U.S. patent application number 11/941510 was filed with the patent office on 2009-05-21 for marking of golf balls using luminescent and optically-stimulable glasses.
Invention is credited to Edmund A. Hebert, William B. Lacy.
Application Number | 20090131203 11/941510 |
Document ID | / |
Family ID | 40642582 |
Filed Date | 2009-05-21 |
United States Patent
Application |
20090131203 |
Kind Code |
A1 |
Hebert; Edmund A. ; et
al. |
May 21, 2009 |
Marking of Golf Balls Using Luminescent and Optically-Stimulable
Glasses
Abstract
A golf ball comprising a core; a cover layer; and an additive
comprising an optically-stimulable glass powder that is invisible
to the naked eye without an external excitation source.
Inventors: |
Hebert; Edmund A.;
(Mattapoisett, MA) ; Lacy; William B.; (Plymouth,
MA) |
Correspondence
Address: |
ACUSHNET COMPANY
333 BRIDGE STREET, P. O. BOX 965
FAIRHAVEN
MA
02719
US
|
Family ID: |
40642582 |
Appl. No.: |
11/941510 |
Filed: |
November 16, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11940420 |
Nov 15, 2007 |
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11941510 |
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Current U.S.
Class: |
473/378 |
Current CPC
Class: |
A63B 37/0022
20130101 |
Class at
Publication: |
473/378 |
International
Class: |
A63B 37/12 20060101
A63B037/12 |
Claims
1. A golf ball comprising: a core; a cover layer; and an additive
comprising an optically-stimulable glass powder that is invisible
to the naked eye without an external excitation source; wherein the
optically-stimulable glass powder is added to a clearcoat, inks,
stains, shellacs, varnishes, glazes, paints, dyes, coating layers,
or indicia.
2. The golf ball of claim 1, wherein the optically-stimulable glass
powder comprises a glass or glass matrix comprising an alkaline
earth sulfide doped with a pair of rare earth elements.
3. The golf ball of claim 2, wherein the alkaline earth sulfide
comprises MgS, CaS, SrS, or BaS.
4. The golf ball of claim 2, wherein the glass or glass matrix
comprises porous glass, fused quartz, fused silica, alumina glass,
silica, borate glass, borosilicate glass, aluminosilicate glass,
aluminoborosilicate glass, sealing glass, or soda lime glass.
5. The golf ball of claim 2, wherein the glass or glass matrix has
an annealing point of 800.degree. C. or less.
6. The golf ball of claim 1, wherein the glass matrix is doped with
ZnS, Cu, Pb, Mn, Ce, Ag, or Eu.
7. The golf ball of claim 2, wherein the glass or glass matrix is
essentially free of metal sulfides or sulfides.
8. The golf ball of claim 1, wherein the optically-stimulable glass
powder is blended in the cover layer.
9. (canceled)
10. The golf ball of claim 1, wherein the indicia comprises a logo,
bar code, hob code, date, trademark, alphanumeric code, symbol, or
serial number.
11. The golf ball of claim 1, wherein the optically-stimulable
glass powder is blended with ionomers, polyurethanes, polyureas,
polyethylenes, polycarbonates, silicones, polymethylmethacrylates,
acrylic acids, or polyvinyl chlorides.
12. The golf ball of claim 1, wherein the optically-stimulable
glass powder has an excitation wavelength in the UV spectrum and an
emission wavelength in the visible spectrum.
13. The golf ball of claim 12, wherein the optically-stimulable
glass powder is energized using a short wavelength source having a
wavelength range of 100 nm to 400 nm and sufficient energy to cause
electrons in the optically-stimulable glass powder to be
trapped.
14. The golf ball of claim 13, wherein the wavelength range is 100
nm to 280 nm.
15. The golf ball of claim 12, wherein the trapped electrons are
released by exposure to an infrared light source, recombine, and
emit photons as optically-stimulated luminescence.
16. The golf ball of claim 1, wherein the cover layer comprises an
ionomer, a partially- or fully-neutralized ionomer, a polyurethane,
or a polyurea.
17. The golf ball of claim 1, wherein the cover layer has a
hardness of 60 Shore D or less.
18. The golf ball of claim 17, wherein the cover layer has a
hardness of 20 Shore D to 55 Shore D.
19. The golf ball of claim 1, wherein the outer cover layer has a
thickness of 0.02 inches to 0.05 inches.
20. A golf ball comprising: a core; and a cover layer; wherein the
cover layer has an indicia formed thereon and at least one of the
cover layer or the indicia comprises a first and second
optically-stimulable glass powder, the first and second glass
powders having a different predetermined excitation or emission
wavelength as to identify the golf ball as original or counterfeit.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of co-pending U.S. patent
application Ser. No. 11/940,420, filed Nov. 15, 2007.
FIELD OF THE INVENTION
[0002] The invention relates generally to anti-counterfeiting
systems using compound additives and, in particular, addition of
specifically formulated covert additives to golf component parts,
such as golf ball, club, or shoe component layers, paints, or ink
systems, to enable positive identification as an authentic
product.
BACKGROUND OF THE INVENTION
[0003] Golf equipment counterfeiting represents a multi-million
dollar industry, and one that has impact on all legitimate product
manufacturers. Many of these manufacturers have investigated
countermeasures to deter counterfeiters, including covert packaging
markings, inks, holograms (and possibly other means of protection
of which the inventor is unaware).
[0004] Obviously, labels that are not apparent to the naked eye are
desired for many manufactured articles and materials, including
golf balls. However, the `marking` of products in a manner that is
not obvious to the unscrupulous counterfeiter, yet that are robust
enough to remain on the product without any deleterious effects, is
not a trivial matter. Labels must be flexible in their
applicability and as robust as possible. For instance, it is
desirable to make labels that can be applied with dyes, inks,
stains, shellacs, varnishes, glazes, polymer coatings, and other
coatings or materials for application to an article or product. It
is also desirable to make such labels robust so that, for instance,
they can survive exposure to moderately high temperatures and
common solvents, as well as have high impact resistance. Suitable
labels must also be non-toxic and have some type of redundancy
built into them--that is, the labels should be able to be read in
more than one way, as a double check on the authenticity of a
labeled article.
[0005] Since labels generally require some type of coding (i.e.,
bar coding, alphanumeric coding, etc.), it is desirable to have
such coding on a label that is likewise not visible to the naked
eye. In practice today, this is often done by putting a "hidden"
number, code, or serial number, for example, in some discreet
location on an article, such as inside a case or housing.
Unfortunately, such placement is inherently difficult to access
when it is desired to read the label. It would be preferred to have
coding that is hidden in plain sight. Coding that requires
stimulation for readability would satisfy this need.
[0006] It is also desirable to have a way of monitoring some time
entity or time relationship for labeled articles, such as shipping
time or shelf time. A label that included some type of timing
capability would satisfy this need. Optimally, such a timing system
would have a broad range, being able to time over scales of days,
weeks, months, or years, as needed.
[0007] This invention calls for incorporation of signature
anti-counterfeiting additives into the product itself, via a
compound, masterbatch, component, ink or paint system, or other
appropriate manufacturing process step. In this manner, the tag is
integral to the product, and could not be separated.
[0008] Further, the addition of a portable scanning system capable
of validating the presence of these additives (be it deployed as an
in-shop kiosk, a hand-held scanner given to sales reps or pros, or
some other means of distribution) would provide a means for the
customer or consumer to quickly feel comfortable with the
authenticity of their product at the point of purchase.
SUMMARY OF THE INVENTION
[0009] The present invention is directed to a golf ball including a
core (single or dual); a cover layer; and an additive comprising an
optically-stimulable glass powder that is invisible to the naked
eye without an external excitation source. The optically-stimulable
glass powder typically includes a glass or glass matrix comprising
an alkaline earth sulfide doped with a pair of rare earth elements.
The alkaline earth sulfide is generally MgS, CaS, SrS, or BaS. The
glass or glass matrix includes porous glass, fused quartz, fused
silica, alumina glass, silica, borate glass, borosilicate glass,
aluminosilicate glass, aluminoborosilicate glass, sealing glass, or
soda lime glass; and has an annealing point of 800.degree. C. or
less. The glass matrix is doped with ZnS, Cu, Pb, Mn, Ce, Ag, or
Eu. The glass or glass matrix is preferably essentially free of
metal sulfides or sulfides.
[0010] In one embodiment, the optically-stimulable glass powder is
blended in the cover layer. In another embodiment, the
optically-stimulable glass powder is added to a clearcoat, inks,
stains, shellacs, varnishes, glazes, paints, dyes, coating layers,
or indicia. The indicia may include a logo, bar code, hob code,
date, trademark, alphanumeric code, symbol, or serial number. In a
further embodiment, the optically-stimulable glass powder is
blended with ionomers, polyurethanes, polyureas, polyethylenes,
polycarbonates, silicones, polymethylmethacrylates, acrylic acids,
or polyvinyl chlorides.
[0011] Preferably, the optically-stimulable glass powder have an
excitation wavelength in the UV spectrum and an emission wavelength
in the visible spectrum. Generally, the optically-stimulable glass
powder is energized using a short wavelength source having a
wavelength range of 100 nm to 400 nm, more preferably 100 nm to 280
nm, and sufficient energy to cause electrons in the
optically-stimulable glass powder to be trapped. The trapped
electrons are released by exposure to an infrared light source,
recombine, and emit photons as optically-stimulated
luminescence.
[0012] In one embodiment, the cover layer comprises an ionomer, a
partially- or fully-neutralized ionomer, a polyurethane, or a
polyurea. The cover layer should have a hardness of 60 Shore D or
less, more preferably 20 Shore D to 55 Shore D. The outer cover
layer has a thickness of 0.02 inches to 0.05 inches.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0013] The invention is directed to incorporation of fluorescent
anti-counterfeiting additives into a product, preferably a golf
ball or packaging therefore, via a compound, masterbatch,
component, ink or paint system, or other appropriate manufacturing
process step. In this manner, the anti-counterfeiting tag is
integral to the product, and cannot be separated.
[0014] In a preferred embodiment, the addition of specifically
formulated covert additives to golf component parts (such as golf
ball cover layers or golf club paint systems) enable positive
identification as an authentic product. The additive may be in the
form of an engineered taggant (derived from melamine particles and
rare earth elements) or an inert chemical tracer. Each of these
emerging technologies represents an inexpensive way of positively
identifying authentic product.
[0015] In an alternative embodiment, the present invention may be
combined or utilized with an `in-shop kiosk` housing appropriate
portable scanning technology calibrated to identify the specific
taggants in the golf products. This embodiment would allow a
unique, interactive way for a buyer or end-user (consumer) to
confirm that their purchase was authentic.
[0016] The product component, coating, and/or decoration layers
(i.e., indicia) is doped with specific formula of quantities of
taggants, each carrying a unique profile of fluorescent (or
alternative wavelength) emission. Some of these tags might
fluoresce back in the visible spectrum (for easy visual
identification), while others might fluoresce at an infrared
frequency (invisible to the naked eye). Some taggants might be
deployed in a paint system, while others are included in an ink
system (further complicating an attempt by a counterfeiter to
emulate the process).
[0017] A remote detector, similar in appearance to a television
remote control, can be programmed to detect the presence and
specific concentration of taggants included in the formulation.
Such a combination of multiple IR to visible and IR-IR fluorescent
taggants would create a "combination lock" that would be extremely
difficult to counterfeit via reverse engineering.
[0018] These chemical taggants are inert compounds, typically added
to a masterbatch, paint, or ink system. The additives are typically
one or more fluorescent taggants or tracers that fluoresce (or emit
light) at a specific wavelength. Detection of these additives allow
confirmation of the correct presence and concentration of all
taggants included in the formulation. Once a series of taggants are
adapted and formulated into authentic product, then the
"combination to the lock" becomes unique to that product or
manufacturer.
[0019] This invention deals specifically with the incorporation of
two emerging technologies in counterfeiting
deterrence--microtaggant identification particles ("taggants") and
inert chemical compounds ("tracers"). Taggants are multicolored
particles, derived from crosslinked melamine and rare earth
elements that are added to component masterbatches in the
manufacturing process. These particles range in size from less than
20 microns to greater than 600 microns. These particles are
typically constructed as a multilayered (i.e., 10-layered) wafer
structure, and can be manufactured with a unique numeric/color code
for a specific product. Each layer has a unique numeric/color
value, and codes are assigned to manufacturers or products.
Suitable taggants are commercially-available from MicroTrace, LLC
of Minneapolis, Minn. The unique combinations of colors or numbered
layers is virtually limitless. The tag can be made more complex
through the addition of nanoparticles to the structure, or through
the inclusion of spectral, elemental, or infrared materials that
emit a specific signature when scanned.
[0020] Chemical tracers aren't as physically sophisticated as
taggants in their composition (they are inert chemical compounds
added to a masterbatch), however, they still provide a high degree
of covert protection that is highly difficult to duplicate.
[0021] Both types of additives have no deleterious effect on the
performance or processability of the materials they are blended
with, and are suitable for use in transparent or opaque materials
in molding or extrusion processes.
[0022] These technologies can be detected in a variety of ways,
including laser scanner, UV light, and spectroscopic analysis. The
additives are designed to be simple to identify in the field by law
enforcement or customs agents, via hand scanners, UV lights,
electronic detectors, or laser devices that can detect the presence
of the material as effectively as a laboratory analysis. The ease
of identification is not a concern because the identification step
is not the "key" to unlock the "code" defining a product as
counterfeit or not--the spectral excitation and response of the
taggant provides the authenticity information.
[0023] Another alternative embodiment of the present invention
relates generally to invisible means for marking golf balls and
other articles, such as golf ball packaging, using luminescent and
optically-stimulable glasses. More particularly, the alternative
embodiment relates to using metal-ion dopants in a glassy matrix in
inks, dyes, and the like, for marking golf balls and packaging, and
for detecting these by fluorescence and optically-stimulated
readout of trapped states.
[0024] The particular glasses and additives selected will depend on
the properties desired, such as (1) the color of the prompt
luminescence or the optically stimulated luminescence, (2) the
desired trap lifetime, or desired combination of lifetimes, and (3)
the desired physical properties of the glass, such as porosity, and
the associated diffusivity.
[0025] A typical embodiment of the invention uses a glass (or glass
matrix) containing an alkaline earth sulfide (i.e., MgS, CaS, SrS,
and BaS) doped with an activator/co-activator pair of rare earth
elements (i.e., samarium, europium, and cerium). Suitable glasses
for this embodiment of the invention include porous Vycor.TM.
glass, fused quartz, fused silica, alumina glass, or borate glass.
Glass matrices (i.e., silica, alumina, or borate glass) may be
doped with ZnS and Cu, Pb, Mn, Ce, Ag, or Eu. Preferably the
glasses are essentially free of metal sulfides or sulfides.
[0026] These optically-stimulated luminescent (OSL) glasses are
typically are prepared by diffusing the dopants into the glass or
glass matrices, which may be either porous or fused (non-porous).
The dopants may be diffused into the glass matrix by a wide variety
of methods, such as by solution contact (for a sufficiently long
time to allow diffusion) followed by drying. A soluble salt of a
generally insoluble metal sulfide component may also be used. After
drying, the glass may be sulfided, consolidated, and activated.
[0027] In fused silica or quartz glass, the dopants may be diffused
by dipping the fused silica or quartz glass matrix into an
organic-inorganic sol gel including a salt or salts of the dopant
metals and slowly withdrawn, resulting in the formation of a
porous, thin (<1 .mu.m) film containing the salt or salts. Upon
drying, the organic constituents of the film volatilize and/or
decompose, leaving behind a porous, film containing the salts
(which then may be sulfided to provide metal sulfides) that is then
activated.
[0028] The dopant salts used in the solutions and sol gels
discussed above are typically selected so that the salt is soluble
in the solution or sol gel and the anion component of the salt,
upon reduction, forms a gas or mixture of gases that are
non-reactive, or beneficially reactive, with the doped glass
matrix. The concentrations of these salts in the sol gels and
solutions may vary widely. For example, each salt is typically
present at a concentration of about 0.001 g/100 ml solution.
[0029] The doped glass matrix provides a mechanically robust,
chemically inert phosphor material. The material withstands cycling
through temperature extremes of up to 1200.degree. C., without any
apparent loss in performance.
[0030] OSL glass powders may be disposed in some other material.
OSL glass powders may be blended with polymers, such as ionomers,
polyurethanes, polyureas, polyethylenes, polycarbonates, silicones,
polymethylmethacrylates, acrylic acids, and polyvinyl chlorides.
The polymers may then be applied as a coating onto an article or
formed into a golf ball component. Preferably, the indices of
refraction of the glass and the polymer are similar, typically in
the range of about 1.4 and 1.5. OSL glass also may be added to
inks, stains, shellacs, varnishes, glazes, paints, conventional
dyes, or even synthetic fibers, such as polyester or rayon, for
inclusion in fabric articles.
[0031] Whatever the morphology of the glass, the methods for
exciting the glass for prompt luminescence and for trap formation
will be the same in most cases. Typically, an article is marked
with a patterned label (i.e., bar code, hob, date, serial number,
etc.) including a powdered glass phosphor pattern according to the
invention and is illuminated with a UV light source. This
illumination excites prompt luminescence and, depending on the
wavelength, populate traps. The prompt luminescence typically is
filtered through a blue-green color glass filter and detected with
a detector, such as a CCD camera. The resulting image may be viewed
on a computer screen or may be printed directly from the camera
unit.
[0032] To observe an OSL image, the patterned label must first be
energized using a short wavelength UV source to cause electrons to
be trapped. While the effect of UV excitation varies with
wavelength, suitable UV excitation ranges from about 100 nm to
about 400 nm. Preferred UV excitation ranges from about 100 nm to
about 280 nm, more preferably at about 185 m and 254 nm. The
trapped electrons then may be released by exposing the patterned
label to an infrared light source. The released charges may then
recombine, and thereby emit photons. The resulting
optically-stimulated luminescence can be viewed with an OSL
detector.
[0033] Patterned emission will be a useful feature of the
invention, especially for coding applications. The invention may be
used to put, for example, an alphanumeric code, bar code,
trademark, symbol, logo, or other product identifier, on an
article, by making this code visible upon UV stimulation for prompt
luminescence and/or the code may also be made visible by near-IR/IR
stimulation of the OSL. The patterns may be written by patterned
application of the marking material and/or by patterned excitation
of the marking material by exposure to patterned short wavelength
UV light. Handheld laser scanners, similar to the ones in use for
bar code reading, may be used for exposing and viewing patterned
luminescence. One or two directional scanning may be used according
to the invention, depending on the emission pattern.
[0034] The marking material may include a matrix of some bulk
material. The OSL glass may be added to the bulk material by any
suitable method, such as coating the OSL glass onto the bulk
material, mixing it with the bulk material, embedding it into the
bulk material, or combinations of these. A wide range of bulk
materials may be used in the marking materials of the invention,
including papers, polymers, glasses, fabrics, metals, ceramics,
dyes, inks, stains, shellacs, varnishes, glazes, polymers, glasses
including borosilicate glass, aluminosilicate glass,
aluminoborosilicate glass, sealing glass, soda lime glass, and
other glasses possessing an annealing point less than or equal to
800.degree. C., and various combinations of these.
[0035] The marking material may be applied in a pattern by any of
the available methods for applying a glass in any of the available
morphologies in a pattern. Typically, this will mean applying a
glass powder in a coating (i.e., an ink) through a mask or stencil,
or with an ink jet. Alternatively, if the OSL glass is incorporated
into a fiber, either a glass fiber or a fiber of another textile
material, this fiber may be woven, sewn, or otherwise applied in a
pattern to an article. Advantages of patterned application include
the permanence of the pattern (once the pattern is made, it will
endure for essentially the life of the article it is applied to),
and the simplicity of excitation.
[0036] Patterned illumination will generally take place through a
mask. Advantages of patterned illumination include the rewrite
capability it entails and the simplicity of the initial
manufacture. Objects coated with the marking material can be
patterned using the mask technique or directly patterned using a
spatially controlled UV light source such as a UV laser.
Alternatively, the marking material may be used as a printing ink
to apply specific patterns on objects.
[0037] Another useful feature of on embodiment the invention is the
time scale of the phosphorescence. The glasses of the present
invention will phosphoresce upon exposure to UV light. After
removal of the UV excitation, this phosphorescence will decay
slowly, over a time scale of seconds to tens of seconds, much
longer than the rapid fadeout of fluorescent materials.
Accordingly, one application of the present invention is to expose
a label to UV light, and time the decay of the phosphorescence
after the removal of the UV excitation. Comparing this fadeout to
an expected fadeout will prove or disprove the presence of the OSL
glasses used in the present invention, allowing one to potentially
determine the presence of a counterfeit product or packaging.
[0038] Golf balls formed according to the invention may, for
example, have a one-piece construction formed from a homogeneous
mass consisting entirely of the polyurethane composition of the
invention. Such balls may further include, if desired, blends of
conventional golf ball cover and/or intermediate layer materials,
such as those discussed herein or other materials available to
those of ordinary skill in the art. One-piece balls formed with the
materials disclosed herein are durable but do not provide great
distance because of their relatively high spin and low velocity.
Other embodiments of the present invention include two-piece,
multi-layer construction, such as dual-core and dual-cover golf
balls, and wound balls having cores, liquid centers, intermediate
layers, and/or covers, with one or more of the layers including the
polyurethane composition disclosed herein.
[0039] As used herein, the term "golf ball core" is used to refer
to any portion of a golf ball surrounded by the cover. In the case
of a golf ball having three or more layers, the term "golf ball
core" includes at least one inner layer and typically refers to a
center surrounded by at least one intermediate layer. Golf balls
having at least two layers in the core are known as "dual core"
golf balls. The center may be solid, gel-filled, hollow, or
fluid-filled, e.g., gas or liquid. The term "inner core" is used
interchangeably with "center" or "golf ball center," while the term
"outer core" is used interchangeably with "intermediate layer" or
"at least one intermediate layer." For example, one optional type
of intermediate layer is a tensioned elastomeric material wound
about the center. When a tensioned elastomeric material is included
as an intermediate layer, the polyurethane compositions of the
invention may be incorporated into the elastomeric material, the
center, or both. An intermediate layer may be included within a
ball having, for example, a single layer or multilayer cover, a
single layer or multilayer core, both a single layer cover and
core, or both a multilayer cover and a multilayer core, or any
similar such combination. Intermediate layers of the type described
above are sometimes referred to in the art, and, thus, herein as
well, as an inner cover layer, as an outer core layer, or as a
mantle layer.
[0040] While any cover material would be suitable, preferably the
golf ball of the present invention includes the reaction product of
polyisocyanate, at least one polyol (or polyamine if a polyurea is
desired), and at least one curing agent. Any polyisocyanate
available to one of ordinary skill in the art is suitable for use
according to the invention. Exemplary polyisocyanates include, but
are not limited to, 4,4'-diphenylmethane diisocyanate ("MDI"),
polymeric MDI, carbodiimide-modified liquid MDI,
4,4'-dicyclohexylmethane diisocyanate, p-phenylene diisocyanate
("PPDI"), m-phenylene diisocyanate, toluene diisocyanate ("TDI"),
3,3'-dimethyl-4,4'-biphenylene diisocyanate,
isophoronediisocyanate, hexamethylene diisocyanate ("HDI"),
naphthalene diisocyanate; xylene diisocyanate; p-tetramethylxylene
diisocyanate; m-tetramethylxylene diisocyanate; ethylene
diisocyanate; propylene-1,2-diisocyanate;
tetramethylene-1,4-diisocyanate; cyclohexyl diisocyanate;
dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate;
cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate;
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane; methyl
cyclohexylene diisocyanate; isocyanurate of HDI; triisocyanate of
2,4,4-trimethyl-1,6-hexane diisocyanate, tetracene diisocyanate,
napthalene diisocyanate, anthracene diisocyanate, and mixtures
thereof. Polyisocyanates are known to those of ordinary skill in
the art as having more than one isocyanate group, e.g., di-, tri-,
and tetra-isocyanate. Preferably, the polyisocyanate includes MDI,
PPDI, TDI, or a mixture thereof, and more preferably, the
polyisocyanate includes MDI. It should be understood that, as used
herein, the term "MDI" includes 4,4'-diphenylmethane diisocyanate,
polymeric MDI, carbodiimide-modified liquid MDI, and mixtures
thereof and, additionally, that the diisocyanate employed may be
"low free monomer," understood by one of ordinary skill in the art
to have lower levels of "free" isocyanate monomer, typically less
than about 0.1% to about 0.5% free monomer. Examples of "low free
monomer" diisocyanates include, but are not limited to Low Free
Monomer MDI, Low Free Monomer TDI, Low Free MPDI, and Low Free
Monomer PPDI.
[0041] The at least one polyisocyanate should have less than about
14% unreacted NCO groups. Preferably, the at least one
polyisocyanate has less than about 7.9% NCO, more preferably,
between about 2.5% and about 7.8%, and most preferably, between
about 4% to about 6.5%. Any polyol available to one of ordinary
skill in the art is suitable for use according to the invention.
Exemplary polyols include, but are not limited to, polyether
polyols, hydroxy-terminated polybutadiene and partially/fully
hydrogenated derivatives, polyester polyols, polycaprolactone
polyols, and polycarbonate polyols. In one preferred embodiment,
the polyol includes polyether polyol, more preferably those polyols
that have the generic structure:
##STR00001##
where R.sub.1 and R.sub.2 are straight or branched hydrocarbon
chains, each containing from 1 to about 20 carbon atoms, and n
ranges from 1 to about 45. Examples include, but are not limited
to, polytetramethylene ether glycol, 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.
[0042] In another embodiment, polyester polyols are included in the
polyurethane material of the invention. Preferred polyester polyols
have the generic structure:
##STR00002##
where R.sub.1 and R.sub.2 are straight or branched hydrocarbon
chains, each containing from 1 to about 20 carbon atoms, and n
ranges from 1 to about 25. Suitable polyester polyols include, but
are not limited to, polyethylene adipate glycol, polybutylene
adipate glycol, polyethylene propylene adipate glycol,
ortho-phthalate-1,6-hexanediol, and mixtures thereof. The
hydrocarbon chain can have saturated or unsaturated bonds, or
substituted or unsubstituted aromatic and cyclic groups.
[0043] In another embodiment, polycaprolactone polyols are included
in the materials of the invention. Preferably, any polycaprolactone
polyols have the generic structure:
##STR00003##
where R.sub.1 is a straight chain or branched hydrocarbon chain
containing from 1 to about 20 carbon atoms, and n is the chain
length and ranges from 1 to about 20. Suitable polycaprolactone
polyols include, but are not limited to, 1,6-hexanediol-initiated
polycaprolactone, diethylene glycol initiated polycaprolactone,
trimethylol propane initiated polycaprolactone, neopentyl glycol
initiated polycaprolactone, 1,4-butanediol-initiated
polycaprolactone, and mixtures thereof. The hydrocarbon chain can
have saturated or unsaturated bonds, or substituted or
unsubstituted aromatic and cyclic groups.
[0044] In yet another embodiment, the polycarbonate polyols are
included in the polyurethane material of the invention. Preferably,
any polycarbonate polyols have the generic structure:
##STR00004##
where R.sub.1 is predominantly bisphenol A units
--(P--C.sub.6H.sub.4)--C(CH.sub.3).sub.2--(P--C.sub.6H.sub.4)-- or
derivatives thereof, and n is the chain length and ranges from 1 to
about 20. Suitable polycarbonates include, but are not limited to,
polyphthalate carbonate. The hydrocarbon chain can have saturated
or unsaturated bonds, or substituted or unsubstituted aromatic and
cyclic groups. In one embodiment, the molecular weight of the
polyol is from about 200 to about 4000. Polyamine curatives are
also suitable for use in the polyurethane composition of the
invention and have been found to improve cut, shear, and impact
resistance of the resultant balls. Preferred polyamine curatives
have the general formula:
##STR00005##
where n and m each separately have values of 0, 1, 2, or 3, and
where Y is ortho-cyclohexyl, meta-cyclohexyl, para-cyclohexyl,
ortho-phenylene, meta-phenylene, or para-phenylene, or a
combination thereof. Preferred polyamine curatives include, but are
not limited to, 3,5-dimethylthio-2,4-toluenediamine and isomers
thereof (tradename ETHACURE 100 and/or ETHACURE 100 LC);
3,5-diethyltoluene-2,4-diamine and isomers thereof, such as
3,5-diethyltoluene-2,6-diamine;
4,4'-bis-(sec-butylamino)-diphenylmethane;
1,4-bis-(sec-butylamino)-benzene,
4,4'-methylene-bis-(2-chloroaniline);
4,4'-methylene-bis-(3-chloro-2,6-diethylaniline); trimethylene
glycol-di-p-aminobenzoate;
polytetramethyleneoxide-di-p-aminobenzoate; N,N'-dialkyldiamino
diphenyl methane; para, para'-methylene dianiline (MDA),
m-phenylenediamine (MPDA), 4,4'-methylene-bis-(2-chloroaniline)
(MOCA), 4,4'-methylene-bis-(2,6-diethylaniline),
4,4'-diamino-3,3'-diethyl-5,5'-dimethyl diphenylmethane, 2,2',
3,3'-tetrachloro diamino diphenylmethane,
4,4'-methylene-bis-(3-chloro-2,6-diethylaniline), (LONZACURE
M-CDEA), trimethylene glycol di-p-aminobenzoate (VERSALINK 740M),
and mixtures thereof. Preferably, the curing agent of the present
invention includes 3,5-dimethylthio-2,4-toluenediamine and isomers
thereof, such as ETHACURE 300, commercially available from
Albermarle Corporation of Baton Rouge, La. Suitable polyamine
curatives, which include both primary and secondary amines,
preferably have molecular weights ranging from about 64 to about
2000. Preferably, n and m, each separately, have values of 1, 2, or
3, and preferably, 1 or 2.
[0045] At least one of a diol, triol, tetraol, hydroxy-terminated,
may be added to the aforementioned polyurethane composition.
Suitable hydroxy-terminated curatives have the following general
chemical structure:
##STR00006##
where n and m each separately have values of 0, 1, 2, or 3, and
where X is ortho-phenylene, meta-phenylene, para-phenylene,
ortho-cyclohexyl, meta-cyclohexyl, or para-cyclohexyl, or mixtures
thereof. Preferably, n and m, each separately, have values of 1, 2,
or 3, and more preferably, 1 or 2.
[0046] Preferred hydroxy-terminated curatives for use in the
present invention include at least one of
1,3-bis(2-hydroxyethoxy)benzene and 1,3-bis-[2-(2-hydroxyethoxy)
ethoxy] benzene, and 1,3-bis-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}
benzene; 1,4-butanediol; resorcinol-di-(.beta.-hydroxyethyl)ether;
and hydroquinone-di-(.beta.-hydroxyethyl)ether; and mixtures
thereof. Preferably, the hydroxy-terminated curatives have
molecular weights ranging from about 48 to 2000. It should be
understood that molecular weight, as used herein, is the absolute
weight average molecular weight and would be understood as such by
one of ordinary skill in the art. Both the hydroxy-terminated and
amine curatives can include one or more saturated, unsaturated,
aromatic, and cyclic groups. Additionally, the hydroxy-terminated
and amine curatives can include one or more halogen groups.
Suitable diol, triol, and tetraol groups include ethylene glycol,
diethylene glycol, polyethylene glycol, propylene glycol,
polypropylene glycol, lower molecular weight polytetramethylene
ether glycol, and mixtures thereof. The polyurethane composition
can be formed with a blend or mixture of curing agents. If desired,
however, the polyurethane composition may be formed with a single
curing agent.
[0047] Any method available to one of ordinary skill in the art may
be used to combine the polyisocyanate, polyol, and curing agent of
the present invention. One commonly employed method, known in the
art as a one-shot method, involves concurrent mixing of the
polyisocyanate, polyol, and curing agent. This method results in a
mixture that is inhomogenous (more random) and affords the
manufacturer less control over the molecular structure of the
resultant composition. A preferred method of mixing is known as the
prepolymer method. In this method, the polyisocyanate and the
polyol are mixed separately prior to addition of the curing agent.
This method affords a more homogeneous mixture resulting in a more
consistent polymer composition.
[0048] An optional, but preferred, filler component may be chosen
to adjust the density of the blends described herein. The selection
of such filler(s) is dependent upon the type of golf ball desired
(i.e., one-piece, two-piece multi-component, or wound), and any
filler available to one of ordinary skill in the art is suitable
for use according to the invention. Examples of useful fillers
include zinc oxide ("ZnO"), barium sulfate, calcium oxide, calcium
carbonate, and silica, as well as any salts and oxides thereof.
Additional fillers, such as foaming agents, glass and/or plastic
microspheres, and various metals, can be added to the polyurethane
compositions of the present invention, in amounts as needed, for
their well-known purposes. Additional components which can be added
to the polyurethane composition include UV stabilizers and other
dyes, as well as optical brighteners, fluorescent pigments, and
dyes. Such additional ingredients may be added in any amounts that
will achieve their desired purpose.
[0049] In one embodiment, the invention is a multilayer golf ball
that includes a core, an inner cover layer, and an outer cover
layer. The cover thickness should be at least about 0.02 inches.
Preferably, the outer cover layer has a thickness of between about
0.02 and about 0.1 inches, more preferably from about 0.02 to about
0.08 inches. Most preferably, the thickness is from about 0.03 to
0.05 inches.
[0050] As discussed herein, the outer cover layer is preferably
formed from a relatively soft polyurethane material. In particular,
the material of the outer cover layer should have a material
hardness, as measured by ASTM D2240-00, of less than about 80 Shore
D, preferably less than about 70 Shore D, more preferably less than
about 60 Shore D, and most preferably from about 20 Shore C to
about 55 Shore D.
[0051] The inner cover layer of the present invention, when
included, may be formed of any material available to one of
ordinary skill in the art, including the polyurethane composition
of the present invention, but it is preferably formed from a hard,
high flexural modulus, resilient material. Preferably, the material
of the inner cover layer has a material hardness, as measured by
ASTM D2240-00, of about 20 to about 80 Shore D, more preferably
about 40 to about 70 Shore D, and most preferably about 60 Shore D
to about 70 Shore D. The thickness of the inner cover layer will
typically be less than about 0.1 inches, but preferably ranges from
about 0.01 inches to about 0.08 inches, more preferably from about
0.02 inches to about 0.06 inches, and most preferably from about
0.03 to about 0.04 inches.
[0052] The optional inner cover layer may be formed from a wide
variety of relatively hard (greater than about 60 Shore D), high
flexural modulus (greater than about 55,000 psi) resilient
materials. Preferably, the optional inner cover layers have a
material hardness of at least about 65 Shore D and more preferably,
between about 65 to about 75 Shore D.
[0053] Among the preferred inner cover materials are hard, high
flexural modulus ionomer resins and blends thereof. These ionomers
can be obtained by providing a cross metallic bond to polymers of
mono-olefin with at least one member selected from the group
consisting of unsaturated mono- or di-carboxylic acids having 3 to
12 carbon atoms and esters thereof (the polymer contains about 1 to
50% by weight of the unsaturated mono- or di-carboxylic acid and/or
ester thereof). More particularly, such acid-containing ethylene
copolymer ionomer component includes E/X/Y copolymers where E is
ethylene, X is a softening comonomer such as acrylate or
methacrylate present in 0 to about 50 (preferably 0 to about 25,
most preferably 0 to about 20), weight percent of the polymer, and
Y is acrylic or methacrylic acid present in about 5 to 35
(preferably at least about 16, more preferably at least about 16 to
35, most preferably at least about 16 to 20) weight percent of the
polymer, wherein the acid moiety is neutralized about 1 to 90%
(preferably at least about 40%, most preferably at least about 60%)
by a cation such as lithium, sodium, potassium, magnesium, calcium,
barium, lead, tin, zinc, or aluminum, or a combination of such
cations, to form an ionomer. Exemplary acid-containing ethylene
copolymers include ethylene/acrylic acid, ethylene/methacrylic
acid, ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic
acid/n-butyl acrylate, ethylene/methacrylic acid/iso-butyl
acrylate, ethylene/acrylic acid/iso-butyl acrylate,
ethylene/methacrylic acid/n-butyl methacrylate, ethylene/acrylic
acid/methyl methacrylate, ethylene/acrylic acid/methyl acrylate,
ethylene/methacrylic acid/methyl acrylate, ethylene/methacrylic
acid/methyl methacrylate, and ethylene/acrylic acid/n-butyl
methacrylate. Preferred acid-containing ethylene copolymers include
ethylene/methacrylic acid, ethylene/acrylic acid,
ethylene/methacrylic acid/n-butyl acrylate, ethylene/acrylic
acid/n-butyl acrylate, ethylene/methacrylic acid/methyl acrylate
and ethylene/acrylic acid/methyl acrylate copolymers. The most
preferred acid-containing ethylene copolymers are
ethylene/methacrylic acid, ethylene/acrylic acid,
ethylene/(meth)acrylic acid/n-butyl acrylate,
ethylene/(meth)acrylic acid/ethyl acrylate, and
ethylene/(meth)acrylic acid/methyl acrylate copolymers. Such
ionomer resins are commercially available, for example, from E.I.
DuPont de Nemours and Co. under the tradename SURLYN, and from
Exxon under the tradename IOTEK. Some particularly suitable SURLYNS
include SURLYN 8140 and SURLYN 8546, each of which has a
methacrylic acid content of about 19%.
[0054] The materials for the inner cover layer, however, are not
limited to ionomer resins. Instead, the present invention
contemplates that virtually any relatively hard, high flexural
modulus, resilient material known to one of ordinary skill in the
art that is compatible with the other materials of the golf ball
may be employed as the inner cover layer. Examples of other
suitable inner cover materials include thermoplastic or thermoset
polyurethanes, thermoplastic or thermoset polyetheresters or
polyetheramides, thermoplastic or thermoset polyester, a
dynamically vulcanized elastomer, a functionalized
styrene-butadiene elastomer, a metallocene polymer, or blends
thereof.
[0055] Suitable thermoplastic polyetheresters include materials
which are commercially available from DuPont under the tradename
HYTREL. Suitable thermoplastic polyetheramides include materials
which are available from Elf-Atochem under the tradename PEBAX.
Other suitable materials for the inner cover layer include
polycarbonates, polyimides, nylons, polyamides, polyureas, epoxies,
urethane ionomers, acrylonitrile-butadiene-styrene copolymer,
polysulfones, and thermoplastic and thermoset polyurethanes, and
combinations thereof.
[0056] In a particularly preferred embodiment of the present
invention, the core is a large, solid core, having a compression of
less than about 80. A large core, as used herein, is defined as
having a diameter of at least about 1.500 inches.
[0057] The materials for solid cores include compositions having a
base rubber, a crosslinking agent, a filler, and a co-crosslinking
or initiator agent. The base rubber typically includes natural or
synthetic rubbers. A preferred base rubber is 1,4-polybutadiene
having a cis-structure of at least 40%. If desired, the
polybutadiene can also be mixed with other elastomers known in the
art such as natural rubber, polyisoprene rubber and/or
styrene-butadiene rubber in order to modify the properties of the
core.
[0058] The crosslinking agent preferably includes a metal salt of
an unsaturated fatty acid such as a zinc salt or a magnesium salt
of an unsaturated fatty acid having 3 to 8 carbon atoms, such as
acrylic or methacrylic acid. Suitable cross linking agents include
metal salt diacrylates, dimethacrylates, and monomethacrylates, or
a mixture thereof, wherein the metal is, for example, magnesium,
calcium, zinc, aluminum, sodium, lithium, or nickel, or a mixture
thereof.
[0059] The initiator agent can be any known polymerization
initiator which decomposes during the cure cycle. Suitable
initiators include peroxide compounds, such as dicumyl peroxide,
1,1-di(t-butylperoxy) 3,3,5-trimethyl cyclohexane, .alpha.-.alpha.'
bis(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5
di(t-butylperoxy)hexane, di-t-butyl peroxide, or mixtures
thereof.
[0060] The core may include about 5 to 50 pph of ZnO in a
diacrylate-peroxide core system. Zinc oxide may be used in
combination with, or be replaced by, about 5 to 50 pph of calcium
oxide in a diacrylate-peroxide system to provide a suitable core
composition.
[0061] As used herein, the term "filler" in connection with the
core includes any compound or composition that can be used to vary
the density and other properties of the core. Fillers typically
includes materials such as zinc oxide, barium sulfate, silica,
calcium carbonate, zinc carbonate, regrind (recycled core material
ground to 30 mesh particle) and the like. Any of the fillers
described herein with respect to the cover or intermediate layers
are also suitable for use in preparing such solid core
formulations.
[0062] The overall outer diameter of the core, including the center
and any intermediate layer(s) or windings, together with the inner
cover layer of the golf balls of the present invention, is about
1.51 inches to about 1.64 inches, preferably about 1.59 inches to
about 1.63 inches, and most preferably from about 1.60 inches to
about 1.62 inches.
[0063] The present multilayer golf ball can have an overall
diameter of any size. Although the United States Golf Association
specifications require the minimum size of a competition golf ball
to at least 1.680 inches in diameter, there is no specification as
to the maximum diameter. Thus, the preferred diameter of the golf
ball of the present invention is about 1.680 inches to about 1.800
inches. The more preferred diameter is from about 1.680 inches to
about 1.760 inches. The most preferred diameter is about 1.680
inches to about 1.740 inches.
[0064] In another embodiment of the present invention, the
anti-counterfeiting system of the present invention may be used in
golf equipment and packaging therefor. Examples of golf equipment
include, but are not limited to, golf clubs (i.e., putters,
drivers, irons, and wedges) and club attachments, additions, or
modifications, such as striking face inserts; golf club components
(i.e., shafts, hosels, and grips); golf club vibration damping
devices; golf gloves and portions thereof, such as glove liners,
securing methods, patches, and reinforcements; golf shoes and
associated components (i.e., soles, footbeds and spike socket
spines, heel counters, toe "puffs," uppers, midsoles, outsoles,
liners, and plastic golf spikes); golf bags and their associated
framework, support legs, and stands; and any portion of the above
items.
[0065] In one particular embodiment of the present invention, the
cover comprises the polyurethane composition, polyurethane/polyurea
blend, or polyurea and polyurethane ionomer compositions.
[0066] The term "about," as used herein in connection with one or
more numbers or numerical ranges, should be understood to refer to
all such numbers, including all numbers in a range.
[0067] As used herein, the term "polyurethane composition" refers
to a combination of the reaction product of a prepolymer including
at least one polyisocyanate and at least one polyol, and at least
one curing agent, in addition to the color stabilizer
component.
[0068] As used herein, the term "ATTI compression" is defined as
the deflection of an object or material relative to the deflection
of a calibrated spring, as measured with an Atti Compression Gauge,
that is commercially available from Atti Engineering Corp. of Union
City, N.J. ATTI compression is typically used to measure the
compression of a golf ball. However, when referring to the
compression of a core, it is preferred to use a compressive load
measurement.
[0069] The invention described and claimed herein is not to be
limited in scope by the specific embodiments herein disclosed,
since these embodiments are intended solely as illustrations of
several aspects of the invention. Any equivalent embodiments are
intended to be within the scope of this invention. Indeed, various
modifications of the invention in addition to those shown and
described herein will become apparent to those of ordinary skill in
the art from the foregoing description. Such modifications are also
intended to fall within the scope of the appended claims.
* * * * *