U.S. patent application number 13/891277 was filed with the patent office on 2013-11-14 for golf ball.
This patent application is currently assigned to DUNLOP SPORTS CO. LTD.. The applicant listed for this patent is DUNLOP SPORTS CO. LTD.. Invention is credited to Yumi KANEMITSU, Chiemi MIKURA, Ryota SAKAMINE, Ayaka SHINDO.
Application Number | 20130303307 13/891277 |
Document ID | / |
Family ID | 49549029 |
Filed Date | 2013-11-14 |
United States Patent
Application |
20130303307 |
Kind Code |
A1 |
SAKAMINE; Ryota ; et
al. |
November 14, 2013 |
GOLF BALL
Abstract
The present invention provides a golf ball having a spherical
core and at least one cover layer covering the spherical core,
wherein the spherical core is formed from a rubber composition
containing (a) a base rubber, (b) an .alpha.,.beta.-unsaturated
carboxylic acid having 3 to 8 carbon atoms and/or a metal salt
thereof as a co-crosslinking agent, (c) a crosslinking initiator,
and (d) an acid and/or a salt thereof, provided that the rubber
composition further contains (e) a metal compound in the case of
containing only (b) the .alpha.,.beta.-unsaturated carboxylic acid
having 3 to 8 carbon atoms as the co-crosslinking agent, wherein
(d) the acid and/or the salt thereof has a relative solubility
parameter to (a) the base rubber and (b) the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and/or the metal salt thereof ranging from 0.45 to 1.10.
Inventors: |
SAKAMINE; Ryota; (Kobe-shi,
JP) ; MIKURA; Chiemi; (Kobe-shi, JP) ; SHINDO;
Ayaka; (Kobe-shi, JP) ; KANEMITSU; Yumi;
(Kobe-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DUNLOP SPORTS CO. LTD. |
Kobe-shi |
|
JP |
|
|
Assignee: |
DUNLOP SPORTS CO. LTD.
Kobe-shi
JP
|
Family ID: |
49549029 |
Appl. No.: |
13/891277 |
Filed: |
May 10, 2013 |
Current U.S.
Class: |
473/372 |
Current CPC
Class: |
A63B 37/0054 20130101;
C08K 5/14 20130101; A63B 37/0063 20130101; C08K 5/098 20130101;
A63B 37/0051 20130101; A63B 37/0074 20130101; C08L 21/00 20130101;
C08L 21/00 20130101; C08L 21/00 20130101; C08K 5/098 20130101; C08K
5/0025 20130101; C08K 5/0025 20130101; C08K 5/14 20130101 |
Class at
Publication: |
473/372 |
International
Class: |
A63B 37/00 20060101
A63B037/00 |
Foreign Application Data
Date |
Code |
Application Number |
May 11, 2012 |
JP |
2012-109717 |
Claims
1. A golf ball having a spherical core and at least one cover layer
covering the spherical core, wherein the spherical core is formed
from a rubber composition containing (a) a base rubber, (b) an
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and/or a metal salt thereof as a co-crosslinking agent, (c) a
crosslinking initiator, and (d) an acid and/or a salt thereof,
provided that the rubber composition further contains (e) a metal
compound in the case of containing only (b) the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms as the co-crosslinking agent, wherein (d) the acid and/or the
salt thereof has a relative solubility parameter ranging from 0.45
to 1.10 to (a) the base rubber and (b) the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and/or the metal salt thereof.
2. The golf ball according to claim 1, wherein (d) the acid and/or
the salt thereof has a relative solubility parameter of 0.48 or
more.
3. The golf ball according to claim 1, wherein (d) the acid and/or
the salt thereof has a relative solubility parameter of 0.52 or
more.
4. The golf ball according to claim 1, wherein (d) the acid and/or
the salt thereof has a relative solubility parameter of 1.05 or
less.
5. The golf ball according to claim 1, wherein (d) the acid and/or
the salt thereof has a proton bond dissociation energy of 270
kcal/mole or less.
6. The golf ball according to claim 1, wherein (d) the acid and/or
the salt thereof is a carboxylic acid and/or a salt thereof.
7. The golf ball according to claim 1, wherein the rubber
composition contains (d) the acid and/or the salt thereof in a
content of 2 parts by mass or more and less than 40 parts by mass
with respect to 100 parts by mass of (a) the base rubber.
8. The golf ball according to claim 1, wherein the rubber
composition further contains (f) an organic sulfur compound.
9. The golf ball according to claim 8, wherein (f) the organic
sulfur compound includes at least one compound selected from the
group consisting of thiophenols, diphenyl disulfides,
thionaphthols, thiuram disulfides, and metal salts thereof.
10. The golf ball according to claim 8, wherein the rubber
composition contains (f) the organic sulfur compound in a content
ranging from 0.05 part to 5 parts by mass with respect to 100 parts
by mass of (a) the base rubber.
11. The golf ball according to claim 1, wherein the rubber
composition contains (b) the .alpha.,.beta.-unsaturated carboxylic
acid having 3 to 8 carbon atoms and/or the metal salt thereof in a
content ranging from 15 parts by mass to 50 parts by mass with
respect to 100 parts by mass of (a) the base rubber.
12. The golf ball according to claim 1, wherein the rubber
composition contains the metal salt of (b) the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms as the co-crosslinking agent.
13. The golf ball according to claim 1, wherein the spherical core
has a hardness difference of 20 or more in JIS-C hardness between a
surface hardness and a center hardness thereof.
14. The golf ball according to claim 1, wherein the spherical core
is such that R.sup.2 of a linear approximation curve obtained from
a least square method is 0.93 or higher, when JIS-C hardness, which
is measured at nine points obtained by dividing a radius of the
spherical core into equal parts having 12.5% intervals
therebetween, is plotted against distance (%) from a core
center.
15. A golf ball having a spherical core and at least one cover
layer covering the spherical core, wherein the spherical core is
formed from a rubber composition containing (a) a base rubber, (b)
an .alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and/or a metal salt thereof as a co-crosslinking agent, (c) a
crosslinking initiator, and (d) a carboxylic acid and/or a salt
thereof, provided that the rubber composition further contains (e)
a metal compound in the case of containing only (b) the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms as the co-crosslinking agent, wherein (d) the carboxylic acid
and/or the salt thereof has a relative solubility parameter ranging
from 0.48 to 1.05 to (a) the base rubber and (b) the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and/or the metal salt thereof.
16. The golf ball according to claim 15, wherein (d) the carboxylic
acid and/or the salt thereof has a proton bond dissociation energy
of 270 kcal/mole or less.
17. The golf ball according to claim 15, wherein the rubber
composition contains (d) the carboxylic acid and/or the salt
thereof in a content of 2 parts by mass or more and less than 40
parts by mass with respect to 100 parts by mass of (a) the base
rubber.
18. The golf ball according to claim 15, wherein the rubber
composition further contains (f) an organic sulfur compound.
19. The golf ball according to claim 15, wherein (d) the carboxylic
acid and/or the salt thereof includes at least one compound
selected from the group consisting of 4-acetoxybenzoic acid,
dimethylaminobenzoic acid, benzoic acid, cyclohexane carboxylic
acid, suberic acid, dodecanedioic acid, octanoic acid,
2-propylpentanoic acid, neodecanoic acid, lauric acid, decanoic
acid, chlorobenzoic acid, myristic acid and salts thereof.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a golf ball traveling a
great distance on driver shots, in particular, an improvement of a
core of a golf ball.
DESCRIPTION OF THE RELATED ART
[0002] As a method for improving flight distance on driver shots,
for example, there are methods of using a core having high
resilience and using a core having a hardness distribution in which
the hardness increases toward the surface of the core from the
center thereof. The former method has an effect of enhancing an
initial speed, and the latter method has an effect of a higher
launch angle and a lower spin rate. A golf ball having a higher
launch angle and a low spin rate travels a great distance.
[0003] For example, Japanese Patent Publications Nos. S61-37178 A,
S61-113475 A, S61-253079 A, 2008-212681 A, 2008-523952 A and
2009-119256 A disclose a technique of enhancing resilience of the
core. Japanese Patent Publication No. S61-37178 A and S61-113475 A
disclose a solid golf ball having an inner core where zinc acrylate
as a co-crosslinking agent, palmitic acid, stearic acid, or
myristic acid as a co-crosslinking activator, zinc oxide as another
co-crosslinking activator, and a reaction rate retarder are
blended.
[0004] Japanese Patent Publication No. S61-253079 A discloses a
solid golf ball formed from a rubber composition containing an
.alpha.,.beta.-unsaturated carboxylic acid in an amount of 15 parts
to 35 parts by weight, a metal compound to react with the
.alpha.,.beta.-unsaturated carboxylic acid and form a salt thereof
in an amount of 7 parts to 60 parts by weight, and a high fatty
acid metal salt in an amount of 1 part to 10 parts by weight with
respect to 100 parts by weight of a base rubber.
[0005] Japanese Patent Publication No. 2008-212681 A discloses a
golf ball comprising, as a component, a molded and crosslinked
product obtained from a rubber composition essentially comprising a
base rubber, a filler, an organic peroxide, an
.alpha.,.beta.-unsaturated carboxylic acid and/or a metal salt
thereof, a copper salt of a saturated or unsaturated fatty
acid.
[0006] Japanese Patent Publication No. 2008-523952 T discloses a
golf ball, or a component thereof, molded from a composition
comprising a base elastomer selected from the group consisting of
polybutadiene and mixtures of polybutadiene with other elastomers,
at least one metallic salt of an unsaturated monocarboxylic acid, a
free radical initiator, and a non-conjugated diene monomer.
[0007] Japanese Patent Publication No. 2009-119256 A discloses a
method of manufacturing a golf ball, comprising preparing a
masterbatch of an unsaturated carboxylic acid and/or a metal salt
thereof by mixing the unsaturated carboxylic acid and/or the metal
salt thereof with a rubber material ahead, using the masterbatch to
prepare a rubber composition containing the rubber material, and
employing a heated and molded product of the rubber composition as
a golf ball component, wherein the masterbatch of the unsaturated
carboxylic acid and/or the metal salt thereof comprises; (A) from
20 wt % to 100 wt % of a modified polybutadiene obtained by
modifying a polybutadiene having a vinyl content of from 0 to 2%, a
cis-1,4 bond content of at least 80% and active terminals, the
active terminal being modified with at least one type of
alkoxysilane compound, and (B) from 80 wt % to 0 wt % of a diene
rubber other than (A) the above rubber component [the figures are
represented by wt % in the case that a total amount of (A) and (B)
equal to 100 wt %] and (C) an unsaturated carboxylic acid and/or a
metal salt thereof.
[0008] For example, Japanese Patent Publications Nos. H6-154357 A,
2008-194471 A, 2008-194473 A and 2010-253268 A disclose a core
having a hardness distribution. Japanese Patent Publication No.
H6-154357 A discloses a two-piece golf ball comprising a core
formed of a rubber composition containing a base rubber, a
co-crosslinking agent, and an organic peroxide, and a cover
covering said core, wherein the core has the following hardness
distribution according to JIS-C type hardness meter readings: (1)
hardness at center: 58-73, (2) hardness at 5 to 10 mm from center:
65-75, (3) hardness at 15 mm from center: 74-82, (4) surface
hardness: 76-84, wherein hardness (2) is almost constant within the
above range, and the relation (1)<(2)<(3)(4) is
satisfied.
[0009] Japanese Patent Publication No. 2008-194471 A discloses a
solid golf ball comprising a solid core and a cover layer that
encases the core, wherein the solid core is formed of a rubber
composition composed of 100 parts by weight of a base rubber that
includes from 60 to 100 parts by weight of a polybutadiene rubber
having a cis-1,4 bond content of at least 60% and synthesized using
a rare-earth catalyst, from 0.1 to 5 parts by weight of an
organosulfur compound, an unsaturated carboxylic acid or a metal
salt thereof, an inorganic filler, and an antioxidant; the solid
core has a deformation from 2.0 mm to 4.0 mm, when applying a load
from an initial load of 10 kgf to a final load of 130 kgf and has
the hardness distribution shown in the following table.
TABLE-US-00001 TABLE 1 Hardness distribution in solid core Shore D
harness Center 30 to 48 Region located 4 mm from center 34 to 52
Region located 8 mm from center 40 to 58 Region located 12 mm from
center (Q) 43 to 61 Region located 2 to 3 mm inside of 36 to 54
surface (R) Surface (S) 41 to 59 Hardness difference [(Q) - (S)] 1
to 10 Hardness difference [(S) - (R)] 3 to 10
[0010] Japanese Patent Publication No. 2008-194473 A discloses a
solid golf ball comprising a solid core and a cover layer that
encases the core, wherein the solid core is formed of a rubber
composition composed of 100 parts by weight of a base rubber that
includes from 60 to 100 parts by weight of a polybutadiene rubber
having a cis-1,4 bond content of at least 60% and synthesized using
a rare-earth catalyst, from 0.1 to 5 parts by weight of an
organosulfur compound, an unsaturated carboxylic acid or a metal
salt thereof, and an inorganic filler; the solid core has a
deformation from 2.0 mm to 4.0 mm, when applying a load from an
initial load of 10 kgf to a final load of 130 kgf and has the
hardness distribution shown in the following table.
TABLE-US-00002 TABLE 2 Hardness distribution in solid core Shore D
harness Center 25 to 45 Region located 5 to 10 mm from center 39 to
58 Region located 15 mm from center 36 to 55 Surface (S) 55 to 75
Hardness difference 20 to 50 between center and surface
[0011] Japanese Patent Publication No. 2010-253268 A discloses a
multi-piece solid golf ball comprising a core, an envelope layer
encasing the core, an intermediate layer encasing the envelope
layer, and a cover which encases the intermediate layer and has
formed on a surface thereof a plurality of dimples, wherein the
core is formed primarily of a rubber material and has a hardness
which gradually increases from a center to a surface thereof, the
hardness difference in JIS-C hardness units between the core center
and the core surface being at least 15 and, letting (I) be the
average value for cross-sectional hardness at a position about 15
mm from the core center and at the core center and letting (II) be
the cross-sectional hardness at a position about 7.5 mm from the
core center, the hardness difference (I)-(II) in JIS-C units being
within .+-.2; and the envelope layer, intermediate layer and cover
have hardness which satisfy the condition: cover
hardness>intermediate layer hardness>envelope layer
hardness.
SUMMARY OF THE INVENTION
[0012] An object of the present invention is to provide a golf ball
traveling a great flight distance on driver shots.
[0013] The present invention provides a golf ball comprising a
spherical core and at least one cover layer covering the spherical
core, wherein the spherical core is formed from a rubber
composition containing (a) a base rubber, (b) an
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and/or a metal salt thereof as a co-crosslinking agent, (c) a
crosslinking initiator, and (d) an acid and/or a salt thereof,
provided that the rubber composition further contains (e) a metal
compound in the case of containing only (b) the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms as the co-crosslinking agent, wherein (d) the acid and/or the
salt thereof has a relative solubility parameter ranging from 0.45
to 1.10 to (a) the base rubber and (b) the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and/or the metal salt thereof. The present invention is
configured as described above and thus provides the spherical core
having a high degree of an outer-hard and inner soft structure,
which reduces a spin rate and provides a greater flight distance on
driver shots.
[0014] In the preferable embodiment of the present invention, the
spherical core has hardness distribution where the hardness
increases linearly or almost linearly from the center of the core
toward the surface thereof. The spherical core having hardness
distribution where the hardness increase linearly or almost
linearly from the center of the core toward the surface thereof,
with a high degree of the outer-hard inner-soft structure reduces
the spin rate on driver shots, thereby providing a greater flight
distance on driver shots. The reason why the core has hardness
distribution where the hardness increases linearly or almost
linearly from the center of the core toward the surface thereof is
considered as follows. The metal salt of (b) the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms blended in the rubber composition is considered to form an
ion cluster in the core thereby crosslinking the rubber molecules
with metals. By blending (d) the acid and/or the salt thereof
having the relative solubility parameter satisfying a predetermined
value to (a) the base rubber and (b) the .alpha.,.beta.-unsaturated
carboxylic acid having 3 to 8 carbon atoms and/or the metal salt
thereof into this rubber composition, (d) the acid and/or the salt
thereof exchanges a cation with the ion cluster formed from the
metal salt of (b) the .alpha.,.beta.-unsaturated carboxylic acid
having 3 to 8 carbon atoms, thereby breaking the metal crosslinking
by the metal salt of the .alpha.,.beta.-unsaturated carboxylic acid
having 3 to 8 carbon atoms. This cation exchange reaction easily
occurs at the core central part where the temperature is high, and
less occurs toward the core surface. When molding a core, the
internal temperature of the core is high at the core central part
and decreases toward the core surface, since reaction heat from a
curing reaction of the rubber composition accumulates at the core
central part. In other words, the breaking of the metal
crosslinking by (d) the acid and/or the salt thereof easily occurs
at the core central part, but less occurs toward the surface. As a
result, it is conceivable that since a crosslinking density in the
core increases from the center of the core toward the surface
thereof, the core hardness increases linearly or almost linearly
from the center of the core toward the surface thereof.
Additionally, in the present invention, it is conceivable that
since the value of the relative solubility parameter falls within
the range from 0.45 to 1.10, the compatibility of (d) the acid
and/or the salt thereof to the metal salt of (b) the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms is enhanced, and the cation exchange reaction occurs more
easily, thereby increasing the effect of breaking the metal
crosslinking.
[0015] According to the present invention, it is possible to
provide a golf ball traveling a great flight distance.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 is a partially cutaway view of the golf ball of the
preferred embodiment of the present invention;
[0017] FIG. 2 is a graph showing the hardness distribution of the
core;
[0018] FIG. 3 is a graph showing the hardness distribution of the
core;
[0019] FIG. 4 is a graph showing the hardness distribution of the
core;
[0020] FIG. 5 is a graph showing the hardness distribution of the
core;
[0021] FIG. 6 is a graph showing the hardness distribution of the
core;
[0022] FIG. 7 is a graph showing the hardness distribution of the
core;
[0023] FIG. 8 is a graph showing the hardness distribution of the
core;
[0024] FIG. 9 is a graph showing the hardness distribution of the
core;
[0025] FIG. 10 is a graph showing the hardness distribution of the
core;
[0026] FIG. 11 is a graph showing the hardness distribution of the
core;
[0027] FIG. 12 is a graph showing the hardness distribution of the
core;
[0028] FIG. 13 is a graph showing the hardness distribution of the
core;
[0029] FIG. 14 is a graph showing the hardness distribution of the
core;
[0030] FIG. 15 is a graph showing the hardness distribution of the
core;
[0031] FIG. 16 is a graph showing the hardness distribution of the
core;
[0032] FIG. 17 is a graph showing the hardness distribution of the
core;
[0033] FIG. 18 is a graph showing the hardness distribution of the
core;
[0034] FIG. 19 is a graph showing the hardness distribution of the
core; and
[0035] FIG. 20 is a graph showing the hardness distribution of the
core.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0036] The present invention provides a golf ball comprising a
spherical core and at least one cover layer covering the spherical
core, wherein the spherical core is formed from a rubber
composition containing (a) a base rubber, (b) an
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and/or a metal salt thereof as a co-crosslinking agent, (c) a
crosslinking initiator, and (d) an acid and/or a salt thereof,
provided that the rubber composition further contains (e) a metal
compound in the case of containing only (b) the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms as the co-crosslinking initiator, wherein (d) the acid and/or
the salt thereof has a relative solubility parameter (hereinafter,
sometimes may be merely referred to as "RS value") ranging from
0.45 to 1.10 to (a) the base rubber and (b) the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and/or the metal salt thereof.
[0037] First, (a) the base rubber used in the present invention
will be described. As (a) the base rubber used in the present
invention, natural rubber and/or synthetic rubber can be used. For
example, polybutadiene rubber, natural rubber, polyisoprene rubber,
styrene polybutadiene rubber, ethylene-propylene-diene rubber
(EPDM), or the like can be used. These rubbers may be used solely
or two or more of these rubbers may be used in combination.
Typically preferred of them is the high cis-polybutadiene having a
cis-1,4 bond in a proportion of 40% or more, more preferably 80% or
more, even more preferably 90% or more in view of its superior
resilience property.
[0038] The high-cis polybutadiene preferably has a 1,2-vinyl bond
in a content of 2 mass % or less, more preferably 1.7 mass % or
less, and even more preferably 1.5 mass % or less. If the content
of 1,2-vinyl bond is excessively high, the resilience may be
lowered.
[0039] The high-cis polybutadiene is preferably one synthesized
using a rare earth element catalyst. When a neodymium catalyst,
which employs a neodymium compound of a lanthanum series rare earth
element compound, is used, a polybutadiene rubber having a high
content of a cis-1,4 bond and a low content of a 1,2-vinyl bond is
obtained with excellent polymerization activity. Such a
polybutadiene rubber is particularly preferred.
[0040] The high-cis polybutadiene preferably has a Mooney viscosity
(ML.sub.1+4 (100.degree. C.)) of 30 or more, more preferably 32 or
more, even more preferably 35 or more, and preferably has a Mooney
viscosity (ML.sub.1+4 (100.degree. C.)) of 140 or less, more
preferably 120 or less, even more preferably 100 or less, and most
preferably 80 or less. It is noted that the Mooney viscosity
(ML.sub.1+4 (100.degree. C.)) in the present invention is a value
measured according to JIS K6300 using an L rotor under the
conditions of: a preheating time of 1 minute; a rotor revolution
time of 4 minutes; and a temperature of 100.degree. C.
[0041] The high-cis polybutadiene preferably has a molecular weight
distribution Mw/Mn (Mw: weight average molecular weight, Mn: number
average molecular weight) of 2.0 or more, more preferably 2.2 or
more, even more preferably 2.4 or more, and most preferably 2.6 or
more, and preferably has a molecular weight distribution Mw/Mn of
6.0 or less, more preferably 5.0 or less, even more preferably 4.0
or less, and most preferably 3.4 or less. If the molecular weight
distribution (Mw/Mn) of the high-cis polybutadiene is excessively
low, the processability deteriorates. If the molecular weight
distribution (Mw/Mn) of the high-cis polybutadiene is excessively
high, the resilience may be lowered. It is noted that the
measurement of the molecular weight distribution is conducted by
gel permeation chromatography ("HLC-8120GPC", manufactured by Tosoh
Corporation) using a differential refractometer as a detector under
the conditions of column: GMHHXL (manufactured by Tosoh
Corporation), column temperature: 40.degree. C., and mobile phase:
tetrahydrofuran, and calculated by converting based on polystyrene
standard.
[0042] Next, (b) the .alpha.,.beta.-unsaturated carboxylic acid
having 3 to 8 carbon atoms and/or a metal salt thereof will be
described. (b) The .alpha.,.beta.-unsaturated carboxylic acid
having 3 to 8 carbon atoms and/or a metal salt thereof is blended
as a co-crosslinking agent in the rubber composition and has an
action of crosslinking a rubber molecule by graft polymerization to
a base rubber molecular chain. In the case that the rubber
composition used in the present invention contains only the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms as the co-crosslinking agent, the rubber composition further
contains (e) a metal compound as an essential component.
Neutralizing the .alpha.,.beta.-unsaturated carboxylic acid having
3 to 8 carbon atoms with the metal compound in the rubber
composition provides substantially the same effect as using the
metal salt of the .alpha.,.beta.-unsaturated carboxylic acid having
3 to 8 carbon atoms. Further, in the case of using the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and the metal salt thereof in combination, (e) the metal
compound may be used as an optional component.
[0043] The .alpha.,.beta.-unsaturated carboxylic acid having 3 to 8
carbon atoms includes, for example, acrylic acid, methacrylic acid,
fumaric acid, maleic acid, crotonic acid, and the like.
[0044] Examples of the metals constituting the metal salts of the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms include: monovalent metal ions such as sodium, potassium,
lithium or the like; divalent metal ions such as magnesium,
calcium, zinc, barium, cadmium or the like; trivalent metal ions
such as aluminum ion or the like; and other metal ions such as tin,
zirconium or the like. The above metal ions can be used solely or
as a mixture of at least two of them. Of these metal ions, divalent
metal ions such as magnesium, calcium, zinc, barium, cadmium or the
like are preferable. Use of the divalent metal salts of the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms easily generates a metal crosslinking between the rubber
molecules. Especially, as the divalent metal salt, zinc acrylate is
preferable, because zinc acrylate enhances the resilience of the
resultant golf ball. The .alpha.,.beta.-unsaturated carboxylic acid
having 3 to 8 carbon atoms and/or a metal salt thereof may be used
solely or in combination at least two of them.
[0045] The content of (b) the .alpha.,.beta.-unsaturated carboxylic
acid having 3 to 8 carbon atoms and/or the metal salt thereof is
preferably 15 parts by mass or more, more preferably 20 parts by
mass or more, and is preferably 50 parts by mass or less, more
preferably 45 parts by mass or less, with respect to 100 parts by
mass of (a) the base rubber. If the content of (b) the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and/or the metal salt thereof is less than 15 parts by mass,
the content of (c) the crosslinking initiator which will be
described below must be increased in order to obtain the
appropriate hardness of the constituting member formed from the
rubber composition, which tends to cause the lower resilience. On
the other hand, if the content of (b) the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and/or the metal salt thereof exceeds 50 parts by mass, the
constituting member formed from the rubber composition becomes
excessively hard, which tends to cause the lower shot feeling.
[0046] (c) The crosslinking initiator is blended in order to
crosslink (a) the base rubber component. As (c) the crosslinking
initiator, an organic peroxide is preferred. Specific examples of
the organic peroxide include organic peroxides such as dicumyl
peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane,
2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and di-t-butyl peroxide.
These organic peroxides may be used solely or two or more of these
organic peroxides may be used in combination. Dicumyl peroxide is
preferably used of the organic peroxides.
[0047] The content of (c) the crosslinking initiator is preferably
0.2 part by mass or more, and more preferably 0.5 part by mass or
more, and is preferably 5.0 parts by mass or less, and more
preferably 2.5 parts by mass or less, with respect to 100 parts by
mass of (a) the base rubber. If the content of (c) the crosslinking
initiator is less than 0.2 part by mass, the constituting member
formed from the rubber composition becomes too soft, and thus the
golf ball may have the lower resilience. If the content of (c) the
crosslinking initiator exceeds 5.0 parts by mass, the amount of (b)
the co-crosslinking agent must be decreased in order to obtain the
appropriate hardness of the constituting member formed from the
rubber composition, resulting in the insufficient resilience and
lower durability of the golf ball.
[0048] Next, (d) the acid and/or the salt thereof will be
described. It is though that (d) the acid and/or the salt thereof
has an action of breaking the metal crosslinking by the metal salt
of (b) the .alpha.,.beta.-unsaturated carboxylic acid having 3 to 8
carbon atoms, in the center part of the core, when molding the
core. In particular, if RS value of (d) the acid and/or the salt
thereof to (a) the base rubber and (b) the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and/or the metal salt thereof falls within the above range,
the compatibility of (d) the acid and/or the salt thereof to (b)
the .alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and/or the metal salt is enhanced, resulting in the greater
effect of breaking the metal crosslinking. In this light, RS value
is preferably 0.45 or more, more preferably 0.48 or more, even more
preferably 0.52 or more, and is preferably 1.10 or less, more
preferably 1.05 or less. If the salt is used as (d) component, RS
value of the acid constituting the salt may fall within the above
range, and RS value of the salt itself may be without the above
range. It is noted that (d) the acid and/or the salt thereof used
in the present invention does not include the metal salt of (b) the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms used as the co-crosslinking agent.
[0049] RS value employed in the present invention is an index that
shows to which the compatibility of the acid and/or the salt
thereof added as (d) component is higher, (a) the base rubber or
(b) the .alpha.,.beta.-unsaturated carboxylic acid having 3 to 8
carbon atoms and/or the metal salt thereof that constitute the
core. That is, RS value that is closer to 1 indicates that the
compatibility of (d) component to (b) the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and/or the metal salt thereof is higher. RS value is
calculated from each SP value of (a) the base rubber, (b) the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and/or the metal salt thereof, and the acid and/or the salt
thereof added as (d) component.
[0050] Hereinafter, a method of calculating RS value will be
described. To calculate RS value, firstly, each SP value of (a) the
base rubber, (b) the .alpha.,.beta.-unsaturated carboxylic acid
having 3 to 8 carbon atoms and/or the metal salt thereof, and the
acid and/or the salt thereof added as (d) component should be
calculated. SP value (at) means at defined by the following
equations.
.delta. d = F di V , .delta. p = F pi 2 V , .delta. h = E hi V
##EQU00001## .delta. t 2 = .delta. d 2 + .delta. p 2 + .delta. h 2
##EQU00001.2##
[0051] In the equations, V means a volume V (cm.sup.3/mole)
according to Fedors, and Fdi, Fpi, and Ehi are solubility parameter
components by the method of Hoftyzer and Van Krevelen. Herein,
.delta.d is a London dispersion component, .delta.p is a dipole
moment component, and .delta.h is hydrogen bonding component. The
method for calculating SP values are described in "Properties of
Polymers, chapter 7 (D. W. VANKREVELEN, Publisher: ELSEVIER,
Published year: Third impression 2003)" in detail. Fdi, Fpi, Ehi
and V of main functional groups are shown in table 3.
TABLE-US-00003 TABLE 3 Kind of Fdi Fpi Ehi V atomic group
J.sup.1/2.cndot.cm.sup.2/3.cndot.mol.sup.-1
J.sup.1/2.cndot.cm.sup.2/3.cndot.mol.sup.-1 J/mol cm.sup.3/mol
--CH.sub.3 420 0 0 33.5 --CH.sub.2-- 270 0 0 16.1 ##STR00001## 80 0
0 -1.0 ##STR00002## -70 0 0 -19.2 .dbd.CH.sub.2 400 0 0 28.5
.dbd.CH-- 200 0 0 13.5 ##STR00003## 70 0 0 --5.5 Phenyl 1430 110 0
71.4 Phenylene 1270 110 0 52.4 (o,m,p) --F (220) -- -- 18.0 --Cl
450 550 400 24.0 --Br (550) -- -- 30.0 --CN 430 1100 2500 24.0 --OH
210 500 20000 10.0 --O-- 100 400 3000 3.8 --COH 470 800 4500 22.3
(aldehyde) --CO-- 290 770 2000 10.8 --COOH 530 420 10000 28.5
--COO-- 390 490 7000 18.0 HCOO-- 530 -- -- 32.5 (formate)
--NH.sub.2 280 -- 8400 19.2 --NH-- 160 210 3100 4.5 ##STR00004## 20
800 5000 -9.0 --NO.sub.2 500 1070 1500 24.0 (aliphatic) --S-- 440
-- -- 12 .dbd.PO.sub.4-- 740 1890 13000 28.0
[0052] Based on the obtained SP value, a three-dimensional graph
with ad on X axis, .sigma.P on y axis, and ah on z axis is prepared
by plotting (a) component, (b) component and (c) component. Herein,
the points of (a) component, (b) component, and (c) component are
represented by A point (x.sub.A, y.sub.A, z.sub.A), B point
(x.sub.B, y.sub.B, Z.sub.B), and P point (x.sub.P, y.sub.P,
Z.sub.P), respectively. To the line AB connecting A point and B
point, a perpendicular line is drawn from P point to determine the
intersection H. Assuming that the length of the line segment AB is
1, RS value is defined as the distance from the point A to the
point H. RS value is calculated by the equation described
below.
RS value = ( x P - x A ) ( x B - x A ) + ( y P - y A ) ( y B - y A
) + ( z P - z A ) ( z B - z A ) ( x B - x A ) 2 + ( y B - y A ) 2 +
( z B - z A ) 2 ##EQU00002##
[0053] (d) The acid and/or the salt thereof may include any one of
an aliphatic acid and/or a salt thereof and an aromatic acid and/or
a salt thereof, as long as it exchanges the cation component with
the .alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and/or the metal salt thereof.
[0054] (d) The acid and/or the salt thereof preferably includes a
protonic acid and/or a salt thereof. The protonic acid includes oxo
acids such as a carboxylic acid, a sulfonic acid, and a phosphoric
acid or the like; and hydroacids such as hydrochloric acid,
hydrofluoric acid or the like. Preferred of the acids is an oxo
acid, and more preferred is a carboxylic acid. As (d) the acid
and/or the salt thereof, 4-acetoxybenzoic acid (0.99),
dimethylaminobenzoic acid (0.96), benzoic acid (0.90), cyclohexane
carboxylic acid (0.90), suberic acid (0.88), dodecanedioic acid
(0.74), octanoic acid (0.61), 2-propylpentanoic acid (0.60),
neodecanoic acid (0.54), lauric acid (0.54), decanoic acid (0.53),
chlorobenzoic acid (0.52), myristic acid (0.50), 2-hexyldecanoic
acid (0.47), stearic acid (0.46), oleic acid (0.46),
2-heptylundecanoic acid (0.45) are exemplified. The numerical value
after the names of compounds is RS value when using polybutadiene
as (a) the base rubber and zinc acrylate as (b) the
.alpha.,.gamma.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and/or the metal salt thereof.
[0055] When the protonic acid and/or the salt thereof is used as
(d) the acid and/or the salt thereof, the protonic acid preferably
has a proton bond dissociation energy of 270 kcal/mole or less. If
the protonic acid has the proton bond dissociation energy of 270
kcal/mole or less, the effect of breaking the metal crosslinking is
enhanced. In this light, the proton bond dissociation energy is
preferably 270 kcal/mole or less, and more preferably 265 kcal/mole
or less. The proton bond dissociation energy is preferably 200
kcal/mole or more, and more preferably 210 kcal/mole or more.
[0056] The bond dissociation energy of (d) the acid and/or the salt
thereof is calculated from the energies of ground states before and
after the dissociation. For example, in case of a carboxylic acid,
the bond dissociation energy is determined by subtracting the
energy of the ground state before the dissociation (RCOOH) from the
energy of the ground state after the dissociation
(RCOO.sup.-+H.sup.+). The energy of RCOOH, RCOO.sup.-, and H.sup.+
can be calculated by a density functional theory
(b3lyp/6-31g*).
[0057] A cation component of the salt of (d) the acid may be any
one of a metal ion, an ammonium ion and an organic cation. The
metal ions include, for example: monovalent metal ions of sodium,
potassium, lithium, silver, and the like; divalent metal ions of
magnesium, calcium, zinc, barium, cadmium, copper, cobalt, nickel,
manganese, and the like; trivalent metal ions of aluminum, iron,
and the like; and other ions of tin, zirconium, titanium, and the
like. The cation component of the salt of the carboxylic acid
preferably includes zinc ion. The cation component may be used
solely or as a mixture of two or more of them.
[0058] The organic cation includes a cation having a carbon chain.
The organic cation includes, for example, without limitation, an
organic ammonium ion. The organic ammonium ion includes, for
example: primary ammonium ions such as stearyl ammonium ion, hexyl
ammonium ion, octyl ammonium ion, and 2-ethylhexyl ammonium ion;
secondary ammonium ions such as dodecyl(lauryl) ammonium ion and
octadecyl(stearyl) ammonium ion; tertiary ammonium ions such as
trioctyl ammonium ion; and quaternary ammonium ions such as
dioctyldimethyl ammonium ion and distearyldimethyl ammonium ion.
The organic cation component may be used solely or as a mixture of
two or more of them.
[0059] The content of (d) the acid and/or the salt thereof is
preferably 2 parts by mass or more, more preferably 2.2 parts by
mass or more, even more preferably 2.4 parts by mass or more, and
is preferably less than 40 parts by mass, more preferably 35 parts
by mass or less, even more preferably 30 parts by mass or less. If
the content is too little, the effect of adding (d) the acid and/or
the salt thereof is not sufficient, and thus the degree of the
outer-hard and inner-soft structure may be lowered. If the content
is too much, the resilience of the core may be lowered, since the
hardness of the resultant core may be lowered as a whole. There are
cases where the surface of zinc acrylate used as the
co-crosslinking agent is treated with (d) the acid and/or the salt
thereof to improve the dispersibility to the rubber. In the case of
using zinc acrylate whose surface is treated with (d) the acid
and/or the salt thereof, in the present invention, the amount of
(d) the acid and/or the salt thereof used as a surface treating
agent is included in the content of (d) component. For example, if
25 parts by mass of zinc acrylate whose surface treatment amount
with (d) the acid and/or the salt thereof is 10 mass % is used, the
amount of (d) the acid and/or the salt thereof is 2.5 parts by mass
and the amount of zinc acrylate is 22.5 parts by mass. Thus, 2.5
parts by mass is counted as the content of (d) component.
[0060] The content of (d) the acid and/or the salt thereof is
preferably determined by the kind and the combination of the acid
and/or the salt thereof. Particularly, the content of (d) the acid
and/or the salt thereof is preferably determined by the carbon
number and the combination of the acid and/or the salt thereof. It
is conceivable that the action of breaking the metal crosslinking
by (d) the acid and/or the salt thereof is affected by the number
of moles of the acid and/or the salt thereof to be added.
Concurrently, the acid and/or the salt thereof acts as a
plasticizer for the spherical core. If the blending amount (mass)
of the acid and/or the salt thereof to be added increases, the
entire core is softened. This plasticizing effect is affected by
the blending amount (mass) of the acid and/or the salt thereof to
be added. In view of those actions, on the same blending amount
(mass), the number of moles of the acid and/or the salt thereof to
be added is made larger by using the acid and/or the salt thereof
having less carbon atoms (small molecular weight) compared to using
the acid and/or the salt thereof having larger carbon atoms (large
molecular weight). That is, the acid and/or the salt thereof having
less carbon atoms can enhance the effect of breaking the metal
crosslinking, while suppressing softening the entire spherical core
by the plasticizing effect.
[0061] For example, if a carboxylic acid having 1 to 14 carbon
atoms and/or a salt thereof is used as (d) the acid and/or the salt
thereof, the content of the carboxylic acid having 1 to 14 carbon
atoms and/or a salt thereof is preferably 2 parts by mass or more,
more preferably 2.2 parts by mass or more, even more preferably 2.4
parts by mass or more, and is preferably 20 parts by mass or less,
more preferably 18 parts by mass or less, even more preferably 16
parts by mass or less with respect to 100 parts by mass of (a) the
base rubber. The carbon number of the salt of the carboxylic acid
having 1 to 14 carbon atoms is the carbon number of the carboxylic
acid component, and the carbon number of the organic cation is not
included.
[0062] For example, if a carboxylic acid having 15 to 30 carbon
atoms and/or a salt thereof is used as (d) the acid and/or the salt
thereof, the content of the carboxylic acid having 15 to 30 carbon
atoms and/or the salt thereof is preferably 5 parts by mass or
more, more preferably 6 parts by mass or more, even more preferably
7 parts by mass or more, and is preferably less than 40 parts by
mass, more preferably 35 parts by mass or less, even more
preferably 30 parts by mass or less. The carbon number of the salt
of the carboxylic acid having 15 to 30 carbon atoms is the carbon
number of the carboxylic acid component, and the carbon number of
the organic cation is not included.
[0063] In the case that the rubber composition used in the present
invention contains only the .alpha.,.beta.-unsaturated carboxylic
acid having 3 to 8 carbon atoms as the co-crosslinking agent, the
rubber composition further contains (e) a metal compound as an
essential component. (e) The metal compound is not limited as long
as it can neutralize (b) the .alpha.,.beta.-unsaturated carboxylic
acid having 3 to 8 carbon atoms in the rubber composition. (e) The
metal compound includes, for example, metal hydroxides such as
magnesium hydroxide, zinc hydroxide, calcium hydroxide, sodium
hydroxide, lithium hydroxide, potassium hydroxide, copper
hydroxide, and the like; metal oxides such as magnesium oxide,
calcium oxide, zinc oxide, copper oxide, and the like; metal
carbonates such as magnesium carbonate, zinc carbonate, calcium
carbonate, sodium carbonate, lithium carbonate, potassium
carbonate, and the like. (e) The metal compound preferably includes
a divalent metal compound, more preferably includes a zinc
compound. The divalent metal compound reacts with the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms, thereby forming a metal crosslinking. Use of the zinc
compound provides a golf ball with excellent resilience. (e) These
metal compounds may be used solely or as a mixture of at least two
of them.
[0064] The rubber composition used in the preset invention
preferably further contains (f) an organic sulfur compound. In the
present invention, by using (f) the organic sulfur compound and (d)
the acid and/or the salt thereof in combination for the core rubber
composition, the degree of the outer-hard and inner-soft structure
of the core can be controlled, while maintaining approximate
linearity of the core hardness distribution. (f) The organic sulfur
compound is not particularly limited, as long as it is an organic
compound having a sulfur atom in the molecule thereof. Examples
thereof include an organic compound having a thiol group (--SH), a
polysulfide bond having 2 to 4 sulfur atoms (--S--S--, --S--S--S--,
or --S--S--S--S--), or a metal salt thereof (--SM, --S-M-S--,
--S-M-S--S--, --S--S-M-S--S--, --S-M-S--S--S--, or the like; M is a
metal atom). Furthermore, (f) the organic sulfur compound may be
any one of aliphatic compounds (aliphatic thiol, aliphatic
thiocarboxylic acid, aliphatic dithiocarboxylic acid, aliphatic
polysulfides, or the like), heterocyclic compounds, alicyclic
compounds (alicyclic thiol, alicyclic thiocarboxylic acid,
alicyclic dithiocarboxylic acid, alicyclic polysulfides, or the
like), and aromatic compounds. (f) The organic sulfur compound
includes, for example, thiophenols, thionaphthols, polysulfides,
thiocarboxylic acids, dithiocarboxylic acids, sulfenamides,
thiurams, dithiocarbamates, and thiazoles. From the aspect of the
larger hardness distribution of the core, (f) the organic sulfur
compound preferably includes, organic compounds having a thiol
group (--SH) or a metal salt thereof, more preferably thiophenols,
thionaphthols, or a metal salt thereof. Examples of the metal salts
are salts of monovalent metals such as sodium, lithium, potassium,
copper (I), and silver (I), and salts of divalent metals such as
zinc, magnesium, calcium, strontium, barium, titanium (II),
manganese (II), iron (II), cobalt (II), nickel(II), zirconium(II),
and tin (II).
[0065] Examples of the thiophenols include, for example,
thiophenol; thiophenols substituted with a fluoro group, such as
4-fluorothiophenol, 2,5-difluorothiophenol,
2,4,5-trifluorothiophenol, 2,4,5,6-tetrafluorothiophenol,
pentafluorothiophenol and the like; thiophenols substituted with a
chloro group, such as 2-chlorothiophenol, 4-chlorothiophenol,
2,4-dichlorothiophenol, 2,5-dichlorothiophenol,
2,6-dichlorothiophenol, 2,4,5-trichlorothiophenol,
2,4,5,6-tetrachlorothiophenol, pentachlorothiophenol and the like;
thiophenols substituted with a bromo group, such as
4-bromothiophenol, 2,5-dibromothiophenol, 2,4,5-tribromothiophenol,
2,4,5,6-tetrabromothiophenol, pentabromothiophenol and the like;
thiophenols substituted with an iodo group, such as
4-iodothiophenol, 2,5-diiodothiophenol, 2,4,5-triiodothiophenol,
2,4,5,6-tetraiodothiophenol, pentaiodothiophenol and the like; or a
metal salt thereof. As the metal salt, zinc salt is preferred.
[0066] Examples of the naphthalenethiols (thionaphthols) are
2-naphthalenethiol, 1-naphthalenethiol,
2-chloro-1-naphthalenethiol, 2-bromo-1-naphthalenethiol,
2-fluoro-1-naphthalenethiol, 2-cyano-1-naphthalenethiol,
2-acetyl-1-naphthalenethiol, 1-chloro-2-naphthalenethiol,
1-bromo-2-naphthalenethiol, 1-fluoro-2-naphthalenethiol,
1-cyano-2-naphthalenethiol, and 1-acetyl-2-naphthalenethiol and
metal salts thereof. Preferable examples include
1-naphthalenethiol, 2-naphthalenethiol and zinc salt thereof.
[0067] The sulfenamide based organic sulfur compound includes, for
example, N-cyclohexyl-2-benzothiazole sulfenamide,
N-oxydiethylene-2-benzothiazole sulfenamide, and
N-t-butyl-2-benzothiazole sulfenamide. The thiuram based organic
sulfur compound includes, for example, tetramethylthiuram
monosulfide, tetramethylthiuram disulfide, tetraethylthiuram
disulfide, tetrabutylthiuram disulfide, and dipentamethylenethiuram
tetrasulfide. The dithiocarbamates include, for example, zinc
dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc
dibutyldithiocarbamate, zinc ethylphenyl dithiocarbamate, sodium
dimethyldithiocarbamate, sodium diethyldithiocarbamate, copper (II)
dimethyldithiocarbate, iron (III) dimethyldithiocarbamate, selenium
diethyldithiocarbamate, and tellurium diethyldithiocarbamate. The
thiazole based organic sulfur compound includes, for example,
2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS),
sodium salt, zinc salt, copper salt, or cyclohexylamine salt of
2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)
mercaptobenzothiazole, and
2-(2,6-diethyl-4-morpholinothio)benzothiazole.
[0068] (f) The organic sulfur compound can be used solely or as a
mixture of at least two of them.
[0069] The content of (f) the organic sulfur compound is preferably
0.05 part by mass or more, more preferably 0.1 part by mass or
more, and is preferably 5.0 parts by mass or less, more preferably
2.0 parts by mass or less, with respect to 100 parts by mass of (a)
the base rubber. If the content of (f) the organic sulfur compound
is less than 0.05 part by mass, the effect of adding (f) the
organic sulfur compound cannot be obtained and thus the resilience
of the golf ball may not improve. If the content of (f) the organic
sulfur compound exceeds 5.0 parts by mass, the compression
deformation amount of the obtained golf ball becomes large and thus
the resilience may be lowered.
[0070] The rubber composition used in the present invention can
include additives such as a pigment, a filler for adjusting weight
or the like, an antioxidant, a peptizing agent, and a softener
where necessary. Further, as described above, if the rubber
composition used in the present invention contains only the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms as the crosslinking agent, the rubber composition preferably
contains (e) the metal compound.
[0071] Examples of the pigment blended in the rubber composition
include a white pigment, a blue pigment, and a purple pigment. As
the white pigment, titanium oxide is preferably used. The type of
titanium oxide is not particularly limited, but rutile type is
preferably used because of the high opacity. The blending amount of
titanium oxide is preferably 0.5 part by mass or more, and more
preferably 2 parts by mass or more, and is preferably 8 parts by
mass or less, and more preferably 5 parts by mass or less, with
respect to 100 parts by mass of (a) the base rubber.
[0072] It is also preferred that the rubber composition contains
both a white pigment and a blue pigment. The blue pigment is
blended in order to cause white color to be vivid, and examples
thereof include ultramarine blue, cobalt blue, and phthalocyanine
blue. Examples of the purple pigment include anthraquinone violet,
dioxazine violet, and methyl violet.
[0073] The blending amount of the blue pigment is preferably 0.001
part by mass or more, and more preferably 0.05 part by mass or
more, and is preferably 0.2 part by mass or less, and more
preferably 0.1 part by mass or less, with respect to 100 parts by
mass of (a) the base rubber. If the blending amount of the blue
pigment is less than 0.001 part by mass, blueness is insufficient,
and the color looks yellowish. If the blending amount of the blue
pigment exceeds 0.2 part by mass, blueness is excessively strong,
and a vivid white appearance is not provided.
[0074] The filler blended in the rubber composition is used as a
weight adjusting agent for mainly adjusting the weight of the golf
ball obtained as an final product. The filler may be blended where
necessary. The filler includes, for example, inorganic fillers such
as zinc oxide, barium sulfate, calcium carbonate, magnesium oxide,
tungsten powder, molybdenum powder, or the like. The content of the
filler is preferably 0.5 part by mass or more, more preferably 1
part by mass or more, and is preferably 30 parts by mass or less,
more preferably 25 parts by mass or less, even more preferably 20
parts by mass or less. If the content of the filler is less than
0.5 part by mass, it is difficult to adjust the weight, while if
the content of the filler exceeds 30 parts by mass, the weight
ratio of the rubber component is reduced and thus the resilience
tends to be lowered.
[0075] The blending amount of the antioxidant is preferably 0.1
part by mass or more and 1 part by mass or less, with respect to
100 parts by mass of (a) the base rubber. In addition, the blending
amount of the peptizing agent is preferably 0.1 part by mass or
more and 5 parts by mass or less, with respect to 100 parts by mass
of (a) the base rubber.
[0076] The rubber composition used in the present invention is
obtained by mixing and kneading (a) the base rubber, (b) the
.alpha.,.delta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and/or the metal salt thereof, (c) the crosslinking
initiator, (d) the acid and/or the salt thereof, and other
additives where necessary. The kneading can be conducted, without
any limitation, with a well-known kneading machine such as a
kneading roll, a banbury mixer, a kneader, or the like.
[0077] The spherical core of the golf ball of the present invention
can be obtained by molding the rubber composition after kneaded.
The temperature for molding the spherical core is preferably
120.degree. C. or more, more preferably 150.degree. C. or more,
even more preferably 160.degree. C. or more, and is preferably
170.degree. C. or less. If the molding temperature exceeds
170.degree. C., the surface hardness of the core tends to decrease.
The molding pressure preferably ranges from 2.9 MPa to 11.8 MPa.
The molding time preferably ranges from 10 minutes to 60
minutes.
[0078] In a preferable embodiment, when the hardness is measured at
nine points obtained by dividing a radius of the spherical core
into equal parts having 12.5% interval and the hardness is plotted
against distance (%) from the center of the spherical core, the
spherical core is such that R.sup.2 of a linear approximation curve
obtained by the least square method is 0.93 or higher. If R.sup.2
is 0.93 or more, the linearity of the core hardness distribution is
enhanced, thus the spin rate on driver shots decreases, resulting
in the improved flying performance.
[0079] The hardness of the spherical core is JIS-C hardness
measured at nine points obtained by dividing a radius of the
spherical core into equal parts having 12.5% interval. That is,
JIS-C hardness is measured at nine points, namely at distances of
0% (core center), 12.5%, 25%, 37.5%, 50%, 62.5%, 75%, 87.5%, 100%
(core surface) from the core center. Next, the measurement results
are plotted to make a graph having JIS-C hardness as a vertical
axis and distances (%) from the core center as a horizontal axis.
In the present invention, R.sup.2 of a linear approximation curve
obtained from this graph by the least square method is preferably
0.93 or higher. R.sup.2 of the linear approximation curve obtained
by the least square method indicates the linearity of the obtained
plot. In the present invention, R.sup.2 of 0.93 or more means that
the core has the hardness distribution where the hardness increases
linearly or almost linearly. If the core having the hardness
distribution where the hardness increases linearly or almost
linearly is used for the golf ball, the spin rate on driver shots
decrease. As a result, the flight distance on driver shots
increases. R.sup.2 of the linear approximation curve is preferably
0.94 or more. The higher linearity provides a greater flight
distance on driver shots.
[0080] The spherical core preferably has a hardness difference
(Hs-Ho) between a surface hardness Hs and a center hardness Ho of
20 or more, more preferably 25 or more, even more preferably 30 or
more, and preferably has a hardness difference of 80 or less, more
preferably 70 or less, even more preferably 60 or less in JIS-C
hardness. If the hardness difference between the center hardness
and the surface hardness is large, the golf ball having a great
flight distance due to the high launch angle and low spin rate is
obtained.
[0081] The spherical core preferably has a center hardness Ho of 30
or more, more preferably 35 or more, and even more preferably 40 or
more in JIS-C hardness. If the center hardness Ho is less than 30
in JIS-C hardness, the core becomes too soft and thus the
resilience may be lowered. Further, the spherical core preferably
has a center hardness Ho of 70 or less, more preferably 65 or less,
even more preferably 60 or less in JIS-C hardness. If the center
hardness Ho exceeds 70 in JIS-C hardness, the core becomes too hard
and thus the shot feeling tends to be lowered.
[0082] The spherical core preferably has a surface hardness Hs of
76 or more, more preferably 78 or more, even more preferably 80 or
more, and preferably has a surface hardness Hs of 100 or less, more
preferably 95 or less in JIS-C hardness. If the surface hardness is
76 or more in JIS-C hardness, the spherical core does not become
excessively soft, and thus the better resilience is obtained.
Further, if the surface hardness of the spherical core is 100 or
less in JIS-C hardness, the spherical core does not become
excessively hard, and thus the better shot feeling is obtained.
[0083] The spherical core preferably has a diameter of 34.8 mm or
more, more preferably 36.8 mm or more, and even more preferably
38.8 mm or more, and preferably has a diameter of 42.2 mm or less,
more preferably 41.8 mm or less, and even more preferably 41.2 mm
or less, and most preferably 40.8 mm or less.
[0084] If the spherical core has a diameter of 34.8 mm or more, the
thickness of the cover does not become too thick and thus the
resilience becomes better. On the other hand, if the spherical core
has a diameter of 42.2 mm or less, the thickness of the cover does
not become too thin, and hence a protection ability of the cover is
sufficiently provided.
[0085] When the spherical core has a diameter from 34.8 mm to 42.2
mm, a compression deformation amount (shrinking deformation amount
of the spherical core along the compression direction) of the
spherical core when applying a load from an initial load of 98N to
a final load of 1275N is preferably 2.0 mm or more, more preferably
2.8 mm or more, and is preferably 6.0 mm or less, more preferably
5.0 mm or less. If the compression deformation amount is 2.0 mm or
more, the shot feeling of the golf ball becomes better. If the
compression deformation amount is 6.0 mm or less, the resilience of
the golf ball becomes better.
[0086] The golf ball cover of the present invention is formed from
a cover composition comprising a resin component. Examples of the
resin component include, for example, an ionomer rein; a
thermoplastic polyurethane elastomer having a commercial name of
"Elastollan (e.g. "Elastollan XNY85A")" commercially available from
BASF Japan Ltd; a thermoplastic polyamide elastomer having a
commercial name of "Pebax (e.g. "Pebax 2533")" commercially
available from Arkema K. K.; a thermoplastic polyester elastomer
having a commercial name of "Hytrel" commercially available from Du
Pont-Toray Co., Ltd.; and a thermoplastic styrene elastomer having
a commercial name of "Rabalon" commercially available from
Mitsubishi Chemical Corporation; and the like.
[0087] The ionomer resin includes a product prepared by
neutralizing at least a part of carboxyl groups in the binary
copolymer composed of an olefin and an .alpha.,.beta.-unsaturated
carboxylic acid having 3 to 8 carbon atoms with a metal ion, a
product prepared by neutralizing at least a part of carboxyl groups
in the ternary copolymer composed of an olefin, an
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms, and an .alpha.,.beta.-unsaturated carboxylic acid ester with
a metal ion, or a mixture of those. The olefin preferably includes
an olefin having 2 to 8 carbon atoms. Examples of the olefin are
ethylene, propylene, butene, pentene, hexene, heptene, and octene.
The olefin more preferably includes ethylene. Examples of the
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms are acrylic acid, methacrylic acid, fumaric acid, maleic acid
and crotonic acid. Acrylic acid and methacrylic acid are
particularly preferred. Examples of the .alpha.,.beta.-unsaturated
carboxylic acid ester include methyl ester, ethyl ester, propyl
ester, n-butyl ester, isobutyl ester of acrylic acid, methacrylic
acid, fumaric acid, maleic acid or the like. In particular, acrylic
acid ester and methacrylic acid ester are preferable. Of these, the
ionomer resin preferably includes the metal ion-neutralized product
of the binary copolymer composed of ethylene-(meth)acrylic acid and
the metal ion-neutralized product of the ternary copolymer composed
of ethylene, (meth)acrylic acid, and (meth)acrylic acid ester.
[0088] Specific examples of the ionomer resins include trade name
"Himilan.RTM. (e.g. the binary copolymerized ionomer such as
Himilan 1555 (Na), Himilan 1557 (Zn), Himilan 1605 (Na), Himilan
1706 (Zn), Himilan 1707 (Na), Himilan AM7311 (Mg); and the ternary
copolymerized ionomer such as Himilan 1856 (Na), Himilan 1855
(Zn))" commercially available from Du Pont-Mitsui Polychemicals
Co., Ltd.
[0089] Further, examples include "Surlyn (registered trademark)
(e.g. the binary copolymerized ionomer such as Surlyn 8945 (Na),
Surlyn 9945 (Zn), Surlyn 8140 (Na), Surlyn 8150 (Na), Surlyn 9120
(Zn), Surlyn 9150 (Zn), Surlyn 6910 (Mg), Surlyn 6120 (Mg), Surlyn
7930 (Li), Surlyn 7940 (Li), Surlyn AD8546 (Li); and the ternary
copolymerized ionomer such as Surlyn 8120 (Na), Surlyn 8320 (Na),
Surlyn 9320 (Zn), Surlyn 6320 (Mg), HPF 1000 (Mg), HPF 2000 (Mg))"
commercially available from E.I. du Pont de Nemours and
Company.
[0090] Further, examples include "lotek (registered trademark)
(e.g. the binary copolymerized ionomer such as lotek 8000 (Na),
lotek 8030 (Na), lotek 7010 (Zn), lotek 7030 (Zn); and the ternary
copolymerized ionomer such as lotek 7510 (Zn), lotek 7520 (Zn))"
commercially available from ExxonMobil Chemical Corporation.
[0091] It is noted that Na, Zn, Li, and Mg described in the
parentheses after the trade names indicate metal types of
neutralizing metal ions for the ionomer resins. The ionomer resin
may be used solely or as a mixture of two or more of them.
[0092] The cover composition constituting the cover of the golf
ball of the present invention preferably includes, as a resin
component, a thermoplastic polyurethane elastomer or an ionomer
rein. In case of using the ionomer rein, it is preferred to use a
thermoplastic styrene elastomer together. The content of the
polyurethane or ionomer resin in the resin component of the cover
composition is preferably 50 mass % or more, more preferably 60
mass % or more, even more preferably 70 mass % or more.
[0093] In the present invention, the cover composition may further
contain a pigment component such as a white pigment (for example,
titanium oxide), a blue pigment, and a red pigment; a weight
adjusting agent such as zinc oxide, calcium carbonate, and barium
sulfate; a dispersant; an antioxidant; an ultraviolet absorber; a
light stabilizer; a fluorescent material or a fluorescent
brightener; and the like, as long as they do not impair the effect
of the present invention.
[0094] The amount of the white pigment (for example, titanium
oxide) is preferably 0.5 part or more, more preferably 1 part or
more, and the content of the white pigment is preferably 10 parts
or less, more preferably 8 parts or less, with respect to 100 parts
of the resin component constituting the cover by mass. If the
amount of the white pigment is 0.5 part by mass or more, it is
possible to impart the opacity to the resultant cover. Further, if
the amount of the white pigment is more than 10 parts by mass, the
durability of the resultant cover may deteriorate.
[0095] The slab hardness of the cover composition is preferably set
in accordance with the desired performance of the golf balls. For
example, in case of a so-called distance golf ball which focuses on
a flight distance, the cover composition preferably has a slab
hardness of 50 or more, more preferably 55 or more, and preferably
has a slab hardness of 80 or less, more preferably 70 or less in
shore D hardness. If the cover composition has a slab hardness of
50 or more, the obtained golf ball has a high launch angle and low
spin rate on driver shots and iron shots, and thus the flight
distance improves. If the cover composition has a slab hardness of
80 or less, the golf ball excellent in durability is obtained.
Further, in case of a so-called spin golf ball which focuses on
controllability, the cover composition preferably has a slab
hardness of less than 50, and preferably has a slab hardness of 20
or more, more preferably 25 or more in shore D hardness. If the
cover composition has a slab hardness of less than 50, the flight
distance on driver shots can be improved by the core of the present
invention, as well as the obtained golf ball readily stops on the
green due to the high spin rate on approach shots. If the cover
composition has a slab hardness of 20 or more, the abrasion
resistance improves. In case of a plurality of cover layers, the
slab hardness of the cover composition constituting each layer can
be identical or different, as long as the slab hardness of each
layer is within the above range.
[0096] An embodiment for molding a cover is not particularly
limited, and includes an embodiment which comprises injection
molding the cover composition directly onto the core, or an
embodiment which comprises molding the cover composition into a
hollow-shell, covering the core with a plurality of the
hollow-shells and subjecting the core with a plurality of the
hollow shells to the compression-molding (preferably an embodiment
which comprises molding the cover composition into a half
hollow-shell, covering the core with the two half hollow-shells,
and subjecting the core with the two half hollow-shells to the
compression-molding).
[0097] When molding the cover in a compression molding method,
molding of the half shell can be performed by either compression
molding method or injection molding method, and the compression
molding method is preferred. The compression-molding of the cover
composition into half shell can be carried out, for example, under
a pressure of 1 MPa or more and 20 MPa or less at a temperature of
-20.degree. C. or more and 70.degree. C. or less relative to the
flow beginning temperature of the cover composition. By performing
the molding under the above conditions, a half shell having a
uniform thickness can be formed. Examples of a method for molding
the cover using half shells include compression molding by covering
the core with two half shells. The compression molding of half
shells into the cover can be carried out, for example, under a
pressure of 0.5 MPa or more and 25 MPa or less at a temperature of
-20.degree. C. or more and 70.degree. C. or less relative to the
flow beginning temperature of the cover composition. By performing
the molding under the above conditions, a golf ball cover having a
uniform thickness can be formed.
[0098] In the case of directly injection molding the cover
composition, the cover composition extruded in the pellet form
beforehand may be used for injection molding or the materials such
as the base resin components and the pigment may be dry blended,
followed by directly injection molding the blended material. It is
preferred to use upper and lower molds having a spherical cavity
and pimples for forming a cover, wherein a part of the pimples also
serves as a retractable hold pin. When molding the cover by
injection molding, the core is charged and held with the protruding
hold pin, the cover composition which has been heated and melted is
charged, and then cooled to obtain a cover. For example, it is
preferred that the cover composition heated and melted at the
temperature ranging from 200.degree. C. to 250.degree. C. is
charged into a mold held under the pressure of 9 MPa to 15 MPa for
0.5 to 5 seconds, and after cooling for 10 to 60 seconds, the mold
is opened and the golf ball with the cover molded is taken out from
the mold.
[0099] The concave portions called "dimple" are usually formed on
the surface of the cover. The total number of the dimples is
preferably 200 or more and 500 or less. If the total number is less
than 200, the dimple effect is hardly obtained. On the other hand,
if the total number exceeds 500, the dimple effect is hardly
obtained because the size of the respective dimples is small. The
shape (shape in a plan view) of dimples includes, for example,
without limitation, a circle, polygonal shapes such as roughly
triangular shape, roughly quadrangular shape, roughly pentagonal
shape, roughly hexagonal shape, and another irregular shape. The
shape of the dimples is employed solely or at least two of them may
be used in combination.
[0100] In the present invention, the cover of the golf ball
preferably has a thickness of 4.0 mm or less, more preferably 3.0
mm or less, even more preferably 2.0 mm or less. If the thickness
of the cover is 4.0 mm or less, the resilience and shot feeling of
the obtained golf ball become better. The cover of the golf ball
preferably has a thickness of 0.3 mm or more, more preferably 0.5
mm or more, and even more preferably 0.8 mm or more, and most
preferably 1.0 mm or more. If the thickness of the cover is less
than 0.3 mm, the durability and the wear resistance of the cover
may deteriorate. If the cover has a plurality of layers, it is
preferred that the total thickness of the cover layers falls within
the above range.
[0101] After the cover is molded, the mold is opened and the golf
ball body is taken out from the mold, and as necessary, the golf
ball body is preferably subjected to surface treatments such as
deburring, cleaning, and sandblast. If desired, a paint film or a
mark may be formed. The paint film preferably has a thickness of,
but not limited to, 5 .mu.m or larger, and more preferably 7 .mu.m
or larger, and preferably has a thickness of 50 .mu.m or smaller,
and more preferably 40 .mu.m or smaller, even more preferably 30
.mu.m or smaller. If the thickness is smaller than 5 .mu.m, the
paint film is easy to wear off due to continued use of the golf
ball, and if the thickness is larger than 50 .mu.m, the effect of
the dimples is reduced, resulting in lowering flying performance of
the golf ball.
[0102] When the golf ball of the present invention has a diameter
in a range from 40 mm to 45 mm, a compression deformation amount of
the golf ball (shrinking amount of the golf ball in the compression
direction thereof) when applying a load from an initial load of 98
N to a final load of 1275 N to the golf ball is preferably 2.0 mm
or more, more preferably 2.4 mm or more, even more preferably 2.5
mm or more, most preferably 2.8 mm or more, and is preferably 5.0
mm or less, more preferably 4.5 mm or less, even more preferably
3.6 mm or less. If the compression deformation amount is 2.0 mm or
more, the golf ball does not become excessively hard, and thus
exhibits the good shot feeling. On the other hand, if the
compression deformation amount is 5.0 mm or less, the resilience is
enhanced.
[0103] The golf ball construction is not limited, as long as the
golf ball of the present invention comprises a spherical core and
at least one cover layer covering the spherical core. FIG. 1 is a
partially cutaway sectional view showing the golf ball 2 according
to the preferable embodiment of the present invention. The golf
ball 2 comprises a spherical core 4, and a cover 12 covering the
spherical core 4. Plurality of dimples 14 are formed on a surface
of the cover. Other portions than dimples 14 on the surface of the
golf ball 2 are referred to as land 16. The golf ball 2 is provided
with a paint layer and a mark layer outside the cover 12, but these
layers are not depicted.
[0104] The spherical core preferably has a single layered
structure. Unlike the multi-layered structure, the spherical core
of the single layered structure does not have an energy loss at the
interface of the multi-layered structure when hitting, and thus has
an enhanced resilience. The cover has a structure of at least one
layer, for example a single layered structure, or a multi-layered
structure of at least two layers. The golf ball of the present
invention includes, for example, a two-piece golf ball comprising a
spherical core and a single layered cover disposed around the
spherical core, a multi-piece golf ball comprising a spherical
core, and at least two cover layers disposed around the spherical
core (including the three-piece golf ball), and a wound golf ball
comprising a spherical core, a rubber thread layer which is formed
around the spherical core, and a cover disposed over the rubber
thread layer. The present invention can be suitably applied to any
one of the above golf balls.
EXAMPLES
[0105] Hereinafter, the present invention will be described in
detail by way of example. The present invention is not limited to
examples described below. Various changes and modifications can be
made without departing from the spirit and scope of the present
invention.
[Evaluation Methods]
(1) Compression Deformation Amount (mm)
[0106] A compression deformation amount of the core or golf ball (a
shrinking amount of the core or golf ball in the compression
direction thereof), when applying a load from an initial load of
98N to a final load of 1275N to the core or golf ball, was
measured.
(2) Coefficient of Restitution
[0107] A 198.4 g of metal cylindrical object was allowed to collide
with each core or golf ball at a speed of 40 m/sec, and the speeds
of the cylindrical object and the core or golf ball before and
after the collision were measured. Based on these speeds and the
mass of each object, coefficient of restitution for each core or
golf ball was calculated. The measurement was conducted by using
twelve samples for each core or golf ball, and the average value
was regarded as the coefficient of restitution for the core or golf
ball. In Tables 4 to 6, the coefficient of restitution is shown as
the difference from that of golf ball (core) No. 17.
(3) Slab Hardness (Shore D Hardness)
[0108] Sheets with a thickness of about 2 mm were produced by
injection molding the cover composition, and stored at 23.degree.
C. for two weeks. Three or more of these sheets were stacked on one
another so as not to be affected by the measuring substrate on
which the sheets were placed, and the hardness of the stack was
measured with a type P1 auto loading durometer manufactured by
Kobunshi Keiki Co., Ltd., provided with a Shore D type spring
hardness tester prescribed in ASTM-D2240.
(4) Hardness Distribution of Spherical Core (JIS-C Hardness)
[0109] A type P1 auto loading durometer manufactured by Kobunshi
Keiki Co., Ltd., provided with a JIS-C type spring hardness tester
was used to measure the hardness of the spherical core. The
hardness measured at the surface of the spherical core was adopted
as the surface hardness of the spherical core. The spherical core
was cut into two hemispheres to obtain a cut plane, and the
hardness was measured at the central point and at predetermined
distances from the central point of the cut plane. The core
hardness was measured at 4 points at predetermined distances from
the central point of the cut plane of the core. The core hardness
was calculated by averaging the hardness measured at 4 points.
(5) Flight Distance (m) and Spin Rate (Rpm) on a Driver Shot
[0110] A metal-headed W#1 driver (XXIO S, loft: 11.degree.,
manufactured by SRI Sports Limited) was installed on a swing robot
M/C manufactured by Golf Laboratories, Inc. A golf ball was hit at
a head speed of 40 m/sec, and the flight distance (the distance
from the launch point to the stop point) and the spin rate right
after hitting the golf ball were measured. This measurement was
conducted twelve times for each golf ball, and the average value
was adopted as the measurement value for the golf ball. A sequence
of photographs of the hit golf ball were taken for measuring the
spin rate (rpm) right after hitting the golf ball. In Tables 4 to
6, the flight distance and the spin rate is shown as the difference
from that of golf ball (core) No. 17.
[Production of Cores]
[0111] The rubber compositions having formulations shown in Tables
4 to 6 were kneaded and heat-pressed in upper and lower molds, each
having a hemispherical cavity, at 170.degree. C. for 20 minutes to
prepare spherical cores having a diameter of 39.8 mm.
TABLE-US-00004 TABLE 4 Golf ball No. 1 2 3 4 5 6 Rubber composition
BR730 100 100 100 100 100 100 (parts by mass) Sanceler SR 34 29 31
31 31 30 Zinc oxide 5 5 5 5 5 5 Barium sulfate *1) *1) *1) *1) *1)
*1) 2-thionaphthol 0.1 0.32 0.1 0.1 0.1 0.1 4-acetoxybenzoic acid
5.1 -- -- -- -- -- Lauric acid -- 7.0 -- -- -- -- Cyclohexane
carboxylic acid -- -- 5.0 -- -- -- Dimethylaminobenzoic acid -- --
-- 5.0 -- -- Benzoic acid -- -- -- -- 5.0 -- Chlorobenzoic acid --
-- -- -- 5.0 Dicumyl peroxide 0.8 0.8 0.8 0.8 0.8 0.8 Relative
solubility parameter 0.99 0.53 0.90 0.96 0.90 1.03 Bond
dissociation energy (kcal/mole) 248.7 257.3 256.3 256.5 251.1 245.5
Core hardness Center hardness 45.1 50.3 46.5 45.6 45.9 47.3
distribution 12.5% point hardness 51.0 55.0 51.3 50.7 51.8 55.1
(JIS-C) 25% point hardness 57.7 59.8 58.0 58.5 59.0 62.0 37.5%
point hardness 61.4 62.9 61.5 63.3 64.2 65.1 50% point hardness
63.6 63.9 62.5 64.4 66.5 65.8 62.5% point hardness 62.7 66.7 68.9
67.4 65.4 69.7 75% point hardness 70.0 75.1 76.0 78.0 77.7 76.1
87.5% point hardness 75.4 77.9 75.2 79.6 83.0 75.2 Surface hardness
82.9 81.9 81.4 83.5 89.3 81.7 Surface hardness-center hardness 37.9
31.7 34.9 37.9 43.4 34.4 R.sup.2 of approximated curve 0.96 0.98
0.98 0.98 0.96 0.95 Slope of approximated curve 0.33 0.31 0.34 0.38
0.41 0.31 Core coefficient of restitution -0.004 -0.011 0.002
-0.009 0.004 -0.009 Core compression deformation amount (mm) 4.0
4.3 4.2 3.9 4.1 4.1 Cover composition A A A A A A Cover hardness
(Shore D) 65 65 65 65 65 65 Cover thickness (mm) 1.5 1.5 1.5 1.5
1.5 1.5 Ball Driver spin rate (rpm) -80 -70 -100 -130 -120 -80
Driver flying distance (m) 2.0 3.3 2.8 3.5 3.9 1.1 Coefficient of
restitution -0.004 -0.011 0.002 -0.009 0.001 -0.010 Compression
deformation amount (mm) 3.3 3.6 3.5 3.2 3.4 3.3
TABLE-US-00005 TABLE 5 Golf ball No. 7 8 9 10 11 12 Rubber
composition BR730 100 100 100 100 100 100 (parts by mass) Sanceler
SR 31 29 32 29 29 29 Zinc oxide 5 5 5 5 5 5 Barium sulfate *1) *1)
*1) *1) *1) *1) 2-thionaphthol 0.32 0.32 0.32 0.32 0.32 0.32
Decanoic acid 5.0 -- -- -- -- -- Octanoic acid -- 2.5 -- -- -- --
Dodecanedioic acid -- -- 4.0 -- -- -- Suberic acid -- -- -- 3.0 --
-- 2-propylvaleric acid -- -- -- -- 2.5 -- Neodecanoic acid -- --
-- -- 9.0 Dicumyl peroxide 0.8 0.8 0.8 0.8 0.8 0.8 Relative
solubility parameter 0.57 0.61 0.74 0.88 0.60 0.56 Bond
dissociation energy (kcal/mole) 257.3 255.9 256.6 255.4 257.0 257.3
Core hardness Center hardness 47.9 50.4 46.6 47.1 45.3 48.0
distribution 12.5% point hardness 54.2 56.2 54.8 56.2 52.5 53.6
(JIS-C) 25% point hardness 60.4 62.3 61.1 62.6 60.6 60.4 37.5%
point hardness 63.6 64.5 63.7 65.5 63.6 63.4 50% point hardness
64.4 65.5 65.1 66.8 64.2 63.9 62.5% point hardness 67.2 66.1 65.9
67.0 63.8 65.1 75% point hardness 75.8 74.1 73.2 72.2 72.5 74.2
87.5% point hardness 79.3 77.9 77.0 75.9 75.6 76.7 Surface hardness
81.7 83.0 84.1 83.6 81.9 82.0 Surface hardness-center hardness 33.8
32.7 37.5 36.6 36.6 34.0 R.sup.2 of approximated curve 0.97 0.96
0.95 0.93 0.94 0.96 Slope of approximated curve 0.33 0.29 0.32 0.30
0.32 0.31 Core coefficient of restitution 0.016 0.004 -0.015 -0.013
0.002 0.003 Core compression deformation amount (mm) 4.0 4.5 4.1
4.1 4.3 4.2 Cover composition A A A A A A Cover hardness (Shore D)
65 65 65 65 65 65 Cover thickness (mm) 1.5 1.5 1.5 1.5 1.5 1.5 Ball
Driver spin rate (rpm) -100 -90 -70 -60 -80 -95 Driver flying
distance (m) 4.0 2.7 1.5 1.3 2.8 4.0 Coefficient of restitution
0.016 0.005 -0.015 -0.013 0.002 0.003 Compression deformation
amount (mm) 3.3 3.8 3.4 3.4 3.6 3.5
TABLE-US-00006 TABLE 6 Golf ball No. 13 14 15 16 17 18 19 Rubber
composition BR730 100 100 100 100 100 100 100 (parts by mass)
Sanceler SR 29 29 29 31 23 32 28 Zinc oxide 5 5 5 5 5 5 5 Barium
sulfate *1) *1) *1) *1) *1) *1) *1) 2-thionaphthol 0.32 0.32 0.32
0.32 -- 0.1 0.32 2-heptylundecanoic acid 10 -- -- -- -- -- -- Zinc
stearate -- -- 30 40 -- -- -- Zinc octanoate -- 5.0 -- -- -- -- --
4-aminobenzoic acid -- -- -- -- -- 5.8 -- Behenic acid -- -- -- --
-- -- 20.0 Dicumyl peroxide 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Relative
solubility parameter 0.45 0.61 0.46 0.46 -- 1.13 0.43 Bond
dissociation energy (kcal/mole) 251.4 255.9 257.3 257.3 -- 255.6
257.3 Core hardness Center hardness 49.4 47.6 57.6 60.3 55.0 49.1
52.9 distribution 12.5% point hardness 56.5 54.2 59.9 61.6 61.4
57.1 56.6 (JIS-C) 25% point hardness 63.5 57.9 62.6 63.7 65.4 63.1
59.8 37.5% point hardness 66.3 60.5 64.1 64.9 67.1 66.4 61.1 50%
point hardness 67.4 62.5 66.1 66.3 67.4 67.4 64.1 62.5% point
hardness 67.2 68.5 68.7 67.1 67.2 67.9 68.3 75% point hardness 73.7
75.1 71.7 68.5 71.3 72.6 72.6 87.5% point hardness 78.0 78.5 72.1
66.9 73.4 74.6 73.2 Surface hardness 81.7 81.6 78.0 69.6 80.2 80.0
77.1 Surface hardness-center hardness 32.3 34.1 20.4 9.3 25.2 30.9
24.2 R.sup.2 of approximated curve 0.95 0.99 0.98 0.91 0.90 0.93
0.99 Slope of approximated curve 0.29 0.34 0.19 0.09 0.20 0.26 0.24
Core coefficient of restitution 0.018 -0.007 0.002 -0.016 0.000
-0.018 -0.003 Core compression deformation amount (mm) 4.1 4.6 4.0
4.4 4.2 4.0 4.2 Cover composition A A A A A A A Cover hardness
(Shore D) 65 65 65 65 65 65 65 Cover thickness (mm) 1.5 1.5 1.5 1.5
1.5 1.5 1.5 Ball Driver spin rate (rpm) -95 -110 -30 60 0 -20 -40
Driver flying distance (m) 4.2 4.0 1.4 -2.1 0.0 -2.0 0.3
Coefficient of restitution 0.018 -0.007 0.002 -0.016 0.000 -0.018
-0.003 Compression deformation amount (mm) 3.4 3.9 3.3 3.7 3.5 3.3
3.5 *1) As to an amount of barium sulfate, adjustment was made such
that the golf ball had a mass of 45.4 g. BR730: a high-cis
polybutadiene (cis-1,4 bond content = 96 mass %, 1,2-vinyl bond
content = 1.3 mass %, Moony viscosity (ML.sub.1+4 (100.degree. C.)
= 55, molecular weight distribution (Mw/Mn) = 3) available from JSR
Corporation Sanceler SR: zinc acrylate (product of 10 mass %
stearic acid coating) available from Sanshin Chemical Industry Co.,
Ltd. Zinc oxide: "Ginrei R" manufactured by Toho Zinc Co., Ltd.
Barium sulfate: "Barium sulfate BD" manufactured by Sakai Chemical
Industry Co., Ltd., adjustment was made such that the finally
obtained golf ball had a mass of 45.4 g. 2-thionaphthol:
manufactured by Tokyo Chemical Industry Co., Ltd. 4-acetoxybenzoic
acid: manufactured by Tokyo Chemical Industry Co., Ltd. Purity
98.0% Lauric acid: manufactured by Tokyo Chemical Industry Co.,
Ltd. Purity 98.0% Cyclohexane carboxylic acid: manufactured by
Tokyo Chemical Industry Co., Ltd. Purity 98.0% Dimethylaminobenzoic
acid: manufactured by Tokyo Chemical Industry Co., Ltd. Purity
98.0% Benzoic acid: manufactured by Tokyo Chemical Industry Co.,
Ltd. Purity 98.0% Chlorobenzoic acid: manufactured by Tokyo
Chemical Industry Co., Ltd. Purity 99.0% Decanoic acid:
manufactured by Tokyo Chemical Industry Co., Ltd. Purity 98.0%
Octanoic acid: manufactured by Tokyo Chemical Industry Co., Ltd.
Purity 98.0 % Dodecanedioic acid: manufactured by Tokyo Chemical
Industry Co., Ltd. Purity 98.0% Suberic acid: manufactured by Tokyo
Chemical Industry Co., Ltd. Purity 99.0% 2-propylvaleric acid:
manufactured by Tokyo Chemical Industry Co., Ltd. Purity 99.0%
Neodecanoic acid: manufactured by Wako Pure Chemical Industries
Purity 100.0% 2-heptylundecanoic acid: manufactured by Tokyo
Chemical Industry Co., Ltd. Purity 95.0% Zinc stearate:
manufactured by Wako Pure Chemical Industries Purity 95.0% Zinc
octanoate: manufactured by Mitsuwa Chemicals Co., Ltd. Purity 99.0%
4-aminobenzoic acid: manufactured by Tokyo Chemical Industry Co.,
Ltd. Purity 99.0% Dicumyl peroxide: "Percumyl (Registered trade
mark) D (dicumyl peroxide)" manufactured by NOF CORPORATION Behenic
acid: manufactured by Tokyo Chemical Industry Co., Ltd. Purity
80.0%
(2) Production of Cover
[0112] Cover materials shown in Table 7 were mixed with a
twin-screw kneading extruder to prepare the cover compositions in
the pellet form. The extruding conditions of the cover composition
were a screw diameter of 45 mm, a screw rotational speed of 200
rpm, and screw L/D=35, and the mixtures were heated to 150 to
230.degree. C. at the die position of the extruder. The cover
compositions obtained above were injection-molded onto the
spherical cores to produce the golf balls having the spherical core
and the cover covering the spherical core.
TABLE-US-00007 TABLE 7 Cover composition No. A Himilan 1605 50
Himilan 1706 50 Titanium oxide 4 Slab hardness (shore D) 65
Formulation: parts by mass Himilan 1605: Sodium ion neutralized
ethylene-methacrylic acid copolymer ionomer resin available from Du
Pont-Mitsui Polychemicals Co., Ltd Himilan 1706: Zinc ion
neutralized ethylene-methacrylic acid copolymer ionomer resin
available from Du Pont-Mitsui Polychemicals Co., Ltd
[0113] As apparent from the results in Tables 4 to 6, the golf
balls comprising a spherical core and at least one cover layer
covering the spherical core, wherein the spherical core is formed
from a rubber composition containing (a) a base rubber, (b) an
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms and/or a metal salt thereof as a co-crosslinking agent, (c) a
crosslinking initiator, and (d) an acid and/or a salt thereof
travel a great flight distance on driver shots, respectively.
[0114] The golf ball of the present invention travels a great
flight distance on driver shots. This application is based on
Japanese Patent applications No. 2012-109717 filed on May 11, 2012
the contents of which are hereby incorporated by reference.
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