U.S. patent application number 14/533282 was filed with the patent office on 2015-02-26 for golf ball compositions.
This patent application is currently assigned to ACUSHNET COMPANY. The applicant listed for this patent is ACUSHNET COMPANY. Invention is credited to Mark L. Binette, Robert Blink, David A. Bulpett, Brian Comeau, Michael J. Sullivan.
Application Number | 20150057104 14/533282 |
Document ID | / |
Family ID | 52480874 |
Filed Date | 2015-02-26 |
United States Patent
Application |
20150057104 |
Kind Code |
A1 |
Sullivan; Michael J. ; et
al. |
February 26, 2015 |
GOLF BALL COMPOSITIONS
Abstract
Disclosed herein are heterogeneous golf ball compositions
comprising discrete particles of crosslinked rubber dispersed
within an acid copolymer-based matrix. Also disclosed herein are
golf ball compositions comprising a silicone ionomer.
Inventors: |
Sullivan; Michael J.; (Old
Lyme, CT) ; Binette; Mark L.; (Mattapoisett, MA)
; Blink; Robert; (Newport, RI) ; Bulpett; David
A.; (Boston, MA) ; Comeau; Brian; (Berkley,
MA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ACUSHNET COMPANY |
Fairhaven |
MA |
US |
|
|
Assignee: |
ACUSHNET COMPANY
Fairhaven
MA
|
Family ID: |
52480874 |
Appl. No.: |
14/533282 |
Filed: |
November 5, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13966394 |
Aug 14, 2013 |
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14533282 |
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13849583 |
Mar 25, 2013 |
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13966394 |
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13531906 |
Jun 25, 2012 |
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13849583 |
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Current U.S.
Class: |
473/373 |
Current CPC
Class: |
A63B 37/0024 20130101;
A63B 37/0043 20130101; C08K 5/14 20130101; A63B 37/0045 20130101;
C08L 2205/22 20130101; A63B 37/0033 20130101; A63B 37/0063
20130101; A63B 37/0051 20130101; C08L 23/0869 20130101; C08L 21/00
20130101; A63B 37/0064 20130101; A63B 37/0074 20130101; A63B
37/0031 20130101; A63B 37/0039 20130101; C08L 67/00 20130101; A63B
37/0062 20130101; A63B 37/0075 20130101; C08L 23/0869 20130101;
C08L 21/00 20130101; C08L 2205/22 20130101 |
Class at
Publication: |
473/373 |
International
Class: |
A63B 37/00 20060101
A63B037/00 |
Claims
1. A golf ball comprising a layer formed from a composition
comprising at least one silicone ionomer.
2. The golf ball of claim 1, wherein the composition is a
thermoplastic composition additionally comprising an E/X/Y-type
ionomer of ethylene (E), an .alpha.,.beta.-unsaturated carboxylic
acid (X), and optionally a softening comonomer (Y).
3. The golf ball of claim 1, wherein the composition is a
thermoplastic composition additionally comprising a thermoplastic
polyurethane.
4. The golf ball of claim 1, wherein the composition is a
thermoplastic composition additionally comprising a polyester.
5. The golf ball of claim 1, wherein the composition is a
thermoplastic composition additionally comprising a polyamide.
6. The golf ball of claim 1, wherein the composition is a thermoset
composition additionally comprising a thermosetting
polyurethane.
7. The golf ball of claim 1, wherein the composition is a thermoset
composition additionally comprising a diene rubber.
8. A golf ball comprising a core and an outer cover layer, wherein
the outer cover layer has a thickness of less than 0.050 inches, a
material hardness of from 20 Shore D to 60 Shore D, and is formed
from a composition comprising at least one silicone ionomer.
9. A golf ball comprising a core, an outer cover layer, and an
intermediate layer disposed between the core and the outer cover
layer, wherein the intermediate layer has a thickness of from 0.030
inches to 0.150 inches, a material hardness of from 10 Shore D to
55 Shore D, and is formed from a composition comprising at least
one silicone ionomer.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation-in-part of U.S.
patent application Ser. No. 13/966,394, filed Aug. 14, 2013, which
is a continuation-in-part of U.S. patent application Ser. No.
13/849,583, filed Mar. 25, 2013, which is a continuation-in-part of
U.S. patent application Ser. No. 13/531,906, filed Jun. 25, 2012,
the entire disclosures of which are hereby incorporated herein by
reference.
FIELD OF THE INVENTION
[0002] The present invention is directed to golf ball compositions
comprising discrete particles of crosslinked rubber within a
thermoplastic matrix. The present invention is also directed to
particularly suitable thermoplastic compositions, optionally
including discrete particles dispersed therein. The present
invention is also directed to particularly suitable thermoset
compositions, optionally including discrete particles dispersed
therein.
BACKGROUND OF THE INVENTION
[0003] U.S. Pat. No. 5,789,486 to Maruoka et al. discloses a golf
ball including a paint layer comprised of a dispersion of
internally-crosslinked polymer gel fine particles. U.S. Pat. No.
6,186,906 to Sullivan et al. discloses golf ball compositions
comprising discrete particles of gel.
[0004] U.S. Pat. No. 7,402,114 to Binette et al. discloses golf
ball materials comprising a partially to highly neutralized blend
of copolymers, a fatty acid or fatty acid salt, and a heavy mass
filler.
[0005] U.S. Pat. No. 7,612,135 to Kennedy, III et al. discloses
golf ball materials comprising a partially to highly neutralized
blend of an acid copolymer, a copolymer comprising a
metallocene-catalyzed alpha-olefin and a softening comonomer, and a
fatty acid or fatty acid salt.
[0006] U.S. Patent Application Publication No. 2008/0234070 to
Comeau et al. discloses the use of crosslinked rubber nanoparticles
in golf ball layers.
[0007] U.S. Pat. No. 5,733,974 to Yamada et al. discloses a golf
ball comprising a core made of an elastomer and a cover covering
said core wherein said cover is made of a thermoplastic material
comprising a rubber powder and a thermoplastic elastomer.
[0008] U.S. Pat. No. 6,465,573 to Maruko et al. discloses a solid
golf ball comprising a core, an intermediate layer, and a cover
improved in rebound, distance, and feel when the intermediate layer
is comprised of a thermoplastic resin in admixture with rubber
powder.
[0009] U.S. Pat. No. 5,779,561 to Sullivan et al. discloses a golf
ball including an inner cover layer comprising (1) a first resin
composition containing at least 50 parts by weight of a
non-ionomeric polyolefin material and (2) at least one part by
weight of a filler.
[0010] U.S. Patent Application Publication No. 2003/0216520 to Irii
et al. discloses a golf ball whose core is covered with a cover,
wherein the core is constituted of a rubber composition containing
polybutadiene rubber and the cover is constituted of a resin
composition composed of ionomer resin and diene rubber.
[0011] U.S. Patent Application Publication No. 2012/0165122 to Kim
et al. discloses a golf ball where at least one of the outer cover
layer and the intermediate layer includes a blend composition of
about 2 to about 40 wt % of a polyamide and about 60 to about 98 wt
% of one or more of either a block copolymer, an acidic copolymer;
an acidic terpolymer; an ionomer, or a multi component blend
composition; and wherein the polyamide has a melting point which is
greater than about 5 and less than about 200.degree. C. above the
melting point of the other blend component.
[0012] U.S. Pat. No. 6,361,453 to Nakamura et al. discloses a solid
golf ball having a solid core and a cover, the solid core is
composed of a core-forming material and particles of a different
material.
SUMMARY OF THE INVENTION
[0013] In one embodiment, the present invention is directed to a
golf ball comprising a layer formed from a heterogeneous
composition, the composition comprising a thermoplastic matrix and
discrete particles dispersed within the matrix. In a particular
aspect of this embodiment, the matrix is formed from an acid
copolymer composition wherein the acid copolymer is selected from
one or more E/X- and E/X/Y-type acid copolymers of ethylene, an
.alpha.,.beta.-unsaturated carboxylic acid, and optionally a
softening comonomer, the particles are formed from a rubber
composition, and less than 5% of all acid groups present in the
matrix composition are neutralized.
[0014] In another embodiment, the present invention is directed to
a golf ball comprising a layer formed from a composition comprising
at least one silicone ionomer.
DETAILED DESCRIPTION
[0015] In one embodiment, the present invention is directed to
heterogeneous golf ball compositions comprising discrete particles
of crosslinked material within a thermoplastic matrix. The
heterogeneous composition is formed by adding the particles to the
matrix composition either prior to or during the process of forming
the golf ball layer. In another embodiment, the present invention
is directed to golf ball compositions comprising at least one
silicone ionomer, optionally including dispersed particles
dispersed therein.
[0016] In a particular embodiment, the heterogeneous composition
has a solid sphere coefficient of restitution, "COR," within a
range having a lower limit of 0.450 or 0.500 or 0.550 or 0.600 or
0.650 or 0.700 and an upper limit of 0.710 or 0.730 or 0.750 or
0.770 or 0.800 or 0.820 or 0.850 or 0.870 or 0.900 or 0.910 or
0.930. For purposes of the present disclosure, the "solid sphere
COR" of a composition refers to the COR of an injection molded 1.55
inch diameter sphere of the composition. COR is determined
according to a known procedure wherein a sphere is fired from an
air cannon at two given velocities and calculated at a velocity of
125 ft/s. Ballistic light screens are located between the air
cannon and the steel plate at a fixed distance to measure ball
velocity. As the sphere travels toward the steel plate, it
activates each light screen, and the time at each light screen is
measured. This provides an incoming transit time period inversely
proportional to the sphere's incoming velocity. The sphere impacts
the steel plate and rebounds through the light screens, which again
measures the time period required to transit between the light
screens. This provides an outgoing transit time period inversely
proportional to the sphere's outgoing velocity. COR is then
calculated as the ratio of the outgoing transit time period to the
incoming transit time period,
COR=V.sub.ont/V.sub.in=T.sub.in/T.sub.out.
[0017] In a particular embodiment, the heterogeneous composition
has a solid sphere compression within a range having a lower limit
of -75 or -50 or -20 or 0 or 10 or 15 and an upper limit of 20 or
25 or 30 or 35 or 40 or 50. In another particular embodiment, the
heterogeneous composition has a solid sphere compression within a
range having a lower limit of 70 or 75 or 80 or 85 or 90 and an
upper limit of 90 or 95 or 100 or 105 or 115 or 120 or 125. In
another particular embodiment, the heterogeneous composition has a
solid sphere compression within a range having a lower limit of 120
or 130 or 140 or 150 or 155 or 160 and an upper limit of 160 or 165
or 170 or 180 or 190 or 200. In another particular embodiment, the
heterogeneous composition has a solid sphere compression of 130 or
greater, or 140 or greater, or 150 or greater, or 155 or greater,
or 160 or greater, or 165 or greater, or 170 or greater. For
purposes of the present disclosure, the "solid sphere compression"
of a composition refers to the compression of an injection molded
1.55 inch diameter sphere of the composition. The compression of
the sphere is determined according to a known procedure, using a
digital Atti compression test device, wherein a piston is used to
compress a sphere against a spring. Conversion from Atti
compression to Riehle (cores), Riehle (balls), 100 kg deflection,
130-10 kg deflection or effective modulus can be carried out
according to the formulas given in Jeff Dalton's Compression by Any
Other Name, Science and Golf IV, Proceedings of the World
Scientific Congress of Golf (Eric Thain ed., Routledge, 2002).
[0018] In a particular embodiment, the heterogeneous composition
has a flexural modulus, as measured according to the method given
in the Examples below, of 5 ksi or greater, 6 ksi or greater, or 8
ksi or greater, or 10 ksi or greater, or 15 ksi or greater, or 20
ksi or greater, or 25 ksi or greater, or 30 ksi or greater, or 35
ksi or greater, or 40 ksi or greater, or 45 ksi or greater, or 48
ksi or greater, or 50 ksi or greater, or 52 ksi or greater, or 55
ksi or greater, or 60 ksi or greater, or 63 ksi or greater, or 65
ksi or greater, or 70 ksi or greater, 100 ksi or greater, or 120
ksi or greater, or 150 ksi or greater, or 160 ksi or greater, or
170 ksi or greater, or 180 ksi or greater, or 195 ksi or greater,
or a flexural modulus within a range having a lower limit of 5 or 6
or 8 or 10 or 15 or 20 or 25 or 30 or 35 or 40 or 45 or 48 or 50 or
52 or 55 or 55 or 60 or 63 or 65 or 70 ksi and an upper limit of 75
or 80 or 85 or 90 or 95 or 100 or 105 or 110 or 115 ksi, or a
flexural modulus within a range having a lower limit of 20 or 25 or
30 or 35 or 40 or 45 or 50 or 55 or 60 ksi and an upper limit of 60
or 65 or 70 or 75 or 80 ksi, or a flexural modulus within a range
having a lower limit of 50 or 60 or 70 or 90 or 120 or 130 and an
upper limit of 150 or 170 or 200 or 210.
[0019] In a particular embodiment, the particles are present in the
composition in an amount of 1 wt % or greater, or 2 wt % or
greater, or 3 wt % or greater, or 5 wt % or greater, or 10 wt % or
greater, or 15 wt % or greater, or 18 wt % or greater, or 20 wt %
or greater, or 25 wt % or greater, or 30 wt % or greater, or 35 wt
% or greater, or 40 wt % or greater, or 45 wt % or greater, or 50
wt % or greater, or 55 wt % or greater, or 60 wt % or greater, or
an amount within a range having a lower limit of 1 or 2 or 3 or 5
or 10 or 15 or 20 or 25 or 30 or 35 or 40 wt % and an upper limit
of 50 or 55 or 60 or 65 or 70 or 75 or 80 or 85 or 90 wt %, based
on the total weight of the composition.
[0020] In another particular embodiment, the composition comprises
at least 500 of the discrete particles.
[0021] In another particular embodiment, the composition is
substantially free of discrete particles. For purposes of the
present disclosure, the composition is substantially free of
discrete particles if the composition does not contain the discrete
particles or comprises less than 1 wt % of the discrete particles,
based on the total weight of the composition.
[0022] In a particular embodiment, the particles have a maximum
particle size of 0.595 mm or 0.707 mm or 0.841 mm or 0.900 mm or
1.00 mm or 1.19 mm or 1.41 mm or 1.68 mm or 2.00 mm or 2.38 mm. In
another embodiment, the crosslinked particles have a particle size
within a range having a lower limit of 0.001 mm or 0.002 mm or
0.005 mm or 0.007 mm or 0.015 mm or 0.030 mm or 0.037 or mm or
0.074 mm and an upper limit of 0.100 mm or 0.125 mm or 0.177 mm or
0.354 mm or 0.420 mm or 0.500 mm or 0.595 mm or 0.707 mm or 0.841
mm or 1.000 mm or 1.19 mm or 1.41 mm or 1.68 mm or 2.00 mm or 2.38
mm.
Particle Composition
[0023] For purposes of the present invention, the particle
composition is crosslinked and ground into particles prior to being
added to the matrix composition.
[0024] Rubber compositions suitable for forming the particles
include a base rubber selected from natural rubber, polybutadiene,
polyisoprene, ethylene propylene rubber (EPR),
ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber,
butyl rubber, halobutyl rubber, polyurethane, polyurea,
acrylonitrile butadiene rubber, polychloroprene, alkyl acrylate
rubber, chlorinated isoprene rubber, acrylonitrile chlorinated
isoprene rubber, polyalkenamer, phenol formaldehyde, melamine
formaldehyde, polyepoxide, polysiloxane, polyester, alkyd,
polyisocyanurate, polycyanurate, polyacrylate, and combinations of
two or more thereof. Diene rubbers are preferred, particularly
polybutadiene, styrene-butadiene, acrylonitrile butadiene, and
mixtures of polybutadiene with other elastomers wherein the amount
of polybutadiene present is at least 40 wt % based on the total
polymeric weight of the mixture.
[0025] Non-limiting examples of suitable commercially available
rubbers are Buna CB high-cis neodymium-catalyzed polybutadiene
rubbers, such as Buna CB 23, Buna CB24 and Buna CB high-cis
cobalt-catalyzed polybutadiene rubbers, such as Buna CB 1203, 1220
and 1221, commercially available from Lanxess Corporation; SE
BR-1220, commercially available from The Dow Chemical Company;
Europrene.RTM. NEOCIS.RTM. BR 40 and BR 60, commercially available
from Polimeri Europa.RTM.; UBEPOL-BR.RTM. rubbers, commercially
available from UBE Industries, Inc.; BR 01, commercially available
from Japan Synthetic Rubber Co., Ltd.; Neodene high-cis
neodymium-catalyzed polybutadiene rubbers, such as Neodene BR 40,
commercially available from Karbochem; TP-301 transpolyisoprene,
commercially available from Kuraray Co., Ltd.; Vestenamer.RTM.
polyoctenamer, commercially available from Evonik Industries; Butyl
065 and Butyl 288 butyl rubbers, commercially available from
ExxonMobil Chemical Company; Butyl 301 and Butyl 101-3,
commercially available from Lanxess Corporation; Bromobutyl 2224
and Chlorobutyl 1066 halobutyl rubbers, commercially available from
ExxonMobil Chemical Company; Bromobutyl X2 and Chlorobutyl 1240
halobutyl rubbers, commercially available from Lanxess Corporation;
BromoButyl 2255 butyl rubber, commercially available from Japan
Synthetic Rubber Co., Ltd.; Vistalon.RTM. 404 and Vistalon.RTM. 706
ethylene propylene rubbers, commercially available from ExxonMobil
Chemical Company; Dutral CO 058 ethylene propylene rubber,
commercially available from Polimeri Europa; Nordel.RTM. IP NDR
5565 and Nordel.RTM. IP 3670 ethylene-propylene-diene rubbers,
commercially available from The Dow Chemical Company; EPT1045 and
EPT1045 ethylene-propylene-diene rubbers, commercially available
from Mitsui Corporation; Buna SE 1721 TE styrene-butadiene rubbers,
commercially available from Lanxess Corporation; Afpol 1500 and
Afpol 552 styrene-butadiene rubbers, commercially available from
Karbochem; Nipol.RTM. DN407 and Nipol.RTM. 1041L acrylonitrile
butadiene rubbers, commercially available from Zeon Chemicals,
L.P.; Neoprene GRT and Neoprene AD30 polychloroprene rubbers;
Vamac.RTM. ethylene acrylic elastomers, commercially available from
E. I. du Pont de Nemours and Company; Hytemp.RTM. AR12 and AR214
alkyl acrylate rubbers, commercially available from Zeon Chemicals,
L.P.; Hypalon.RTM. chlorosulfonated polyethylene rubbers,
commercially available from E. I. du Pont de Nemours and Company;
and Goodyear Budene.RTM. 1207 polybutadiene, commercially available
from Goodyear Chemical.
[0026] The rubber is crosslinked using, for example, a peroxide or
sulfur cure system, C-C initiators, high energy radiation sources
capable of generating free radicals, resin cure, or a combination
thereof.
[0027] In a particular embodiment, the rubber is crosslinked using
a peroxide initiator and optionally a coagent. Suitable peroxide
initiators include, but are not limited to, organic peroxides, such
as 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; lauryl peroxide; benzoyl peroxide;
and combinations thereof. Examples of suitable commercially
available peroxides include, but are not limited to Perkadox.RTM.
BC dicumyl peroxide, commercially available from Akzo Nobel, and
Varox.RTM. peroxides, such as Varox.RTM. ANS benzoyl peroxide and
Varox.RTM. 231 1,1-di(t-butylperoxy)3,3,5-trimethylcyclohexane,
commercially available from RT Vanderbilt Company, Inc.
[0028] Coagents are commonly used with peroxides to increase the
state of cure. Suitable coagents include, but are not limited to,
metal salts of unsaturated carboxylic acids; unsaturated vinyl
compounds and polyfunctional monomers (e.g., trimethylolpropane
trimethacrylate); maleimides (e.g., phenylene bismaleimide); and
combinations thereof. Particular examples of suitable metal salts
of unsaturated carboxylic acids 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, nickel, and sodium. In a
particular embodiment, the coagent is selected from zinc salts of
acrylates, diacrylates, methacrylates, dimethacrylates, and
mixtures thereof. In another particular embodiment, the coagent is
zinc diacrylate.
[0029] The amount of peroxide initiator and coagent can be varied
to achieve the desired hardness of the crosslinked particle
composition. For example, in one embodiment, the crosslinked
particle composition is a coagent-cured rubber comprising a
peroxide initiator and a high level of coagent (e.g., 35 phr or
greater, or greater than 35 phr, or 50 phr or greater, or greater
than 50 phr, or 75 phr or greater, or greater than 75 phr of
coagent, or 100 phr or greater, or 150 hr or greater, or 200 phr or
greater, or 250 phr or greater, or 300 phr or greater, or 350 phr
or greater, or 400 phr or greater). In a particular aspect of this
embodiment, the crosslinked particle composition has a Shore D
hardness of 55 or greater, or greater than 55, or 60 or greater, or
greater than 60, or 65 or greater, or greater than 65, or 70 or
greater, or greater than 70, or 75 or greater, or greater than 75,
or 80 or greater, or greater than 80, or 85 or greater, or greater
than 85, or 90 or greater, or greater than 90. In another
embodiment, the crosslinked particle composition is a
peroxide-cured rubber comprising a peroxide initiator and is free
of coagent, substantially free of coagent (i.e., <1 phr
coagent), or includes a low level of coagent (e.g., 10 phr or less,
or less than 10 phr, or 5 phr or less, or less than 5 phr, or 1 phr
or less, or less than 1 phr). In a particular aspect of this
embodiment, the crosslinked particle composition has a Shore C
hardness of 50 or less, or less than 50, or 45 or less, or less
than 45, or 40 or less, or less than 40, or 35 or less, or less
than 35, or 30 or less, or less than 30, or 25 or less, or less
than 25, or 20 or less, or less than 20, or 15 or less, or 12 or
less, or 10 or less, or a Shore A hardness of 55 or less, or less
than 55, or 50 or less, or less than 50, or 40 or less, or 30 or
less. In another embodiment, the crosslinked particle composition
is a peroxide-cured rubber comprising a peroxide initiator and a
coagent, wherein the peroxide initiator is present in an amount of
at least 0.05 phr, or an amount within a range having a lower limit
of 0.05 or 0.1 or 0.8 or 1 or 1.25 or 1.5 phr and an upper limit of
2.5 or 3 or 5 or 6 or 10 or 15 phr, and wherein the coagent is
present in an amount within a range having a lower limit of 1 or 5
or 10 or 15 or 19 or 20 phr and an upper limit of 24 or 25 or 30 or
35 or 40 or 45 or 50 or 60 phr. In a particular aspect of this
embodiment, the crosslinked particle composition has a Shore C
hardness within a range having a lower limit of 20 or 25 or 30 or
35 or 40 or 45 or 50 or 55 or 60 or 70 or 80 or 82 or 85 and an
upper limit of 60 or 70 or 75 or 80 or 90 or 92 or 93 or 95,
wherein the upper limit is greater than the lower limit (e.g., when
the lower limit is 70, the upper limit is 75, 80, 90, 92, 93, or
95).
[0030] In another particular embodiment, the rubber is crosslinked
using sulfur and/or an accelerator. Suitable accelerators include,
but are not limited to, guanidines (e.g., diphenyl guanidine,
triphenyl guanidine, and di-ortho-tolyl guanidine); thiazoles
(e.g., mercaptobenzothiazole, dibenzothiazyldisulfide, sodium salt
of mercaptobenzothiazole, zinc salt of mercaptobenzothiazole, and
2,4-dinitrophenyl mercaptobenzothiazole); sulfenamides (e.g.,
N-cyclohexylbenzothiazylsulfenamide,
N-oxydiethylbenzothiazylsulfenamide,
N-t-butylbenzothiazylsulfenamide, and
N,N'-dicyclohexylbenzothiazylsulfenamide); thiuram sulfides (e.g.,
tetramethyl thiuram disulfide, tetraethyl thiuram disulfide,
tetrabutylthiuram disulfide, tetramethyl thiuram monosulfide,
dipentamethylene thiuram tetrasulfate,
4-morpholinyl-2-benzothiazole disulfide, and
dipentamethylenethiuram hexasulfide); dithiocarbamates (e.g.,
piperidine pentamethylene dithiocarbamate, zinc diethyl
dithiocarbamate, sodium diethyl dithiocarbamate, zinc ethyl phenyl
dithiocarbamate, and bismuth dimethyldithiocarbamate); thioureas
(e.g., ethylene thiourea, N,N'-diethylthiourea, and
N,N'-diphenylthiourea); xanthates (e.g., zinc isopropyl xanthate,
sodium isopropyl xanthate, and zinc butyl xanthate);
dithiophosphates; and aldehyde amines (e.g., hexamethylene
tetramine and ethylidene aniline).
[0031] The crosslinking system optionally includes one or more
activators selected from metal oxides (e.g., zinc oxide and
magnesium oxide), and fatty acids and salts of fatty acids (e.g.,
stearic acid, zinc stearate, oleic acid, and dibutyl ammonium
oleate).
[0032] The rubber particle composition optionally includes a scorch
retarder to prevent scorching of the rubber during processing
before vulcanization. Suitable scorch retarders include, but are
not limited to, salicylic acid, benzoic acid, acetylsalicylic acid,
phthalic anhydride, sodium acetate, and
N-cyclohexylthiophthalimide.
[0033] The rubber particle composition optionally includes one or
more antioxidants to inhibit or prevent the oxidative degradation
of the base rubber. Some antioxidants also act as free radical
scavengers; thus, when antioxidants are included in the crosslinked
particle composition, the amount of initiator agent used may be as
high as or higher than the amounts disclosed herein. Suitable
antioxidants include, but are not limited to, hydroquinoline
antioxidants, phenolic antioxidants, and amine antioxidants.
[0034] The rubber particle composition optionally includes from
0.05 phr to 10.0 phr of a soft and fast agent selected from
organosulfur and metal-containing organosulfur compounds; organic
sulfur compounds, including mono, di, and polysulfides, thiol, and
mercapto compounds; inorganic sulfide compounds; blends of an
organosulfur compound and an inorganic sulfide compound; Group VIA
compounds; substituted and unsubstituted aromatic organic compounds
that do not contain sulfur or metal; aromatic organometallic
compounds; hydroquinones; benzoquinones; quinhydrones; catechols;
resorcinols; and combinations thereof. In a particular embodiment,
the soft and fast agent is selected from zinc
pentachlorothiophenol, pentachlorothiophenol, ditolyl disulfide,
diphenyl disulfide, dixylyl disulfide, 2-nitroresorcinol, and
combinations thereof.
[0035] The rubber particle composition optionally contains one or
more fillers. Exemplary fillers include precipitated hydrated
silica, clay, talc, asbestos, glass fibers, aramid fibers, mica,
calcium metasilicate, zinc sulfate, barium sulfate, zinc sulfide,
lithopone, silicates, silicon carbide, diatomaceous earth,
carbonates (e.g., calcium carbonate, zinc carbonate, barium
carbonate, and magnesium carbonate), metals (e.g., titanium,
tungsten, aluminum, bismuth, nickel, molybdenum, iron, lead,
copper, boron, cobalt, beryllium, zinc, and tin), metal alloys
(e.g., steel, brass, bronze, boron carbide whiskers, and tungsten
carbide whiskers), oxides (e.g., zinc oxide, tin oxide, iron oxide,
calcium oxide, aluminum oxide, titanium dioxide, magnesium oxide,
and zirconium oxide), particulate carbonaceous materials (e.g.,
graphite, carbon black, cotton flock, natural bitumen, cellulose
flock, and leather fiber), microballoons (e.g., glass and ceramic),
fly ash, core material that is ground and recycled, nanofillers and
combinations thereof. The amount of particulate material(s) present
in the rubber particle composition is typically within a range
having a lower limit of 5 parts or 10 parts by weight per 100 parts
of the base polymer, and an upper limit of 30 parts or 50 parts or
100 parts by weight per 100 parts of the base polymer. Filler
materials may be dual-functional fillers, such as zinc oxide (which
may be used as a filler/acid scavenger) and titanium dioxide (which
may be used as a filler/brightener material).
[0036] The rubber particle composition may also contain one or more
additives selected from processing aids, such as transpolyisoprene
(e.g., TP-301 transpolyisoprene, commercially available from
Kuraray Co., Ltd.), transbutadiene rubber, and polyalkenamer
rubber; processing oils; plasticizers; coloring agents; fluorescent
agents; chemical blowing and foaming agents; defoaming agents;
stabilizers; softening agents; impact modifiers; free radical
scavengers; antiozonants (e.g., p-phenylenediames); and the like.
The amount of additive(s) typically present in the crosslinked
particle composition is typically within a range having a lower
limit of 0 parts or 5 parts by weight per 100 parts of the base
polymer, and an upper limit of 10 parts or 20 parts or 50 parts or
100 parts or 150 parts by weight per 100 parts of the base
polymer.
[0037] Suitable types and amounts of rubber, initiator agent,
coagent, filler, and additives are more fully described in, for
example, U.S. Pat. Nos. 6,566,483, 6,695,718, 6,939,907, 7,041,721,
and 7,138,460, the entire disclosures of which are hereby
incorporated herein by reference. Particularly suitable diene
rubber compositions are further disclosed, for example, in U.S.
Patent Application Publication No. 2007/0093318, the entire
disclosure of which is hereby incorporated herein by reference.
[0038] Preferably, the crosslinked particles are formed from a
rubber composition that is substantially free of reactive metal
ingredients including, for example, reactive metal-containing
coagents, reactive metal-containing soft and fast agents, reactive
metal-containing fillers and processing aids, reactive metal
oxides, reactive metal carbonates, reactive metal carboxylates, and
reactive metals and metal alloys (e.g., zinc diacrylate, zinc
pentachlorothiophenol, zinc stearate, and the like).
[0039] In a particular embodiment, the crosslinked particle
composition has a Shore D hardness within a limit having a lower
limit of 20 or 30 or 35 or 45 or 55 and an upper limit of 55 or 60
or 65 or 70 or 75 or 80 or 85 or 90 or 95, or a Shore D hardness of
55 or greater, or greater than 55, or 60 or greater, or greater
than 60, or 65 or greater, or greater than 65, or 70 or greater, or
greater than 70, or 75 or greater, or greater than 75, or 80 or
greater, or greater than 80, or 85 or greater, or greater than 85,
or 90 or greater, or greater than 90.
[0040] In another particular embodiment, the crosslinked rubber
particle composition has a Shore C hardness of 50 or less, or less
than 50, or 45 or less, or less than 45, or 40 or less, or less
than 40, or 35 or less, or less than 35, or 30 or less, or less
than 30, or 25 or less, or less than 25, or 20 or less, or less
than 20, or 15 or less, or 12 or less, or 10 or less.
[0041] In another particular embodiment, the crosslinked rubber
particle composition has a Shore A hardness of 55 or less, or less
than 55, or 50 or less, or less than 50, or 40 or less, or 30 or
less.
[0042] In another particular embodiment, the crosslinked rubber
particle composition has a Shore C hardness within a range having a
lower limit of 20 or 25 or 30 or 35 or 40 or 45 or 50 or 55 or 60
or 70 or 80 or 82 or 85 and an upper limit of 60 or 70 or 75 or 80
or 90 or 92 or 93 or 95, wherein the upper limit is greater than
the lower limit (e.g., when the lower limit is 70, the upper limit
is 75, 80, 90, 92, 93, or 95).
[0043] For purposes of the present disclosure, the hardness of the
crosslinked rubber particle composition refers to the surface
hardness of a 0.25 inch plaque of the composition cured under the
same conditions as those used to cure the particle composition that
is added to the matrix composition to form the heterogeneous
composition. Hardness measurements are made pursuant to ASTM D-2240
using a calibrated, digital durometer, capable of reading to 0.1
hardness units and set to record the maximum hardness reading
obtained for each measurement.
Thermoplastic Matrix Composition
[0044] In a particular embodiment, the matrix composition is
non-ionomeric, i.e., the matrix composition does not include an
ionomer. In another particular embodiment, the matrix composition
includes an ionomer in an amount of 70 wt % or less, or 65 wt % or
less, or 60 wt % or less, or 55 wt % or less, or 50 wt % or less,
or less than 50 wt %, or 40 wt % or less, or 35 wt % or less, or 30
wt % or less, or 25 wt % or less, or 20 wt % or less, or 15 wt % or
less, or 10 wt % or less, or 5 wt % or less, based on the total
polymeric weight of the matrix composition. In another particular
embodiment, the matrix composition includes an ionomer in an amount
of 5 wt % or greater, or 10 wt % or greater, or 20 wt % or greater,
or 25 wt % or greater, or 40 wt % or greater, or 50 wt % or
greater, or 55 wt % or greater, or 70 wt % or greater, or 90 wt %
or greater, or 95 wt % or greater, or 99 wt % or greater, or 100 wt
%, based on the total polymeric weight of the matrix
composition.
[0045] Suitable ionomer compositions include partially neutralized
ionomers and highly neutralized ionomers, including ionomers formed
from blends of two or more partially neutralized ionomers, blends
of two or more highly neutralized ionomers, and blends of one or
more partially neutralized ionomers with one or more highly
neutralized ionomers. Preferred ionomers are salts of O/X- and
O/X/Y-type acid copolymers, wherein O is an .alpha.-olefin, X is a
C.sub.3-C.sub.8 .alpha.,.beta.-ethylenically unsaturated carboxylic
acid, and Y is a softening monomer. O is preferably selected from
ethylene and propylene. X is preferably selected from methacrylic
acid, acrylic acid, ethacrylic acid, crotonic acid, and itaconic
acid. Methacrylic acid and acrylic acid are particularly preferred.
As used herein, "(meth) acrylic acid" means methacrylic acid and/or
acrylic acid. Likewise, "(meth) acrylate" means methacrylate and/or
acrylate. Y is preferably selected from (meth) acrylate and alkyl
(meth) acrylates wherein the alkyl groups have from 1 to 8 carbon
atoms, including, but not limited to, n-butyl (meth) acrylate,
isobutyl (meth) acrylate, methyl (meth) acrylate, and ethyl (meth)
acrylate. Particularly preferred O/X/Y-type copolymers are
ethylene/(meth) acrylic acid/n-butyl (meth) acrylate,
ethylene/(meth) acrylic acid/isobutyl (meth) acrylate,
ethylene/(meth) acrylic acid/methyl (meth) acrylate, and
ethylene/(meth) acrylic acid/ethyl (meth) acrylate. The acid is
typically present in the acid copolymer in an amount of 6 wt % or
greater, or 9 wt % or greater, or 10 wt % or greater, or 11 wt % or
greater, or 15 wt % or greater, or 16 wt % or greater, or 19 wt %
or greater, or 20 wt % or greater, or in an amount within a range
having a lower limit of 1 or 4 or 6 or 8 or 10 or 11 or 12 or 15 wt
% and an upper limit of 15 or 16 or 17 or 19 or 20 or 20.5 or 21 or
25 or 30 or 35 or 40 wt %, based on the total weight of the acid
copolymer. The acid copolymer is at least partially neutralized
with a cation source, optionally in the presence of a high
molecular weight organic acid, such as those disclosed in U.S. Pat.
No. 6,756,436, the entire disclosure of which is hereby
incorporated herein by reference. In a particular embodiment, less
than 40% of the acid groups present in the composition are
neutralized. In another particular embodiment, from 40% to 60% of
the acid groups present in the composition are neutralized. In
another particular embodiment, from 60% to 70% of the acid groups
present in the composition are neutralized. In another particular
embodiment, from 60% to 80% of the acid groups present in the
composition are neutralized. In another particular embodiment, from
70% to 80% of the acid groups present in the composition are
neutralized. In another embodiment, from 80% to 100% of the acid
groups present in the composition are neutralized. Suitable cation
sources include, but are not limited to, metal ion sources, such as
compounds of alkali metals, alkaline earth metals, transition
metals, and rare earth elements; ammonium salts and monoamine
salts; and combinations thereof. Preferred cation sources are
compounds of magnesium, sodium, potassium, cesium, calcium, barium,
manganese, copper, zinc, tin, lithium, and rare earth metals. In a
particular embodiment, the ionomer composition includes a bimodal
ionomer, for example, DuPont.RTM. AD1043 ionomers, and the ionomers
disclosed in U.S. Patent Application Publication No. 2004/0220343
and U.S. Pat. Nos. 6,562,906, 6,762,246 and 7,273,903, the entire
disclosures of which are hereby incorporated herein by reference.
Suitable ionomers are further disclosed, for example, in U.S.
Patent Application Publication Nos. 2005/0049367, 2005/0148725,
2005/0020741, 2004/0220343, and 2003/0130434, and U.S. Pat. Nos.
5,587,430, 5,691,418, 5,866,658, 6,100,321, 6,562,906, 6,653,382,
6,756,436, 6,777,472, 6,762,246, 6,815,480, 6,894,098, 6,919,393,
6,953,820, 6,994,638, 7,375,151, and 7,652,086, the entire
disclosures of which are hereby incorporated herein by
reference.
[0046] Also suitable are polyester ionomers, including, but not
limited to, those disclosed, for example, in U.S. Pat. Nos.
6,476,157 and 7,074,465, the entire disclosures of which are hereby
incorporated herein by reference.
[0047] Also suitable are compositions comprising a silicone
ionomer. Suitable thermoplastic silicone ionomer compositions
include a silicone ionomer optionally blended with one or more
additional polymer components selected from E/X/Y-type ionomers of
ethylene (E), an .alpha.,.beta.-unsaturated carboxylic acid (X),
and optionally a softening comonomer (Y); thermoplastic
polyurethanes; polyesters; and polyamides. Suitable thermoset
silicone ionomer compositions include a silicone ionomer optionally
blended with one or more additional polymer components selected
from thermosetting polyurethanes and diene rubbers, particularly
polybutadienes.
[0048] Silicone ionomers are further disclosed, for example, in
U.S. Pat. No. 8,329,156 to Horstman et al.; U.S. Pat. No. 8,835,583
to Saxena et al.; and Batra, Ashish, Claude Cohen, and T. M.
Duncan. "Synthesis and Rheology of Tailored Poly(dimethylsiloxane)
Zinc and Sodium Ionomers." Macromolecules (2005): 426-38. American
Chemical Society. Web. 1 Oct. 2014; the entire disclosures of which
are hereby incorporated herein by reference.
[0049] Suitable non-ionomeric polymers for forming the matrix
include: [0050] (a) non-ionomeric acid copolymers, particularly
O/X- and O/X/Y-type acid copolymers, wherein O is an .alpha.-olefin
preferably selected from ethylene and propylene, X is a
C.sub.3-C.sub.8 .alpha.,.beta.-ethylenically unsaturated carboxylic
acid preferably selected from methacrylic acid, acrylic acid,
ethacrylic acid, crotonic acid, and itaconic acid, and Y is a
softening monomer; [0051] (b) polyesters, and polyesters modified
with a compatibilizing group such as sulfonate or phosphonate,
including poly(ethylene terephthalate), poly(butylene
terephthalate), poly(propylene terephthalate), poly(trimethylene
terephthalate), poly(ethylene naphthenate), and derivates thereof,
including, but not limited to, 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; [0052] (c)
polyamides, polyether amides, and polyester amides, including, but
not limited to, 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; [0053] (d) polyimides,
polyetherketones, and polyamideimides; [0054] (e) polyurethanes,
polyureas, and copolymers and blends thereof, including, but not
limited to, those disclosed in U.S. Pat. Nos. 5,334,673, 5,484,870,
6,506,851, 6,756,436, 6,835,794, 6,867,279, 6,960,630, and
7,105,623, U.S. Patent Application Publication No. 2007/0117923,
and U.S. Patent Application Ser. Nos. 60/401,047 and 13/613,095,
the entire disclosures of which are hereby incorporated herein by
reference; [0055] (f) polystyrenes, such as poly(styrene-co-maleic
anhydride), acrylonitrile-butadiene-styrene, poly(styrene
sulfonate), polyethylene styrene; [0056] (g) polypropylenes,
polyethylenes, and copolymers of propylene and ethylene; [0057] (h)
ethylene elastomers; [0058] (i) propylene elastomers; [0059] (j)
styrenic copolymers and styrenic block copolymers; [0060] (k)
dynamically vulcanized elastomers; [0061] (l) ethylene vinyl
acetates; [0062] (m) polyvinyl chlorides; [0063] (n) engineering
thermoplastic vulcanizates, such as those disclosed, for example,
in
[0064] U.S. Patent Application Publication No. 2008/0132359, the
entire disclosure of which is hereby incorporated herein by
reference; [0065] (o) functionalized derivatives of the above; and
[0066] (p) combinations of two or more thereof.
[0067] In a particular embodiment, the matrix is formed from a
blend of at least two different polymers. In a particular aspect of
this embodiment, at least one polymer is an ionomer.
[0068] In another particular embodiment, the matrix is formed from
a blend of at least a first and a second ionomer.
[0069] In another particular embodiment, the matrix is formed from
a blend of one or more ionomers and one or more additional polymers
selected from non-ionomeric polyolefins, polyesters, polyamides,
polyurethanes, polystyrenes, and functionalized derivatives
thereof.
[0070] In another particular embodiment, the matrix is formed from
a blend of at least a functionalized polyethylene and a
functionalized polymer selected from polyethylenes, including
metallocene-catalyzed and non-metallocene-catalyzed polyethylenes,
ethylene vinyl acetates, ethylene acid copolymers, ethylene
acrylate copolymers, ethylene elastomers, and polypropylenes. In a
particular aspect of this embodiment, the functionalized
polyethylene is a maleic anhydride-grafted polymer selected from
ethylene homopolymers, ethylene-hexene copolymers, ethylene-octene
copolymers, and ethylene-butene copolymers.
[0071] In another particular embodiment, the matrix is formed from
a blend of at least an ionomer and a functionalized polymer
selected from polyethylenes, including metallocene-catalyzed and
non-metallocene-catalyzed polyethylenes, ethylene vinyl acetates,
ethylene acid copolymers, ethylene elastomers, and polypropylenes.
In a particular aspect of this embodiment, the functionalized
polymer is a polyethylene selected from ethylene homopolymers,
ethylene-hexene copolymers, ethylene-octene copolymers, and
ethylene-butene copolymers.
[0072] In another particular embodiment, the matrix is formed from
a blend of at least an ionomer and an acid copolymer.
[0073] In another particular embodiment, the matrix is formed from
a blend of at least an ionomer and a styrenic block copolymer or
functionalized derivative thereof.
[0074] In another particular embodiment, the matrix is formed from
a blend of at least an ionomer and an ethylene acrylate based
polymer or functionalized derivative thereof.
[0075] In another particular embodiment, the matrix is formed from
a blend of at least an ionomer and a polyoctenamer or a
functionalized derivative thereof.
[0076] In another particular embodiment, the matrix is formed from
a blend including at least an ionomer and a thermoplastic
polyurethane. In a particular aspect of this embodiment, the
polyurethane is selected from the polyurethanes disclosed in U.S.
Patent Application Publication No. 2005/0256294, the entire
disclosure of which is hereby incorporated herein by reference.
[0077] In another particular embodiment, the matrix is formed from
a blend including: [0078] (a) a first component selected from
polyester elastomers (e.g., Hytrel.RTM. polyester elastomers,
commercially available from E. I. du Pont de Nemours and Company,
and Riteflex.RTM. polyester elastomers, commercially available from
Ticona); polyether block amides (e.g., Pebax.RTM. polyether and
polyester amides); polyester-ether amides; and polypropylene ether
glycol compositions, such as those disclosed, e.g., in U.S. Patent
Application Publication No. 2005/0256294, the entire disclosure of
which is hereby incorporated herein by reference; and combinations
of two or more thereof; [0079] (b) a second component selected from
O/X/Y-type and O/X-type ionomers, including partially and
highly-neutralized ionomers, particularly highly neutralized
ionomers comprising fatty acid salts, such as DuPont.RTM. HPF 1000
and HPF 2000 highly neutralized ionomers, and VLMI-type ionomers,
such as Surlyn.RTM. 9320 ionomer; O/X/Y-type acid copolymers;
polyamides and polyamide blends, particularly selected from the
polyamides and polyamide blends disclosed above; and silicone
ionomers. In a particular aspect of this embodiment, the matrix is
formed from a blend including at least a polyester elastomer and a
highly neutralized ionomer comprising fatty acid salts. Such blend
is disclosed, for example, in U.S. Pat. No. 7,375,151, the entire
disclosure of which is hereby incorporated herein by reference.
[0080] Non-limiting examples of suitable commercially available
thermoplastics for use in forming the matrix are Surlyn.RTM.
ionomers, DuPont.RTM. HPF 1000 and HPF 2000 highly neutralized
ionomers, and DuPont.RTM. AD 1043 ionomers, commercially available
from E. I. du Pont de Nemours and Company; Clarix.RTM. ionomers,
commercially available from A. Schulman, Inc.; Iotek.RTM. ionomers,
commercially available from ExxonMobil Chemical Company;
Amplify.RTM. IO ionomers, commercially available from The Dow
Chemical Company; Amplify.RTM. GR functional polymers and
Amplify.RTM. TY functional polymers, commercially available from
The Dow Chemical Company; Fusabond.RTM. functionalized polymers,
including ethylene vinyl acetates, polyethylenes,
metallocene-catalyzed polyethylenes, ethylene propylene rubbers,
and polypropylenes, commercially available from E. I. du Pont de
Nemours and Company; Exxelor.RTM. maleic anhydride grafted
polymers, including high density polyethylene, polypropylene,
semi-crystalline ethylene copolymer, amorphous ethylene copolymer,
commercially available from ExxonMobil Chemical Company;
ExxonMobil.RTM. PP series polypropylene impact copolymers, such as
PP7032E3, PP7032KN, PP7033E3, PP7684KN, commercially available from
ExxonMobil Chemical Company; Vistamaxx.RTM. propylene-based
elastomers, commercially available from ExxonMobil Chemical
Company; Vistalon.RTM. EPDM rubbers, commercially available from
ExxonMobil Chemical Company; Exact.RTM. plastomers, commercially
available from ExxonMobil Chemical Company; Santoprene.RTM.
thermoplastic vulcanized elastomers, commercially available from
ExxonMobil Chemical Company; Nucrel.RTM. acid copolymers,
commercially available from E. I. du Pont de Nemours and Company;
Escor.RTM. acid copolymers, commercially available from ExxonMobil
Chemical Company; Primacor.RTM. acid copolymers, commercially
available from The Dow Chemical Company; Kraton.RTM. styrenic block
copolymers, commercially available from Kraton Performance Polymers
Inc.; Septon.RTM. styrenic block copolymers, commercially available
from Kuraray Co., Ltd.; Lotader.RTM. ethylene acrylate based
polymers, commercially available from Arkema Corporation;
Polybond.RTM. grafted polyethylenes and polypropylenes,
commercially available from Chemtura Corporation; Royaltuf.RTM.
chemically modified EPDM, commercially available from Chemtura
Corporation; Vestenamer.RTM. polyoctenamer, commercially available
from Evonik Industries; Pebax.RTM. polyether and polyester amides,
commercially available from Arkema Inc.; polyester-based
thermoplastic elastomers, such as Hytrel.RTM. polyester elastomers,
commercially available from E. I. du Pont de Nemours and Company,
and Riteflex.RTM. polyester elastomers, commercially available from
Ticona; Estane.RTM. thermoplastic polyurethanes, commercially
available from The Lubrizol Corporation; Grivory.RTM. polyamides
and Grilamid.RTM. polyamides, commercially available from EMS
Grivory; Zytel.RTM. polyamide resins and Elvamide.RTM. nylon
multipolymer resins, commercially available from E. I. du Pont de
Nemours and Company; and Elvaloy.RTM. acrylate copolymer resins,
commercially available from E. I. du Pont de Nemours and
Company.
[0081] The matrix composition optionally includes additive(s)
and/or filler(s) in an amount of 50 wt % or less, or 30 wt % or
less, or 20 wt % or less, or 15 wt % or less, based on the total
weight of the matrix composition. Suitable additives and fillers
include, but are not limited to, chemical blowing and foaming
agents, optical brighteners, coloring agents, fluorescent agents,
whitening agents, UV absorbers, light stabilizers, defoaming
agents, processing aids, antioxidants, stabilizers, softening
agents, fragrance components, plasticizers, impact modifiers,
TiO.sub.2, acid copolymer wax, surfactants, performance additives
(e.g., A-C.RTM. performance additives, particularly A-C.RTM. low
molecular weight ionomers and copolymers, A-C.RTM.oxidized
polyethylenes, A-C.RTM. ethylene vinyl acetate waxes, and
AClyn.RTM. low molecular weight ionomers, commercially available
from Honeywell International Inc.), fatty acid amides (e.g.,
ethylene bis-stearamide and ethylene bis-oleamide), fatty acids and
salts thereof (e.g., stearic acid, oleic acid, zinc stearate,
magnesium stearate, zinc oleate, and magnesium oleate), oxides
(e.g., zinc oxide, tin oxide, iron oxide, calcium oxide, aluminum
oxide, titanium dioxide, magnesium oxide, and zirconium oxide),
carbonates (e.g., calcium carbonate, zinc carbonate, barium
carbonate, and magnesium carbonate), barium sulfate, zinc sulfate,
tungsten, tungsten carbide, silica, lead silicate, clay, mica,
talc, nano-fillers, carbon black, glass flake, milled glass, flock,
fibers, and mixtures thereof. Suitable additives and fillers are
more fully described in, for example, U.S. Patent Application
Publication No. 2003/0225197, the entire disclosure of which is
hereby incorporated herein by reference. In a particular
embodiment, the total amount of additive(s) and filler(s) present
in the matrix composition is 20 wt % or less, or 15 wt % or less,
or 12 wt % or less, or 10 wt % or less, or 9 wt % or less, or 6 wt
% or less, or 5 wt % or less, or 4 wt % or less, or 3 wt % or less,
or within a range having a lower limit of 0 or 2 or 3 or 5 wt %,
based on the total weight of the matrix composition, and an upper
limit of 9 or 10 or 12 or 15 or 20 wt %, based on the total weight
of the matrix composition. In a particular aspect of this
embodiment, the matrix composition includes filler(s) selected from
carbon black, micro- and nano-scale clays and organoclays,
including (e.g., Cloisite.RTM. and Nanofil.RTM. nanoclays,
commercially available from Southern Clay Products, Inc.;
Nanomax.RTM. and Nanomer.RTM. nanoclays, commercially available
from Nanocor, Inc., and Perkalite.RTM. nanoclays, commercially
available from Akzo Nobel Polymer Chemicals), micro- and nano-scale
talcs (e.g., Luzenac HAR.RTM. high aspect ratio talcs, commercially
available from Luzenac America, Inc.), glass (e.g., glass flake,
milled glass, microglass, and glass fibers), micro- and nano-scale
mica and mica-based pigments (e.g., Iriodin.RTM. pearl luster
pigments, commercially available from The Merck Group), and
combinations thereof. Particularly suitable combinations of fillers
include, but are not limited to, micro-scale filler(s) combined
with nano-scale filler(s), and organic filler(s) with inorganic
filler(s).
[0082] The matrix composition optionally includes one or more melt
flow modifiers. Suitable melt flow modifiers include materials
which increase the melt flow of the composition, as measured using
ASTM D-1238, condition E, at 190.degree. C., using a 2160 gram
weight. Examples of suitable melt flow modifiers include, but are
not limited to, fatty acids and fatty acid salts, including, but
not limited to, those disclosed in U.S. Pat. No. 5,306,760, the
entire disclosure of which is hereby incorporated herein by
reference; fatty amides; polyhydric alcohols, including, but not
limited to, those disclosed in U.S. Pat. No. 7,365,128, and U.S.
Patent Application Publication No. 2010/0099514, the entire
disclosures of which are hereby incorporated herein by reference;
polylactic acids, including, but not limited to, those disclosed in
U.S. Pat. No. 7,642,319, the entire disclosure of which is hereby
incorporated herein by reference; and the modifiers disclosed in
U.S. Patent Application Publication No. 2010/0099514 and
2009/0203469, the entire disclosures of which are hereby
incorporated herein by reference. Flow enhancing additives also
include, but are not limited to, montanic acids, esters of montanic
acids and salts thereof, bis-stearoylethylenediamine, mono- and
polyalcohol esters such as pentaerythritol tetrastearate,
zwitterionic compounds, and metallocene-catalyzed polyethylene and
polypropylene wax, including maleic anhydride modified versions
thereof, amide waxes and alkylene diamides such as bistearamides.
Particularly suitable fatty amides include, but are not limited to,
saturated fatty acid monoamides (e.g., lauramide, palmitamide,
arachidamide behenamide, stearamide, and 12-hydroxy stearamide);
unsaturated fatty acid monoamides (e.g., oleamide, erucamide, and
ricinoleamide); N-substituted fatty acid amides (e.g., N-stearyl
stearamide, N-behenyl behenamide, N-stearyl behenamide, N-behenyl
stearamide, N-oleyl oleamide, N-oleyl stearamide, N-stearyl
oleamide, N-stearyl erucamide, erucyl erucamide, and erucyl
stearamide, N-oleyl palmitamide, methylol amide (more preferably,
methylol stearamide, methylol behenamide); saturated fatty acid
bis-amides (e.g., methylene bis-stearamide, ethylene
bis-stearamide, ethylene bis-isostearamide, ethylene
bis-hydroxystearamide, ethylene bis-behenamide, hexamethylene
bis-stearamide, hexamethylene bis-behenamide, hexamethylene
bis-hydroxystearamide, N,N'-distearyl adipamide, and N,N'-distearyl
sebacamide); unsaturated fatty acid bis-amides (e.g., ethylene
bis-oleamide, hexamethylene bis-oleamide, N,N'-dioleyl adipamide,
N,N'-dioleyl sebacamide); and saturated and unsaturated fatty acid
tetra amides, stearyl erucamide, ethylene bis stearamide and
ethylene bis oleamide. Suitable examples of commercially available
fatty amides include, but are not limited to, Kemamide.RTM. fatty
acids, such as Kemamide.RTM. B (behenamide/arachidamide),
Kemamide.RTM. W40 (N,N'-ethylenebisstearamide), Kemamide.RTM. P181
(oleyl palmitamide), Kemamide.RTM. S (stearamide), Kemamide.RTM. U
(oleamide), Kemamide.RTM. E (erucamide), Kemamide.RTM. O
(oleamide), Kemamide.RTM. W45 (N,N'-ethylenebisstearamide),
Kenamide.RTM. W20 (N,N'-ethylenebisoleamide), Kemamide.RTM. E180
(stearyl erucamide), Kemamide.RTM. E221 (erucyl erucamide),
Kemamide.RTM. S180 (stearyl stearamide), Kemamide.RTM. 5221 (erucyl
stearamide), commercially available from Chemtura Corporation; and
Crodamide.RTM. fatty amides, such as Crodamide.RTM. OR (oleamide),
Crodamide.RTM. ER (erucamide), Crodamide.RTM. SR (stereamide),
Crodamide.RTM. BR (behenamide), Crodamide.RTM. 203 (oleyl
palmitamide), and Crodamide.RTM. 212 (stearyl erucamide),
commercially available from Croda Universal Ltd.
[0083] In a particular embodiment, the matrix composition is
modified with organic fiber micropulp, as disclosed, for example,
in U.S. Pat. No. 7,504,448, the entire disclosure of which is
hereby incorporated herein by reference.
[0084] In another particular embodiment, the matrix composition is
modified with rosin, particularly when the matrix composition
includes an ionomer, as disclosed, for example, in U.S. Pat. Nos.
7,429,624 and 7,238,737, the entire disclosures of which are hereby
incorporated herein by reference.
[0085] In another particular embodiment, the matrix composition
comprises at least one nanoclay, preferably wherein the total
amount of nanoclay present is from 3 to 25 wt % based on the total
weight of the composition, and an ionomer. In a particular aspect
of this embodiment, the ionomer is at least partially neutralized
with zinc. In another particular aspect of this embodiment, the
ionomer is at least partially neutralized with sodium. In another
particular aspect of this embodiment, the ionomer is at least
partially neutralized with a first and a second cation, wherein the
first cation is zinc.
Heterogeneous Golf Ball Composition
[0086] In a particular embodiment, the heterogeneous composition
comprises discrete particles of rubber within a thermoplastic
matrix formed from an acid copolymer composition wherein the acid
copolymer is selected from one or more E/X- and E/X/Y-type acid
copolymers of ethylene, an .alpha.,.beta.-unsaturated carboxylic
acid, and optionally a softening comonomer. The rubber particles
are preferably formed from a rubber composition that is
substantially free of reactive metal ingredients, such that less
than 5% of all acid groups present in the matrix composition are
neutralized. Alternatively, the rubber particles are formed from a
rubber composition that includes reactive metal(s), however, when
the heterogeneous composition and golf ball layer formed therefrom
are processed, reaction conditions are selected such that less than
5% of all acid groups present in the matrix composition are
neutralized.
[0087] In a particular aspect of this embodiment, less than 5% of
all acid groups present in the matrix composition are neutralized.
In another particular aspect of this embodiment, less than 3% of
all acid groups present in the matrix composition are neutralized.
In another particular aspect of this embodiment, less than 1% of
all acid groups present in the matrix composition are
neutralized.
Golf Ball Applications
[0088] Golf ball compositions according to the present invention
can be used in a variety of constructions. For example, the
compositions are suitable for use in one-piece, two-piece (i.e., a
core and a cover), multi-layer (i.e., a core of one or more layers
and a cover of one or more layers), and wound golf balls, having a
variety of core structures, intermediate layers, covers, and
coatings.
[0089] In golf balls of the present invention, at least one layer
comprises a heterogeneous composition comprising discrete particles
of crosslinked material within a thermoplastic matrix, as described
herein. In golf balls having two or more layers comprising a
composition of the present invention, the inventive composition of
one layer may be the same as or a different inventive composition
than another layer. The layer(s) comprising a composition of the
present invention can be any one or more of a core layer, an
intermediate layer, or a cover layer.
Core Layer(s)
[0090] Cores of the golf balls formed according to the invention
may be solid, semi-solid, hollow, fluid-, powder-, or gas-filled,
and may be one-piece or multi-layered. Multilayer cores include a
center, innermost portion, which may be solid, semi-solid, hollow,
fluid-, powder-, or gas-filled, surrounded by at least one outer
core layer. The outer core layer may be solid, or it may be a wound
layer formed of a tensioned elastomeric material. For purposes of
the present disclosure, the term "semi-solid" refers to a paste, a
gel, or the like.
[0091] In a particular embodiment, the present invention provides a
golf ball having an innermost core layer formed from a
heterogeneous composition of the present invention. In another
particular embodiment, the present invention provides a golf ball
having an outer core layer formed from a heterogeneous composition
of the present invention. In another particular embodiment, the
present invention provides a golf ball having an intermediate core
layer formed from a heterogeneous composition of the present
invention.
[0092] Golf ball cores of the present invention may include one or
more layers formed from a suitable material other than a
heterogeneous composition of the present invention. Suitable core
materials include, but are not limited to, thermoset materials,
such as styrene butadiene rubber, polybutadiene, synthetic or
natural polyisoprene, and trans-polyisoprene; thermoplastics, such
as ionomer resins, polyamides and polyesters; and thermoplastic and
thermoset polyurethane and polyureas.
Intermediate Layer(s)
[0093] When the golf ball of the present invention includes one or
more intermediate layers, i.e., layer(s) disposed between the core
and the cover of a golf ball, each intermediate layer can include
any materials known to those of ordinary skill in the art including
thermoplastic and thermosetting materials.
[0094] In one embodiment, the present invention provides a golf
ball having one or more intermediate layers formed from a
heterogeneous composition of the present invention.
[0095] Also suitable for forming intermediate layer(s) are the
compositions disclosed above for forming core layers.
[0096] A moisture vapor barrier layer is optionally employed
between the core and the cover. Moisture vapor barrier layers are
further disclosed, for example, in U.S. Pat. Nos. 6,632,147,
6,838,028, 6,932,720, 7,004,854, and 7,182,702, and U.S. Patent
Application Publication Nos. 2003/0069082, 2003/0069085,
2003/0130062, 2004/0147344, 2004/0185963, 2006/0068938,
2006/0128505 and 2007/0129172, the entire disclosures of which are
hereby incorporated herein by reference.
Cover
[0097] Golf ball covers of the present invention include single,
dual, and multilayer covers. Dual and multilayer covers have an
inner cover layer and an outer cover layer, and multilayer covers
additionally have at least one intermediate cover layer disposed
between the inner cover layer and the outer cover layer.
[0098] In a particular embodiment, the present invention provides a
golf ball having an outermost cover layer formed from a
heterogeneous composition of the present invention. In another
particular embodiment, the present invention provides a golf ball
having an inner cover layer formed from a heterogeneous composition
of the present invention. In another particular embodiment, the
present invention provides a golf ball having an intermediate cover
layer formed from a heterogeneous composition of the present
invention.
[0099] Golf ball covers of the present invention may include one or
more layers formed from a suitable material other than a
heterogeneous composition of the present invention. The cover
material is preferably a tough, cut-resistant material, selected
based on the desired performance characteristics. Suitable cover
materials for the golf balls disclosed herein include, but are not
limited to, polyurethanes, polyureas, and hybrids of polyurethane
and polyurea; ionomer resins and blends thereof (e.g., Surlyn.RTM.
ionomer resins and DuPont.RTM. HPF 1000 and HPF 2000 highly
neutralized ionomers, commercially available from E. I. du Pont de
Nemours and Company; 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.); polyisoprene; polyoctenamer, such
as Vestenamer.RTM. polyoctenamer, commercially available from
Evonik Industries; polyethylene, including, for example, low
density polyethylene, linear low density polyethylene, and high
density polyethylene; polypropylene; rubber-toughened olefin
polymers; non-ionomeric acid copolymers, e.g., ethylene
(meth)acrylic acid; plastomers; flexomers;
styrene/butadiene/styrene block copolymers; polybutadiene; styrene
butadiene rubber; ethylene propylene rubber; ethylene propylene
diene rubber; styrene/ethylene-butylene/styrene block copolymers;
dynamically vulcanized elastomers; ethylene vinyl acetates;
ethylene (meth)acrylates; polyvinyl chloride resins; polyamides,
amide-ester elastomers, and copolymers of ionomer and polyamide,
including, for example, Pebax.RTM. thermoplastic polyether and
polyester amides, commercially available from Arkema Inc;
crosslinked trans-polyisoprene and blends thereof; polyester-based
thermoplastic elastomers, such as Hytrel.RTM. polyester elastomers,
commercially available from E. I. du Pont de Nemours and Company,
and Riteflex.RTM. polyester elastomers, commercially available from
Ticona; polyurethane-based thermoplastic elastomers, such as
Elastollan.RTM., commercially available from BASF; synthetic or
natural vulcanized rubber; and combinations thereof.
[0100] Polyurethanes, polyureas, and polyurethane-polyurea hybrids
(i.e., blends and copolymers of polyurethanes and polyureas) are
particularly suitable for forming cover layers of the present
invention. Suitable polyurethanes and polyureas are further
disclosed, for example, in U.S. Pat. Nos. 5,334,673, 5,484,870,
6,506,851, 6,756,436, 6,835,794, 6,867,279, 6,960,630, and
7,105,623; U.S. Patent Application Publication No. 2009/0011868;
and U.S. Patent Application No. 60/401,047, the entire disclosures
of which are hereby incorporated herein by reference. Suitable
polyurethane-urea cover materials include polyurethane/polyurea
blends and copolymers comprising urethane and urea segments, as
disclosed in U.S. Patent Application Publication No. 2007/0117923,
the entire disclosure of which is hereby incorporated herein by
reference.
[0101] Compositions comprising an ionomer or a blend of two or more
ionomers are also particularly suitable for forming cover layers.
Preferred ionomeric cover compositions include: [0102] (a) a
composition comprising a "high acid ionomer" (i.e., having an acid
content of greater than 16 wt %), such as Surlyn.RTM. 8150; [0103]
(b) a composition comprising a high acid ionomer and a maleic
anhydride-grafted non-ionomeric polymer (e.g., Fusabond.RTM.
functionalized polymers). A particularly preferred blend of high
acid ionomer and maleic anhydride-grafted polymer is a 84 wt %/16
wt % blend of Surlyn.RTM. 8150 and Fusabond.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; [0104] (c) a composition comprising a 50/45/5 blend of
Surlyn.RTM. 8940/Surlyn.RTM. 9650/Nucrel.RTM. 960, preferably
having a material hardness of from 80 to 85 Shore C; [0105] (d) a
composition comprising a 50/25/25 blend of Surlyn.RTM.
8940/Surlyn.RTM. 9650/Surlyn.RTM. 9910, preferably having a
material hardness of about 90 Shore C; [0106] (e) a composition
comprising a 50/50 blend of Surlyn.RTM. 8940/Surlyn.RTM. 9650,
preferably having a material hardness of about 86 Shore C; [0107]
(f) a composition comprising a blend of Surlyn.RTM.
7940/Surlyn.RTM. 8940, optionally including a melt flow modifier;
[0108] (g) a composition comprising a blend of a first high acid
ionomer and a second high acid ionomer, wherein the first high acid
ionomer is neutralized with a different cation than the second high
acid ionomer (e.g., 50/50 blend of Surlyn.RTM. 8150 and Surlyn.RTM.
9150), optionally including one or more melt flow modifiers such as
an ionomer, ethylene-acid polymer or ester polymer; and [0109] (h)
a composition comprising a blend of a first high acid ionomer and a
second high acid ionomer, wherein the first high acid ionomer is
neutralized with a different cation than the second high acid
ionomer, and from 0 to 10 wt % of an ethylene/acid/ester ionomer
wherein the ethylene/acid/ester ionomer is neutralized with the
same cation as either the first high acid ionomer or the second
high acid ionomer or a different cation than the first and second
high acid ionomers (e.g., a blend of 40-50 wt % Surlyn.RTM. 8150,
40-50 wt % Surlyn.RTM. 9120, and 0-10 wt % Surlyn.RTM. 6320).
[0110] Surlyn.RTM. 8150 and Surlyn.RTM. 8940 are different grades
of E/MAA copolymer in which the acid groups have been partially
neutralized with sodium ions. Surlyn.RTM. 9650, Surlyn.RTM. 9910,
Surlyn.RTM. 9150, and Surlyn.RTM. 9120 are different grades of
E/MAA copolymer in which the acid groups have been partially
neutralized with zinc ions. Surlyn.RTM. 7940 is an E/MAA copolymer
in which the acid groups have been partially neutralized with
lithium ions. Surlyn.RTM. 6320 is a very low modulus magnesium
ionomer with a medium acid content. Nucrel.RTM. 960 is an E/MAA
copolymer resin nominally made with 15 wt % methacrylic acid.
Surlyn.RTM. ionomers, Fusabond.RTM. polymers, and Nucrel.RTM.
copolymers are commercially available from E. I. du Pont de Nemours
and Company.
[0111] Ionomeric cover compositions can be blended with non-ionic
thermoplastic resins, such as polyurethane, poly-ether-ester,
poly-amide-ether, polyether-urea, thermoplastic polyether block
amides (e.g., Pebax.RTM. polyether and polyester amides,
commercially available from Arkema Inc.), styrene-butadiene-styrene
block copolymers, styrene(ethylene-butylene)-styrene block
copolymers, polyamides, polyesters, polyolefins (e.g.,
polyethylene, polypropylene, ethylene-propylene copolymers,
polyethylene-(meth)acrylate, polyethylene-(meth)acrylic acid,
functionalized polymers with maleic anhydride grafting,
Fusabond.RTM. functionalized polymers commercially available from
E. I. du Pont de Nemours and Company, functionalized polymers with
epoxidation, elastomers (e.g., ethylene propylene diene monomer
rubber, metallocene-catalyzed polyolefin) and ground powders of
thermoset elastomers.
[0112] Ionomer golf ball cover compositions may include a flow
modifier, such as, but not limited to, acid copolymer resins (e.g.,
Nucrel.RTM. acid copolymer resins, and particularly Nucrel.RTM.
960, commercially available from E. I. du Pont de Nemours and
Company), performance additives (e.g., A-C.RTM. performance
additives, particularly A-C.RTM. low molecular weight ionomers and
copolymers, A-C.RTM. oxidized polyethylenes, and A-C.RTM. ethylene
vinyl acetate waxes, commercially available from Honeywell
International Inc.), fatty acid amides (e.g., ethylene
bis-stearamide and ethylene bis-oleamide), fatty acids and salts
thereof
[0113] Suitable ionomeric cover materials are further disclosed,
for example, in U.S. Pat. Nos. 6,653,382, 6,756,436, 6,894,098,
6,919,393, and 6,953,820, the entire disclosures of which are
hereby incorporated by reference.
[0114] Suitable cover materials and constructions also include, but
are not limited to, those disclosed in U.S. Patent Application
Publication No. 2005/0164810, U.S. Pat. Nos. 5,919,100, 6,117,025,
6,767,940, and 6,960,630, and PCT Publications WO00/23519 and
WO00/29129, the entire disclosures of which are hereby incorporated
herein by reference.
Component Dimensions
[0115] Dimensions of golf ball components, i.e., thickness and
diameter, may vary depending on the desired properties. For the
purposes of the invention, any layer thickness may be employed.
[0116] The present invention relates to golf balls of any size.
While USGA specifications limit the size of a competition golf ball
to more than 1.68 inches in diameter, golf balls of any size can be
used for leisure golf play. The preferred diameter of the golf
balls is from about 1.68 inches to about 1.8 inches. The more
preferred diameter is from about 1.68 inches to about 1.76 inches.
A diameter of from about 1.68 inches to about 1.74 inches is most
preferred, however diameters anywhere in the range of from 1.7 to
about 1.95 inches can be used.
[0117] Golf ball cores of the present invention include single,
dual, and multilayer cores, and preferably have an overall diameter
within the range having a lower limit of 0.75 inches or 1 inch or
1.25 inches or 1.4 inches and an upper limit of 1.55 inches or 1.6
inches or 1.62 inches or 1.63 inches. In a particular embodiment,
the golf ball comprises a core and a cover, wherein the core is a
solid, single layer having a diameter within a range having a lower
limit of 0.750 or 1.00 or 1.10 or 1.15 or 1.20 or 1.25 or 1.30 or
1.40 or 1.50 or 1.53 or 1.55 inches and an upper limit of 1.55 or
1.60 or 1.62 or 1.63 or 1.65 inches. In another particular
embodiment, the golf ball comprises a core and a cover, wherein the
core comprises an inner core layer and an outer core layer, the
inner core layer having a diameter within a range having a lower
limit of 0.500 or 0.750 or 0.900 or 0.950 or 1.000 inches and an
upper limit of 1.100 or 1.200 or 1.250 or 1.400 or 1.550 or 1.570
or 1.580 inches, and the outer core having a thickness within the
range having a lower limit of 0.020 or 0.025 or 0.032 or 0.050 or
0.100 or 0.200 inches and an upper limit of 0.310 or 0.440 or 0.500
or 0.560 or 0.800 inches.
[0118] When present in a golf ball of the present invention, each
intermediate layer has a thickness within a range having a lower
limit of 0.002 or 0.010 or 0.020 or 0.025 or 0.030 inches and an
upper limit of 0.035 or 0.040 or 0.045 or 0.050 or 0.060 or 0.090
or 0.100 or 0.150 or 0.200 inches. The total thickness of
intermediate core layer(s) in golf balls of the present invention
is preferably within the range having a lower limit of 0.020 or
0.0250 or 0.032 inches and an upper limit of 0.150 or 0.220 or 0.28
inches.
[0119] Golf ball covers of the present invention include single,
dual, and multilayer covers, and preferably have an overall
thickness within the range having a lower limit of 0.01 inches or
0.02 inches or 0.025 inches or 0.03 inches or 0.04 inches or 0.045
inches or 0.05 inches or 0.06 inches and an upper limit of 0.07
inches or 0.075 inches or 0.08 inches or 0.09 inches or 0.1 inches
or 0.15 inches or 0.2 inches or 0.3 inches or 0.5 inches. Dual and
multilayer covers have an inner cover layer and an outer cover
layer, and multilayer covers additionally have at least one
intermediate cover layer disposed between the inner cover layer and
the outer cover layer. In a particular embodiment, the cover is a
single layer having a thickness within a range having a lower limit
of 0.020 or 0.025 or 0.030 inches and an upper limit of 0.030 or
0.040 or 0.045 or 0.050 or 0.070 or 0.100 or 0.120 or 0.150 or
0.350 or 0.400 or inches. In another particular embodiment, the
cover comprises an inner cover layer and an outer cover layer, the
inner cover having a thickness within a range having a lower limit
of 0.010 or 0.020 or 0.025 or 0.030 inches and an upper limit of
0.035 or 0.040 or 0.050 or 0.150 or 0.200 inches, and the outer
cover having a thickness within a range having a lower limit of
0.010 or 0.020 or 0.025 or 0.030 inches and an upper limit of 0.035
or 0.040 or 0.050 inches.
[0120] The golf balls of the present invention may be painted,
coated, or surface treated for further benefits.
EXAMPLES
[0121] It should be understood that the examples below are for
illustrative purposes only. In no manner is the present invention
limited to the specific disclosures therein.
[0122] The following polymer materials were used in the below
examples: [0123] Amplify.RTM. GR204 maleic anhydride grafted HDPE
having a density of 0.953 g/cm and Amplify.RTM. GR205 maleic
anhydride grafted HDPE having a density of 0.962 g/cm, commercially
available from The Dow Chemical Company; [0124] Elvaloy.RTM. AC
3427 ethylene-butyl acrylate copolymer having a comonomer content
of 27 wt %, commercially available from E. I. du Pont de Nemours
and Company; [0125] Estane.RTM. 58133 thermoplastic polyurethane
having a Shore D hardness of 55, commercially available from The
Lubrizol Corporation; [0126] Fusabond.RTM. 525D
metallocene-catalyzed polyethylene, Fusabond.RTM. E100 anhydride
modified HDPE, Fusabond.RTM. N416 chemically modified ethylene
elastomer, Fusabond.RTM. P613 functionalized polypropylene,
commercially available from E. I. du Pont de Nemours and Company;
[0127] Grivory.RTM. GTR45 partially aromatic polyamide,
commercially available from EMS Grivory; [0128] DuPont.RTM. HPF
1000 and HPF 2000 ethylene/acrylic acid copolymer in which the acid
groups have been highly neutralized with magnesium ions,
commercially available from E. I. du Pont de Nemours and Company;
[0129] Hytrel.RTM. 3078 very low modulus thermoplastic polyester
elastomer having a Shore D hardness of 30, and Hytrel.RTM. 8241
thermoplastic polyester elastomer having a Shore D hardness of 65,
commercially available from E. I. du Pont de Nemours and Company;
[0130] Lotader.RTM. 4700 ethylene/acrylic ester/maleic anhydride
random copolymer, commercially available from Arkema Corporation;
[0131] NBR 6300 nitrile butadiene rubber powder, commercially
available from LG Chem; [0132] Nucrel.RTM. 0910, Nucrel.RTM. 2906,
Nucrel.RTM. 9-1, Nucrel.RTM. 960, and Nucrel.RTM. AE ethylene
methacrylic acid copolymers, commercially available from E. I. du
Pont de Nemours and Company; [0133] Pebax.RTM. 2533 polyether block
amide, commercially available from Arkema Inc.; [0134]
Pliolite.RTM. styrene butadiene, commercially available from
Eliokem; [0135] Royaltuf.RTM. 485 maleic anhydride modified
polyolefin based on a semi-crystalline EPDM, and Royaltuf.RTM. 498
maleic anhydride modified polyolefin based on an amorphous EPDM,
commercially available from Chemtura Corporation; [0136]
Surlyn.RTM. 7940 ethylene/methacrylic acid/acrylate copolymer (15
wt % acid) in which the acid groups have been partially neutralized
with lithium ions, Suryln.RTM. 8320 very low modulus
ethylene/methacrylic acid/acrylate copolymer (9 wt % acid) in which
the acid groups have been partially neutralized with sodium ions,
Surlyn.RTM. 8528 E/MAA copolymer (10 wt % acid) in which the acid
groups have been partially neutralized with sodium ions,
Surlyn.RTM. AD8546 E/MAA copolymer (19 wt % acid) in which the acid
groups have been partially neutralized with lithium ions,
Surlyn.RTM. 8940 E/MAA copolymer (15 wt % acid) in which the acid
groups have been partially neutralized with sodium ions,
Surlyn.RTM. 9150 E/MAA copolymer in which the acid groups have been
partially neutralized with zinc ions, commercially available from
E. I. du Pont de Nemours and Company; [0137] Texin.RTM. 970 U
aromatic polyether-based thermoplastic polyurethane having a Shore
D hardness of 70, commercially available from Bayer AG; [0138] Tire
Tread ground tire tread, commercially available from Edge Rubber;
[0139] TP-301 transpolyisoprene, commercially available from
Kuraray; [0140] Vestenamer.RTM. 8012 high trans content
polyoctenamer rubber, commercially available from Evonik
Industries; [0141] X Outer Rgnd--2007, regrind (i.e., ground flash)
from production of the outer core of the 2007 model ProVlx.RTM.
golf ball; and [0142] X Outer Rgnd--2011, regrind (i.e., ground
flash) from production of the outer core of the 2011 model
ProVlx.RTM. golf ball.
[0143] Various compositions were melt blended using components as
given in Table 1 below. The relative amounts of each component used
are also indicated in Table 1 below, and are reported in wt %,
based on the total weight of the composition.
TABLE-US-00001 TABLE 1 Ex- Component Component Component ample 1 wt
% 2 wt % 3 wt % 1 Amplify 100 -- -- -- -- GR204 2 Amplify 45 X
Outer 55 -- -- GR204 Rgnd-2011 3 Amplify 100 -- -- -- -- GR205 4
Amplify 45 X Outer 55 -- -- GR205 Rgnd-2011 5 Amplify 66 X Outer 33
-- -- GR205 Rgnd-2011 6 Amplify 83.5 X Outer 16.5 -- -- GR205
Rgnd-2011 7 Elvaloy 100 -- -- -- -- 3427AC 8 Elvaloy 70 X Outer 30
-- -- 3427AC Rgnd-2007 9 Elvaloy 60 X Outer 40 -- -- 3427AC
Rgnd-2007 10 Elvaloy 50 X Outer 50 -- -- 3427AC Rgnd-2007 11
Elvaloy 100 -- -- -- -- 3427AC 12 Elvaloy 50 NBR 6300 50 -- --
3427AC 13 Estane 58133 100 -- -- -- -- 14 Estane 58133 70 NBR 6300
30 -- -- 15 Fusabond 100 -- -- -- -- 525D 16 Fusabond 70 X Outer 30
-- -- 525D Rgnd-2007 17 Fusabond 60 X Outer 40 -- -- 525D Rgnd-2007
18 Fusabond 50 X Outer 50 -- -- 525D Rgnd-2007 19 Fusabond 20 X
Outer 80 -- -- 525D Rgnd-2011 20 Fusabond 100 -- -- -- -- E100 21
Fusa bond 45 X Outer 55 -- -- E100 Rgnd-2011 22 Fusabond 100 -- --
-- -- N416 23 Fusabond 100 -- -- -- -- P613 24 Fusabond 25 X Outer
75 -- -- P613 Rgnd-2011 25 Fusabond 45 X Outer 55 -- -- P613
Rgnd-2011 26 Fusabond 60 X Outer 40 -- -- P613 Rgnd-2011 27
Fusabond 70 X Outer 30 -- -- P613 Rgnd-2011 28 Fusabond 80 X Outer
20 -- -- P613 Rgnd-2011 29 Grivory 67 NBR 6300 33 -- -- GTR45 30
Grivory 100 -- -- -- -- GTR45 31 Grivory 45 X Outer 55 -- -- GTR45
Rgnd-2011 32 Grivory 70 X Outer 30 -- -- GTR45 Rgnd-2011 33 Grivory
60 X Outer 40 -- -- GTR45 Rgnd-2011 34 Grivory 90 X Outer 10 -- --
GTR45 Rgnd-2011 35 Grivory 80 X Outer 20 -- -- GTR45 Rgnd-2011 36
HPF 1000 100 -- -- -- -- 37 HPF 1000 70 NBR 6300 30 -- -- 38 HPF
1000 60 X Outer 40 -- -- Rgnd-2011 39 HPF 1000 70 X Outer 30 -- --
Rgnd-2011 40 HPF 1000 80 X Outer 20 -- -- Rgnd-2011 41 HPF 1000 90
X Outer 10 -- -- Rgnd-2011 42 HPF 2000 60 X Outer 40 -- --
Rgnd-2011 43 HPF 2000 70 X Outer 30 -- -- Rgnd-2011 44 HPF 2000 80
X Outer 20 -- -- Rgnd-2011 45 HPF 2000 90 X Outer 10 -- --
Rgnd-2011 46 Hytrel 3078 100 -- -- -- -- 47 Hytrel 3078 45 X Outer
55 -- -- Rgnd-2011 48 Hytrel 3078 60 X Outer 40 -- -- Rgnd-2011 49
Hytrel 3078 80 X Outer 20 -- -- Rgnd-2011 50 Hytrel 3078 50 NBR
6300 50 -- -- 51 Hytrel 8241 100 -- -- -- -- 52 Hytrel 8241 80 NBR
6300 20 -- -- 53 Lotader 4700 100 -- -- -- -- 54 Lotader 4700 45 X
Outer 55 -- -- Rgnd-2011 55 Lotader 4700 60 X Outer 40 -- --
Rgnd-2011 56 Lotader 4700 70 X Outer 30 -- -- Rgnd-2011 57 Lotader
4700 80 X Outer 20 -- -- Rgnd-2011 58 Nucrel 0910 100 -- -- -- --
59 Nucrel 0910 45 X Outer 55 -- -- Rgnd-2007 60 Nucrel 2906 45 X
Outer 55 -- -- Rgnd-2007 61 Nucrel 2906 100 -- -- -- -- 62 Nucrel
9-1 100 -- -- -- -- 63 Nucrel 9-1 45 X Outer 55 -- -- Rgnd-2007 64
Nucrel 9-1 100 -- -- -- -- 65 Nucrel 9-1 45 NBR 6300 55 -- -- 66
Nucrel 9-1 100 -- -- -- -- 67 Nucrel 960 100 -- -- -- -- 68 Nucrel
960 45 X Outer 55 -- -- Rgnd-2007 69 Nucrel 960 100 -- -- -- -- 70
Nucrel 960 100 -- -- -- -- 71 Nucrel 960 45 NBR 6300 55 -- -- 72
Nucrel AE 100 -- -- -- -- 73 Nucrel AE 45 NBR 6300 55 -- -- 74
Pebax 2533 100 -- -- -- -- 75 Pebax 2533 45 X Outer 55 -- --
Rgnd-2011 76 Pebax 2533 60 X Outer 40 -- -- Rgnd-2011 77 Pebax 2533
70 X Outer 30 -- -- Rgnd-2011 78 Pebax 2533 80 X Outer 20 -- --
Rgnd-2011 79 Pebax 2533 90 X Outer 10 -- -- Rgnd-2011 80 Pliolite
100 -- -- -- -- 81 Pliolite 70 NBR 6300 30 -- -- 82 Royaltuf 485 45
X Outer 55 -- -- Rgnd-2011 83 Royaltuf 498 45 X Outer 55 -- --
Rgnd-2011 84 Surlyn 7940 50 Surlyn 8940 50 -- -- 85 Surlyn 7940
47.5 Surlyn 8940 47.5 X Outer 5 Rgnd-2011 86 Surlyn 7940 45 Surlyn
8940 45 X Outer 10 Rgnd-2011 87 Surlyn 7940 40 Surlyn 8940 40 X
Outer 20 Rgnd-2011 88 Surlyn 7940 35 Surlyn 8940 35 X Outer 30
Rgnd-2011 89 Surlyn 7940 30 Surlyn 8940 30 X Outer 40 Rgnd-2011 90
Surlyn 7940 22.5 Surlyn 8940 22.5 X Outer 55 Rgnd-2011 91 Surlyn
7940 49.5 Surlyn 8940 49.5 Tire Tread 1 92 Surlyn 7940 49 Surlyn
8940 49 Tire Tread 2 93 Surlyn 7940 47.5 Surlyn 8940 47.5 Tire
Tread 5 94 Surlyn 7940 45 Surlyn 8940 45 Tire Tread 10 95 Surlyn
7940 40 Surlyn 8940 40 Tire Tread 20 96 Surlyn 7940 35 Surlyn 8940
35 Tire Tread 30 97 Surlyn 7940 30 Surlyn 8940 30 Tire Tread 40 98
Surlyn 7940 22.5 Surlyn 8940 22.5 Tire Tread 55 99 Surlyn 8320 100
-- -- -- -- 100 Surlyn 8320 60 NBR 6300 40 -- -- 101 Surlyn 8528
100 -- -- -- -- 102 Surlyn 9150 100 -- -- -- -- 103 Surlyn 100 --
-- -- -- AD8546 104 Surlyn 70 NBR 6300 30 -- -- AD8546 105 Texin
970U 100 -- -- -- -- 106 Texin 970U 50 NBR 6300 50 -- -- 107 TP-301
70 NBR 6300 30 -- -- 108 TP-301 100 -- -- -- -- 109 TP-301 70 X
Outer 30 -- -- Rgnd-2011 110 TP-301 80 X Outer 20 -- -- Rgnd-2011
111 TP-301 90 X Outer 10 -- -- Rgnd-2011 112 Vestenamer 100 -- --
-- -- 8012 113 Vestenamer 70 X Outer 30 -- -- 8012 Rgnd-2011 114
Vestenamer 80 X Outer 20 -- -- 8012 Rgnd-2011 115 Vestenamer 90 X
Outer 10 -- -- 8012 Rgnd-2011 116 Vestenamer 60 X Outer 40 -- --
8012 Rgnd-2011 117 Vestenamer 45 X Outer 55 -- -- 8012 Rgnd-2011
118 Vestenemer 70 NBR 6300 30 -- -- 8012
[0144] Melt flow of each composition was measured according to ASTM
D-1238, condition E, at 190.degree. C., using a 2.16 kg weight, and
the results are reported in Table 2 below.
[0145] Flex modulus of each composition was measured according to
the following procedure, and the results are reported in Table 2
below. Flex bars are prepared by compression molding the
composition under sufficient temperature and pressure for a
sufficient amount of time to produce void- and defect-free plaques
of appropriate dimensions to produce the required flex bars. The
flex bar dimensions are about 0.125 inches by about 0.5 inches, and
of a length sufficient to satisfy the test requirements. Flex bars
are died out from the compression molded plaque(s) soon after the
blend composition has reached room temperature. The flex bars are
then aged for 14 days at 23.degree. C. and 50% RH before testing.
Flex modulus is then measured according to ASTM D790 Procedure B,
using a load span of 1.0 inches, a support span length of 2.0
inches, a support span-to-depth ratio of 16:1 and a crosshead rate
of 0.5 inches/minute. The support and loading noses have a radius
of 5 mm.
[0146] Solid spheres of each composition were injection molded, and
the solid sphere COR, compression, Shore C hardness, and Shore D
hardness of the resulting spheres were measured. The results are
reported in Table 2 below. The surface hardness of a sphere is
obtained from the average of a number of measurements taken from
opposing hemispheres, taking care to avoid making measurements on
the parting line of the sphere or on surface defects, such as holes
or protrusions. Hardness measurements are made pursuant to ASTM
D-2240 "Indentation Hardness of Rubber and Plastic by Means of a
Durometer." Because of the curved surface, care must be taken to
insure that the sphere is centered under the durometer indentor
before a surface hardness reading is obtained. A calibrated,
digital durometer, capable of reading to 0.1 hardness units is used
for all hardness measurements and is set to record the maximum
hardness reading obtained for each measurement. The digital
durometer must be attached to, and its foot made parallel to, the
base of an automatic stand. The weight on the durometer and attack
rate conform to ASTM D-2240.
TABLE-US-00002 TABLE 2 Melt Flow Flex Solid Solid Solid Solid
(190.degree. C., Modulus Sphere Sphere Sphere Sphere Ex. 2.16 kg)
(ksi) COR Compression Shore C Shore D 1 * * 0.490 172 98 69 2 * *
0.568 152 94 66 3 * 206.3 0.492 176 100 71 4 * * 0.546 153 95 66 5
* * 0.531 162 96 69 6 * * 0.503 169 98 70 7 3.74 3.4 0.561 4 45 25
8 1.46 4.9 0.588 31 55 29 9 1.01 6.2 0.600 35 58 31 10 0.54 7.3
0.616 43 61 33 11 * * 0.560 4 49.4 29.3 12 * * * * * * 13 * * 0.552
148 90 62 14 * * 0.493 131 78 51 15 * 2.2 0.668 -45 44 27 16 0.74
3.4 0.686 * 50 29 17 0.42 4 0.692 3 54 30 18 0.06 5.3 0.685 6 58 31
19 * * * * * * 20 * * 0.491 174 100 70 21 * * * * * * 22 * * 0.655
-54 36 20 23 * * ** 177 101 76 24 * * 0.645 146 93 69 25 * * 0.611
158 96 71 26 * * ** 174 99 74 27 * * ** 177 100 76 28 * * ** 174
100 77 29 * * 0.664 176 99.9 74.5 30 * * 0.870 183 * * 31 * * **
166 97 78 32 * * 0.728 181 100 87 33 * * ** 169 97 81 34 * * * 184
100 88 35 * * ** 183 100 89 36 * * 0.835 104 87 55 37 * * 0.759 85
77 50 38 * * 0.812 94 85 55 39 * * 0.826 103 86 55 40 * * 0.827 105
86 55 41 * * 0.828 107 87 56 42 * * 0.833 82 80 48 43 * * 0.851 83
78 48 44 * * 0.853 84 78 48 45 * * 0.856 86 78 48 46 * * 0.721 -10
52 30 47 * * 0.695 50 66 39 48 * * 0.714 28 60 35 49 * * 0.717 -7
54 31 50 * * 0.581 -61 36 22 51 * * 0.638 155 96 67 52 * * 0.583
144 89 61 53 * * 0.580 -71 36 22 54 * * 0.645 13 58 35 55 * * 0.607
-17 50 29 56 * * 0.594 -32 44 26 57 * * 0.582 -45 41 23 58 * 36.4
0.504 132 83 50 59 * * 0.626 125 86 56 60 1.2 * 0.687 133 90 57 61
* * * * * * 62 * * 0.448 -35 37 22 63 0.6 7.8 0.623 55 70 43 64 * *
0.449 -32 40 23 65 * * 0.435 -74 33 19 66 * 3 0.449 -32 40 23 67 *
15.1 0.554 129 84 53 68 2 31.3 0.666 123 87 57 69 * * 0.559 129 84
54 70 * * 0.554 129 84 53 71 * * 0.439 70 60 35 72 * 18.6 0.495 114
76 47 73 * * 0.427 47 53 32 74 * * 0.679 -36 45 26 75 * * 0.710 42
64 37 76 * * 0.683 0 50 29 77 * * 0.684 -3 47 27 78 * * 0.680 -11
43 26 79 * * 0.677 -16 42 25 80 * * * * * * 81 * * 0.501 175 99 70
82 * * * * * * 83 * * * * * * 84 * * 0.744 158 97 70 85 * * 0.734
157 96 69 86 * * 0.740 155 96 70 87 * * 0.745 152 95 69 88 * *
0.737 151 94 68 89 * * 0.733 147 94 67 90 * * 0.752 138 92 65 91 *
* 0.742 161 96 69 92 * * 0.742 162 96 69 93 * * 0.738 161 96 69 94
* * 0.739 157 95 68 95 * * 0.720 155 95 68 96 * * 0.715 152 93 67
97 * * 0.703 149 92 64 98 * * 0.658 111 83 55 99 * 4.7 0.601 55 61
36 100 * * 0.551 9 56 32 101 * 35.6 0.628 147 91 63 102 * 50.6
0.700 157 96 70 103 * 80.7 0.778 162 96 70 104 * * 0.715 149 92 65
105 * * 0.574 152 95 69 106 * * 0.486 99 71 51 107 * * 0.535 126 75
45 108 * * 0.600 144 84 54 109 * * 0.621 134 86 56 110 * * 0.594
142 84 55 111 * * 0.590 140 85 55 112 * 26 0.568 102 75 44 113 * *
0.588 100 73 44 114 * * 0.582 98 72 44 115 * * 0.578 98 72 43 116 *
* 0.595 101 73 44 117 * * 0.648 100 76 45 118 * * 0.529 78 63 38 *
not measured ** sphere broke during measurement
[0147] When numerical lower limits and numerical upper limits are
set forth herein, it is contemplated that any combination of these
values may be used.
[0148] 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.
[0149] While the illustrative embodiments of the invention have
been described with particularity, it will be understood that
various other modifications will be apparent to and can be readily
made by those of ordinary skill in the art without departing from
the spirit and scope of the invention. Accordingly, it is not
intended that the scope of the claims appended hereto be limited to
the examples and descriptions set forth herein, but rather that the
claims be construed as encompassing all of the features of
patentable novelty which reside in the present invention, including
all features which would be treated as equivalents thereof by those
of ordinary skill in the art to which the invention pertains.
* * * * *