U.S. patent application number 13/606378 was filed with the patent office on 2013-03-14 for golf ball.
This patent application is currently assigned to DUNLOP SPORTS CO. LTD.. The applicant listed for this patent is Yoshiko MATSUYAMA. Invention is credited to Yoshiko MATSUYAMA.
Application Number | 20130065707 13/606378 |
Document ID | / |
Family ID | 47830352 |
Filed Date | 2013-03-14 |
United States Patent
Application |
20130065707 |
Kind Code |
A1 |
MATSUYAMA; Yoshiko |
March 14, 2013 |
GOLF BALL
Abstract
A golf ball 2 includes a spherical core 4, an inner mid layer 6
positioned outside the core 4, an outer mid layer 8 positioned
outside the inner mid layer 6, a reinforcing layer 10 positioned
outside the outer mid layer 8, and a cover 12 positioned outside
the reinforcing layer 10. When distances (%) from a central point
of the core 4 to nine points and JIS-C hardnesses at the nine
points, which nine points are obtained by dividing a region from
the central point of the core 4 to a surface of the core 4 at
intervals of 12.5% of a radius of the core 4, are plotted in a
graph, R.sup.2 of a linear approximation curve obtained by a
least-square method is equal to or greater than 0.95.
Inventors: |
MATSUYAMA; Yoshiko;
(Kobe-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
MATSUYAMA; Yoshiko |
Kobe-shi |
|
JP |
|
|
Assignee: |
DUNLOP SPORTS CO. LTD.
Kobe-shi
JP
|
Family ID: |
47830352 |
Appl. No.: |
13/606378 |
Filed: |
September 7, 2012 |
Current U.S.
Class: |
473/373 ;
473/376 |
Current CPC
Class: |
A63B 37/0003 20130101;
C08K 5/09 20130101; A63B 37/0045 20130101; B32B 27/40 20130101;
A63B 37/0064 20130101; A63B 37/0096 20130101; A63B 37/0031
20130101; A63B 37/0044 20130101; A63B 37/0062 20130101; B32B 7/02
20130101; B32B 25/16 20130101; A63B 37/0076 20130101; A63B 37/0033
20130101; B32B 25/08 20130101; A63B 37/0092 20130101 |
Class at
Publication: |
473/373 ;
473/376 |
International
Class: |
A63B 37/06 20060101
A63B037/06; A63B 37/02 20060101 A63B037/02 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 8, 2011 |
JP |
2011-195635 |
Claims
1. A golf ball comprising a spherical core, an inner mid layer
positioned outside the core, an outer mid layer positioned outside
the inner mid layer, and a cover positioned outside the outer mid
layer, wherein when distances (%) from a central point of the core
to nine points and JIS-C hardnesses at the nine points, which nine
points are obtained by dividing a region from the central point of
the core to a surface of the core at intervals of 12.5% of a radius
of the core, are plotted in a graph, R.sup.2 of a linear
approximation curve obtained by a least-square method is equal to
or greater than 0.95, a difference (H (100)-H(0)) between a JIS-C
hardness H(100) at the surface of the core and a JIS-C hardness
H(0) at the central point of the core is equal to or greater than
15, a Shore D hardness Hmo of the outer mid layer is greater than a
Shore D hardness Hmi of the inner mid layer, and a Shore D hardness
Hc of the cover is less than the hardness Hmo.
2. The golf ball according to claim 1, wherein a difference
(Hmo-Hc) between the hardness Hmo and the hardness Hc is equal to
or greater than 20 but equal to or less than 40.
3. The golf ball according to claim 1, wherein the hardness Hc is
less than the hardness Hmi.
4. The golf ball according to claim 3, wherein a difference
(Hmi-Hc) between the hardness Hmi and the hardness Hc is equal to
or greater than 10 but equal to or less than 30.
5. The golf ball according to claim 1, wherein the hardness H(100)
is greater than a JIS-C hardness of the cover.
6. The golf ball according to claim 5, wherein a difference between
the hardness H(100) and the JIS-C hardness of the cover is equal to
or greater than 10.
7. The golf ball according to claim 1, wherein a difference
(Hmo-Hmi) between the hardness Hmo and the hardness Hmi is equal to
or greater than 5.
8. The golf ball according to claim 1, wherein a JIS-C hardness of
the inner mid layer is greater than the hardness H(100), and a
difference between the JIS-C hardness of the inner mid layer and
the hardness H(100) is equal to or greater than 2.
9. The golf ball according to claim 1, wherein the core is obtained
by a rubber composition being crosslinked, the rubber composition
includes: (a) a base rubber; (b) a co-crosslinking agent; (c) a
crosslinking initiator; and (d) a carboxylic acid and/or a salt
thereof, the co-crosslinking agent (b) is: (b1) an
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms; and/or (b2) a metal salt of an .alpha.,.beta.-unsaturated
carboxylic acid having 3 to 8 carbon atoms, and when the rubber
composition includes the .alpha.,.beta.-unsaturated carboxylic acid
(b1), the rubber composition further includes (e) a metal
compound.
10. The golf ball according to claim 9, wherein the rubber
composition includes 100 parts by weight of the base rubber (a) and
15 parts by weight or greater but 50 parts by weight or less of the
co-crosslinking agent (b).
11. The golf ball according to claim 9, wherein the rubber
composition includes the metal salt (b2) of the
.alpha.,.beta.-unsaturated carboxylic acid.
12. The golf ball according to claim 9, wherein the rubber
composition includes 100 parts by weight of the base rubber (a) and
5 parts by weight or greater but 40 parts by weight or less of the
carboxylic acid and/or the salt thereof (d).
13. The golf ball according to claim 9, wherein the carboxylic acid
and/or the salt thereof (d) is a fatty acid and/or a fatty acid
salt.
14. The golf ball according to claim 9, wherein the carboxylic acid
and/or the salt thereof (d) is a zinc salt of a carboxylic
acid.
15. The golf ball according to claim 14, wherein the zinc salt is
zinc octoate, zinc laurate, zinc myristate, or zinc stearate.
16. The golf ball according to claim 9, wherein a carbon number of
a carboxylic acid component of the carboxylic acid and/or the salt
thereof (d) is equal to or greater than 4 but equal to or less than
30.
17. The golf ball according to claim 9, wherein the rubber
composition further includes (f) an organic sulfur compound.
18. The golf ball according to claim 17, wherein the organic sulfur
compound (f) is at least one member selected from the group
consisting of thiophenols, diphenyl disulfides, thionaphthols and
thiuram disulfides, and metal salts thereof.
19. The golf ball according to claim 17, wherein the rubber
composition includes 100 parts by weight of the base rubber (a) and
0.05 parts by weight or greater but 5 parts by weight or less of
the organic sulfur compound (f).
20. A golf ball comprising a spherical core, an inner mid layer
positioned outside the core, an outer mid layer positioned outside
the inner mid layer, and a cover positioned outside the outer mid
layer, wherein when distances (%) from a central point of the core
to nine points and JIS-C hardnesses at the nine points, which nine
points are obtained by dividing a region from the central point of
the core to a surface of the core at intervals of 12.5% of a radius
of the core, are plotted in a graph, R.sup.2 of a linear
approximation curve obtained by a least-square method is equal to
or greater than 0.95, the core is obtained by a rubber composition
being crosslinked, the inner mid layer is formed from a resin
composition of which a principal component of a base resin is an
ionomer resin, the outer mid layer is formed from a resin
composition of which a principal component of a base resin is an
ionomer resin, the cover is formed from a resin composition of
which a principal component of a base resin is a polyurethane, and
a Shore D hardness Hmo of the outer mid layer is greater than a
Shore D hardness Hmi of the inner mid layer.
Description
[0001] This application claims priority on Patent Application No.
2011-195635 filed in JAPAN on Sep. 8, 2011. The entire contents of
this Japanese Patent Application are hereby incorporated by
reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to golf balls. Specifically,
the present invention relates to golf balls that include a solid
core, an inner mid layer, an outer mid layer, and a cover.
[0004] 2. Description of the Related Art
[0005] Golf players' foremost requirement for golf balls is flight
performance. In particular, golf players place importance on flight
performance upon a shot with a driver. Flight performance
correlates with the resilience performance of a golf ball. When a
golf ball having excellent resilience performance is hit, the golf
ball flies at a high speed, thereby achieving a large flight
distance. Golf balls that include a core having excellent
resilience performance are disclosed in JP61-37178, JP2008-212681
(US2008/0214324), JP2008-523952 (US2006/0135287 and
US2007/0173607), and JP2009-119256 (US2009/0124757).
[0006] The core disclosed in JP61-37178 is obtained from a rubber
composition that includes a co-crosslinking agent and a
crosslinking activator. This publication discloses palmitic acid,
stearic acid, and myristic acid as the crosslinking activator.
[0007] The core disclosed in JP2008-212681 is obtained from a
rubber composition that includes an organic peroxide, a metal salt
of an .alpha.,.beta.-unsaturated carboxylic acid, and a copper salt
of a fatty acid.
[0008] The core disclosed in JP2008-523952 is obtained from a
rubber composition that includes a metal salt of an unsaturated
monocarboxylic acid, a free radical initiator, and a non-conjugated
diene monomer.
[0009] The core disclosed in JP2009-119256 is obtained from a
rubber composition that includes a polybutadiene whose vinyl
content is equal to or less than 2%, whose cis 1,4-bond content is
equal to or greater than 80%, and which has an active end modified
with an alkoxysilane compound.
[0010] An appropriate trajectory height is required in order to
achieve a large flight distance. A trajectory height depends on a
spin rate and a launch angle. In a golf ball that achieves a high
trajectory by a high spin rate, a flight distance is insufficient.
In a golf ball that achieves a high trajectory by a high launch
angle, a large flight distance is obtained. Use of an
outer-hard/inner-soft structure in a golf ball can achieve a low
spin rate and a high launch angle. Modifications regarding a
hardness distribution of a core are disclosed in JP6-154357 (U.S.
Pat. No. 5,403,010), JP2008-194471 (U.S. Pat. No. 7,344,455,
US2008/0194359, US2008/0194358, and US2008/0214325), and
JP2008-194473 (US2008/0194357 and US2008/0312008).
[0011] In the core disclosed in JP6-154357, a JIS-C hardness H1 at
the central point of the core is 58 to 73, a JIS-C hardness H2 in a
region that extends over a distance range from equal to or greater
than 5 mm to equal to or less than 10 mm from the central point of
the core is equal to or greater than 65 but equal to or less than
75, a JIS-C hardness H3 at a point located at a distance of 15 mm
from the central point is equal to or greater than 74 but equal to
or less than 82, and a JIS-C hardness H4 at the surface of the core
is equal to or greater than 76 but equal to or less than 84. The
hardness H2 is greater than the hardness H1, the hardness H3 is
greater than the hardness H2, and the hardness H4 is equal to or
greater than the hardness H3.
[0012] In the core disclosed in JP2008-194471, a Shore D hardness
at the central point of the core is equal to or greater than 30 but
equal to or less than 48, a Shore D hardness at a point located at
a distance of 4 mm from the central point is equal to or greater
than 34 but equal to or less than 52, a Shore D hardness at a point
located at a distance of 8 mm from the central point is equal to or
greater than 40 but equal to or less than 58, a Shore D hardness at
a point located at a distance of 12 mm from the central point is
equal to or greater than 43 but equal to or less than 61, a Shore D
hardness in a region that extends over a distance range from equal
to or greater than 2 mm to equal to or less than 3 mm from the
surface of the core is equal to or greater than 36 but equal to or
less than 54, and a Shore D hardness at the surface of the core is
equal to or greater than 41 but equal to or less than 59.
[0013] In the core disclosed in JP2008-194473, a Shore D hardness
at the central point of the core is equal to or greater than 25 but
equal to or less than 45, a Shore D hardness in a region that
extends over a distance range from equal to or greater than 5 mm to
equal to or less than 10 mm from the central point is equal to or
greater than 39 but equal to or less than 58, a Shore D hardness at
a point located at a distance of 15 mm from the central point is
equal to or greater than 36 but equal to or less than 55, and a
Shore D hardness at the surface of the core is equal to or greater
than 55 but equal to or less than 75.
[0014] JP2010-253268 (US2010/0273575) discloses a golf ball that
includes a core, an envelope layer, a mid layer, and a cover. In
the core, the hardness gradually increases from the central point
of the core to the surface of the core. The difference between a
JIS-C hardness at the surface and a JIS-C hardness at the central
point is equal to or greater than 15. The hardness of the cover is
greater than the hardness of the mid layer, and the hardness of the
mid layer is greater than the hardness of the envelope layer.
[0015] Golf players also place importance on spin performance of
golf balls. When a backspin rate is high, the run is short. It is
easy for golf players to cause a golf ball, to which backspin is
easily provided, to stop at a target point. When a sidespin rate is
high, the golf ball tends to curve. It is easy for golf players to
intentionally cause a golf ball, to which sidespin is easily
provided, to curve. A golf ball to which spin is easily provided
has excellent controllability. In particular, advanced golf players
place importance on controllability upon a shot with a short
iron.
[0016] As described above, when a golf ball having a high launch
angle and a low spin rate is hit with a driver, a large flight
distance is obtained. However, a golf ball having a low spin rate
has inferior controllability. Golf players desire achievement of
both a desired flight distance and desired controllability.
[0017] FIG. 3 shows a broken line of a hardness distribution of a
core of a conventional golf ball. The horizontal axis of the graph
indicates the ratio (%) of a distance from the central point of the
core to the radius of the core. The vertical axis of the graph
indicates a JIS-C hardness. FIG. 3 also shows a linear
approximation curve (approximate straight line) obtained by a
least-square method. In the core, a region in which the hardness
greatly increases from the central point of the core toward the
surface of the core, and a region in which the hardness does not
increase much, are present. The core has a high energy loss when
being hit. This hardness distribution impairs resilience
performance.
[0018] An object of the present invention is to provide a golf ball
having excellent flight performance upon a shot with a driver and
excellent controllability upon a shot with a short iron.
SUMMARY OF THE INVENTION
[0019] A golf ball according to the present invention comprises a
spherical core, an inner mid layer positioned outside the core, an
outer mid layer positioned outside the inner mid layer, and a cover
positioned outside the outer mid layer. When distances (%) from a
central point of the core to nine points and JIS-C hardnesses at
the nine points, which nine points are obtained by dividing a
region from the central point of the core to a surface of the core
at intervals of 12.5% of a radius of the core, are plotted in a
graph, R.sup.2 of a linear approximation curve obtained by a
least-square method is equal to or greater than 0.95. A difference
(H(100)-H(0)) between a JIS-C hardness H(100) at the surface of the
core and a JIS-C hardness H(0) at the central point of the core is
equal to or greater than 15. A Shore D hardness Hmo of the outer
mid layer is greater than a Shore D hardness Hmi of the inner mid
layer. A Shore D hardness Hc of the cover is less than the hardness
Hmo.
[0020] In the golf ball according to the present invention, a
hardness distribution is appropriate. In the golf ball, the energy
loss is low when being hit. The golf ball has excellent resilience
performance. When the golf ball is hit with a driver, the spin rate
is low. The great resilience performance and the low spin rate
achieve a large flight distance. When the golf ball is hit with a
short iron, the spin rate is high. The golf ball has excellent
controllability.
[0021] Preferably, the hardness Hc is less than the hardness Hmi.
Preferably, the hardness H(100) is greater than a hardness of the
cover. Preferably, a difference (Hmo-Hmi) between the hardness Hmo
and the hardness Hmi is equal to or greater than 5.
[0022] The core is obtained by a rubber composition being
crosslinked. Preferably, the rubber composition includes:
[0023] (a) a base rubber;
[0024] (b) a co-crosslinking agent;
[0025] (c) a crosslinking initiator; and
[0026] (d) a carboxylic acid and/or a salt thereof.
The co-crosslinking agent (b) is:
[0027] (b1) an .alpha.,.beta.-unsaturated carboxylic acid having 3
to 8 carbon atoms; and/or
[0028] (b2) a metal salt of an .alpha.,.beta.-unsaturated
carboxylic acid having 3 to 8 carbon atoms.
When the rubber composition includes the .alpha.,.beta.-unsaturated
carboxylic acid (b1), the rubber composition further includes (e) a
metal compound.
[0029] Preferably, the rubber composition includes 100 parts by
weight of the base rubber (a) and 15 parts by weight or greater but
50 parts by weight or less of the co-crosslinking agent (b).
Preferably, the rubber composition includes the metal salt (b2) of
the .alpha.,.beta.-unsaturated carboxylic acid.
[0030] Preferably, the rubber composition includes 100 parts by
weight of the base rubber (a) and 5 parts by weight or greater but
40 parts by weight or less of the carboxylic acid and/or the salt
thereof (d). Preferably, the carboxylic acid and/or the salt
thereof (d) is a fatty acid and/or a fatty acid salt. Preferably, a
carbon number of a carboxylic acid component of the carboxylic acid
and/or the salt thereof (d) is equal to or greater than 4 but equal
to or less than 30.
[0031] Preferably, the rubber composition further includes (f) an
organic sulfur compound. Preferably, the organic sulfur compound
(f) is at least one member selected from the group consisting of
thiophenols, diphenyl disulfides, thionaphthols and thiuram
disulfides, and metal salts thereof. Preferably, the rubber
composition includes 100 parts by weight of the base rubber (a) and
0.05 parts by weight or greater but 5 parts by weight or less of
the organic sulfur compound (f).
BRIEF DESCRIPTION OF THE DRAWINGS
[0032] FIG. 1 is a partially cutaway cross-sectional view of a golf
ball according to one embodiment of the present invention;
[0033] FIG. 2 is a line graph showing a hardness distribution of a
core of the golf ball in FIG. 1; and
[0034] FIG. 3 is a line graph showing a hardness distribution of a
core of a conventional golf ball.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0035] The following will describe in detail the present invention,
based on preferred embodiments with reference to the accompanying
drawings.
[0036] A golf ball 2 shown in FIG. 1 includes a spherical core 4,
an inner mid layer 6 positioned outside the core 4, an outer mid
layer 8 positioned outside the inner mid layer 6, a reinforcing
layer 10 positioned outside the outer mid layer 8, and a cover 12
positioned outside the reinforcing layer 10. On the surface of the
cover 12, a large number of dimples 14 are formed. Of the surface
of the golf ball 2, a part other than the dimples 14 is a land 16.
The golf ball 2 includes a paint layer and a mark layer on the
external side of the cover 12, but these layers are not shown in
the drawing.
[0037] The golf ball 2 has a diameter of 40 mm or greater but 45 mm
or less. From the standpoint of conformity to the rules established
by the United States Golf Association (USGA), the diameter is
preferably equal to or greater than 42.67 mm. In light of
suppression of air resistance, the diameter is preferably equal to
or less than 44 mm and more preferably equal to or less than 42.80
mm. The golf ball 2 has a weight of 40 g or greater but 50 g or
less. In light of attainment of great inertia, the weight is
preferably equal to or greater than 44 g and more preferably equal
to or greater than 45.00 g. From the standpoint of conformity to
the rules established by the USGA, the weight is preferably equal
to or less than 45.93 g.
[0038] FIG. 2 is a line graph showing a hardness distribution of
the core 4 of the golf ball 2 in FIG. 1. The horizontal axis of the
graph indicates the ratio (%) of a distance from the central point
of the core 4 to the radius of the core 4. The vertical axis of the
graph indicates a JIS-C hardness. Nine measuring points obtained by
dividing a region from the central point of the core 4 to the
surface of the core 4 at intervals of 12.5% of the radius of the
core 4 are plotted in the graph. The ratio of the distance from the
central point of the core 4 to each of these measuring points to
the radius of the core 4 is as follows.
[0039] First point: 0.0% (central point)
[0040] Second point: 12.5%
[0041] Third point: 25.0%
[0042] Fourth point: 37.5%
[0043] Fifth point: 50.0%
[0044] Sixth point: 62.5%
[0045] Seventh point: 75.0%
[0046] Eighth point: 87.5%
[0047] Ninth point: 100.0% (surface)
[0048] Hardnesses at the first to eighth points are measured by
pressing a JIS-C type hardness scale against a cut plane of the
core 4 that has been cut into two halves. A hardness at the ninth
point is measured by pressing the JIS-C type hardness scale against
the surface of the core 4. For the measurement, an automated rubber
hardness measurement machine (trade name "P1", manufactured by
Kobunshi Keiki Co., Ltd.), to which this hardness scale is mounted,
is used.
[0049] FIG. 2 also shows a linear approximation curve obtained by a
least-square method on the basis of the distances and the
hardnesses of the nine measuring points. As is clear from the
comparison of FIGS. 2 and 3, the broken line does not greatly
deviate from the linear approximation curve in FIG. 2. In other
words, the broken line has a shape close to the linear
approximation curve. In the core 4, the hardness linearly increases
from its central point to its surface. When the core 4 is hit with
a driver, the energy loss is low. The core 4 has excellent
resilience performance. When the golf ball 2 is hit with a driver,
the flight distance is large.
[0050] In the core 4, R.sup.2 of the linear approximation curve
obtained by the least-square method is equal to or greater than
0.95. R.sup.2 is an index indicating the linearity of the broken
line. For the core 4 for which R.sup.2 is equal to or greater than
0.95, the shape of the broken line of the hardness distribution is
close to a straight line. The core 4 for which R.sup.2 is equal to
or greater than 0.95 has excellent resilience performance. R.sup.2
is more preferably equal to or greater than 0.96 and particularly
preferably equal to or greater than 0.97. R.sup.2 is calculated by
squaring a correlation coefficient R. The correlation coefficient R
is calculated by dividing the covariance of the distance (%) from
the central point and the hardness (JIS-C) by the standard
deviation of the distance (%) from the central point and the
standard deviation of the hardness (JIS-C).
[0051] In the present invention, a JIS-C hardness at a measuring
point whose ratio of the distance from the central point of the
core 4 to the radius of the core 4 is x % is represented by H(x).
The hardness at the central point of the core 4 is represented by
H(0), and the surface hardness of the core 4 is represented by
H(100). The difference (H(100)-H(0)) between the surface hardness
H(100) and the central hardness H(0) is equal to or greater than
15. The difference is great. In other words, the core 4 has an
outer-hard/inner-soft structure. When the core 4 is hit with a
driver, the recoil (torsional return) is great, and thus spin is
suppressed. The core 4 contributes to the flight performance of the
golf ball 2. In light of flight performance, the difference
(H(100)-H(0)) is more preferably equal to or greater than 25 and
particularly preferably equal to or greater than 30. From the
standpoint that the core 4 can easily be formed, the difference
(H(100)-H(0)) is preferably equal to or less than 50.
[0052] The core 4 is obtained by crosslinking a rubber composition.
The rubber composition includes:
[0053] (a) a base rubber;
[0054] (b) a co-crosslinking agent;
[0055] (c) a crosslinking initiator; and
[0056] (d) a carboxylic acid and/or a salt thereof.
[0057] Examples of the base rubber (a) include polybutadienes,
polyisoprenes, styrene-butadiene copolymers,
ethylene-propylene-diene copolymers, and natural rubbers. In light
of resilience performance, polybutadienes are preferred. When a
polybutadiene and another rubber are used in combination, it is
preferred that the polybutadiene is included as a principal
component. Specifically, the proportion of the polybutadiene to the
entire base rubber is preferably equal to or greater than 50% by
weight and more preferably equal to or greater than 80% by weight.
The proportion of cis-1,4 bonds in the polybutadiene is preferably
equal to or greater than 40% by weight and more preferably equal to
or greater than 80% by weight.
[0058] A polybutadiene in which the proportion of 1,2-vinyl bonds
is equal to or less than 2.0% by weight is preferred. The
polybutadiene can contribute to the resilience performance of the
core 4. In this respect, the proportion of 1,2-vinyl bonds is
preferably equal to or less than 1.7% by weight and particularly
preferably equal to or less than 1.5% by weight.
[0059] From the standpoint that a polybutadiene having a low
proportion of 1,2-vinyl bonds and excellent polymerization activity
is obtained, a polybutadiene synthesized with a
rare-earth-element-containing catalyst is preferred. In particular,
a polybutadiene synthesized with a catalyst containing neodymium,
which is a lanthanum-series rare earth element compound, is
preferred.
[0060] The polybutadiene has a Mooney viscosity
(ML.sub.1+4(100.degree. C.)) of preferably 30 or greater, more
preferably 32 or greater, and particularly preferably 35 or
greater. The Mooney viscosity (ML.sub.1+4(100.degree. C.)) is
preferably equal to or less than 140, more preferably equal to or
less than 120, even more preferably equal to or less than 100, and
particularly preferably equal to or less than 80. The Mooney
viscosity (ML.sub.1+4(100.degree. C.)) is measured according to the
standards of "JIS K6300". The measurement conditions are as
follows.
[0061] Rotor: L rotor
[0062] Preheating time: 1 minute
[0063] Rotating time of rotor: 4 minutes
[0064] Temperature: 100.degree. C.
[0065] In light of workability, the polybutadiene has a molecular
weight distribution (Mw/Mn) of preferably 2.0 or greater, more
preferably 2.2 or greater, even more preferably 2.4 or greater, and
particularly preferably 2.6 or greater. In light of resilience
performance, the molecular weight distribution (Mw/Mn) is
preferably equal to or less than 6.0, more preferably equal to or
less than 5.0, even more preferably equal to or less than 4.0, and
particularly preferably equal to or less than 3.4. The molecular
weight distribution (Mw/Mn) is calculated by dividing the weight
average molecular weight Mw by the number average molecular weight
Mn.
[0066] The molecular weight distribution is measured by gel
permeation chromatography ("HLC-8120GPC" manufactured by Tosoh
Corporation). The measurement conditions are as follows.
[0067] Detector: differential refractometer
[0068] Column: GMHHXL (manufactured by Tosoh Corporation)
[0069] Column temperature: 40.degree. C.
[0070] Mobile phase: tetrahydrofuran
The molecular weight distribution is calculated as a value obtained
by conversion using polystyrene standard.
[0071] The co-crosslinking agent (b) is:
[0072] (b1) an .alpha.,.beta.-unsaturated carboxylic acid having 3
to 8 carbon atoms; and/or
[0073] (b2) a metal salt of an .alpha.,.beta.-unsaturated
carboxylic acid having 3 to 8 carbon atoms.
[0074] The rubber composition may include only the
.alpha.,.beta.-unsaturated carboxylic acid (b1) or only the metal
salt (b2) of the .alpha.,.beta.-unsaturated carboxylic acid as the
co-crosslinking agent (b). The rubber composition may include both
the .alpha.,.beta.-unsaturated carboxylic acid (b1) and the metal
salt (b2) of the .alpha.,.beta.-unsaturated carboxylic acid as the
co-crosslinking agent (b).
[0075] The metal salt (b2) of the .alpha.,.beta.-unsaturated
carboxylic acid graft-polymerizes with the molecular chain of the
base rubber, thereby crosslinking the rubber molecules. When the
rubber composition includes the .alpha.,.beta.-unsaturated
carboxylic acid (b1), the rubber composition preferably further
includes a metal compound (e). The metal compound (e) reacts with
the .alpha.,.beta.-unsaturated carboxylic acid (b1) in the rubber
composition. A salt obtained by this reaction graft-polymerizes
with the molecular chain of the base rubber.
[0076] Examples of the metal compound (e) include metal hydroxides
such as magnesium hydroxide, zinc hydroxide, calcium hydroxide,
sodium hydroxide, lithium hydroxide, potassium hydroxide, and
copper hydroxide; metal oxides such as magnesium oxide, calcium
oxide, zinc oxide, and copper oxide; and metal carbonates such as
magnesium carbonate, zinc carbonate, calcium carbonate, sodium
carbonate, lithium carbonate, and potassium carbonate. A compound
that includes a bivalent metal is preferred. The compound that
includes the bivalent metal reacts with the co-crosslinking agent
(b) to form metal crosslinks. The metal compound (e) is
particularly preferably a zinc compound. Two or more metal
compounds may be used in combination.
[0077] Examples of the .alpha.,.beta.-unsaturated carboxylic acids
include acrylic acid, methacrylic acid, fumaric acid, maleic acid,
and crotonic acid. Examples of the metal component in the metal
salt (b2) of the .alpha.,.beta.-unsaturated carboxylic acid include
sodium ion, potassium ion, lithium ion, magnesium ion, calcium ion,
zinc ion, barium ion, cadmium ion, aluminum ion, tin ion, and
zirconium ion. The metal salt (b2) of the
.alpha.,.beta.-unsaturated carboxylic acid may include two or more
types of ions. From the standpoint that metal crosslinks are likely
to occur between the rubber molecules, bivalent metal ions such as
magnesium ion, calcium ion, zinc ion, barium ion, and cadmium ion
are preferred. The metal salt (b2) of the
.alpha.,.beta.-unsaturated carboxylic acid is particularly
preferably zinc acrylate.
[0078] In light of resilience performance of the golf ball 2, the
amount of the co-crosslinking agent (b) is preferably equal to or
greater than 15 parts by weight and particularly preferably equal
to or greater than 20 parts by weight, per 100 parts by weight of
the base rubber. In light of feel at impact, the amount is
preferably equal to or less than 50 parts by weight, more
preferably equal to or less than 45 parts by weight, and
particularly preferably equal to or less than 40 parts by weight,
per 100 parts by weight of the base rubber.
[0079] The crosslinking initiator (c) is preferably an organic
peroxide. The organic peroxide contributes to the resilience
performance of the golf ball 2. Examples of preferable organic
peroxides include 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.
In light of versatility, dicumyl peroxide is preferred.
[0080] In light of resilience performance of the golf ball 2, the
amount of the crosslinking initiator (c) is preferably equal to or
greater than 0.2 parts by weight and particularly preferably equal
to or greater than 0.5 parts by weight, per 100 parts by weight of
the base rubber. In light of feel at impact and durability of the
golf ball 2, the amount is preferably equal to or less than 5.0
parts by weight and particularly preferably equal to or less than
2.5 parts by weight, per 100 parts by weight of the base
rubber.
[0081] In the present invention, the co-crosslinking agent (b) is
not included in the concept of the carboxylic acid and/or the salt
thereof (d). The carboxylic acid component of the carboxylic acid
and/or the salt thereof (d) has a carboxyl group. The carboxylic
acid component exchanges a cationic component with the
co-crosslinking agent (b). It is inferred that the carboxylic acid
and/or the salt thereof (d) breaks the metal crosslinks by the
co-crosslinking agent (b) at the central portion of the core 4
during heating and forming of the core 4.
[0082] The carbon number of the carboxylic acid component of the
carboxylic acid and/or the salt thereof (d) is preferably equal to
or greater than 4 but equal to or less than 30, and is particularly
preferably equal to or greater than 8 but equal to or less than 30.
Examples of the carboxylic acid include aliphatic carboxylic acids
(fatty acids) and aromatic carboxylic acids. Fatty acids and salts
thereof are preferred.
[0083] The rubber composition may include a saturated fatty acid or
a salt thereof, or may include an unsaturated fatty acid or a salt
thereof. The saturated fatty acid and the salt thereof are
preferred.
[0084] Examples of fatty acids include butyric acid (C4), valeric
acid (C5), caproic acid (C6), enanthic acid (C7), caprylic acid
(octanoic acid) (C8), pelargonic acid (C9), capric acid (decanoic
acid) (C10), lauric acid (C12), myristic acid (C14), myristoleic
acid (C14), pentadecylic acid (C15), palmitic acid (C16),
palmitoleic acid (C16), margaric acid (C17), stearic acid (C18),
elaidic acid (C18), vaccenic acid (C18), oleic acid (C18), linolic
acid (C18), linolenic acid (C18), 12-hydroxystearic acid (C18),
arachidic acid (C20), gadoleic acid (C20), arachidonic acid (C20),
eicosenoic acid (C20), behenic acid (C22), erucic acid (C22),
lignoceric acid (C24), nervonic acid (C24), cerotic acid (C26),
montanic acid (C28), and melissic acid (C30). Two or more fatty
acids may be used in combination.
[0085] An aromatic carboxylic acid has an aromatic ring and a
carboxyl group. Examples of aromatic carboxylic acids include
benzoic acid, phthalic acid, isophthalic acid, terephthalic acid,
hemimellitic acid (benzene-1,2,3-tricarboxylic acid), trimellitic
acid (benzene-1,2,4-tricarboxylic acid), trimesic acid
(benzene-1,3,5-tricarboxylic acid), mellophanic acid
(benzene-1,2,3,4-tetracarboxylic acid), prehnitic acid
(benzene-1,2,3,5-tetracarboxylic acid), pyromellitic acid
(benzene-1,2,4,5-tetracarboxylic acid), mellitic acid (benzene
hexacarboxylic acid), diphenic acid (biphenyl-2,2'-dicarboxylic
acid), toluic acid (methylbenzoic acid), xylic acid, prehnitylic
acid (2,3,4-trimethylbenzoic acid), .gamma.-isodurylic acid
(2,3,5-trimethylbenzoic acid), durylic acid (2,4,5-trimethylbenzoic
acid), .beta.-isodurylic acid (2,4,6-trimethylbenzoic acid),
.alpha.-isodurylic acid (3,4,5-trimethylbenzoic acid), cuminic acid
(4-isopropylbenzoic acid), uvitic acid (5-methylisophthalic acid),
.alpha.-toluic acid (phenylacetic acid), hydratropic acid
(2-phenylpropanoic acid), and hydrocinnamic acid (3-phenylpropanoic
acid).
[0086] The rubber composition may include an aromatic carboxylic
acid substituted with a hydroxyl group, an alkoxy group, or an oxo
group, or a salt thereof. Examples of this carboxylic acid can
include salicylic acid (2-hydroxybenzoic acid), anisic acid
(methoxybenzoic acid), cresotinic acid (hydroxy(methyl) benzoic
acid), o-homosalicylic acid (2-hydroxy-3-methylbenzoic acid),
m-homosalicylic acid (2-hydroxy-4-methylbenzoic acid),
p-homosalicylic acid (2-hydroxy-5-methylbenzoic acid),
o-pyrocatechuic acid (2,3-dihydroxybenzoic acid), p-resorcylic acid
(2,4-dihydroxybenzoic acid), .gamma.-resorcylic acid
(2,6-dihydroxybenzoic acid), protocatechuic acid
(3,4-dihydroxybenzoic acid), .alpha.-resorcylic acid
(3,5-dihydroxybenzoic acid), vanillic acid
(4-hydroxy-3-methoxybenzoic acid), isovanillic acid
(3-hydroxy-4-methoxybenzoic acid), veratric acid
(3,4-dimethoxybenzoic acid), o-veratric acid (2,3-dimethoxybenzoic
acid), orsellinic acid (2,4-dihydroxy-6-methylbenzoic acid),
m-hemipinic acid (4,5-dimethoxyphthalic acid), gallic acid
(3,4,5-trihydroxybenzoic acid), syringic acid
(4-hydroxy-3,5-dimethoxybenzoic acid), asaronic acid
(2,4,5-trimethoxybenzoic acid), mandelic acid
(hydroxy(phenyl)acetic acid), vanillylmandelic acid
(hydroxy(4-hydroxy-3-methoxyphenyl)acetic acid), homoanisic acid
((4-methoxyphenyl)acetic acid), homogentisic acid
((2,5-dihydroxyphenyl)acetic acid), homoprotocatechuic acid
((3,4-dihydroxyphenyl)acetic acid), homovanillic acid
((4-hydroxy-3-methoxyphenyl)acetic acid), homoisovanillic acid
((3-hydroxy-4-methoxyphenyl)acetic acid), homoveratric acid
((3,4-dimethoxyphenyl)acetic acid), o-homoveratric acid
((2,3-dimethoxyphenyl)acetic acid), homophthalic acid
(2-(carboxymethyl)benzoic acid), homoisophthalic acid
(3-(carboxymethyl)benzoic acid), homoterephthalic acid
(4-(carboxymethyl)benzoic acid), phthalonic acid
(2-(carboxycarbonyl)benzoic acid), isophthalonic acid
(3-(carboxycarbonyl)benzoic acid), terephthalonic acid
(4-(carboxycarbonyl)benzoic acid), benzilic acid
(hydroxydiphenylacetic acid), atrolactic acid
(2-hydroxy-2-phenylpropanoic acid), tropic acid
(3-hydroxy-2-phenylpropanoic acid), melilotic acid
(3-(2-hydroxyphenyl)propanoic acid), phloretic acid
(3-(4-hydroxyphenyl)propanoic acid), hydrocaffeic acid
(3-(3,4-dihydroxyphenyl)propanoic acid), hydroferulic acid
(3-(4-hydroxy-3-methoxyphenyl)propanoic acid), hydroisoferulic acid
(3-(3-hydroxy-4-methoxyphenyl)propanoic acid), p-coumaric acid
(3-(4-hydroxyphenyl)acrylic acid), umbellic acid
(3-(2,4-dihydroxyphenyl)acrylic acid), caffeic acid
(3-(3,4-dihydroxyphenyl)acrylic acid), ferulic acid
(3-(4-hydroxy-3-methoxyphenyl)acrylic acid), isoferulic acid
(3-(3-hydroxy-4-methoxyphenyl)acrylic acid), and sinapic acid
(3-(4-hydroxy-3,5-dimethoxyphenyl)acrylic acid).
[0087] The cationic component of the carboxylate is a metal ion or
an organic cation. Examples of the metal ion include sodium ion,
potassium ion, lithium ion, silver ion, magnesium ion, calcium ion,
zinc ion, barium ion, cadmium ion, copper ion, cobalt ion, nickel
ion, manganese ion, aluminum ion, iron ion, tin ion, zirconium ion,
and titanium ion. Two or more types of ions may be used in
combination.
[0088] The organic cation has a carbon chain. Examples of the
organic cation include organic ammonium ions. Examples of organic
ammonium ions include primary ammonium ions such as stearylammonium
ion, hexylammonium ion, octylammonium ion, and 2-ethylhexylammonium
ion; secondary ammonium ions such as dodecyl(lauryl)ammonium ion,
and octadecyl(stearyl)ammonium ion; tertiary ammonium ions such as
trioctylammonium ion; and quaternary ammonium ions such as
dioctyldimethylammonium ion, and distearyldimethylammonium ion. Two
or more types of organic cations may be used in combination.
[0089] Examples of preferable carboxylates include a potassium
salt, a magnesium salt, an aluminum salt, a zinc salt, an iron
salt, a copper salt, a nickel salt, or a cobalt salt of octanoic
acid, lauric acid, myristic acid, palmitic acid, stearic acid,
behenic acid, or oleic acid. Zinc salts of carboxylic acids are
preferred. Zinc octoate, zinc laurate, zinc myristate, and zinc
stearate are particularly preferred.
[0090] In light of linearity of the hardness distribution of the
core 4, the amount of the carboxylic acid and/or the salt thereof
(d) is preferably equal to or greater than 5.0 parts by weight,
more preferably equal to or greater than 7.5 parts by weight, even
more preferably equal to or greater than 10.0 parts by weight, and
particularly preferably equal to or greater than 12.0 parts by
weight, per 100 parts by weight of the base rubber. In light of
resilience performance, the amount is preferably equal to or less
than 40 parts by weight, more preferably equal to or less than 30
parts by weight, and particularly preferably equal to or less than
20 parts by weight, per 100 parts by weight of the base rubber.
[0091] When the rubber composition includes only a carboxylate as
the carboxylic acid and/or the salt thereof (d), the amount of the
carboxylate is preferably equal to or greater than 10 parts by
weight and particularly preferably equal to or greater than 12
parts by weight, per 100 parts by weight of the base rubber. The
amount is preferably less than 40 parts by weight, more preferably
equal to or less than 30 parts by weight, and particularly
preferably equal to or less than 25 parts by weight, per 100 parts
by weight of the base rubber.
[0092] As the co-crosslinking agent (b), zinc acrylate is
preferably used. Zinc acrylate whose surface is coated with stearic
acid or zinc stearate for the purpose of improving dispersibility
to rubber is present. When the rubber composition includes this
zinc acrylate, the stearic acid and the zinc stearate serve as the
carboxylic acid and/or the salt thereof (d). For example, when the
rubber composition includes 25 parts by weight of zinc acrylate
that includes 10% by weight of stearic acid, the amount of the
stearic acid is regarded as 2.5 parts by weight, and the amount of
the zinc acrylate is regarded as 22.5 parts by weight.
[0093] The rubber composition preferably further includes an
organic sulfur compound (f). The organic sulfur compound (f) can
contribute to control of: the linearity of the hardness
distribution of the core 4; and the degree of the
outer-hard/inner-soft structure. An example of the organic sulfur
compound (f) is an organic compound having a thiol group or a
polysulfide linkage having 2 to 4 sulfur atoms. A metal salt of
this organic compound is also included in the organic sulfur
compound (f). Examples of the organic sulfur compound (f) include
aliphatic compounds such as aliphatic thiols, aliphatic
thiocarboxylic acids, aliphatic dithiocarboxylic acids, and
aliphatic polysulfides; heterocyclic compounds; alicyclic compounds
such as alicyclic thiols, alicyclic thiocarboxylic acids, alicyclic
dithiocarboxylic acids, and alicyclic polysulfides; and aromatic
compounds. Specific examples of the organic sulfur compound (f)
include thiophenols, thionaphthols, polysulfides, thiocarboxylic
acids, dithiocarboxylic acids, sulfenamides, thiurams,
dithiocarbamates, and thiazoles. Preferable organic sulfur
compounds are thiophenols, polysulfides having 2 to 4 sulfur atoms,
thionaphthols, thiurams, and metal salts thereof.
[0094] Specific examples of the organic sulfur compound (f) are
represented by the following chemical formulas (1) to (4).
##STR00001##
[0095] In the chemical formula (1), R1 to R5 each represent H or a
substituent.
##STR00002##
[0096] In the chemical formula (2), R1 to R10 each represent H or a
substituent.
##STR00003##
[0097] In the chemical formula (3), R1 to R5 each represent H or a
substituent, and M1 represents a monovalent metal atom.
##STR00004##
[0098] In the chemical formula (4), R1 to R10 each represent H or a
substituent, and M2 represents a bivalent metal atom.
[0099] In the formulas (1) to (4), each substituent is at least one
group selected from the group consisting of a halogen group (F, Cl,
Br, I), an alkyl group, a carboxyl group (--COOH), an ester
(--COOR) of a carboxyl group, a formyl group (--CHO), an acyl group
(--COR), a carbonyl halide group (--COX), a sulfo group
(--SO.sub.3H), an ester (--SO.sub.3R) of a sulfo group, a sulfonyl
halide group (--SO.sub.2X), a sulfino group (--SO.sub.2H), an
alkylsulfinyl group (--SOR), a carbamoyl group (--CONH.sub.2), an
alkyl halide group, a cyano group (--CN), and an alkoxy group
(--OR).
[0100] Examples of the organic sulfur compound represented by the
chemical formula (1) include thiophenol; thiophenols substituted
with halogen groups, such as 4-fluorothiophenol,
2,5-difluorothiophenol, 2,4,5-trifluorothiophenol,
2,4,5,6-tetrafluorothiophenol, pentafluorothiophenol,
2-chlorothiophenol, 4-chlorothiophenol, 2,4-dichlorothiophenol,
2,5-dichlorothiophenol, 2,6-dichlorothiophenol,
2,4,5-trichlorothiophenol, 2,4,5,6-tetrachlorothiophenol,
pentachlorothiophenol, 4-bromothiophenol, 2,5-dibromothiophenol,
2,4,5-tribromothiophenol, 2,4,5,6-tetrabromothiophenol,
pentabromothiophenol, 4-iodothiophenol, 2,5-diiodothiophenol,
2,4,5-triiodothiophenol, 2,4,5,6-tetraiodothiophenol, and
pentaiodothiophenol; thiophenols substituted with alkyl groups,
such as 4-methylthiophenol, 2,4,5-trimethylthiophenol,
pentamethylthiophenol, 4-t-butylthiophenol,
2,4,5-tri-t-butylthiophenol, and penta-t-butylthiophenol;
thiophenols substituted with carboxyl groups, such as
4-carboxythiophenol, 2,4,6-tricarboxythiophenol, and
pentacarboxythiophenol; thiophenols substituted with alkoxycarbonyl
groups, such as 4-methoxycarbonylthiophenol,
2,4,6-trimethoxycarbonylthiophenol, and
pentamethoxycarbonylthiophenol; thiophenols substituted with formyl
groups, such as 4-formylthiophenol, 2,4,6-triformylthiophenol, and
pentaformylthiophenol; thiophenols substituted with acyl groups,
such as 4-acetylthiophenol, 2,4,6-triacetylthiophenol, and
pentaacetylthiophenol; thiophenols substituted with carbonyl halide
groups, such as 4-chlorocarbonylthiophenol,
2,4,6-tri(chlorocarbonyl)thiophenol, and
penta(chlorocarbonyl)thiophenol; thiophenols substituted with sulfo
groups, such as 4-sulfothiophenol, 2,4,6-trisulfothiophenol, and
pentasulfothiophenol; thiophenols substituted with alkoxysulfonyl
groups, such as 4-methoxysulfonylthiophenol,
2,4,6-trimethoxysulfonylthiophenol, and
pentamethoxysulfonylthiophenol; thiophenols substituted with
sulfonyl halide groups, such as 4-chlorosulfonylthiophenol,
2,4,6-tri(chlorosulfonyl)thiophenol, and
penta(chlorosulfonyl)thiophenol; thiophenols substituted with
sulfino groups, such as 4-sulfinothiophenol,
2,4,6-trisulfinothiophenol, and pentasulfinothiophenol; thiophenols
substituted with alkylsulfinyl groups, such as
4-methylsulfinylthiophenol, 2,4,6-tri(methylsulfinyl)thiophenol,
and penta(methylsulfinyl)thiophenol; thiophenols substituted with
carbamoyl groups, such as 4-carbamoylthiophenol,
2,4,6-tricarbamoylthiophenol, and pentacarbamoylthiophenol;
thiophenols substituted with alkyl halide groups, such as
4-trichloromethylthiophenol, 2,4,6-tri(trichloromethyl)thiophenol,
and penta(trichloromethyl)thiophenol; thiophenols substituted with
cyano groups, such as 4-cyanothiophenol, 2,4,6-tricyanothiophenol,
and pentacyanothiophenol; and thiophenols substituted with alkoxy
groups, such as 4-methoxythiophenol, 2,4,6-trimethoxythiophenol,
and pentamethoxythiophenol. Each of these thiophenols is
substituted with one type of substituent.
[0101] Another example of the organic sulfur compound represented
by the chemical formula (1) is a compound substituted with at least
one type of the above substituents and another substituent.
Examples of the other substituent include a nitro group
(--NO.sub.2), an amino group (--NH.sub.2), a hydroxyl group (--OH),
and a phenylthio group (--SPh). Specific examples of the compound
include 4-chloro-2-nitrothiophenol, 4-chloro-2-aminothiophenol,
4-chloro-2-hydroxythiophenol, 4-chloro-2-phenylthiothiophenol,
4-methyl-2-nitrothiophenol, 4-methyl-2-aminothiophenol,
4-methyl-2-hydroxythiophenol, 4-methyl-2-phenylthiothiophenol,
4-carboxy-2-nitrothiophenol, 4-carboxy-2-aminothiophenol,
4-carboxy-2-hydroxythiophenol, 4-carboxy-2-phenylthiothiophenol,
4-methoxycarbonyl-2-nitrothiophenol,
4-methoxycarbonyl-2-aminothiophenol,
4-methoxycarbonyl-2-hydroxythiophenol,
4-methoxycarbonyl-2-phenylthiothiophenol,
4-formyl-2-nitrothiophenol, 4-formyl-2-aminothiophenol,
4-formyl-2-hydroxythiophenol, 4-formyl-2-phenylthiothiophenol,
4-acetyl-2-nitrothiophenol, 4-acetyl-2-aminothiophenol,
4-acetyl-2-hydroxythiophenol, 4-acetyl-2-phenylthiothiophenol,
4-chlorocarbonyl-2-nitrothiophenol,
4-chlorocarbonyl-2-aminothiophenol,
4-chlorocarbonyl-2-hydroxythiophenol,
4-chlorocarbonyl-2-phenylthiothiophenol, 4-sulfo-2-nitrothiophenol,
4-sulfo-2-aminothiophenol, 4-sulfo-2-hydroxythiophenol,
4-sulfo-2-phenylthiothiophenol,
4-methoxysulfonyl-2-nitrothiophenol,
4-methoxysulfonyl-2-aminothiophenol,
4-methoxysulfonyl-2-hydroxythiophenol,
4-methoxysulfonyl-2-phenylthiothiophenol,
4-chlorosulfonyl-2-nitrothiophenol,
4-chlorosulfonyl-2-aminothiophenol,
4-chlorosulfonyl-2-hydroxythiophenol,
4-chlorosulfonyl-2-phenylthiothiophenol,
4-sulfino-2-nitrothiophenol, 4-sulfino-2-aminothiophenol,
4-sulfino-2-hydroxythiophenol, 4-sulfino-2-phenylthiothiophenol,
4-methylsulfinyl-2-nitrothiophenol,
4-methyl-2-aminosulfinylthiophenol,
4-methylsulfinyl-2-hydroxythiophenol,
4-methylsulfinyl-2-phenylthiothiophenol,
4-carbamoyl-2-nitrothiophenol, 4-carbamoyl-2-aminothiophenol,
4-carbamoyl-2-hydroxythiophenol,
4-carbamoyl-2-phenylthiothiophenol,
4-trichloromethyl-2-nitrothiophenol,
4-trichloromethyl-2-aminothiophenol,
4-trichloromethyl-2-hydroxythiophenol,
4-trichloromethyl-2-phenylthiothiophenol,
4-cyano-2-nitrothiophenol, 4-cyano-2-aminothiophenol,
4-cyano-2-hydroxythiophenol, 4-cyano-2-phenylthiothiophenol,
4-methoxy-2-nitrothiophenol, 4-methoxy-2-aminothiophenol,
4-methoxy-2-hydroxythiophenol, and
4-methoxy-2-phenylthiothiophenol.
[0102] Still another example of the organic sulfur compound
represented by the chemical formula (1) is a compound substituted
with two or more types of substituents. Specific examples of the
compound include 4-acetyl-2-chlorothiophenol,
4-acetyl-2-methylthiophenol, 4-acetyl-2-carboxythiophenol,
4-acetyl-2-methoxycarbonylthiophenol, 4-acetyl-2-formylthiophenol,
4-acetyl-2-chlorocarbonylthiophenol, 4-acetyl-2-sulfothiophenol,
4-acetyl-2-methoxysulfonylthiophenol,
4-acetyl-2-chlorosulfonylthiophenol, 4-acetyl-2-sulfinothiophenol,
4-acetyl-2-methylsulfinylthiophenol,
4-acetyl-2-carbamoylthiophenol,
4-acetyl-2-trichloromethylthiophenol, 4-acetyl-2-cyanothiophenol,
and 4-acetyl-2-methoxythiophenol.
[0103] Examples of the organic sulfur compound represented by the
chemical formula (2) include diphenyl disulfide; diphenyl
disulfides substituted with halogen groups, such as
bis(4-fluorophenyl)disulfide, bis(2,5-difluorophenyl)disulfide,
bis(2,4,5-trifluorophenyl)disulfide,
bis(2,4,5,6-tetrafluorophenyl)disulfide,
bis(pentafluorophenyl)disulfide, bis(4-chlorophenyl)disulfide,
bis(2,5-dichlorophenyl)disulfide,
bis(2,4,5-trichlorophenyl)disulfide,
bis(2,4,5,6-tetrachlorophenyl)disulfide,
bis(pentachlorophenyl)disulfide, bis(4-bromophenyl)disulfide,
bis(2,5-dibromophenyl)disulfide,
bis(2,4,5-tribromophenyl)disulfide,
bis(2,4,5,6-tetrabromophenyl)disulfide,
bis(pentabromophenyl)disulfide, bis(4-iodophenyl)disulfide,
bis(2,5-diiodophenyl)disulfide, bis(2,4,5-triiodophenyl)disulfide,
bis(2,4,5,6-tetraiodophenyl)disulfide, and
bis(pentaiodophenyl)disulfide; diphenyl disulfides substituted with
alkyl groups, such as bis(4-methylphenyl)disulfide,
bis(2,4,5-trimethylphenyl)disulfide,
bis(pentamethylphenyl)disulfide, bis(4-t-butylphenyl)disulfide,
bis(2,4,5-tri-t-butylphenyl)disulfide, and
bis(penta-t-butylphenyl)disulfide; diphenyl disulfides substituted
with carboxyl groups, such as bis(4-carboxyphenyl)disulfide,
bis(2,4,6-tricarboxyphenyl)disulfide, and
bis(pentacarboxyphenyl)disulfide; diphenyl disulfides substituted
with alkoxycarbonyl groups, such as
bis(4-methoxycarbonylphenyl)disulfide,
bis(2,4,6-trimethoxycarbonylphenyl)disulfide, and
bis(pentamethoxycarbonylphenyl)disulfide; diphenyl disulfides
substituted with formyl groups, such as
bis(4-formylphenyl)disulfide, bis(2,4,6-triformylphenyl)disulfide,
and bis(pentaformylphenyl)disulfide; diphenyl disulfides
substituted with acyl groups, such as bis(4-acetylphenyl)disulfide,
bis(2,4,6-triacetylphenyl)disulfide, and
bis(pentaacetylphenyl)disulfide; diphenyl disulfides substituted
with carbonyl halide groups, such as
bis(4-chlorocarbonylphenyl)disulfide,
bis(2,4,6-tri(chlorocarbonyl)phenyl)disulfide, and
bis(penta(chlorocarbonyl)phenyl)disulfide; diphenyl disulfides
substituted with sulfo groups, such as bis(4-sulfophenyl)disulfide,
bis(2,4,6-trisulfophenyl)disulfide, and
bis(pentasulfophenyl)disulfide; diphenyl disulfides substituted
with alkoxysulfonyl groups, such as
bis(4-methoxysulfonylphenyl)disulfide,
bis(2,4,6-trimethoxysulfonylphenyl)disulfide, and
bis(pentamethoxysulfonylphenyl)disulfide; diphenyl disulfides
substituted with sulfonyl halide groups, such as
bis(4-chlorosulfonylphenyl)disulfide,
bis(2,4,6-tri(chlorosulfonyl)phenyl)disulfide, and
bis(penta(chlorosulfonyl)phenyl)disulfide; diphenyl disulfides
substituted with sulfino groups, such as
bis(4-sulfinophenyl)disulfide,
bis(2,4,6-trisulfinophenyl)disulfide, and
bis(pentasulfinophenyl)disulfide; diphenyl disulfides substituted
with alkylsulfinyl groups, such as
bis(4-methylsulfinylphenyl)disulfide,
bis(2,4,6-tri(methylsulfinyl)phenyl)disulfide, and
bis(penta(methylsulfinyl)phenyl)disulfide; diphenyl disulfides
substituted with carbamoyl groups, such as
bis(4-carbamoylphenyl)disulfide,
bis(2,4,6-tricarbamoylphenyl)disulfide, and
bis(pentacarbamoylphenyl)disulfide; diphenyl disulfides substituted
with alkyl halide groups, such as
bis(4-trichloromethylphenyl)disulfide,
bis(2,4,6-tri(trichloromethyl)phenyl)disulfide, and
bis(penta(trichloromethyl)phenyl)disulfide; diphenyl disulfides
substituted with cyano groups, such as bis(4-cyanophenyl)disulfide,
bis(2,4,6-tricyanophenyl)disulfide, and
bis(pentacyanophenyl)disulfide; and diphenyl disulfides substituted
with alkoxy groups, such as bis(4-methoxyphenyl)disulfide,
bis(2,4,6-trimethoxyphenyl)disulfide, and
bis(pentamethoxyphenyl)disulfide. Each of these diphenyl disulfides
is substituted with one type of substituent.
[0104] Another example of the organic sulfur compound represented
by the chemical formula (2) is a compound substituted with at least
one type of the above substituents and another substituent.
Examples of the other substituent include a nitro group
(--NO.sub.2), an amino group (--NH.sub.2), a hydroxyl group (--OH),
and a phenylthio group (--SPh). Specific examples of the compound
include bis(4-chloro-2-nitrophenyl)disulfide,
bis(4-chloro-2-aminophenyl)disulfide,
bis(4-chloro-2-hydroxyphenyl)disulfide,
bis(4-chloro-2-phenylthiophenyl)disulfide,
bis(4-methyl-2-nitrophenyl)disulfide,
bis(4-methyl-2-aminophenyl)disulfide,
bis(4-methyl-2-hydroxyphenyl)disulfide,
bis(4-methyl-2-phenylthiophenyl)disulfide,
bis(4-carboxy-2-nitrophenyl)disulfide,
bis(4-carboxy-2-aminophenyl)disulfide,
bis(4-carboxy-2-hydroxyphenyl)disulfide,
bis(4-carboxy-2-phenylthiophenyl)disulfide,
bis(4-methoxycarbonyl-2-nitrophenyl)disulfide,
bis(4-methoxycarbonyl-2-aminophenyl)disulfide,
bis(4-methoxycarbonyl-2-hydroxyphenyl)disulfide,
bis(4-methoxycarbonyl-2-phenylthiophenyl)disulfide,
bis(4-formyl-2-nitrophenyl)disulfide,
bis(4-formyl-2-aminophenyl)disulfide,
bis(4-formyl-2-hydroxyphenyl)disulfide,
bis(4-formyl-2-phenylthiophenyl)disulfide,
bis(4-acetyl-2-nitrophenyl)disulfide,
bis(4-acetyl-2-aminophenyl)disulfide,
bis(4-acetyl-2-hydroxyphenyl)disulfide,
bis(4-acetyl-2-phenylthiophenyl)disulfide,
bis(4-chlorocarbonyl-2-nitrophenyl)disulfide,
bis(4-chlorocarbonyl-2-aminophenyl)disulfide,
bis(4-chlorocarbonyl-2-hydroxyphenyl)disulfide,
bis(4-chlorocarbonyl-2-phenylthiophenyl)disulfide,
bis(4-sulfo-2-nitrophenyl)disulfide,
bis(4-sulfo-2-aminophenyl)disulfide,
bis(4-sulfo-2-hydroxyphenyl)disulfide,
bis(4-sulfo-2-phenylthiophenyl)disulfide,
bis(4-methoxysulfonyl-2-nitrophenyl)disulfide,
bis(4-methoxysulfonyl-2-aminophenyl)disulfide,
bis(4-methoxysulfonyl-2-hydroxyphenyl)disulfide,
bis(4-methoxysulfonyl-2-phenylthiophenyl)disulfide,
bis(4-chlorosulfonyl-2-nitrophenyl)disulfide,
bis(4-chlorosulfonyl-2-aminophenyl)disulfide,
bis(4-chlorosulfonyl-2-hydroxyphenyl)disulfide,
bis(4-chlorosulfonyl-2-phenylthiophenyl)disulfide,
bis(4-sulfino-2-nitrophenyl)disulfide,
bis(4-sulfino-2-aminophenyl)disulfide,
bis(4-sulfino-2-hydroxyphenyl)disulfide,
bis(4-sulfino-2-phenylthiophenyl)disulfide,
bis(4-methylsulfinyl-2-nitrophenyl)disulfide,
bis(4-methylsulfinyl-2-aminophenyl)disulfide,
bis(4-methylsulfinyl-2-hydroxyphenyl)disulfide,
bis(4-methylsulfinyl-2-phenylthiophenyl)disulfide,
bis(4-carbamoyl-2-nitrophenyl)disulfide,
bis(4-carbamoyl-2-aminophenyl)disulfide,
bis(4-carbamoyl-2-hydroxyphenyl)disulfide,
bis(4-carbamoyl-2-phenylthiophenyl)disulfide,
bis(4-trichloromethyl-2-nitrophenyl)disulfide,
bis(4-trichloromethyl-2-aminophenyl)disulfide,
bis(4-trichloromethyl-2-hydroxyphenyl)disulfide,
bis(4-trichloromethyl-2-phenylthiophenyl)disulfide,
bis(4-cyano-2-nitrophenyl)disulfide,
bis(4-cyano-2-aminophenyl)disulfide,
bis(4-cyano-2-hydroxyphenyl)disulfide,
bis(4-cyano-2-phenylthiophenyl)disulfide,
bis(4-methoxy-2-nitrophenyl)disulfide,
bis(4-methoxy-2-aminophenyl)disulfide,
bis(4-methoxy-2-hydroxyphenyl)disulfide, and
bis(4-methoxy-2-phenylthiophenyl)disulfide.
[0105] Still another example of the organic sulfur compound
represented by the chemical formula (2) is a compound substituted
with two or more types of substituents. Specific examples of the
compound include bis(4-acetyl-2-chlorophenyl)disulfide,
bis(4-acetyl-2-methylphenyl)disulfide,
bis(4-acetyl-2-carboxyphenyl)disulfide,
bis(4-acetyl-2-methoxycarbonylphenyl)disulfide,
bis(4-acetyl-2-formylphenyl)disulfide,
bis(4-acetyl-2-chlorocarbonylphenyl)disulfide,
bis(4-acetyl-2-sulfophenyl)disulfide,
bis(4-acetyl-2-methoxysulfonylphenyl)disulfide,
bis(4-acetyl-2-chlorosulfonylphenyl)disulfide,
bis(4-acetyl-2-sulfinophenyl)disulfide,
bis(4-acetyl-2-methylsulfinylphenyl)disulfide,
bis(4-acetyl-2-carbamoylphenyl)disulfide,
bis(4-acetyl-2-trichloromethylphenyl)disulfide,
bis(4-acetyl-2-cyanophenyl)disulfide, and
bis(4-acetyl-2-methoxyphenyl)disulfide.
[0106] Examples of the organic sulfur compound represented by the
chemical formula (3) include thiophenol sodium salt; thiophenol
sodium salts substituted with halogen groups, such as
4-fluorothiophenol sodium salt, 2,5-difluorothiophenolsodium salt,
2,4,5-trifluorothiophenol sodium salt,
2,4,5,6-tetrafluorothiophenol sodium salt, pentafluorothiophenol
sodium salt, 4-chlorothiophenol sodium salt, 2,5-dichlorothiophenol
sodium salt, 2,4,5-trichlorothiophenol sodium salt,
2,4,5,6-tetrachlorothiophenol sodium salt, pentachlorothiophenol
sodium salt, 4-bromothiophenol sodium salt, 2,5-dibromothiophenol
sodium salt, 2,4,5-tribromothiophenol sodium salt,
2,4,5,6-tetrabromothiophenol sodium salt, pentabromothiophenol
sodium salt, 4-iodothiophenol sodium salt, 2,5-diiodothiophenol
sodium salt, 2,4,5-triiodothiophenol sodium salt,
2,4,5,6-tetraiodothiophenol sodium salt, and pentaiodothiophenol
sodium salt; thiophenol sodium salts substituted with alkyl groups,
such as 4-methylthiophenol sodium salt, 2,4,5-trimethylthiophenol
sodium salt, pentamethylthiophenol sodium salt, 4-t-butylthiophenol
sodium salt, 2,4,5-tri-t-butylthiophenol sodium salt, and
penta(t-butyl)thiophenol sodium salt; thiophenol sodium salts
substituted with carboxyl groups, such as 4-carboxythiophenol
sodium salt, 2,4,6-tricarboxythiophenol sodium salt, and
pentacarboxythiophenol sodium salt; thiophenol sodium salts
substituted with alkoxycarbonyl groups, such as
4-methoxycarbonylthiophenol sodium salt,
2,4,6-trimethoxycarbonylthiophenol sodium salt, and
pentamethoxycarbonylthiophenol sodium salt; thiophenol sodium salts
substituted with formyl groups, such as 4-formylthiophenol sodium
salt, 2,4,6-triformylthiophenol sodium salt, and
pentaformylthiophenol sodium salt; thiophenol sodium salts
substituted with acyl groups, such as 4-acetylthiophenol sodium
salt, 2,4,6-triacetylthiophenol sodium salt, and
pentaacetylthiophenol sodium salt; thiophenol sodium salts
substituted with carbonyl halide groups, such as
4-chlorocarbonylthiophenol sodium salt,
2,4,6-tri(chlorocarbonyl)thiophenol sodium salt, and
penta(chlorocarbonyl)thiophenol sodium salt; thiophenol sodium
salts substituted with sulfo groups, such as 4-sulfothiophenol
sodium salt, 2,4,6-trisulfothiophenol sodium salt, and
pentasulfothiophenol sodium salt; thiophenol sodium salts
substituted with alkoxysulfonyl groups, such as
4-methoxysulfonylthiophenol sodium salt,
2,4,6-trimethoxysulfonylthiophenol sodium salt, and
pentamethoxysulfonylthiophenol sodium salt; thiophenol sodium salts
substituted with sulfonyl halide groups, such as
4-chlorosulfonylthiophenol sodium salt,
2,4,6-tri(chlorosulfonyl)thiophenol sodium salt, and
penta(chlorosulfonyl)thiophenol sodium salt; thiophenol sodium
salts substituted with sulfino groups, such as 4-sulfinothiophenol
sodium salt, 2,4,6-trisulfinothiophenol sodium salt, and
pentasulfinothiophenol sodium salt; thiophenol sodium salts
substituted with alkylsulfinyl groups, such as
4-methylsulfinylthiophenol sodium salt,
2,4,6-tri(methylsulfinyl)thiophenol sodium salt, and
penta(methylsulfinyl)thiophenol sodium salt; thiophenol sodium
salts substituted with carbamoyl groups, such as
4-carbamoylthiophenol sodium salt, 2,4,6-tricarbamoylthiophenol
sodium salt, and pentacarbamoylthiophenol sodium salt; thiophenol
sodium salts substituted with alkyl halide groups, such as
4-trichloromethylthiophenol sodium salt,
2,4,6-tri(trichloromethyl)thiophenol sodium salt, and
penta(trichloromethyl)thiophenol sodium salt; thiophenol sodium
salts substituted with cyano groups, such as 4-cyanothiophenol
sodium salt, 2,4,6-tricyanothiophenol sodium salt, and
pentacyanothiophenol sodium salt; and thiophenol sodium salts
substituted with alkoxy groups, such as 4-methoxythiophenol sodium
salt, 2,4,6-trimethoxythiophenol sodium salt, and
pentamethoxythiophenol sodium salt. Each of these thiophenol sodium
salts is substituted with one type of substituent.
[0107] Another example of the organic sulfur compound represented
by the chemical formula (3) is a compound substituted with at least
one type of the above substituents and another substituent.
[0108] Examples of the other substituent include a nitro group
(--NO.sub.2), an amino group (--NH.sub.2), a hydroxyl group (--OH),
and a phenylthio group (--SPh). Specific examples of the compound
include 4-chloro-2-nitrothiophenol sodium salt,
4-chloro-2-aminothiophenol sodium salt,
4-chloro-2-hydroxythiophenol sodium salt,
4-chloro-2-phenylthiothiophenol sodium salt,
4-methyl-2-nitrothiophenol sodium salt, 4-methyl-2-aminothiophenol
sodium salt, 4-methyl-2-hydroxythiophenol sodium salt,
4-methyl-2-phenylthiothiophenol sodium salt,
4-carboxy-2-nitrothiophenol sodium salt,
4-carboxy-2-aminothiophenol sodium salt,
4-carboxy-2-hydroxythiophenol sodium salt,
4-carboxy-2-phenylthiothiophenol sodium salt,
4-methoxycarbonyl-2-nitrothiophenol sodium salt,
4-methoxycarbonyl-2-aminothiophenol sodium salt,
4-methoxycarbonyl-2-hydroxythiophenol sodium salt,
4-methoxycarbonyl-2-phenylthiothiophenol sodium salt,
4-formyl-2-nitrothiophenol sodium salt, 4-formyl-2-aminothiophenol
sodium salt, 4-formyl-2-hydroxythiophenol sodium salt,
4-formyl-2-phenylthiothiophenol sodium salt,
4-acetyl-2-nitrothiophenol sodium salt, 4-acetyl-2-aminothiophenol
sodium salt, 4-acetyl-2-hydroxythiophenol sodium salt,
4-acetyl-2-phenylthiothiophenol sodium salt,
4-chlorocarbonyl-2-nitrothiophenol sodium salt,
4-chlorocarbonyl-2-aminothiophenol sodium salt,
4-chlorocarbonyl-2-hydroxythiophenol sodium salt,
4-chlorocarbonyl-2-phenylthiothiophenol sodium salt,
4-sulfo-2-nitrothiophenol sodium salt, 4-sulfo-2-aminothiophenol
sodium salt, 4-sulfo-2-hydroxythiophenol sodium salt,
4-sulfo-2-phenylthiothiophenol sodium salt,
4-methoxysulfonyl-2-nitrothiophenol sodium salt,
4-methoxysulfonyl-2-aminothiophenol sodium salt,
4-methoxysulfonyl-2-hydroxythiophenol sodium salt,
4-methoxysulfonyl-2-phenylthiothiophenol sodium salt,
4-chlorosulfonyl-2-nitrothiophenol sodium salt,
4-chlorosulfonyl-2-aminothiophenol sodium salt,
4-chlorosulfonyl-2-hydroxythiophenol sodium salt,
4-chlorosulfonyl-2-phenylthiothiophenol sodium salt,
4-sulfino-2-nitrothiophenol sodium salt,
4-sulfino-2-aminothiophenol sodium salt,
4-sulfino-2-hydroxythiophenol sodium salt,
4-sulfino-2-phenylthiothiophenol sodium salt,
4-methylsulfinyl-2-nitrothiophenol sodium salt,
4-methylsulfinyl-2-aminothiophenol sodium salt,
4-methylsulfinyl-2-hydroxythiophenol sodium salt,
4-methylsulfinyl-2-phenylthiothiophenol sodium salt,
4-carbamoyl-2-nitrothiophenol sodium salt,
4-carbamoyl-2-aminothiophenol sodium salt,
4-carbamoyl-2-hydroxythiophenol sodium salt,
4-carbamoyl-2-phenylthiothiophenol sodium salt,
4-trichloromethyl-2-nitrothiophenol sodium salt,
4-trichloromethyl-2-aminothiophenol sodium salt,
4-trichloromethyl-2-hydroxythiophenol sodium salt,
4-trichloromethyl-2-phenylthiothiophenol sodium salt,
4-cyano-2-nitrothiophenol sodium salt, 4-cyano-2-aminothiophenol
sodium salt, 4-cyano-2-hydroxythiophenol sodium salt,
4-cyano-2-phenylthiothiophenol sodium salt,
4-methoxy-2-nitrothiophenol sodium salt,
4-methoxy-2-aminothiophenol sodium salt,
4-methoxy-2-hydroxythiophenol sodium salt, and
4-methoxy-2-phenylthiothiophenol sodium salt.
[0109] Still another example of the organic sulfur compound
represented by the chemical formula (3) is a compound substituted
with two or more types of substituents. Specific examples of the
compound include 4-acetyl-2-chlorothiophenol sodium salt,
4-acetyl-2-methylthiophenol sodium salt,
4-acetyl-2-carboxythiophenol sodium salt,
4-acetyl-2-methoxycarbonylthiophenol sodium salt,
4-acetyl-2-formylthiophenol sodium salt,
4-acetyl-2-chlorocarbonylthiophenol sodium salt,
4-acetyl-2-sulfothiophenol sodium salt,
4-acetyl-2-methoxysulfonylthiophenol sodium salt,
4-acetyl-2-chlorosulfonylthiophenol sodium salt,
4-acetyl-2-sulfinothiophenol sodium salt,
4-acetyl-2-methylsulfinylthiophenol sodium salt,
4-acetyl-2-carbamoylthiophenol sodium salt,
4-acetyl-2-trichloromethylthiophenol sodium salt,
4-acetyl-2-cyanothiophenol sodium salt, and
4-acetyl-2-methoxythiophenol sodium salt. Examples of the
monovalent metal represented by M1 in the chemical formula (3)
include sodium, lithium, potassium, copper (I), and silver (I).
[0110] Examples of the organic sulfur compound represented by the
chemical formula (4) include thiophenol zinc salt; thiophenol zinc
salts substituted with halogen groups, such as 4-fluorothiophenol
zinc salt, 2,5-difluorothiophenol zinc salt,
2,4,5-trifluorothiophenol zinc salt, 2,4,5,6-tetrafluorothiophenol
zinc salt, pentafluorothiophenol zinc salt, 4-chlorothiophenol zinc
salt, 2,5-dichlorothiophenol zinc salt, 2,4,5-trichlorothiophenol
zinc salt, 2,4,5,6-tetrachlorothiophenol zinc salt,
pentachlorothiophenol zinc salt, 4-bromothiophenol zinc salt,
2,5-dibromothiophenol zinc salt, 2,4,5-tribromothiophenol zinc
salt, 2,4,5,6-tetrabromothiophenol zinc salt, pentabromothiophenol
zinc salt, 4-iodothiophenol zinc salt, 2,5-diiodothiophenol zinc
salt, 2,4,5-triiodothiophenol zinc salt,
2,4,5,6-tetraiodothiophenol zinc salt, and pentaiodothiophenol zinc
salt; thiophenol zinc salts substituted with alkyl groups, such as
4-methylthiophenol zinc salt, 2,4,5-trimethylthiophenol zinc salt,
pentamethylthiophenol zinc salt, 4-t-butylthiophenol zinc salt,
2,4,5-tri-t-butylthiophenol zinc salt, and penta-t-butylthiophenol
zinc salt; thiophenol zinc salts substituted with carboxyl groups,
such as 4-carboxythiophenol zinc salt, 2,4,6-tricarboxythiophenol
zinc salt, and pentacarboxythiophenol zinc salt; thiophenol zinc
salts substituted with alkoxycarbonyl groups, such as
4-methoxycarbonylthiophenol zinc salt,
2,4,6-trimethoxycarbonylthiophenol zinc salt, and
pentamethoxycarbonylthiophenol zinc salt; thiophenol zinc salts
substituted with formyl groups, such as 4-formylthiophenol zinc
salt, 2,4,6-triformylthiophenol zinc salt, and
pentaformylthiophenol zinc salt; thiophenol zinc salts substituted
with acyl groups, such as 4-acetylthiophenol zinc salt,
2,4,6-triacetylthiophenol zinc salt, and pentaacetylthiophenol zinc
salt; thiophenol zinc salts substituted with carbonyl halide
groups, such as 4-chlorocarbonylthiophenol zinc salt,
2,4,6-tri(chlorocarbonyl)thiophenol zinc salt, and
penta(chlorocarbonyl)thiophenol zinc salt; thiophenol zinc salts
substituted with sulfo groups, such as 4-sulfothiophenol zinc salt,
2,4,6-trisulfothiophenol zinc salt, and pentasulfothiophenol zinc
salt; thiophenol zinc salts substituted with alkoxysulfonyl groups,
such as 4-methoxysulfonylthiophenol zinc salt,
2,4,6-trimethoxysulfonylthiophenol zinc salt, and
pentamethoxysulfonylthiophenol zinc salt; thiophenol zinc salts
substituted with sulfonyl halide groups, such as
4-chlorosulfonylthiophenol zinc salt,
2,4,6-tri(chlorosulfonyl)thiophenol zinc salt, and
penta(chlorosulfonyl)thiophenol zinc salt; thiophenol zinc salts
substituted with sulfino groups, such as 4-sulfinothiophenol zinc
salt, 2,4,6-trisulfinothiophenol zinc salt, and
pentasulfinothiophenol zinc salt; thiophenol zinc salts substituted
with alkylsulfinyl groups, such as 4-methylsulfinylthiophenol zinc
salt, 2,4,6-tri(methylsulfinyl)thiophenol zinc salt, and
penta(methylsulfinyl)thiophenol zinc salt; thiophenol zinc salts
substituted with carbamoyl groups, such as 4-carbamoylthiophenol
zinc salt, 2,4,6-tricarbamoylthiophenol zinc salt, and
pentacarbamoylthiophenol zinc salt; thiophenol zinc salts
substituted with alkyl halide groups, such as
4-trichloromethylthiophenol zinc salt,
2,4,6-tri(trichloromethyl)thiophenol zinc salt, and
penta(trichloromethyl)thiophenol zinc salt; thiophenol zinc salts
substituted with cyano groups, such as 4-cyanothiophenol zinc salt,
2,4,6-tricyanothiophenol zinc salt, and pentacyanothiophenol zinc
salt; and thiophenol zinc salts substituted with alkoxy groups,
such as 4-methoxythiophenol zinc salt, 2,4,6-trimethoxythiophenol
zinc salt, and pentamethoxythiophenol zinc salt. Each of these
thiophenol zinc salts is substituted with one type of
substituent.
[0111] Another example of the organic sulfur compound represented
by the chemical formula (4) is a compound substituted with at least
one type of the above substituents and another substituent.
Examples of the other substituent include a nitro group
(--NO.sub.2), an amino group (--NH.sub.2), a hydroxyl group (--OH),
and a phenylthio group (--SPh). Specific examples of the compound
include 4-chloro-2-nitrothiophenol zinc salt,
4-chloro-2-aminothiophenol zinc salt, 4-chloro-2-hydroxythiophenol
zinc salt, 4-chloro-2-phenylthiothiophenol zinc salt,
4-methyl-2-nitrothiophenol zinc salt, 4-methyl-2-aminothiophenol
zinc salt, 4-methyl-2-hydroxythiophenol zinc salt,
4-methyl-2-phenylthiothiophenol zinc salt,
4-carboxy-2-nitrothiophenol zinc salt, 4-carboxy-2-aminothiophenol
zinc salt, 4-carboxy-2-hydroxythiophenol zinc salt,
4-carboxy-2-phenylthiothiophenol zinc salt,
4-methoxycarbonyl-2-nitrothiophenol zinc salt,
4-methoxycarbonyl-2-aminothiophenol zinc salt,
4-methoxycarbonyl-2-hydroxythiophenol zinc salt,
4-methoxycarbonyl-2-phenylthiothiophenol zinc salt,
4-formyl-2-nitrothiophenol zinc salt, 4-formyl-2-aminothiophenol
zinc salt, 4-formyl-2-hydroxythiophenol zinc salt,
4-formyl-2-phenylthiothiophenol zinc salt,
4-acetyl-2-nitrothiophenol zinc salt, 4-acetyl-2-aminothiophenol
zinc salt, 4-acetyl-2-hydroxythiophenol zinc salt,
4-acetyl-2-phenylthiothiophenol zinc salt,
4-chlorocarbonyl-2-nitrothiophenol zinc salt,
4-chlorocarbonyl-2-aminothiophenol zinc salt,
4-chlorocarbonyl-2-hydroxythiophenol zinc salt,
4-chlorocarbonyl-2-phenylthiothiophenol zinc salt,
4-sulfo-2-nitrothiophenol zinc salt, 4-sulfo-2-aminothiophenol zinc
4-sulfa-2-hydroxythiophenol zinc salt,
4-sulfo-2-phenylthiothiophenol zinc salt,
4-methoxysulfonyl-2-nitrothiophenol zinc salt,
4-methoxysulfonyl-2-aminothiophenol zinc salt,
4-methoxysulfonyl-2-hydroxythiophenol zinc salt,
4-methoxysulfonyl-2-phenylthiothiophenol zinc salt,
4-chlorosulfonyl-2-nitrothiophenol zinc salt,
4-chlorosulfonyl-2-aminothiophenol zinc salt,
4-chlorosulfonyl-2-hydroxythiophenol zinc salt,
4-chlorosulfonyl-2-phenylthiothiophenol zinc salt,
4-sulfino-2-nitrothiophenol zinc salt, 4-sulfino-2-aminothiophenol
zinc salt, 4-sulfino-2-hydroxythiophenol zinc salt,
4-sulfino-2-phenylthiothiophenol zinc salt,
4-methylsulfinyl-2-nitrothiophenol zinc salt,
4-methylsulfinyl-2-aminothiophenol zinc salt,
4-methylsulfinyl-2-hydroxythiophenol zinc salt,
4-methylsulfinyl-2-phenylthiothiophenol zinc salt,
4-carbamoyl-2-nitrothiophenol zinc salt,
4-carbamoyl-2-aminothiophenol zinc salt,
4-carbamoyl-2-hydroxythiophenol zinc salt,
4-carbamoyl-2-phenylthiothiophenol zinc salt,
4-trichloromethyl-2-nitrothiophenol zinc salt,
4-trichloromethyl-2-aminothiophenol zinc salt,
4-trichloromethyl-2-hydroxythiophenol zinc salt,
4-trichloromethyl-2-phenylthiothiophenol zinc salt,
4-cyano-2-nitrothiophenol zinc salt, 4-cyano-2-aminothiophenol zinc
salt, 4-cyano-2-hydroxythiophenol zinc salt,
4-cyano-2-phenylthiothiophenol zinc salt,
4-methoxy-2-nitrothiophenol zinc salt, 4-methoxy-2-aminothiophenol
zinc salt, 4-methoxy-2-hydroxythiophenol zinc salt, and
4-methoxy-2-phenylthiothiophenol zinc salt.
[0112] Still another example of the organic sulfur compound
represented by the chemical formula (4) is a compound substituted
with two or more types of substituents. Specific examples of the
compound include 4-acetyl-2-chlorothiophenol zinc salt,
4-acetyl-2-methylthiophenol zinc salt, 4-acetyl-2-carboxythiophenol
zinc salt, 4-acetyl-2-methoxycarbonylthiophenol zinc salt,
4-acetyl-2-formylthiophenol zinc salt,
4-acetyl-2-chlorocarbonylthiophenol zinc salt,
4-acetyl-2-sulfothiophenol zinc salt,
4-acetyl-2-methoxysulfonylthiophenol zinc salt,
4-acetyl-2-chlorosulfonylthiophenol zinc salt,
4-acetyl-2-sulfinothiophenol zinc salt,
4-acetyl-2-methylsulfinylthiophenol zinc salt,
4-acetyl-2-carbamoylthiophenol zinc salt,
4-acetyl-2-trichloromethylthiophenol zinc salt,
4-acetyl-2-cyanothiophenol zinc salt, and
4-acetyl-2-methoxythiophenol zinc salt. Examples of the bivalent
metal represented by M2 in the chemical formula (4) include zinc,
magnesium, calcium, strontium, barium, titanium (II), manganese
(II), iron (II), cobalt (II), nickel (II), zirconium (II), and tin
(II).
[0113] Examples of naphthalenethiols include 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,
1-acetyl-2-naphthalenethiol, and metal salts thereof.
1-naphthalenethiol, 2-naphthalenethiol, and zinc salts thereof are
preferred.
[0114] Examples of sulfenamide type organic sulfur compounds
include N-cyclohexyl-2-benzothiazole sulfenamide,
N-oxydiethylene-2-benzothiazole sulfenamide, and
N-t-butyl-2-benzothiazole sulfenamide. Examples of thiuram type
organic sulfur compounds include tetramethylthiuram monosulfide,
tetramethylthiuram disulfide, tetraethylthiuram disulfide,
tetrabutylthiuram disulfide, and dipentamethylenethiuram
tetrasulfide. Examples of dithiocarbamates include zinc
dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc
dibutyldithiocarbamate, zinc ethylphenyldithiocarbamate, sodium
dimethyldithiocarbamate, sodium diethyldithiocarbamate, copper (II)
dimethyldithiocarbamate, iron (III) dimethyldithiocarbamate,
selenium diethyldithiocarbamate, and tellurium
diethyldithiocarbamate. Examples of thiazole type organic sulfur
compounds include 2-mercaptobenzothiazole (MBT); dibenzothiazyl
disulfide (METS); a sodium salt, a zinc salt, a copper salt, or a
cyclohexylamine salt of 2-mercaptobenzothiazole;
2-(2,4-dinitrophenyl)mercaptobenzothiazole; and
2-(2,6-diethyl-4-morpholinothio)benzothiazole.
[0115] In light of resilience performance, the amount of the
organic sulfur compound (f) is preferably equal to or greater than
0.05 parts by weight and particularly preferably equal to or
greater than 0.1 parts by weight, per 100 parts by weight of the
base rubber. In light of resilience performance, the amount is
preferably equal to or less than 5.0 parts by weight and
particularly preferably equal to or less than 2.0 parts by weight,
per 100 parts by weight of the base rubber.
[0116] For the purpose of adjusting specific gravity and the like,
a filler may be included in the core 4. Examples of suitable
fillers include zinc oxide, barium sulfate, calcium carbonate, and
magnesium carbonate. The amount of the filler is determined as
appropriate so that the intended specific gravity of the core 4 is
accomplished. A particularly preferable filler is zinc oxide. Zinc
oxide serves not only as a specific gravity adjuster but also as a
crosslinking activator.
[0117] According to need, an anti-aging agent, a coloring agent, a
plasticizer, a dispersant, sulfur, a vulcanization accelerator, and
the like are added to the rubber composition of the core 4.
Crosslinked rubber powder or synthetic resin powder may also be
dispersed in the rubber composition.
[0118] During heating and forming of the core 4, the heat of the
crosslinking reaction of the base rubber remains near the central
point of the core 4. Thus, during heating and forming of the core
4, the temperature at the central portion is high. The temperature
gradually decreases from the central point toward the surface. The
carboxylic acid and/or the salt thereof (d) reacts with a metal
salt of the co-crosslinking agent (b) to exchange cation. This
exchange reaction is likely to take place in the central portion of
the core 4 where the temperature is high, and is unlikely to take
place near the surface of the core 4. In other words, breaking of
metal crosslinks is likely to occur in the central portion of the
core 4 and is unlikely to occur near the surface of the core 4. As
a result, the crosslinking density of the core 4 increases from its
central point toward its surface. In the core 4, the hardness
linearly increases from its central point toward its surface.
Further, since the rubber composition includes the organic sulfur
compound (f) together with the carboxylic acid and/or the salt
thereof (d), the gradient of the hardness distribution can be
controlled, and the degree of the outer-hard/inner-soft structure
of the core 4 can be increased.
[0119] The hardness H(0) at the central point of the core 4 is
preferably equal to or greater than 40.0 but equal to or less than
70.0. The golf ball 2 having a hardness H(0) of 40.0 or greater has
excellent resilience performance. In this respect, the hardness
H(0) is more preferably equal to or greater than 45.0 and
particularly preferably equal to or greater than 47.0. The core 4
having a hardness H(0) of 70.0 or less can achieve an
outer-hard/inner-soft structure. In the golf ball 2 that includes
the core 4, spin can be suppressed. In this respect, the hardness
H(0) is more preferably equal to or less than 65.0 and particularly
preferably equal to or less than 63.0.
[0120] The hardness H(100) at the surface of the core 4 is
preferably equal to or greater than 78.0 but equal to or less than
95.0. The core 4 having a hardness H(100) of 78.0 or greater can
achieve an outer-hard/inner-soft structure. In the golf ball 2 that
includes the core 4, spin can be suppressed. In this respect, the
hardness H(100) is more preferably equal to or greater than 80.0
and particularly preferably equal to or greater than 82.0. The golf
ball 2 having a hardness H(100) of 95.0 or less has excellent
durability. In this respect, the hardness H(100) is more preferably
equal to or less than 93.0 and particularly preferably equal to or
less than 90.0.
[0121] The core 4 preferably has a diameter of 33.0 mm or greater
but 41.0 mm or less. The core 4 having a diameter of 33.0 mm or
greater can achieve excellent resilience performance of the golf
ball 2. The core 4 having a diameter of 33.0 mm or greater can
achieve an outer-hard/inner-soft structure of the golf ball 2. In
this respect, the diameter is particularly preferably equal to or
greater than 35.0 mm. In the golf ball 2 that includes the core 4
having a diameter of 41.0 mm or less, the inner mid layer 6, the
outer mid layer 8, and the cover 12 can have sufficient
thicknesses. The golf ball 2 that includes the inner mid layer 6,
the outer mid layer 8, and the cover 12 which have large
thicknesses has excellent durability. In this respect, the diameter
is more preferably equal to or less than 38 mm and particularly
preferably equal to or less than 36 mm. The core 4 may have two or
more layers.
[0122] In light of feel at impact, the core 4 has an amount of
compressive deformation Dc of preferably 3.0 mm or greater and
particularly preferably 3.2 mm or greater. In light of resilience
performance, the amount of compressive deformation Dc is preferably
equal to or less than 3.8 mm and particularly preferably equal to
or less than 3.5 mm.
[0123] For the inner mid layer 6, a resin composition is suitably
used. Examples of the base polymer of the resin composition include
ionomer resins, polystyrenes, polyesters, polyamides, and
polyolefins.
[0124] Particularly preferable base polymers are ionomer resins.
The golf ball 2 that includes the inner mid layer 6 including an
ionomer resin has excellent resilience performance. An ionomer
resin and another resin may be used in combination for the inner
mid layer 6. In this case, the principal component of the base
polymer is preferably the ionomer resin. Specifically, the
proportion of the ionomer resin to the entire base polymer is
preferably equal to or greater than 50% by weight, more preferably
equal to or greater than 60% by weight, and particularly preferably
equal to or greater than 70% by weight.
[0125] Examples of preferable ionomer resins include binary
copolymers formed with an .alpha.-olefin and an
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms. A preferable binary copolymer includes 80% by weight or more
and 90% by weight or less of an .alpha.-olefin, and 10% by weight
or more and 20% by weight or less of an .alpha.,.beta.-unsaturated
carboxylic acid. The binary copolymer has excellent resilience
performance. Examples of other preferable ionomer resins include
ternary copolymers formed with: an .alpha.-olefin; an
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms; and an .alpha.,.beta.-unsaturated carboxylate ester having 2
to 22 carbon atoms. A preferable ternary copolymer includes 70% by
weight or more and 85% by weight or less of an .alpha.-olefin, 5%
by weight or more and 30% by weight or less of an
.alpha.,.beta.-unsaturated carboxylic acid, and 1% by weight or
more and 25% by weight or less of an .alpha.,.beta.-unsaturated
carboxylate ester. The ternary copolymer has excellent resilience
performance. For the binary copolymers and the ternary copolymers,
preferable .alpha.-olefins are ethylene and propylene, while
preferable .alpha.,.beta.-unsaturated carboxylic acids are acrylic
acid and methacrylic acid. A particularly preferable ionomer resin
is a copolymer formed with ethylene and acrylic acid or methacrylic
acid.
[0126] In the binary copolymers and the ternary copolymers, some of
the carboxyl groups are neutralized with metal ions. Examples of
metal ions for use in neutralization include sodium ion, potassium
ion, lithium ion, zinc ion, calcium ion, magnesium ion, aluminum
ion, and neodymium ion. The neutralization may be carried out with
two or more types of metal ions. Particularly suitable metal ions
in light of resilience performance and durability of the golf ball
2 are sodium ion, zinc ion, lithium ion, and magnesium ion.
[0127] Specific examples of ionomer resins include trade names
"Himilan 1555", "Himilan 1557", "Himilan 1605", "Himilan 1706",
"Himilan 1707", "Himilan 1856", "Himilan 1855", "Himilan AM7311",
"Himilan AM7315", "Himilan AM7317", "Himilan AM7318", "Himilan
AM7329", "Himilan MK7320", and "Himilan MK7329", manufactured by Du
Pont-MITSUI POLYCHEMICALS Co., Ltd.; trade names "Surlyn 6120",
"Surlyn 6910", "Surlyn 7930", "Surlyn 7940", "Surlyn 8140", "Surlyn
8150", "Surlyn 8940", "Surlyn 8945", "Surlyn 9120", "Surlyn 9150",
"Surlyn 9910", "Surlyn 9945", "SurlynAD8546", "HPF1000", and
"HPF2000", manufactured by E.I. du Pont de Nemours and Company; and
trade names "IOTEK 7010", "IOTEK7030", "IOTEK7510", "IOTEK7520",
"IOTEK8000", and "IOTEK 8030", manufactured by ExxonMobil Chemical
Corporation.
[0128] Two or more ionomer resins may be used in combination for
the inner mid layer 6. An ionomer resin neutralized with a
monovalent metal ion, and an ionomer resin neutralized with a
bivalent metal ion may be used in combination.
[0129] A preferable resin that can be used in combination with an
ionomer resin is a styrene block-containing thermoplastic
elastomer. The styrene block-containing thermoplastic elastomer has
excellent compatibility with ionomer resins. A resin composition
including the styrene block-containing thermoplastic elastomer has
excellent fluidity.
[0130] The styrene block-containing thermoplastic elastomer
includes a polystyrene block as a hard segment, and a soft segment.
A typical soft segment is a diene block. Examples of compounds for
the diene block include butadiene, isoprene, 1,3-pentadiene, and
2,3-dimethyl-1,3-butadiene. Butadiene and isoprene are preferred.
Two or more compounds may be used in combination.
[0131] Examples of styrene block-containing thermoplastic
elastomers include styrene-butadiene-styrene block copolymers
(SBS), styrene-isoprene-styrene block copolymers (SIS),
styrene-isoprene-butadiene-styrene block copolymers (SIBS),
hydrogenated SBS, hydrogenated SIS, and hydrogenated SIBS. Examples
of hydrogenated SBS include styrene-ethylene-butylene-styrene block
copolymers (SEBS). Examples of hydrogenated SIS include
styrene-ethylene-propylene-styrene block copolymers (SEPS).
Examples of hydrogenated SIBS include
styrene-ethylene-ethylene-propylene-styrene block copolymers
(SEEPS).
[0132] In light of resilience performance of the golf ball 2, the
content of the styrene component in the styrene block-containing
thermoplastic elastomer is preferably equal to or greater than 10%
by weight, more preferably equal to or greater than 12% by weight,
and particularly preferably equal to or greater than 15% by weight.
In light of feel at impact of the golf ball 2, the content is
preferably equal to or less than 50% by weight, more preferably
equal to or less than 47% by weight, and particularly preferably
equal to or less than 45% by weight.
[0133] In the present invention, styrene block-containing
thermoplastic elastomers include alloys of olefin and one or more
members selected from the group consisting of SBS, SIS, SIBS, SEBS,
SEPS, and SEEPS. The olefin component in the alloy is presumed to
contribute to improvement of compatibility with ionomer resins. Use
of this alloy improves the resilience performance of the golf ball
2. An olefin having 2 to 10 carbon atoms is preferably used.
Examples of suitable olefins include ethylene, propylene, butene,
and pentene. Ethylene and propylene are particularly preferred.
[0134] Specific examples of polymer alloys include trade names
"RabalonT3221C", "RabalonT3339C", "RabalonSJ4400N", "Rabalon
SJ5400N", "Rabalon SJ6400N", "Rabalon SJ7400N", "Rabalon SJ8400N",
"Rabalon SJ9400N", and "Rabalon SR04", manufactured by Mitsubishi
Chemical Corporation. Other specific examples of styrene
block-containing thermoplastic elastomers include trade name
"Epofriend A1010" manufactured by Daicel Chemical Industries, Ltd.,
and trade name "Septon HG-252" manufactured by Kuraray Co.,
Ltd.
[0135] According to need, a coloring agent such as titanium
dioxide, a filler such as barium sulfate, a dispersant, an
antioxidant, an ultraviolet absorber, a light stabilizer, a
fluorescent material, a fluorescent brightener, and the like are
included in the resin composition of the inner mid layer 6 in an
adequate amount.
[0136] From the standpoint that an outer-hard/inner-soft structure
can be achieved in the sphere consisting of the core 4 and the
inner mid layer 6, the inner mid layer 6 has a Shore D hardness Hmi
of preferably 50 or greater, more preferably 55 or greater, and
particularly preferably 58 or greater. In light of feel at impact
of the golf ball 2, the hardness Hmi is preferably equal to or less
than 70 and particularly preferably equal to or less than 65. The
hardness Hmi is measured according to the standards of "ASTM-D
2240-68" with a Shore D type hardness scale mounted to an automated
rubber hardness measurement machine (trade name "P1", manufactured
by Kobunshi Keiki Co., Ltd.). For the measurement, a slab that is
formed by hot press and that has a thickness of about 2 mm is used.
A slab kept at 23.degree. C. for two weeks is used for the
measurement. At the measurement, three slabs are stacked. A slab
formed from the same resin composition as the resin composition of
the inner mid layer 6 is used.
[0137] From the standpoint that an outer-hard/inner-soft structure
can be achieved in the sphere consisting of the core 4 and the
inner mid layer 6, the inner mid layer 6 preferably has a JIS-C
hardness greater than the surface hardness H(100) of the core 4. In
light of suppression of spin, the difference between both
hardnesses is preferably equal to or greater than 2 and
particularly preferably equal to or greater than 4.
[0138] The inner mid layer 6 preferably has a thickness of 0.3 mm
or greater but 2.2 mm or less. In the sphere that includes the
inner mid layer 6 having a thickness of 0.3 mm or greater, the spin
suppression effect provided by the outer-hard/inner-soft structure
is great. In this respect, the thickness is more preferably equal
to or greater than 0.5 mm and particularly preferably equal to or
greater than 0.8 mm. The golf ball 2 that includes the inner mid
layer 6 having a thickness of 2.2 mm or less can include a large
core 4. The large core 4 can contribute to the resilience
performance of the golf ball 2. In this respect, the thickness is
more preferably equal to or less than 2.0 mm and particularly
preferably equal to or less than 1.8 mm.
[0139] For the outer mid layer 8, a resin composition is suitably
used. Examples of the base polymer of the resin composition include
ionomer resins, polystyrenes, polyesters, polyamides, and
polyolefins.
[0140] Particularly preferable base polymers are ionomer resins.
The golf ball 2 that includes the outer mid layer 8 including an
ionomer resin has excellent resilience performance. An ionomer
resin and another resin may be used in combination for the outer
mid layer 8. In this case, the principal component of the base
polymer is preferably the ionomer resin. Specifically, the
proportion of the ionomer resin to the entire base polymer is
preferably equal to or greater than 50% by weight, more preferably
equal to or greater than 60% by weight, and particularly preferably
equal to or greater than 70% by weight. The ionomer resins
described above for the inner mid layer 6 can also be used for the
outer mid layer 8. The styrene block-containing thermoplastic
elastomers described above for the inner mid layer 6 may also be
used for the outer mid layer 8.
[0141] As described later, a hardness Hmo of the outer mid layer 8
is great. By causing the amount of the styrene block-containing
thermoplastic elastomer included in the resin composition of the
outer mid layer 8 to be small, a great hardness Hmo can be
achieved. By the resin composition including a highly-elastic
resin, a great hardness Hmo may be achieved. Specific examples of
the highly elastic resin include polyamides.
[0142] According to need, a coloring agent such as titanium
dioxide, a filler such as barium sulfate, a dispersant, an
antioxidant, an ultraviolet absorber, a light stabilizer, a
fluorescent material, a fluorescent brightener, and the like are
included in the resin composition of the outer mid layer 8 in an
adequate amount.
[0143] From the standpoint that an outer-hard/inner-soft structure
can be achieved in the sphere consisting of the core 4, the inner
mid layer 6, and the outer mid layer 8, the Shore D hardness Hmo of
the outer mid layer 8 is preferably equal to or greater than 55,
more preferably equal to or greater than 60, and particularly
preferably equal to or greater than 65. In light of feel at impact
of the golf ball 2, the hardness Hmo is preferably equal to or less
than 75 and particularly preferably equal to or less than 70. The
hardness Hmo is measured by the same measurement method as that for
the hardness Hmi.
[0144] From the standpoint that an outer-hard/inner-soft structure
can be achieved in the sphere consisting of the core 4, the inner
mid layer 6, and the outer mid layer 8, the hardness Hmo of the
outer mid layer 8 is preferably greater than the hardness Hmi of
the inner mid layer 6. In the golf ball 2 that includes the sphere,
spin is suppressed upon a shot with a driver. In this respect, the
difference (Hmo-Hmi) is preferably equal to or greater than 5 and
particularly preferably equal to or greater than 6.
[0145] The outer mid layer 8 preferably has a thickness of 0.3 mm
or greater but 1.6 mm or less. In the sphere that includes the
outer mid layer 8 having a thickness of 0.3 mm or greater, the spin
suppression effect provided by the outer-hard/inner-soft structure
is great. In this respect, the thickness is more preferably equal
to or greater than 0.5 mm and particularly preferably equal to or
greater than 0.8 mm. The golf ball 2 that includes the outer mid
layer 8 having a thickness of 1.6 mm or less can include a large
core 4. The large core 4 can contribute to the resilience
performance of the golf ball 2. In this respect, the thickness is
more preferably equal to or less than 1.4 mm and particularly
preferably equal to or less than 1.2 mm.
[0146] For forming the outer mid layer 8, known methods such as
injection molding, compression molding, and the like can be
used.
[0147] A resin composition is suitably used for the cover 12. A
preferable base polymer of the resin composition is a polyurethane.
The polyurethane is flexible. When the golf ball 2 that includes
the cover 12 formed from the resin composition that includes the
polyurethane is hit with a short iron, the spin rate is high. The
cover 12 formed from this resin composition contributes to
controllability upon a shot with a short iron. The polyurethane
also contributes to the scuff resistance of the cover 12. Further,
the polyurethane can contribute to excellent feel at impact when
the golf ball 2 is hit with a putter or a short iron.
[0148] In light of ease of forming the cover 12, a preferable base
polymer is a thermoplastic polyurethane elastomer. The
thermoplastic polyurethane elastomer includes a polyurethane
component as a hard segment, and a polyester component or a
polyether component as a soft segment. Examples of isocyanates for
the polyurethane component include alicyclic diisocyanates,
aromatic diisocyanates, and aliphatic diisocyanates. Two or more
diisocyanates may be used in combination.
[0149] Examples of alicyclic diisocyanates include
4,4'-dicyclohexylmethane diisocyanate (H.sub.12MDI),
1,3-bis(isocyanatomethyl)cyclohexane (H.sub.6XDI), isophorone
diisocyanate (IPDI), and trans-1,4-cyclohexane diisocyanate (CHDI).
In light of versatility and processability, H.sub.12MDI is
preferred.
[0150] Examples of aromatic diisocyanates include
4,4'-diphenylmethane diisocyanate (MDI) and toluene diisocyanate
(TDI). Examples of aliphatic diisocyanates include hexamethylene
diisocyanate (HDI).
[0151] Particularly, alicyclic diisocyanates are preferred. Since
an alicyclic diisocyanate does not have any double bond in the main
chain, the alicyclic diisocyanate suppresses yellowing of the cover
12. In addition, since an alicyclic diisocyanate has excellent
strength, the alicyclic diisocyanate suppresses a scuff on the
cover 12.
[0152] Specific examples of thermoplastic polyurethane elastomers
include trade names "Elastollan NY80A", "Elastollan NY82A",
"Elastollan NY84A", "Elastollan NY85A", "Elastollan NY88A",
"Elastollan NY90A", "Elastollan NY97A", "Elastollan NY585",
"Elastollan XKP016N", "Elastollan 1195ATR", "Elastollan ET890A",
and "Elastollan ET88050", manufactured by BASF Japan Ltd.; and
trade names "RESAMINE P4585LS" and "RESAMINE PS62490", manufactured
by Dainichiseika Color & Chemicals Mfg. Co., Ltd. From the
standpoint that a low hardness of the cover 12 can be achieved,
"Elastollan NY80A", "Elastollan NY82A", "Elastollan NY84A",
"Elastollan NY85A", and "Elastollan NY90A" are particularly
preferred.
[0153] A thermoplastic polyurethane elastomer and another resin may
be used in combination. Examples of the resin that can be used in
combination include thermoplastic polyester elastomers,
thermoplastic polyamide elastomers, thermoplastic polyolefin
elastomers, styrene block-containing thermoplastic elastomers, and
ionomer resins. When a thermoplastic polyurethane elastomer and
another resin are used in combination, the thermoplastic
polyurethane elastomer is included as the principal component of
the base polymer, in light of spin performance and scuff
resistance. The proportion of the thermoplastic polyurethane
elastomer to the entire base polymer is preferably equal to or
greater than 50% by weight, more preferably equal to or greater
than 70% by weight, and particularly preferably equal to or greater
than 85% by weight.
[0154] According to need, a coloring agent such as titanium
dioxide, a filler such as barium sulfate, a dispersant, an
antioxidant, an ultraviolet absorber, a light stabilizer, a
fluorescent material, a fluorescent brightener, and the like are
included in the cover 12 in an adequate amount.
[0155] The cover 12 has a Shore D hardness Hc of preferably 50 or
less. The golf ball 2 that includes the cover 12 having a hardness
Hc of 50 or less has excellent controllability. In this respect,
the hardness Hc is more preferably equal to or less than 45 and
particularly preferably equal to or less than 42. In light of
flight distance upon a shot with a driver, the hardness Hc is
preferably equal to or greater than 10, more preferably equal to or
greater than 15, and particularly preferably equal to or greater
than 20. The hardness Hc is measured by the same measurement method
as that for the hardness Hmi.
[0156] The hardness Hc of the cover 12 is less than the hardness
Hmo of the outer mid layer 8 and is less than the hardness Hmi of
the inner mid layer 6. When the golf ball 2 is hit with a driver,
the sphere consisting of the core 4, the inner mid layer 6, and the
outer mid layer 8 becomes significantly distorted since the head
speed is high. Since this sphere has an outer-hard/inner-soft
structure, the spin rate is suppressed. The hardness of the core 4
linearly changes. Thus, the golf ball 2 is launched at a high speed
due to deformation and restoration of the core 4. The suppression
of the spin rate and the high launch speed achieve a large flight
distance. When the golf ball 2 is hit with a short iron, this
sphere becomes less distorted since the head speed is low. When the
golf ball 2 is hit with a short iron, the behavior of the golf ball
2 mainly depends on the cover 12. Since the cover 12 is flexible, a
slip between the golf ball 2 and a clubface is suppressed. Due to
the suppression of the slip, a high spin rate is obtained. The high
spin rate achieves excellent controllability. In the golf ball 2,
both desired flight performance upon a shot with a driver and
desired controllability upon a shot with a short iron are
achieved.
[0157] When the golf ball 2 is hit, the cover 12 including the
polyurethane absorbs the shock. This absorption achieves soft feel
at impact. Particularly, when the golf ball 2 is hit with a short
iron or a putter, the cover 12 achieves excellent feel at
impact.
[0158] In light of achievement of both desired flight performance
and desired controllability, the difference (Hmi-Hc) between the
hardness Hmi of the inner mid layer 6 and the hardness Hc of the
cover 12 is preferably equal to or greater than 10 and particularly
preferably equal to or greater than 15. The difference (Hmi-Hc) is
preferably equal to or less than 30. In light of achievement of
both desired flight performance and desired controllability, the
difference (Hmo-Hc) between the hardness Hmo of the outer mid layer
8 and the hardness Hc of the cover 12 is preferably equal to or
greater than 20 and particularly preferably equal to or greater
than 25. The difference (Hmo-Hc) is preferably equal to or less
than 40.
[0159] The hardness Hc of the cover 12 is preferably less than the
surface hardness H(100) of the core 4. When the golf ball 2 is hit
with a short iron, the flexible cover 12 is squeezed between the
hard core 4 and the hard clubface. This squeeze suppresses a slip
of the golf ball 2 relative to the clubface. Due to the suppression
of the slip, a high spin rate is obtained. The suppression of the
slip suppresses variation of a spin rate. In light of suppression
of a slip, the difference between the surface hardness H(100) of
the core 4 and a JIS-C hardness of the cover 12 is preferably equal
to or greater than 10 and particularly preferably equal to or
greater than 15.
[0160] In light of flight performance upon a shot with a driver,
the cover 12 has a thickness of preferably 1.2 mm or less and
particularly preferably 1.0 mm or less. In light of controllability
upon a shot with a short iron, the thickness is preferably equal to
or greater than 0.10 mm and particularly preferably equal to or
greater than 0.15 mm.
[0161] For forming the cover 12, known methods such as injection
molding, compression molding, and the like can be used. When
forming the cover 12, the dimples 14 are formed by pimples formed
on the cavity face of a mold.
[0162] The reinforcing layer 10 is positioned between the outer mid
layer 8 and the cover 12. The reinforcing layer 10 firmly adheres
to the outer mid layer 8 and also to the cover 12. The reinforcing
layer 10 suppresses separation of the cover 12 from the outer mid
layer 8. As described above, the cover 12 of the golf ball 2 is
thin. When the golf ball 2 is hit by the edge of a clubface, a
wrinkle is likely to occur. The reinforcing layer 10 suppresses
occurrence of a wrinkle.
[0163] As the base polymer of the reinforcing layer 10, a
two-component curing type thermosetting resin is suitably used.
Specific examples of two-component curing type thermosetting resins
include epoxy resins, urethane resins, acrylic resins, polyester
resins, and cellulose resins. In light of strength and durability
of the reinforcing layer 10, two-component curing type epoxy resins
and two-component curing type urethane resins are preferred.
[0164] A two-component curing type epoxy resin is obtained by
curing an epoxy resin with a polyamide type curing agent. Examples
of epoxy resins used in two-component curing type epoxy resins
include bisphenol A type epoxy resins, bisphenol F type epoxy
resins, and bisphenol AD type epoxy resins. A bisphenol A type
epoxy resin is obtained by a reaction of bisphenol A and an epoxy
group-containing compound such as epichlorohydrin or the like. A
bisphenol F type epoxy resin is obtained by a reaction of bisphenol
F and an epoxy group-containing compound. A bisphenol AD type epoxy
resin is obtained by a reaction of bisphenol AD and an epoxy
group-containing compound. In light of balance among flexibility,
chemical resistance, heat resistance, and toughness, bisphenol A
type epoxy resins are preferred.
[0165] The polyamide type curing agent has a plurality of amino
groups and one or more amide groups. The amino groups can react
with epoxy groups. Specific examples of the polyamide type curing
agent include polyamide amine curing agents and modified products
thereof. A polyamide amine curing agent is obtained by a
condensation reaction of a polymerized fatty acid and a polyamine.
A typical polymerized fatty acid is obtained by heating and
combining natural fatty acids including a large amount of
unsaturated fatty acids, such as linoleic acid, linolenic acid, and
the like, in the presence of a catalyst. Specific examples of
unsaturated fatty acids include tall oil, soybean oil, linseed oil,
and fish oil. A hydrogenated polymerized fatty acid having a dimer
content of 90% by weight or greater and a trimer content of 10% by
weight or less is preferred. Examples of preferable polyamines
include polyethylene diamines, polyoxyalkylene diamines, and
derivatives thereof.
[0166] In a mixture of an epoxy resin and a polyamide type curing
agent, the ratio of the epoxy equivalent of the epoxy resin to the
amine active hydrogen equivalent of the polyamide type curing agent
is preferably equal to or greater than 1.0/1.4 but equal to or less
than 1.0/1.0.
[0167] A two-component curing type urethane resin is obtained by a
reaction of a base material and a curing agent. A two-component
curing type urethane resin obtained by a reaction of a base
material containing a polyol component and a curing agent
containing a polyisocyanate or a derivative thereof, and a
two-component curing type urethane resin obtained by a reaction of
a base material containing an isocyanate group-terminated urethane
prepolymer and a curing agent having active hydrogen, can be used.
Particularly, a two-component curing type urethane resin obtained
by a reaction of a base material containing a polyol component and
a curing agent containing a polyisocyanate or a derivative thereof,
is preferred.
[0168] As the polyol component of the base material, a urethane
polyol is preferably used. The urethane polyol has urethane bonds
and at least two or more hydroxyl groups. Preferably, the urethane
polyol has hydroxyl groups at its ends. The urethane polyol can be
obtained by causing a reaction of a polyol and a polyisocyanate at
such a ratio that the hydroxyl groups of the polyol component are
excessive in mole ratio with respect to the isocyanate groups of
the polyisocyanate.
[0169] The polyol used for producing the urethane polyol has a
plurality of hydroxyl groups. Polyols having a weight average
molecular weight of 50 or greater but 2000 or less are preferred,
and polyols having a weight average molecular weight of 100 or
greater but 1000 or less are particularly preferred. Examples of
low-molecular-weight polyols include diols and triols. Specific
examples of diols include ethylene glycol, diethylene glycol,
triethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl
glycol, and 1,6-hexanediol. Specific examples of triols include
trimethylol propane and hexanetriol. Examples of
high-molecular-weight polyols include polyether polyols such as
polyoxyethylene glycol (PEG), polyoxypropylene glycol (PPG), and
polyoxytetramethylene glycol (PTMG); condensed polyester polyols
such as polyethylene adipate (PEA), polybutylene adipate (PBA), and
polyhexamethylene adipate (PHMA); lactone polyester polyols such as
poly-.epsilon.-caprolactone (PCL); polycarbonate polyols such as
polyhexamethylene carbonate; and acrylic polyols. Two or more
polyols may be used in combination.
[0170] The polyisocyanate used for producing the urethane polyol
has a plurality of isocyanate groups. Specific examples of the
polyisocyanate include aromatic polyisocyanates such as 2,4-toluene
diisocyanate, 2,6-toluene diisocyanate, a mixture (TDI) of
2,4-toluenediisocyanate and 2,6-toluene diisocyanate,
4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene
diisocyanate (NDI), 3,3'-bitolylene-4,4'-diisocyanate (TODI),
xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate
(TMXDI), and paraphenylene diisocyanate (PPDI); alicyclic
polyisocyanates such as 4,4'-dicyclohexylmethane diisocyanate
(H.sub.12MDI), hydrogenated xylylene diisocyanate (H.sub.6XDI), and
isophorone diisocyanate (IPDI); and aliphatic polyisocyanates such
as hexamethylene diisocyanate (HDI). Two or more of these
polyisocyanates may be used in combination. In light of weather
resistance, TMXDI, XDI, HDI, H.sub.6XDI, IPDI, and H.sub.12MDI are
preferred.
[0171] In the reaction of the polyol and the polyisocyanate for
producing the urethane polyol, a known catalyst can be used. A
typical catalyst is dibutyl tin dilaurate.
[0172] In light of strength of the reinforcing layer 10, the
proportion of the urethane bonds included in the urethane polyol is
preferably equal to or greater than 0.1 mmol/g. In light of
followability of the reinforcing layer 10 to the cover 12, the
proportion of the urethane bonds included in the urethane polyol is
preferably equal to or less than 5 mmol/g. The proportion of the
urethane bonds can be adjusted by adjusting the molecular weight of
the polyol, which is the material for the urethane polyol, and
adjusting the blending ratio of the polyol and the
polyisocyanate.
[0173] From the standpoint that a time taken for the reaction of
the base material and the curing agent is short, the weight average
molecular weight of the urethane polyol is preferably equal to or
greater than 4000 and particularly preferably equal to or greater
than 4500. In light of adhesion of the reinforcing layer 10, the
weight average molecular weight of the urethane polyol is
preferably equal to or less than 10000 and particularly preferably
equal to or less than 9000.
[0174] In light of adhesion of the reinforcing layer 10, the
hydroxyl value (mg KOH/g) of the urethane polyol is preferably
equal to or greater than 15 and particularly preferably equal to or
greater than 73. From the standpoint that a time taken for the
reaction of the base material and the curing agent is short, the
hydroxyl value of the urethane polyol is preferably equal to or
less than 130 and particularly preferably equal to or less than
120.
[0175] The base material may contain, together with a urethane
polyol, a polyol that does not have any urethane bond. The
aforementioned polyol that is the material for the urethane polyol
can be used in the base material. Polyols compatible with the
urethane polyol are preferred. From the standpoint that a time
taken for the reaction of the base material and the curing agent is
short, the proportion of the urethane polyol in the base material
on the solid content basis is preferably equal to or greater than
50% by weight and particularly preferably equal to or greater than
80% by weight. Ideally, the proportion is 100% by weight.
[0176] The curing agent contains a polyisocyanate or a derivative
thereof. The aforementioned polyisocyanate that is the material for
the urethane polyol can be used in the curing agent.
[0177] The reinforcing layer 10 may include additives such as a
coloring agent (typically, titanium dioxide), a phosphate-based
stabilizer, an antioxidant, a light stabilizer, a fluorescent
brightener, an ultraviolet absorber, an anti-blocking agent, and
the like. The additives may be added to the base material of the
two-component curing type thermosetting resin, or may be added to
the curing agent of the two-component curing type thermosetting
resin.
[0178] The reinforcing layer 10 is obtained by applying, to the
surface of the outer mid layer 8, a liquid that is prepared by
dissolving or dispersing the base material and the curing agent in
a solvent. In light of workability, application with a spray gun is
preferred. After the application, the solvent is volatilized to
permit a reaction of the base material with the curing agent,
thereby forming the reinforcing layer 10. Examples of preferable
solvents include toluene, isopropyl alcohol, xylene, methyl ethyl
ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether,
ethylbenzene, propylene glycol monomethyl ether, isobutyl alcohol,
and ethyl acetate.
[0179] In light of feel at impact, the golf ball 2 has an amount of
compressive deformation Db of preferably 2.1 mm or greater, more
preferably 2.2 mm or greater, and particularly preferably 2.3 mm or
greater. In light of resilience performance, the amount of
compressive deformation Db is preferably equal to or less than 3.2
mm, more preferably equal to or less than 3.0 mm, and particularly
preferably equal to or less than 2.8 mm.
[0180] At measurement of the amount of compressive deformation,
first, a sphere (the golf ball 2, the core 4, or the like) is
placed on a hard plate made of metal. Next, a cylinder made of
metal gradually descends toward the sphere. The sphere, squeezed
between the bottom face of the cylinder and the hard plate, becomes
deformed. A migration distance of the cylinder, starting from the
state in which an initial load of 98 N is applied to the sphere up
to the state in which a final load of 1274 N is applied thereto, is
measured.
EXAMPLES
Example 1
[0181] A rubber composition was obtained by kneading 100 parts by
weight of a high-cis polybutadiene (trade name "BR-730",
manufactured by JSR Corporation), 34 parts by weight of zinc
diacrylate (trade name "Sanceler SR", manufactured by SANSHIN
CHEMICAL INDUSTRY CO., LTD.), 5 parts by weight of zinc oxide, an
appropriate amount of barium sulfate, 0.32 parts by weight of
2-naphthalenethiol, 10 parts by weight of zinc stearate, and 0.8
parts by weight of dicumyl peroxide. This rubber composition was
placed into a mold including upper and lower mold halves each
having a hemispherical cavity, and heated at 170.degree. C. for 25
minutes to obtain a core with a diameter of 35.40 mm. The amount of
barium sulfate was adjusted such that the weight of a golf ball is
45.4 g.
[0182] A resin composition was obtained by kneading 52 parts by
weight of an ionomer resin (the aforementioned "Himilan 1605"), 40
parts by weight of another ionomer resin (the aforementioned
"Himilan AM7329"), 8 parts by weight of a styrene block-containing
thermoplastic elastomer (the aforementioned "Rabalon T3221C"), and
4 parts by weight of titanium dioxide with a twin-screw kneading
extruder. The core was placed into a mold. The core was covered
with the resin composition by injection molding to form an inner
mid layer with a thickness of 1.70 mm.
[0183] A resin composition was obtained by kneading 60 parts by
weight of an ionomer resin (the aforementioned "Surlyn 8150"), 40
parts by weight of another ionomer resin (the aforementioned
"Surlyn 9150"), and 4 parts by weight of titanium dioxide with a
twin-screw kneading extruder. The sphere consisting of the core and
the inner mid layer was placed into a mold. The sphere was covered
with the resin composition by injection molding to form an outer
mid layer with a thickness of 1.10 mm.
[0184] A paint composition (trade name "POLIN 750LE", manufactured
by SHINTO PAINT CO., LTD.) including a two-component curing type
epoxy resin as a base polymer was prepared. The base material
liquid of this paint composition includes 30 parts by weight of a
bisphenol A type solid epoxy resin and 70 parts by weight of a
solvent. The curing agent liquid of this paint composition includes
40 parts by weight of a modified polyamide amine, 55 parts by
weight of a solvent, and 5 parts by weight of titanium oxide. The
weight ratio of the base material liquid to the curing agent liquid
is 1/1. This paint composition was applied to the surface of the
outer mid layer with a spray gun, and kept at 40.degree. C. for 24
hours to obtain a reinforcing layer with a thickness of 10
.mu.m.
[0185] A resin composition was obtained by kneading 50 parts by
weight of a thermoplastic polyurethane elastomer (the
aforementioned "Elastollan ET890A"), 50 parts by weight of another
thermoplastic polyurethane elastomer (the aforementioned
"Elastollan ET88050", and 4 parts by weight of titanium dioxide
with a twin-screw kneading extruder. Half shells were formed from
this resin composition by compression molding. The sphere
consisting of the core, the mid layer, and the reinforcing layer
was covered with two of these half shells. The sphere and the half
shells were placed into a final mold that includes upper and lower
mold halves each having a hemispherical cavity and that has a large
number of pimples on its cavity face. A cover was obtained by
compression molding. The thickness of the cover was 0.85 mm.
Dimples having a shape that is the inverted shape of the pimples
were formed on the cover. A clear paint including a two-component
curing type polyurethane as a base material was applied to this
cover to obtain a golf ball of Example 1 with a diameter of 42.7
mm.
Examples 2 to 20 and Comparative Examples 1 to 6
[0186] Golf balls of Examples 2 to 20 and Comparative Examples 1 to
6 were obtained in the same manner as Example 1, except the
specifications of the core, the inner mid layer, the outer mid
layer, and the cover were as shown in Tables 6 to 10 below. The
composition and hardness of the core are shown in detail in Tables
1 to 4 below. The compositions of the inner mid layer, the outer
mid layer, and the cover are shown in detail in Table 5 below.
[0187] [Hit with Driver (W#1)]
[0188] A driver with a titanium head (trade name "XXIO",
manufactured by SRI Sports Limited, shaft hardness: S, loft angle:
11.0.degree.) was attached to a swing machine manufactured by Golf
Laboratories, Inc. A golf ball was hit under the condition of a
head speed of 50 m/sec. The spin rate was measured immediately
after the hit. Further, the distance from the launch point to the
stop point was measured. The average value of data obtained by 12
measurements is shown in Tables 6 to 10 below.
[0189] [Hit with Sand Wedge (SW)]
[0190] A sand wedge (SW) was attached to a swing machine
manufactured by Golf Laboratories, Inc. A golf ball was hit under
the condition of a head speed of 21 m/sec. The spin rate was
measured immediately after the hit. The average value of data
obtained by 12 measurements is shown in Tables 6 to 10 below.
TABLE-US-00001 TABLE 1 Composition and Hardness of Core Type A B C
D E BR730 100 100 100 100 100 Sanceler SR 34 37 40 35 35 Zn--DA90S
-- -- -- -- -- Zinc oxide 5 5 5 5 5 Barium sulfate * * * * *
2-naphthalenethiol 0.32 0.32 0.32 0.32 0.32 Zinc stearate 10 10 10
20 30 Aluminum stearate -- -- -- -- -- Octanoic acid -- -- -- -- --
Decanoic acid -- -- -- -- -- Lauric acid -- -- -- -- -- Myristic
acid -- -- -- -- -- Stearic acid -- -- -- -- -- Zinc octoate -- --
-- -- -- Zinc laurate -- -- -- -- -- Zinc myristate -- -- -- -- --
Dicumyl peroxide 0.8 0.8 0.8 0.8 0.8 Total amount of carboxylic
13.4 13.7 14.0 23.5 33.5 acid/salt H(0) 61.0 58.0 60.1 60.7 59.0
H(12.5) 63.0 61.4 63.4 64.5 63.4 H(25) 68.2 66.0 67.8 69.5 68.4
H(37.5) 69.0 68.4 70.4 72.2 72.5 H(50) 70.0 70.0 72.0 71.4 71.2
H(62.5) 72.0 71.8 74.2 74.0 73.6 H(75) 79.8 79.0 81.1 76.8 75.9
H(87.5) 81.5 85.2 87.6 82.0 82.1 H(100) 82.0 87.0 88.8 81.7 81.8 *
Appropriate amount
TABLE-US-00002 TABLE 2 Composition and Hardness of Core Type F G H
I J BR730 100 100 100 100 100 Sanceler SR 35 -- 38 41 38 Zn-DA90S
-- 34 -- -- -- Zinc oxide 5 5 5 5 5 Barium sulfate * * * * *
2-naphthalenethiol 0.32 0.32 0.32 0.32 0.32 Zinc stearate -- 10 --
-- -- Aluminum stearate 10 -- -- -- -- Octanoic acid -- -- 2.5 --
-- Decanoic acid -- -- -- 6 -- Lauric acid -- -- -- -- 7 Myristic
acid -- -- -- -- -- Stearic acid -- -- -- -- -- Zinc octoate -- --
-- -- -- Zinc laurate -- -- -- -- -- Zinc myristate -- -- -- -- --
Dicumyl peroxide 0.8 0.8 0.8 0.8 0.8 Total amount of carboxylic
13.5 13.4 6.3 10.1 10.8 acid/salt H(0) 60.0 61.0 56.4 55.5 56.3
H(12.5) 63.1 62.9 62.2 61.0 61.0 H(25) 67.9 68.2 68.3 66.0 65.8
H(37.5) 70.9 70.1 70.5 68.5 68.9 H(50) 71.0 70.8 71.5 69.6 69.9
H(62.5) 73.4 73.2 72.1 74.6 72.7 H(75) 75.0 74.9 80.1 82.0 81.1
H(87.5) 81.9 82.0 83.9 84.6 83.9 H(100) 81.5 83.0 89.0 89.6 87.9 *
Appropriate amount
TABLE-US-00003 TABLE 3 Composition and Hardness of Core Type K L M
N O BR730 100 100 100 100 100 Sanceler SR 36 32 41 38 29 Zn--DA90S
-- -- -- -- -- Zinc oxide 5 5 5 5 5 Barium sulfate * * * * *
2-naphthalenethiol 0.32 -- 0.32 0.32 -- Zinc stearate -- -- -- --
-- Aluminum stearate -- -- -- -- -- Octanoic acid -- -- -- -- --
Decanoic acid -- -- -- -- -- Lauric acid -- -- -- -- -- Myristic
acid 5 -- -- -- -- Stearic acid -- 10 -- -- -- Zinc octoate -- -- 5
-- -- Zinc laurate -- -- -- 10 15 Zinc myristate -- -- -- -- --
Dicumyl peroxide 0.8 0.8 0.8 0.8 0.8 Total amount of carboxylic 8.6
13.2 9.1 13.8 17.9 acid/salt H(0) 54.5 62.9 55.6 56.7 47.2 H(12.5)
60.8 67.7 62.2 61.2 51.0 H(25) 67.1 71.7 65.9 66.0 55.5 H(37.5)
69.3 73.2 68.5 68.4 58.8 H(50) 69.8 73.8 70.5 70.4 62.3 H(62.5)
71.7 76.4 76.5 74.5 68.1 H(75) 80.2 80.6 83.1 82.3 76.0 H(87.5)
83.9 82.2 86.5 85.9 81.4 H(100) 88.8 86.7 89.6 88.9 86.5 *
Appropriate amount
TABLE-US-00004 TABLE 4 Composition and Hardness of Core Type P Q R
S T U BR730 100 100 100 100 100 100 Sanceler SR 38 25 27 40 38 24
Zn-DA90S -- -- -- -- -- -- Zinc oxide 5 5 5 -- 5 5 Barium sulfate *
* * * * * 2-naphthalen- 0.32 0.32 0.32 0.32 -- -- ethiol Diphenyl
-- -- -- -- -- 0.22 disulfide Zinc stearate -- 5 -- 40 -- --
Aluminum -- -- -- -- -- -- stearate Octanoic acid -- -- -- -- -- --
Decanoic acid -- -- -- -- -- -- Lauric acid -- -- -- -- -- --
Myristic acid -- -- -- -- -- -- Stearic acid -- -- -- -- -- 10 Zinc
octoate -- -- -- -- -- -- Zinc laurate -- -- -- -- -- -- Zinc
myristate 10 -- -- -- -- -- Dicumyl peroxide 0.8 0.8 0.8 0.8 0.8
0.8 Total amount 13.8 7.5 2.7 44 3.8 12.4 of carboxylic acid/salt
H(0) 56.6 62.8 56.7 63.0 62.0 62.3 H(12.5) 60.4 65.8 62.0 64.2 67.4
66.0 H(25) 64.6 68.0 66.0 66.5 71.0 68.4 H(37.5) 68.0 69.5 67.3
67.0 71.8 69.4 H(50) 69.4 69.4 66.6 68.4 71.9 70.0 H(62.5) 73.8
70.0 66.7 70.0 72.5 72.3 H(75) 79.5 78.0 73.4 71.2 78.0 75.7
H(87.5) 84.7 80.4 79.6 71.9 80.0 76.4 H(100) 88.4 84.2 84.0 72.4
85.8 80.4 * Appropriate amount
[0191] The details of the compounds listed in Tables 1 to 4 are as
follows.
[0192] BR730: a high-cis polybutadiene manufactured by JSR
Corporation (cis-1,4-bond content: 96% by weight, 1,2-vinyl bond
content: 1.3% by weight, Mooney viscosity (ML.sub.1+4(100.degree.
C.)): 55, molecular weight distribution (Mw/Mn): 3)
[0193] Sanceler SR: zinc diacrylate manufactured by SANSHIN
CHEMICAL INDUSTRY CO., LTD. (a product coated with 10% by weight of
stearic acid)
[0194] ZN-DA90S: zinc diacrylate manufactured by Nihon Jyoryu Kogyo
Co., Ltd. (a product coated with 10% by weight of zinc
stearate)
[0195] Zinc oxide: trade name "Ginrei R" manufactured by Toho Zinc
Co., Ltd.
[0196] Barium sulfate: trade name "Barium Sulfate BD" manufactured
by Sakai Chemical Industry Co., Ltd.
[0197] 2-naphthalenethiol: a product of Tokyo Chemical Industry
Co., Ltd.
[0198] Zinc stearate: a product of Wako Pure Chemical Industries,
Ltd. (purity: 99% or greater)
[0199] Aluminum stearate: a product of Mitsuwa Chemicals Co.,
Ltd.
[0200] Octanoic acid: a product of Tokyo Chemical Industry Co.,
Ltd. (purity: 98% or greater)
[0201] Decanoic acid: a product of Tokyo Chemical Industry Co.,
Ltd. (purity: 98% or greater)
[0202] Lauric acid: a product of Tokyo Chemical Industry Co., Ltd.
(purity: 98% or greater)
[0203] Myristic acid: a product of Tokyo Chemical Industry Co.,
Ltd. (purity: 98% or greater)
[0204] Stearic acid: a product of Tokyo Chemical Industry Co., Ltd.
(purity: 98% or greater)
[0205] Zinc octoate: a product of Mitsuwa Chemicals Co., Ltd.
(purity: 99% or greater)
[0206] Zinc laurate: a product of Mitsuwa Chemicals Co., Ltd.
(purity: 99% or greater)
[0207] Zinc myristate: a product of NOF Corporation (purity: 90% or
greater)
[0208] Dicumyl peroxide: trade name "Percumyl D" manufactured by
NOF Corporation
TABLE-US-00005 TABLE 5 Compositions of Inner Mid Layer, Outer Mid
Layer, and Cover Type (1) (2) (3) (4) (5) (6) Himilan 1605 52 50 --
-- -- -- Himilan AM7329 40 50 -- -- -- -- Rabalon T3221C 8 -- -- --
-- -- Surlyn 8150 -- -- 60 -- -- -- Surlyn 9150 -- -- 40 -- -- --
Elastollan ET890A -- -- -- 50 30 -- Elastollan 1195ATR -- -- -- --
70 -- Elastollan ET88050 -- -- -- 50 -- -- Elastollan NY88A10 clear
-- -- -- -- -- 100 Crossnate EM-30 -- -- -- 4 4 -- Titanium dioxide
4 4 4 4 4 4 Hardness (JIS-C) 86 94 97 59 53 53 Hardness (Shore D)
59 65 67 40 36 36
[0209] Crossnate EM-30 in Table 5 is supplied from Dainichiseika
Color & Chemicals Mfg. Co., Ltd. In Crossnate EM-30, MDI is
dispersed in a thermoplastic polyester resin. The MDI content is
30% by weight.
TABLE-US-00006 TABLE 6 Results of Evaluation Ex. Ex. Ex. Ex. Ex. 1
2 3 4 5 Core Type A B C A A Carboxylic acid/ 13.4 13.7 14.0 13.4
13.4 Carboxylate H(100)--H(0) 21.0 29.0 28.7 21.0 21.0 R.sup.2 0.95
0.97 0.97 0.95 0.95 Gradient of 0.22 0.29 0.29 0.22 0.22
approximation curve Diameter (mm) 35.40 37.70 38.50 35.40 35.40
Deformation Dc (mm) 3.60 3.25 2.92 3.60 3.60 Inner mid layer
Composition (1) (1) (1) (1) (1) Hardness Hmi (Shore D) 59.0 59.0
59.0 59.0 59.0 Thickness (mm) 1.70 1.20 0.80 1.70 1.70 Outer mid
layer Composition (3) (3) (2) (3) (3) Hardness Hmo (Shore D) 67.0
67.0 65.0 67.0 67.0 Thickness (mm) 1.10 1.00 0.80 1.10 1.10 Cover
Composition (4) (4) (4) (5) (6) Hardness Hc (Shore D) 40 40 40 36
36 Hardness (JIS--C) 59 59 59 53 53 Thickness (mm) 0.85 0.30 0.50
0.85 0.85 Deformation Db (mm) 2.36 2.40 2.44 2.36 2.35 W#1 spin
rate (rpm) 2550 2400 2600 2670 2600 W#1 flight distance (yds) 281.1
282.0 281.5 280.0 281.5 SW spin rate (rpm) 6740 6490 6590 6980
6800
TABLE-US-00007 TABLE 7 Results of Evaluation Ex. Ex. Ex. Ex. Ex. 6
7 8 9 10 Core Type D E F G H Carboxylic acid/ 23.5 33.5 13.5 13.4
6.3 Carboxylate H(100)--H(0) 21.0 22.8 21.5 22.0 32.7 R.sup.2 0.95
0.97 0.96 0.96 0.96 Gradient of 0.20 0.22 0.21 0.22 0.29
approximation curve Diameter (mm) 35.40 35.40 35.40 35.40 35.40
Deformation Dc (mm) 3.66 3.70 3.75 3.62 3.41 Inner mid layer
Composition (1) (1) (1) (1) (1) Hardness Hmi (Shore D) 59.0 59.0
59.0 59.0 59.0 Thickness (mm) 1.70 1.70 1.70 1.70 1.70 Outer mid
layer Composition (3) (3) (3) (3) (3) Hardness Hmo (Shore D) 67.0
67.0 67.0 67.0 67.0 Thickness (mm) 1.10 1.10 1.10 1.10 1.10 Cover
Composition (4) (4) (4) (4) (4) Hardness Hc (Shore D) 40 40 40 40
40 Hardness (JIS--C) 59 59 59 59 59 Thickness (mm) 0.85 0.85 0.85
0.85 0.85 Deformation Db (mm) 2.42 2.46 2.51 2.35 2.17 W#1 spin
rate (rpm) 2570 2510 2590 2520 2460 W#1 flight distance (yds) 281.0
281.5 281.0 281.0 284.0 SW spin rate (rpm) 6750 6770 6760 6750
6630
TABLE-US-00008 TABLE 8 Results of Evaluation Ex. Ex. Ex. Ex. Ex. 11
12 13 14 15 Core Type I J K L M Carboxylic acid/ 10.1 10.8 8.6 13.2
9.1 Carboxylate H(100)--H(0) 34.1 31.7 34.4 23.8 34.1 R.sup.2 0.97
0.98 0.96 0.97 0.99 Gradient of 0.33 0.31 0.31 0.21 0.34
approximation curve Diameter (mm) 35.40 35.40 35.40 35.40 35.40
Deformation Dc (mm) 3.21 3.40 3.29 3.41 3.38 Inner mid layer
Composition (1) (1) (1) (1) (1) Hardness Hmi (Shore D) 59.0 59.0
59.0 59.0 59.0 Thickness (mm) 1.70 1.70 1.70 1.70 1.70 Outer mid
layer Composition (3) (3) (3) (3) (3) Hardness Hmo (Shore D) 67.0
67.0 67.0 67.0 67.0 Thickness (mm) 1.10 1.10 1.10 1.10 1.10 Cover
Composition (4) (4) (4) (4) (4) Hardness Hc (Shore D) 40 40 40 40
40 Hardness (JIS--C) 59 59 59 59 59 Thickness (mm) 0.85 0.85 0.85
0.85 0.85 Deformation Db (mm) 2.16 2.16 2.05 2.17 2.14 W#1 spin
rate (rpm) 2470 2530 2450 2520 2420 W#1 flight distance (yds) 284.0
282.0 283.8 281.0 283.5 SW spin rate (rpm) 6650 6700 6620 6750
6600
TABLE-US-00009 TABLE 9 Results of Evaluation Ex. Ex. Ex. Ex. Ex. 16
17 18 19 20 Core Type N O P U A Carboxylic acid/ 13.8 17.9 13.8
12.4 13.4 Carboxylate H(100)--H(0) 32.2 39.4 31.9 18.1 21.0 R.sup.2
0.98 0.98 0.99 0.97 0.95 Gradient of 0.32 0.40 0.31 0.16 0.22
approximation curve Diameter (mm) 35.40 35.40 35.40 35.40 35.40
Deformation Dc (mm) 3.30 4.41 3.47 3.95 3.60 Inner mid layer
Composition (1) (1) (1) (1) (1) Hardness Hmi (Shore D) 59.0 59.0
59.0 59.0 59.0 Thickness (mm) 1.70 1.70 1.70 1.70 1.70 Outer mid
layer Composition (3) (3) (3) (3) (2) Hardness Hmo (Shore D) 67.0
67.0 67.0 67.0 65.0 Thickness (mm) 1.10 1.10 1.10 1.10 1.10 Cover
Composition (4) (4) (4) (4) (4) Hardness Hc (Shore D) 40 40 40 40
40 Hardness (JIS--C) 59 59 59 59 59 Thickness (mm) 0.85 0.85 0.85
0.85 0.85 Deformation Db (mm) 2.06 3.17 2.23 2.71 2.39 W#1 spin
rate (rpm) 2450 2400 2425 2530 2560 W#1 flight distance (yds) 283.7
284.5 283.9 282.5 281.0 SW spin rate (rpm) 6625 6560 6610 6740
6740
TABLE-US-00010 TABLE 10 Results of Evaluation Com. Com. Com. Com.
Com. Com. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Core Type A A Q R S T
Carboxylic acid/ 13.4 13.4 7.5 2.7 44 3.8 Carboxylate H(100)-H(0)
21.0 21.0 21.4 27.3 9.4 23.8 R.sup.2 0.95 0.95 0.91 0.89 0.98 0.92
Gradient of 0.22 0.22 0.20 0.23 0.10 0.20 approximation curve
Diameter (mm) 35.40 35.40 35.40 35.40 35.40 35.40 Deformation Dc
(mm) 3.60 3.60 4.10 4.40 4.20 4.10 Inner mid layer Composition (2)
(1) (1) (1) (1) (1) Hardness Hmi (Shore D) 65.0 59.0 59.0 59.0 59.0
59.0 Thickness (mm) 1.80 1.70 1.70 1.70 1.70 1.70 Outer mid layer
Composition (2) (6) (3) (3) (3) (3) Hardness Hmo (Shore D) 65.0
36.0 67.0 67.0 67.0 67.0 Thickness (mm) 1.30 1.10 1.10 1.10 1.10
1.10 Cover Composition (4) (4) (4) (4) (4) (4) Hardness Hc (Shore
D) 40 40 40 40 40 40 Hardness (JIS-C) 59 59 59 59 59 59 Thickness
(mm) 0.55 0.85 0.85 0.85 0.85 0.85 Deformation Db (mm) 2.30 2.70
2.86 3.16 2.96 2.86 W#1 spin rate (rpm) 2750 2800 2510 2720 2830
2670 W#1 flight distance (yds) 274.5 275.0 278.0 276.4 274.0 277.5
SW spin rate (rpm) 6400 6520 6500 6202 6970 6950
[0210] As shown in Tables 6 to 9, the golf balls according to
Examples are excellent in various performance characteristics. From
the results of evaluation, advantages of the present invention are
clear.
[0211] The above descriptions are merely for illustrative examples,
and various modifications can be made without departing from the
principles of the present invention.
* * * * *