene-propylene-diene ("EPDM") rubber, styrene-butadiene rubber,
styrenic block copolymer rubbers (such as "SI", "SIS", "SB", "SBS",
"SIBS", and the like, where "S" is styrene, "I" is isobutylene, and
"B" is butadiene), polyalkenamers such as, for example,
polyoctenamer, butyl rubber, halobutyl rubber, polystyrene
elastomers, polyethylene elastomers, polyurethane elastomers,
polyurea elastomers, metallocene-catalyzed elastomers and
plastomers, copolymers of isobutylene and p-alkylstyrene,
halogenated copolymers of isobutylene and p-alkylstyrene,
copolymers of butadiene with acrylonitrile, polychloroprene, alkyl
acrylate rubber, chlorinated isoprene rubber, acrylonitrile
chlorinated isoprene rubber, and combinations of two or more
thereof.
[0034] More preferably, the rubber composition comprises
polybutadiene. In general, polybutadiene is a homopolymer of
1,3-butadiene. The double bonds in the 1,3-butadiene monomer are
attacked by catalysts to grow the polymer chain and form a
polybutadiene polymer having a desired molecular weight. Any
suitable catalyst may be used to synthesize the polybutadiene
rubber depending upon the desired properties. Normally, a
transition metal complex (for example, neodymium, nickel, or
cobalt) or an alkyl metal such as alkyllithium is used as a
catalyst. Other catalysts include, but are not limited to,
aluminum, boron, lithium, titanium, and combinations thereof. The
catalysts produce polybutadiene rubbers having different chemical
structures. In a cis-bond configuration, the main internal polymer
chain of the polybutadiene appears on the same side of the
carbon-carbon double bond contained in the polybutadiene. In a
trans-bond configuration, the main internal polymer chain is on
opposite sides of the internal carbon-carbon double bond in the
polybutadiene. The polybutadiene rubber can have various
combinations of cis- and trans-bond structures. A preferred
polybutadiene rubber has a 1,4 cis-bond content of at least 40%,
preferably greater than 80%, and more preferably greater than 90%.
In general, polybutadiene rubbers having a high 1,4 cis-bond
content have high tensile strength. The polybutadiene rubber may
have a relatively high or low Mooney viscosity.
[0035] Examples of commercially available polybutadiene rubbers
that can be used in accordance with this invention, include, but
are not limited to, BR 01 and BR 1220, available from BST
Elastomers of Bangkok, Thailand; SE BR 1220LA and SE BR1203,
available from DOW Chemical Co of Midland, Mich.; BUDENE 1207,
1207s, 1208, and 1280 available from Goodyear, Inc of Akron, Ohio;
BR 01, 51 and 730, available from Japan Synthetic Rubber (JSR) of
Tokyo, Japan; BUNA CB 21, CB 22, CB 23, CB 24, CB 25, CB 29 MES, CB
60, CB Nd 60, CB 55 NF, CB 70 B, CB KA 8967, and CB 1221, available
from Lanxess Corp. of Pittsburgh. Pennsylvania; BR1208, available
from LG Chemical of Seoul, South Korea; UBEPOL BR130B, BR150,
BR150B, BR150L, BR230, BR360L, BR710, and VCR617, available from
UBE Industries, Ltd. of Tokyo, Japan; EUROPRENE NEOCIS BR 60,
INTENE 60 AF and P30AF, and EUROPRENE BR HV80, available from
Polimeri Europa of Rome, Italy; AFDENE 50 and NEODENE BR40, BR45,
BR50 and BR60, available from Karbochem (PTY) Ltd. of Bruma, South
Africa; KBR 01, NdBr 40, NdBR-45, NdBr 60, KBR 710S, KBR 710H, and
KBR 750, available from Kumho Petrochemical Co., Ltd. Of Seoul,
South Korea; DIENE 55NF, 70AC, and 320 AC, available from Firestone
Polymers of Akron, Ohio; and PBR-Nd Group II and Group III,
available from Nizhnekamskneftekhim, Inc. of Nizhnekamsk,
Tartarstan Republic.
[0036] The polybutadiene rubber preferably 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
polybutadiene rubber is about 40 to about 95 weight percent. Lesser
amounts of other thermoset materials may be incorporated into the
base rubber. Such materials include the rubbers discussed above,
for example, cis-polyisoprene, trans-polyisoprene, balata,
polychloroprene, polynorbornene, polyoctenamer, polypentenamer,
butyl rubber, EPR, EPDM, styrene-butadiene, and the like.
[0037] The rubber compositions of this invention may be cured using
conventional curing processes. Suitable curing processes include,
for example, peroxide-curing, sulfur-curing, high-energy radiation,
and combinations thereof. Preferably, the rubber composition
contains a free-radical initiator selected from organic peroxides,
high energy radiation sources capable of generating free-radicals,
and combinations thereof. In one preferred version, the rubber
composition is peroxide-cured. Suitable organic peroxides include,
but are not limited to, dicumyl peroxide;
n-butyl-4,4-di(t-butylperoxy) valerate;
1,1-di(t-butylperoxy)3,3,5-trimethylcyclohexane;
2,5-dimethyl-2,5-di(t-butylperoxy) hexane; di-t-butyl peroxide;
di-t-amyl peroxide; t-butyl peroxide; t-butyl cumyl peroxide;
2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3;
di(2-t-butyl-peroxyisopropyl)benzene; dilauroyl peroxide; dibenzoyl
peroxide; t-butyl hydroperoxide; and combinations thereof. In a
particular embodiment, the free radical initiator is dicumyl
peroxide, including, but not limited to Perkadox.RTM. BC,
commercially available from Akzo Nobel. Peroxide free-radical
initiators are generally present in the rubber composition in an
amount of at least 0.05 parts by weight per 100 parts of the total
rubber, or an amount within the range having a lower limit of 0.05
parts or 0.1 parts or 1 part or 1.25 parts or 1.5 parts or 2.5
parts or 5 parts by weight per 100 parts of the total rubbers, and
an upper limit of 2.5 parts or 3 parts or 5 parts or 6 parts or 10
parts or 15 parts by weight per 100 parts of the total rubber.
Concentrations are in parts per hundred (phr) unless otherwise
indicated. As used herein, the term, "parts per hundred," also
known as "phr" or "pph" is defined as the number of parts by weight
of a particular component present in a mixture, relative to 100
parts by weight of the polymer component. Mathematically, this can
be expressed as the weight of an ingredient divided by the total
weight of the polymer, multiplied by a factor of 100.
[0038] The rubber compositions may further include a reactive
cross-linking co-agent. Suitable co-agents include, but are not
limited to, metal salts of unsaturated carboxylic acids having from
3 to 8 carbon atoms; unsaturated vinyl compounds and polyfunctional
monomers (e.g., trimethylolpropane trimethacrylate); phenylene
bismaleimide; and combinations thereof. Particular examples of
suitable metal salts include, but are not limited to, one or more
metal salts of acrylates, diacrylates, methacrylates, and
dimethacrylates, wherein the metal is selected from magnesium,
calcium, zinc, aluminum, lithium, and nickel. In a particular
embodiment, the co-agent is selected from zinc salts of acrylates,
diacrylates, methacrylates, and dimethacrylates. In another
particular embodiment, the agent is zinc diacrylate (ZDA). When the
co-agent is zinc diacrylate and/or zinc dimethacrylate, the
co-agent is typically included in the rubber composition in an
amount within the range having a lower limit of 1 or 5 or 10 or 15
or 19 or 20 parts by weight per 100 parts of the total rubber, and
an upper limit of 24 or 25 or 30 or 35 or 40 or 45 or 50 or 60
parts by weight per 100 parts of the base rubber.
[0039] Radical scavengers such as a halogenated organosulfur,
organic disulfide, or inorganic disulfide compounds may be added to
the rubber composition. These compounds also may function as "soft
and fast agents." As used herein, "soft and fast agent" means any
compound or a blend thereof that is capable of making a core: 1)
softer (having a lower compression) at a constant "coefficient of
restitution" (COR); and/or 2) faster (having a higher COR at equal
compression), when compared to a core equivalently prepared without
a soft and fast agent. Preferred halogenated organosulfur compounds
include, but are not limited to, pentachlorothiophenol (PCTP) and
salts of PCTP such as zinc pentachlorothiophenol (ZnPCTP). Using
PCTP and ZnPCTP in golf ball inner cores helps produce softer and
faster inner cores. The PCTP and ZnPCTP compounds help increase the
resiliency and the coefficient of restitution of the core. In a
particular embodiment, the soft and fast agent is selected from
ZnPCTP, PCTP, ditolyl disulfide, diphenyl disulfide, dixylyl
disulfide, 2-nitroresorcinol, and combinations thereof.
[0040] In addition, the rubber compositions may include
antioxidants to prevent the breakdown of the elastomers. Also,
processing aids such as high molecular weight organic acids and
salts thereof may be added to the composition. Suitable organic
acids are aliphatic organic acids, aromatic organic acids,
saturated mono-functional organic acids, unsaturated monofunctional
organic acids, multi-unsaturated mono-functional organic acids, and
dimerized derivatives thereof. Particular examples of suitable
organic acids include, but are not limited to, caproic acid,
caprylic acid, capric acid, lauric acid, stearic acid, behenic
acid, erucic acid, oleic acid, linoleic acid, myristic acid,
benzoic acid, palmitic acid, phenylacetic acid, naphthalenoic acid,
and dimerized derivatives thereof. The organic acids are aliphatic,
mono-functional (saturated, unsaturated, or multi-unsaturated)
organic acids. Salts of these organic acids may also be employed.
The salts of organic acids include the salts of barium, lithium,
sodium, zinc, bismuth, chromium, cobalt, copper, potassium,
strontium, titanium, tungsten, magnesium, cesium, iron, nickel,
silver, aluminum, tin, or calcium, salts of fatty acids,
particularly stearic, behenic, erucic, oleic, linoelic or dimerized
derivatives thereof. It is preferred that the organic acids and
salts of the present invention be relatively non-migratory (they do
not bloom to the surface of the polymer under ambient temperatures)
and non-volatile (they do not volatilize at temperatures required
for melt-blending.)
[0041] Ethylene Acid Copolymers
[0042] In a second preferred embodiment, the entire core or at
least one core layer in a multi-layered structure is formed of an
ionomer composition comprising an ethylene acid copolymer
containing acid groups that are at least partially neutralized. As
discussed further below, preferably, the neutralization level is
greater than 70%, more preferably at least 90% and even more
preferably at least 100%. Suitable ethylene acid copolymers that
may be used to form the compositions of this invention are
generally referred to as copolymers of ethylene; C.sub.3 to C.sub.8
.alpha., .beta.-ethylenically unsaturated mono-or dicarboxylic
acid; and optional softening monomer. Copolymers may 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. The preferred
.alpha., .beta.-ethylenically unsaturated mono- or dicarboxylic
acids are (meth) acrylic acid, ethacrylic acid, maleic acid,
crotonic acid, fumaric acid, and 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.
[0043] 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.
[0044] The amount of ethylene in the acid copolymer 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 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 comonomer in the 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. "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.
[0045] The acidic groups in the copolymeric 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.
[0046] For example, ionomeric resins having acid groups that are
neutralized from about 10 percent to about 100 percent 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.
[0047] On the other hand, the ionomer composition may contain acid
groups that are highly or fully-neutralized. These highly
neutralized polymers (HNPs) are preferred for forming at least one
core layer in the present invention. 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.
[0048] "Ionic plasticizers" such as organic acids or salts of
organic acids, particularly fatty acids, may be added to the
ionomer resin 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. 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. 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).
[0049] Composite Layer
[0050] The golf balls of this invention further include a composite
layer comprising a first substantially transparent polymeric
matrix. By the term, "substantially transparent" as used herein, it
is meant a layer that is sufficiently clear for a person to see an
underlying decorative insert member. The amount of light that
passes through the first substantially transparent polymeric matrix
may be measured so that the layer is considered optically
transparent, semi-transparent, translucent, or the like. In each
instance, however, the insert member lying in the composite layer
must be plainly visible to the human eye. The above-described
rubber and ionomer compositions may be used to form the polymeric
matrix of the composite layer. Other suitable polymers that may be
used to form the composite layer include, but are not limited to,
the following polymers (including homopolymers, copolymers, and
derivatives thereof.)
[0051] (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;
[0052] (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;
[0053] (c) polyurethanes, polyureas, polyurethane-polyurea hybrids,
and blends of two or more thereof;
[0054] (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;
[0055] (e) polystyrenes, such as poly(styrene-co-maleic anhydride),
acrylonitrile-butadiene-styrene, poly(styrene sulfonate),
polyethylene styrene, and blends of two or more thereof;
[0056] (f) polyvinyl chlorides and grafted polyvinyl chlorides, and
blends of two or more thereof;
[0057] (g) polycarbonates, blends of
polycarbonate/acrylonitrile-butadiene-styrene, blends of
polycarbonate/polyurethane, blends of polycarbonate/polyester, and
blends of two or more thereof;
[0058] (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;
[0059] (i) polyimides, polyetherketones, polyamideimides, and
blends of two or more thereof; and
[0060] (j) polycarbonate/polyester copolymers and blends.
[0061] A decorative insert member is enclosed in the substantially
transparent polymeric matrix comprising the composite layer. As
discussed above, in one preferred embodiment, the composite layer
containing the insert surrounds the core structure and lies beneath
the cover structure. The insert is pre-formed prior to placing it
the composite layer and may be molded using any known molding
technique such as injection, compression, or reaction injection
molding. The insert also may be forged, machined, cast, die-cut,
formed by stereo-lithography, laser-etched or cut, or otherwise
formed using any known methods of creating 3-D objects. The
decorative insert may be made from a metal, any plastic or
polymeric material, composite or inorganic or hybrid
organic-inorganic, or organo-metallic material. The insert shape
may include virtually any 3-D object and may be spherical; any
non-spherical shape including regular and irregular-shaped
polygons, twisted ribbons, bows, or ties; or very complex shapes
such as any living or inanimate object. The decorative insert may
be any ornamental object that a customer could custom order. In
this manner, the golf ball could be considered an article of
functional jewelry comprising an insert in a shape of a figurine,
charm, jewelry piece, or any other ornamental article that is
desired by a customer. Insert shapes also include spheres,
spheroids, or near spheres such as egg-shapes, any fraction of a
sphere, facetted spheres or any facetted geometric shapes,
pyramidal shapes, cubes, diamonds, cylindrical shapes, cone or
truncated cones, torus, prisms, star or multi-armed shapes, any
alpha-numeric figures or text, or combinations thereof. In the
present invention, the inserts do not include fibrous materials or
particles, that is, the inserts do not encompass continuous
filaments, staple fiber, flock, chopped fiber, particulate,
powders, granules, or any other fiber- or particle-like materials.
The hardness and modulus of the insert may be the same as the
polymeric matrix material, or be softer or harder and lower or
higher in flex modulus than the matrix material. In one embodiment,
the insert has a hardness of at least 5 Shore D greater than the
hardness of the surrounding polymeric matrix and may have a
hardness of at least 20 Shore D greater than hardness of the
polymeric matrix. In one embodiment the insert is made of a metal
material (for example, brass, bronze, stainless steel, copper, gold
(plated), silver (plated), or the like) and the matrix is made of
substantially clear ionomer (partially or fully-neutralized),
polyurethane, or polyurea. In another embodiment, the insert is
made of a cast acrylic (PMMA or MMA copolymer) and the matrix is
made of substantially clear ionomer (partially or
fully-neutralized), polyurethane, or polyurea. In still another
version, the insert is made of diamond, artificial diamond, glass,
or other inorganic material. In one example, the insert is made
from pre-molded thermoset polyurethane spheres which are pigmented
with a metallic and/or pearlescent pigment. The insert may be
coated or treated with a material which improves the adhesion of
the insert (if needed) to the surrounding polymeric matrix
material, such as a chemical-coupling agent or adhesive (for
example, epoxy, titanate, or silane) or treated with plasma,
corona, or the like.
[0062] The size and volume of the insert(s) are limited only be the
thickness and volume of the layer into which they are placed, but
typically have a mean diameter of about 0.005 to 0.5 inches,
preferably about 0.01 to 0.25 inches, more preferably about 0.05 to
0.150 inches and may be randomly placed or may be strategically
placed in a pattern of relatively uniform separation or uniform
overlapping. In one embodiment, the insert occupies from about 0.1
to about 60%, preferably about 1 to 50%, more preferably about 5 to
25% of the total volume of the composite layer. A single insert or
a plurality of inserts may be placed in the composite layer. In
general, the layer contains from one (1) to five-hundred (500)
decorative insert members depending upon the geometries and
dimensions of the inserts and the desired aesthetics. The
geometries and dimensions of the various inserts may be identical
or different. Preferably, the layer contains from 5 to 250 insert
members, and most preferably from 25 to 100.
[0063] The United States Golf Association ("USGA") has set total
weight limits for golf balls. Particularly, the USGA has
established a maximum weight of 45.93 g (1.62 ounces) for golf
balls. Although the total weight of the golf ball is controlled,
the distribution of weight within the ball can vary. Redistributing
the weight or mass of the golf ball either towards the center of
the ball or towards the outer surface of the ball changes its
flight and spin characteristics, and these factors should be
considered when incorporating the decorative insert into the golf
balls of this invention. In one embodiment, the densities of the
decorative insert and encapsulating polymeric matrix are
substantially the same. That is, the decorative insert has a first
density and the surrounding polymeric matrix has a second density,
and these densities are approximately equivalent. In this manner,
the ball has a balanced density and this helps minimize changes to
the ball's flight and spin characteristics. The difference, if any,
between the specific gravities of the insert and surrounding layer
can be kept to a minimum by making these components with the same
material. For example, the composite layer and decorative insert
could be made of the same rubber or plastic material. Preferably,
the difference between the first density (decorative insert) and
second density (surrounding polymer matrix) is thirty percent or
less, more preferably twenty percent or less, and most preferably
ten percent or less. In this embodiment, where the components have
nominally different densities, either the decorative insert or
polymeric matrix may be of greater density. In another embodiment,
the specific gravity of the decorative insert is substantially
greater than the specific gravity of the surrounding polymeric
matrix, but the insert is of such geometry and dimensions that
there is no or minimal observable effect on the ball's flight and
spin characteristics. In yet another embodiment, the specific
gravity of the decorative insert is substantially greater than the
specific gravity of the surrounding polymeric matrix, and multiple
inserts are added to and uniformly distributed throughout the
layer. The evenly distributed decorative inserts provide symmetry
so there is no or minimal observable effect on the ball's flight
and spin characteristics.
[0064] Furthermore, it is important that the weight of the
decorative insert be considered and the amount of fillers and other
ingredients used in the polymeric matrix be adjusted, as needed, so
the weight of the finished golf ball does not exceed limits set by
the USGA. As noted above, for play outside of USGA competition,
there is no maximum limit; thus, the golf balls can be constructed
so they weigh more than 1.62 ounces. In addition, the USGA requires
that golf balls used in competition have a diameter of at least
1.68 inches. There is no upper limit so many golf balls have an
overall diameter falling within the range of about 1.68 to about
1.80 inches. In accordance with the present invention, the diameter
and thickness of the core, composite, and cover layers may be
adjusted, as needed, so that the ball meets USGA specifications of
at least 1.68 inches in diameter.
[0065] The substantially transparent polymeric matrix is
sufficiently free of light-reflective fillers, pigments, dyes,
fluorescent materials, optical brighteners, glitter specks,
metallics, particularly metalized films and foils, and the like so
that it can admit the necessary amount of light for making the
insert member visible. In some instances, however, it may be
desirable to include a relatively small amount of such additives in
the polymeric matrix to enhance the decorative effect. For example,
light-reflective fillers including, but not limited to, pearlescent
pigments, glitter specks, metallics, particularly metalized films
and foils, and mixtures thereof can be incorporated into the
polymeric matrix; provided, the matrix remains clear enough to see
the decorative insert.
[0066] It also should be understood that the decorative insert, by
and in itself, may include these light-reflective fillers (for
example, pearlescent pigments, glitter specks, color-flop pigments,
edge-effect pigments, metallics, and mixtures thereof.) That is,
the composition used to form the decorative insert may be filled
with these light-reflective fillers or the surface of the insert
may be coated with such fillers. These fillers can enhance the
visibility and ornamental effect of the insert within the ball.
[0067] Pearlescent pigments are particularly preferred, because
these materials can provide special luster effects. Pearlescent
pigment is generally made up of multiple platelet-like
semi-transparent particles. When light strikes the platelets, it is
partially reflected and partially transmitted through them. There
are many platelet surfaces in parallel orientation and many layers
of pigment at different depths within the pearlescent
pigment-containing paint, coating, or other composition. As light
reflects off the platelet surfaces in the different layers, this
creates a pearly luster effect. A person looking at the composition
will see different reflections and scattering of light depending
upon their viewing angle. Some pearlescent pigments do not have a
layered structure, that is, they comprise discrete particles and do
not contain coated substrates. For example, metal-effect
pearlescent pigments such as aluminum, copper, copper-zinc (bronze)
alloys, and zinc particles may be used. Basic lead carbonate and
bismuth oxychloride pigment particles also can be used. Other
pearlescent pigments have a layered structure, that is, they
contain a substrate. For example, natural or synthetic mica
platelets may be coated with iron oxide or titanium dioxide to form
special effect pearlescent pigments. Organic pigments also can be
crystallized to form pigment flakes and pigments having a natural
pearlescence such as pigment suspensions derived from fish scales
may be used.
[0068] Metallics, particularly metalized films and foils, and
glitter specks, which comprise very small plastic pieces painted in
metallic, neon, and iridescent colors to reflect light also can be
used as reflective fillers in accordance with this invention. Any
suitable metal, especially highly lustrous metals, may be used and
these metallics can be in the form of flakes, particles, and the
like. Metalized polyester films and aluminum foil are also highly
reflective metallics that can be used in the various layers and
decorative inserts of the golf ball.
[0069] Titanium dioxide pigment is preferably used as
light-reflective filler, because of its light scattering properties
including reflectivity and refraction. As the light strikes the
surface of the composition, most of the light will be reflected
because of the titanium dioxide pigment concentration. The light
strikes the surface of the pigment (which has a relatively high
refractive index in contrast to the binder resin), the light is
bent and reflected outwardly. The portion of light which is not
reflected will pass through the particles and will be bent in
different direction. Other useful metal (or metal alloy) flakes,
plates, powders, or particles may include bismuth boron, brass,
bronze, cobalt, copper, nickel, chrome, iron, molybdenum, nickel
powder, stainless steel, zirconium aluminum, tungsten metal,
beryllium metal, zinc, or tin. Other metal oxides may include zinc
oxide, iron oxide, aluminum oxide, magnesium oxide, zirconium
oxide, and tungsten trioxide also may be suitable.
[0070] In other instances, the substantially transparent polymeric
matrix may be lightly colored or tinted so long as the insert
member remains visible. For example, a relatively small amount of
colored pigments such as blue, green, red, or yellow pigments or
the like may be blended in the polymeric matrix to impart some
color to the composite layer, but it is important that the insert
member remains visible. Suitable pigments include nickel and chrome
titanates, chrome yellow, cadmium types, carbon black, chrome oxide
green types, phthalocyanine blue or green, perylene and
quinacridone types, and other conventional pigments. Pigment
extenders include, for example, barytes, heavy spar, microtalc,
kaolin, micaceous iron oxide, magnesium mica, quartz flour,
powdered slate, and silicon carbide. In a similar manner, the
decorative insert, by and in itself, may be colored or tinted with
these pigments to provide additional colored effects. Color flop
pigments, as disclosed in Ohira et al, U.S. Pat. Nos. 7,018,307 and
6,558,277, which show a change in color as the viewing angle
changes may be used in accordance with the present invention.
Edge-effect pigments, which are attracted to the edges or sharper
contours of the surfaces to which they are applied, also may be
used.
[0071] Likewise, if a fluorescent effect is desired, a relatively
small amount of fluorescent dye may be added to the polymeric
matrix so long as the insert member remains visible. Suitable
fluorescent dyes include, for example, dyes from the thioxanthene,
xanthene, perylene, perylene imide, coumarin, thioindigoid,
naphthalimide and methine dye classes. Representative yellow
fluorescent dye examples include, but are not limited to: Lumogen F
Orange.TM. 240 (BASF, Rensselaer, N.Y.); Lumogen F Yellow.TM. 083
(BASF, Rensselaer, N.Y.); Hostasol Yellow.TM. 3G (Hoechst-Celanese,
Somerville, N.J.); Oraset Yellow.TM. 8GF (Ciba-Geigy, Hawthorne,
N.Y.); Fluorol 088.TM. (BASF, Rensselaer, N.Y.); Thermoplast F
Yellow.TM. 084 (BASF, Rensselaer, N.Y.); Golden Yellow.TM. D-304
(DayGlo, Cleveland, Ohio); Mohawk Yellow.TM. D-299 (DayGlo,
Cleveland, Ohio); Potomac YellowT.TM. D-838 (DayGlo, Cleveland,
Ohio) and Polyfast Brilliant Red.TM. SB (Keystone, Chicago, Ill.)
Conventional non-fluorescent dyes also may be used including, but
not limited to, azo, heterocyclic azo, anthraquinone,
benzodifuranone, polycyclic aromatic carbonyl, indigoid,
polymethine, styryl, di- and tri-aryl carbonium, phthalocyanines,
quinopphthalones, sulfur, nitro and nitroso, stilbene, and formazan
dyes. The decorative insert also may be treated with these
fluorescent dyes to provide the insert with a bright glow.
[0072] Optical brighteners, which typically emit a bluish light,
also may be added to the polymer composition and/or decorative
insert. In general, optical brighteners absorb the invisible
ultra-violet portion of the daylight spectrum and convert this
energy into the longer-wavelength visible portion of the spectrum.
Suitable optical brighteners include, for example, stilbene
derivatives, styryl derivatives of benzene and biphenyl,
bis(benzazol-2-yl) derivatives, coumarins, carbostyrils,
naphthalimides, derivatives of dibenzothiophene-5,5-dioxide, pyrene
derivatives, and pyridotriazoles. In accordance with the present
invention, any of these or other known optical brighteners
including derivatives of 4,4'-diamino stilbene-2,2'-disulfonic
acid, 4-mthyl-7-diethylamino coumarin and
2,5-bis(5-tert-butyl)-2-benzoxazolyl)thiophene.
[0073] The decorative insert is embedded in the substantially
transparent composite layer, and in one preferred version, the
composite layer is surrounded by an underlying core structure and
an overlying cover structure. This construction provides the ball
with unique aesthetics. Particularly, in one preferred embodiment,
the underlying core structure has an optically opaque appearance.
More particularly, the composition used to form the core may have a
high concentration of white pigment (for example, titanium dioxide)
so that the core has high reflectance. The white pigments reflect
the light rays to provide a bright, white, opaque core. The
incident light rays (except for a small amount that are absorbed by
the polymer and/or pigment) that strike the surface of the core are
reflected outwardly so the core appears opaque and white. At least
a portion of these reflected light rays enter the surrounding
composite layer containing the decorative insert. Some of the light
entering the composite layer will strike the solid, embedded
decorative insert and bounce off in multiple directions to provide
a striking appearance. In addition, light rays pass through the
overlying cover material and enter the composite layer from
different directions. As the light enters the composite layer from
different directions and path lengths, it is scattered randomly to
enhance the appearance of the composite layer and embedded
decorative insert.
[0074] In a second preferred embodiment, the underlying core
structure has an optically opaque appearance, because the
composition used to form the core has a high concentration of
colored pigment. The colored pigments provide opacity by absorbing
the incident light at selective wavelengths. In general, the
pigments only absorb certain light wavelengths of the visible
spectrum (red, orange, yellow, green, and blue). The light
frequencies, which are not absorbed, are transmitted back to give
the appearance of a specific color. Thus, in colored cores, the
incident light rays that strike the surface of the core are
selectively absorbed so the core appears opaquely colored. Such a
colored core can provide color vibrancy and depth to the
substantially transparent surrounding composite layer. Thus, a
person looking through the substantially transparent cover and
composite layer can see the underlying insert against a richly
colored background. Different colored cores and decorative inserts
can be used to create different coloring effects. In another
example, the substantially transparent cover layer can be lightly
colored. The colored cover material, which lies above the composite
layer, and the colored core, which lies beneath the composite
layer, can provide the ball with color striking highlights. The
substantially transparent composite layer and embedded insert,
which is disposed between the core and cover structures, may
scatter the colored light in different directions to produce unique
visuals. In addition, reflective fillers and other ingredients can
be added to the core and cover structures to provide the ball with
a glossy, semi-glossy, or matte-like finished appearance. Another
advantage of the present invention is that the decorative insert
can be added to the composite layer to provide a unique ornamental
affect without sacrificing the playing performance properties of
the ball such as resiliency and spin control.
[0075] The above-described golf ball assembly comprising a core
structure, surrounding composite layer, and enclosing cover layer
is one embodiment and not meant to be restrictive. Other golf ball
constructions can be made in accordance with this invention as
noted above. For example, in an alternative version, the composite
layer containing the decorative insert is used as the innermost
core (or center) of the ball. In another version, the composite
layer is used as the outer core layer. In yet another version, the
composite layer is used as the inner and/or outer cover layer.
[0076] Cover Structure
[0077] The preferred golf ball sub-assembly (ball with core and
composite layers) may be enclosed with a cover in accordance with
this invention. The cover comprises a second substantially
transparent polymeric matrix. The substantially transparent cover
layer(s) may allow a measured amount of light to pass through so
that the layer(s) is characterized as being optically transparent,
semi-transparent, translucent, or the like. In each instance,
however, the insert member lying in the composite layer must be
plainly visible to the human eye looking at the exterior of the
ball. The above-described polymeric compositions used to form the
composite layer may be used to form the polymeric matrix of the
cover layer(s) in accordance with this invention. In a similar
manner, the substantially transparent polymeric matrix comprising
the cover layer(s) must be sufficiently free of light-reflective
fillers, pigments, dyes, fluorescent materials, optical
brighteners, glitter specks, metallics, and the like so that it can
admit the light needed for rendering the underlying insert member
visible. In some instances, however, it may be desirable to include
a relatively small amount of such additives in the polymeric matrix
of the cover layer(s) to enhance the overall aesthetics of the
ball.
[0078] A wide variety of materials may be used for forming the
second substantially transparent polymeric matrix of the cover
including, for example, polyurethanes; polyureas; copolymers,
blends and hybrids of polyurethane and polyurea; ethylene acid
copolymer ionomer resins (for example, Surlyn.RTM. ionomer resins
and 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; 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 help 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.
[0079] 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.
[0080] In one preferred embodiment, the ball includes a dual-cover
comprising inner and outer cover layers, each of the layers being
substantially transparent. 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. The inner
cover layer preferably has a material hardness of 95 Shore C or
less, or less than 95 Shore C, or 92 Shore C or less, or 90 Shore C
or less, or a material hardness within a range having a lower limit
of 60 or 65 or 70 or 75 or 80 or 84 or 85 Shore C and an upper
limit of 90 or 92 or 95 Shore C. The thickness of the inner cover
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. The outer cover layer preferably
comprises a thermoplastic or thermosetting polyurethane, polyurea,
or blend or hybrid of polyurethane/polyurea.
[0081] 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),
which 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. In another embodiment, the outer cover layer
comprises an ionomer and inner cover layer comprises a
thermoplastic or thermosetting polyurethane, polyurea, or blend or
hybrid of polyurethane/polyurea. In this embodiment, both cover
layers are relatively thin (thickness of about 0.010 to about 0.040
inches) and the Shore D hardness of the ionomer outer layer is
greater than the Shore D hardness of the polyurethane inner cover
layer.
[0082] As discussed above, the golf ball sub-assembly may be
enclosed with a single-layered or multi-layered covers. In one
embodiment, a single-layered cover having a thickness in the range
of about 0.015 to about 0.090 inches, more preferably about 0.030
to about 0.070 inches, is formed. The cover has a hardness of about
Shore D 80 or less, more preferably 70 or less, and most preferably
about 60 or less. In another 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.
[0083] Manufacturing of Golf Ball Components
[0084] The core and cover compositions may be prepared using
conventional mixing techniques. The core composition can be formed
into an inner core structure by ordinary techniques such as, for
example, injection or compression molding the composition.
Injection molding, compression molding, or other conventional
methods can be used to form additional core layer(s) for a
multi-layered core structure. The composite layer is subsequently
molded over the core structure to produce an intermediate ball
(sub-assembly). More particularly, in compression molding, the
polymer composition for the composite layer is formed into smooth
surfaced hemispherical shells which are then positioned around the
core structure in a mold having the desired thickness and subjected
to molding under heat followed by cooling. This process fuses the
shells together to form a unitary intermediate ball. Alternatively,
the intermediate balls may be produced by injection molding,
wherein the composite layer composition is injected directly around
the core placed at the center of a ball mold under heat and
pressure.
[0085] In the present invention, the decorative insert is pressed
into the partially-cured layer so that it is fully embedded
therein. Under ordinary circumstances, it would be difficult to
press the insert into the composite layer. However, because the
composite layer is only partially-cured at this point, the insert
can be placed easily in the layer and properly oriented. It is easy
to work move the insert in the layer and the position of the insert
can be adjusted as needed. The partially-cured layer is not fully
hard at this point. Rather, the partially hardened material is in a
highly moldable condition. The material has a generally soft,
wax-like consistency. Still, the partially-cured layer has
sufficient hardness and stability such that the insert is not
easily moved out of position. In this invention, it is preferable
that the insert be fully encapsulated by the polymer matrix. That
is, the insert is preferably fully enclosed by the composite layer
and there are no portions of the insert exposed or protruding into
the surrounding cover.
[0086] After the insert has been placed in the desired location,
the composite layer is fully-cured. This hardens the golf ball and
helps the embedded insert to mechanically bond strongly to the
encapsulating polymeric matrix of the composite layer. In addition,
the surface of the insert may be treated with silane-coupling
agents, corona discharge, sand blasting, or the like to improve
adhesion of the insert to the surrounding polymeric matrix.
[0087] The cover layer(s) is subsequently molded over the
intermediate ball to produce a final golf ball. The polymer
composition used to form the cover may be molded over the
intermediate ball using known techniques such as injection molding,
compression molding, reaction injection molding, and casting. After
molding, the golf balls produced may undergo various further
processing steps such as marking, coating, and polishing to produce
a finished ball.
[0088] Referring to FIG. 1, a front view of a finished golf ball
that can be made in accordance with this invention is generally
indicated at (10). The ball (10) includes a substantially
transparent cover (12) having a dimpled surface (14). The dimples
(14) may have various shapes and be arranged in various patterns to
modify the aerodynamic properties of the ball as is known in the
art. The ball includes a decorative insert member (16) that is
visible through the substantially transparent cover (12). (In this
version, the decorative insert (16) is in the shape of a shamrock
charm.) In FIG. 2, a cut-away view of the ball (10) in FIG. 1 is
shown. The ball (10) includes a solid inner core (18) that is
opaque, and a composite layer (20) and single-layered cover (12)
that are both substantially transparent. The decorative insert
member (16) is fully encapsulated in the substantially transparent
composite layer (20) and is visible through the substantially
transparent cover (12). FIG. 3 shows a side cross-sectional view of
a three-piece golf ball (22) of this invention. The ball (22)
contains a core (24), a surrounding substantially transparent
composite layer (26) containing an embedded decorative insert
member (not shown in this cross-sectional view), and a
substantially transparent cover layer (28) that is disposed about
the composite layer (26). In FIG. 4, a side cross-sectional view of
a four-piece ball (30) of this invention is shown. The ball
includes an inner core (center) (32) and outer core layer (34); a
surrounding substantially transparent composite inner cover layer
(36) encapsulating a decorative insert member (not shown in this
cross-sectional view); and a substantially transparent outer cover
layer (38) that is disposed about the composite inner cover layer
(36). It should be understood the golf balls shown in FIGS. 1-4 are
for illustrative purposes only and not meant to be restrictive.
Other golf ball constructions can be made in accordance with this
invention.
[0089] For example, the golf ball may be a five-piece ball having
an inner core (center), outer core layer, a composite layer with an
embedded decorative insert, inner cover layer, and surrounding
outer cover layer. In another version, the golf ball may have a
multi-layered core construction comprising an inner core,
intermediate core layer, and outer core layer. The composite layer
containing the embedded decorative insert may surround the
multi-layered core structure, and an outer cover layer may be
disposed about the composite layer.
[0090] In a multi-layered core construction, the center preferably
has a diameter within a range having a lower limit of 0.100 or
0.125 or 0.250 inches or 0.300 and an upper limit of 0.375 or 0.400
or 0.500 or 0.750 or 1.00 or 1.25 or 1.40 or 1.60 inches. More
preferably, the center has a diameter within a range of about 0.25
to about 1.40 inches. The intermediate core layer preferably has a
thickness within a range having a lower limit of 0.050 or 0.100 or
0.150 or 0.200 inches and an upper limit of 0.300 or 0.350 or 0.400
or 0.500 inches. The outer core layer encloses the center and
intermediate core layer such that the multi-layer core has an
overall diameter within a range having a lower limit of 1.40 or
1.45 or 1.50 or 1.55 inches and an upper limit of 1.58 or 1.60 or
1.62 or 1.66 inches.
[0091] In this multi-layered core construction, the center
preferably has an outer surface hardness of 70 Shore C or greater,
more preferably a surface hardness of 80 Shore C or greater, and
most preferably a surface hardness of 85 Shore C or greater. For
example, the center may have an outer surface hardness within a
range having a lower limit of 70 or 75 or 80 Shore C and an upper
limit of 90 or 95 Shore C. The outer core layer preferably has an
outer surface hardness that is less than that of the center and is
preferably 50 Shore C or less; or 60 Shore C or less; or 70 Shore C
or less; or 75 Shore C or less; or 80 Shore C or less. The
intermediate layer preferably has an inner surface hardness greater
than that of the center and outer core layer hardness values.
Preferably, the intermediate layer has a surface hardness of 80
Shore C or greater.
[0092] 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.
[0093] 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.
[0094] It is understood that the compositions and golf ball
products 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 and products without departing from the spirit and
scope of this invention. It is intended that all such embodiments
be covered by the appended claims.
* * * * *