U.S. patent application number 13/846597 was filed with the patent office on 2013-12-05 for golf ball.
This patent application is currently assigned to DUNLOP SPORTS CO. LTD.. The applicant listed for this patent is DUNLOP SPORTS CO. LTD.. Invention is credited to Kazuhiko ISOGAWA, Kosuke TACHIBANA.
Application Number | 20130324313 13/846597 |
Document ID | / |
Family ID | 48139822 |
Filed Date | 2013-12-05 |
United States Patent
Application |
20130324313 |
Kind Code |
A1 |
TACHIBANA; Kosuke ; et
al. |
December 5, 2013 |
GOLF BALL
Abstract
A golf ball 2 includes a core 4, a mid layer 6, a reinforcing
layer 8, an inner cover 10, and an outer cover 12. The core 4
includes a center 18 and an envelope layer 20. The envelope layer
20 is formed by a rubber composition being crosslinked. The rubber
composition includes a base rubber, a co-crosslinking agent, a
crosslinking initiator, and an acid and/or a salt. The
co-crosslinking agent is (1) an .alpha.,.beta.-unsaturated
carboxylic acid having 3 to 8 carbon atoms; and/or (2) a metal salt
of an .alpha.,.beta.-unsaturated carboxylic acid having 3 to 8
carbon atoms. A hardness Hc1 of the inner cover is greater than a
hardness Hc2 of the outer cover. A thickness T1 of the inner cover
is equal to or greater than 0.1 mm but equal to or less than 0.8
mm.
Inventors: |
TACHIBANA; Kosuke;
(Kobe-shi, JP) ; ISOGAWA; Kazuhiko; (Kobe-shi,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DUNLOP SPORTS CO. LTD. |
Kobe-shi |
|
JP |
|
|
Assignee: |
DUNLOP SPORTS CO. LTD.
Kobe-shi
JP
|
Family ID: |
48139822 |
Appl. No.: |
13/846597 |
Filed: |
March 18, 2013 |
Current U.S.
Class: |
473/373 ;
473/376 |
Current CPC
Class: |
A63B 37/0039 20130101;
A63B 37/0051 20130101; A63B 37/0092 20130101; A63B 37/0043
20130101; C08K 5/09 20130101; A63B 37/0054 20130101; C08K 5/0025
20130101; A63B 37/0003 20130101; C08K 5/09 20130101; A63B 37/0045
20130101; C08L 21/00 20130101; C08L 21/00 20130101; A63B 37/0076
20130101; A63B 37/0032 20130101; C08K 5/0025 20130101 |
Class at
Publication: |
473/373 ;
473/376 |
International
Class: |
A63B 37/00 20060101
A63B037/00 |
Foreign Application Data
Date |
Code |
Application Number |
May 29, 2012 |
JP |
2012-122531 |
May 29, 2012 |
JP |
2012-122543 |
May 30, 2012 |
JP |
2012-122578 |
May 30, 2012 |
JP |
2012-122961 |
Claims
1. A golf ball comprising a core, amid layer positioned outside the
core, an inner cover positioned outside the mid layer, and an outer
cover positioned outside the inner cover, wherein the core
comprises a center and an envelope layer positioned outside the
center, the envelope layer is formed 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)
an acid and/or a salt, 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, a Shore D hardness Hc1
of the inner cover is greater than a Shore D hardness Hc2 of the
outer cover, and a thickness T1 of the inner cover is equal to or
greater than 0.1 mm but equal to or less than 0.8 mm.
2. The golf ball according to claim 1, wherein an amount of the
acid and/or the salt (d) is equal to or greater than 0.5 parts by
weight but equal to or less than 45 parts by weight, per 100 parts
by weight of the base rubber (a).
3. The golf ball according to claim 1, wherein the acid and/or the
salt (d) is a carboxylic acid and/or a salt thereof (d1).
4. The golf ball according to claim 3, wherein a carbon number of a
carboxylic acid component of the carboxylic acid and/or the salt
thereof (d1) is equal to or greater than 1 but equal to or less
than 30.
5. The golf ball according to claim 3, wherein the carboxylic acid
and/or the salt thereof (d1) is a fatty acid and/or a salt
thereof.
6. The golf ball according to claim 1, wherein a JIS-C hardness
H(0) at a central point of the core is equal to or greater than 40
but equal to or less than 70, and a JIS-C hardness H(100) at a
surface of the core is equal to or greater than 78 but equal to or
less than 96.
7. The golf ball according to claim 6, wherein a difference
(H(100)-H(0)) between the hardness H(100) and the hardness H(0) is
equal to or greater than 15.
8. The golf ball according to claim 1, wherein a Shore D hardness
Hm of the mid layer is greater than the hardness Hc1.
9. The golf ball according to claim 8, wherein a difference
(Hm-Hc1) between the hardness Hm and the hardness Hc1 is equal to
or greater than 15.
10. The golf ball according to claim 1, wherein a Shore D hardness
Hm of the mid layer is greater than the hardness Hc2.
11. The golf ball according to claim 10, wherein a difference
(Hm-Hc2) between the hardness Hm and the hardness Hc2 is equal to
or greater than 20.
12. The golf ball according to claim 1, wherein a difference
(Hc1-Hc2) between the hardness Hc1 and the hardness Hc2 is equal to
or greater than 5.
13. The golf ball according to claim 1, wherein a thickness Tm of
the mid layer is equal to or greater than 0.5 mm but equal to or
less than 1.6 mm.
14. The golf ball according to claim 1, wherein a thickness T2 of
the outer cover is equal to or greater than 0.1 mm but equal to or
less than 0.8 mm.
15. The golf ball according to claim 1, wherein a difference
(T1-T2) between the thickness T1 and a thickness T2 of the outer
cover is equal to or greater than -0.4 mm but equal to or less than
0.4 mm.
16. The golf ball according to claim 1, wherein a sum (T1+T2) of
the thickness T1 and a thickness T2 of the outer cover is equal to
or less than 1.0 mm.
17. The golf ball according to claim 1, wherein the rubber
composition further includes an organic sulfur compound (e).
18. The golf ball according to claim 17, wherein the organic sulfur
compound (e) is at least one member selected from the group
consisting of thiophenols, diphenyl disulfides, thionaphthols,
thiuram disulfides, and metal salts thereof.
19. The golf ball according to claim 17, wherein the rubber
composition includes 0.05 parts by weight or greater but 5.0 parts
by weight or less of the organic sulfur compound (e) per 100 parts
by weight of the base rubber (a).
20. The golf ball according to claim 1, wherein the rubber
composition includes the .alpha.,.beta.-unsaturated carboxylic acid
(b1), and the rubber composition further includes a metal compound
(f).
21. The golf ball according to claim 1, wherein the mid layer is
formed from a resin composition, the inner cover is formed from a
resin composition whose base resin is different from a base resin
of the mid layer, and the golf ball further comprises a reinforcing
layer between the mid layer and the inner cover.
22. The golf ball according to claim 1, wherein a diameter of the
center is equal to or greater than 10 mm but equal to or less than
20 mm.
23. The golf ball according to claim 1, wherein the acid and/or the
salt (d) is a zinc salt of a carboxylic acid.
24. The golf ball according to claim 23, wherein the zinc salt of
the carboxylic acid is one or more members selected from the group
consisting of zinc octoate, zinc laurate, zinc myristate, and zinc
stearate.
25. A golf ball comprising a core, amid layer positioned outside
the core, an inner cover positioned outside the mid layer, and an
outer cover positioned outside the inner cover, wherein the core
comprises a center and an envelope layer positioned outside the
center, the envelope layer is formed 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)
an acid and/or a salt, 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, a Shore D hardness Hm
of the mid layer is greater than a Shore D hardness Hc1 of the
inner cover, and the Shore D hardness Hc1 of the inner cover is
less than a Shore D hardness Hc2 of the outer cover.
26. The golf ball according to claim 25, wherein an amount of the
acid and/or the salt (d) is equal to or greater than 0.5 parts by
weight but equal to or less than 45 parts by weight, per 100 parts
by weight of the base rubber (a).
27. The golf ball according to claim 25, wherein the acid and/or
the salt (d) is a carboxylic acid and/or a salt thereof (d1).
28. The golf ball according to claim 27, wherein a carbon number of
a carboxylic acid component of the carboxylic acid and/or the salt
thereof (d1) is equal to or greater than 1 but equal to or less
than 30.
29. The golf ball according to claim 27, wherein the carboxylic
acid and/or the salt thereof (d1) is a fatty acid and/or a salt
thereof.
30. The golf ball according to claim 25, wherein a JIS-C hardness
H(0) at a central point of the core is equal to or greater than 40
but equal to or less than 70, and a JIS-C hardness H(100) at a
surface of the core is equal to or greater than 78 but equal to or
less than 96.
31. The golf ball according to claim 30, wherein a difference
(H(100)-H(0)) between the hardness H(100) and the hardness H(0) is
equal to or greater than 15.
32. The golf ball according to claim 25, wherein a difference
(Hm-Hc1) between the Shore D hardness Hm of the mid layer and the
hardness Hc1 of the inner cover is equal to or greater than 20.
33. The golf ball according to claim 25, wherein a difference
(Hc2-Hc1) between the hardness Hc2 of the outer cover and the
hardness Hc1 of the inner cover is equal to or greater than 5.
34. The golf ball according to claim 25, wherein the hardness Hm is
greater than the hardness Hc2.
35. The golf ball according to claim 34, wherein a difference
(Hm-Hc2) between the hardness Hm and the hardness Hc2 is equal to
or greater than 15.
36. The golf ball according to claim 25, wherein a thickness Tm of
the mid layer is equal to or greater than 0.5 mm but equal to or
less than 1.6 mm.
37. The golf ball according to claim 25, wherein a thickness T1 of
the inner cover is equal to or greater than 0.1 mm but equal to or
less than 0.8 mm.
38. The golf ball according to claim 25, wherein a thickness T2 of
the outer cover is equal to or greater than 0.1 mm but equal to or
less than 0.8 mm.
39. The golf ball according to claim 25, wherein a difference
(T1-T2) between a thickness T1 of the inner cover and a thickness
T2 of the outer cover is equal to or greater than -0.4 mm but equal
to or less than 0.4 mm.
40. The golf ball according to claim 25, wherein a sum (T1+T2) of a
thickness T1 of the inner cover and a thickness T2 of the outer
cover is equal to or less than 1.0 mm.
41. The golf ball according to claim 25, wherein the rubber
composition further includes an organic sulfur compound (e).
42. The golf ball according to claim 41, wherein the organic sulfur
compound (e) is at least one member selected from the group
consisting of thiophenols, diphenyl disulfides, thionaphthols,
thiuram disulfides, and metal salts thereof.
43. The golf ball according to claim 41, wherein the rubber
composition includes 0.05 parts by weight or greater but 5.0 parts
by weight or less of the organic sulfur compound (e) per 100 parts
by weight of the base rubber (a).
44. The golf ball according to claim 25, wherein the rubber
composition includes the .alpha.,.beta.-unsaturated carboxylic acid
(b1), and the rubber composition further includes a metal compound
(f).
45. The golf ball according to claim 25, wherein the mid layer is
formed from a resin composition, the inner cover is formed from a
resin composition whose base resin is different from a base resin
of the mid layer, and the golf ball further comprises a reinforcing
layer between the mid layer and the inner cover.
46. The golf ball according to claim 25, wherein a diameter of the
center is equal to or greater than 10 mm but equal to or less than
20 mm.
47. The golf ball according to claim 25, wherein the rubber
composition includes 15 parts by weight or greater but 50 parts by
weight or less of the co-crosslinking agent (b) per 100 parts by
weight of the base rubber (a).
48. The golf ball according to claim 25, wherein the rubber
composition includes 0.2 parts by weight or greater but 5.0 parts
by weight or less of the crosslinking initiator (c) per 100 parts
by weight of the base rubber (a).
49. The golf ball according to claim 25, wherein the acid and/or
the salt (d) is a zinc salt of a carboxylic acid.
50. The golf ball according to claim 49, wherein the zinc salt of
the carboxylic acid is one or more members selected from the group
consisting of zinc octoate, zinc laurate, zinc myristate, and zinc
stearate.
51. 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 the core comprises a center and an envelope layer
positioned outside the center, when distances (%) from a boundary
between the center and the envelope layer to nine points and JIS-C
hardnesses at the nine points, which nine points are obtained by
dividing a distance from the boundary between the center and the
envelope layer to a surface of the core at intervals of 12.5% of
the distance, 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 Shore D hardness Hm1 of the inner mid layer
is less than a Shore D hardness Hm2 of the outer mid layer, and the
hardness Hm2 is greater than a Shore D hardness Hc of the
cover.
52. The golf ball according to claim 51, wherein a JIS-C hardness
Ho at a central point of the core is equal to or greater than 40
but equal to or less than 70, and a JIS-C hardness Hs at the
surface of the core is equal to or greater than 80 but equal to or
less than 96.
53. The golf ball according to claim 51, wherein a JIS-C hardness
Hs at the surface of the core is greater than a JIS-C hardness Ho
at a central point of the core, and a difference (Hs-Ho) between
the hardness Hs and the hardness Ho is equal to or greater than
20.
54. The golf ball according to claim 51, wherein a difference
(Hm2-Hm1) between the hardness Hm2 and the hardness Hm1 is equal to
or greater than 8, and a difference (Hm2-Hc) between the hardness
Hm2 and the hardness Hc is equal to or greater than 30.
55. The golf ball according to claim 51, wherein a sum (Tm1+Tm2) of
a thickness Tm1 of the inner mid layer and a thickness Tm2 of the
outer mid layer is equal to or greater than 1.0 mm but equal to or
less than 3.0 mm, and a thickness Tc of the cover is equal to or
less than 0.8 mm.
56. The golf ball according to claim 51, wherein a diameter of the
center is equal to or greater than 10 mm but equal to or less than
25 mm.
57. The golf ball according to claim 51, wherein the envelope layer
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) an acid and/or a salt,
and 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.
58. The golf ball according to claim 57, wherein the acid and/or
the salt (d) is a carboxylic acid and/or a salt thereof (d1).
59. The golf ball according to claim 58, wherein a carbon number of
a carboxylic acid component of the carboxylic acid and/or the salt
thereof (d1) is equal to or greater than 1 but equal to or less
than 30.
60. The golf ball according to claim 58, wherein the carboxylic
acid and/or the salt thereof (d1) is a fatty acid and/or a salt
thereof.
61. The golf ball according to claim 58, wherein the carboxylic
acid and/or the salt thereof (d1) is a zinc salt of a carboxylic
acid.
62. The golf ball according to claim 58, wherein the carboxylic
acid and/or the salt thereof (d1) is one or more members selected
from the group consisting of zinc octoate, zinc laurate, zinc
myristate, and zinc stearate.
63. The golf ball according to claim 57, wherein the rubber
composition includes 100 parts by weight of the base rubber (a) and
1.0 parts by weight or greater but less than 40 parts by weight of
the acid and/or the salt (d).
64. The golf ball according to claim 57, wherein the rubber
composition includes the .alpha.,.beta.-unsaturated carboxylic acid
(b1), and the rubber composition further includes a metal compound
(f).
65. The golf ball according to claim 57, 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).
66. The golf ball according to claim 57, wherein the rubber
composition includes 100 parts by weight of the base rubber (a) and
0.2 parts by weight or greater but 5 parts by weight or less of the
crosslinking initiator (c).
67. The golf ball according to claim 57, wherein the rubber
composition includes the metal salt (b2) of the
.alpha.,.beta.-unsaturated carboxylic acid.
68. The golf ball according to claim 51, wherein the outer mid
layer is formed from a resin composition, the cover is formed from
another resin composition, a principal component of a base resin of
the resin composition of the outer mid layer is different from a
principal component of a base resin of the resin composition of the
cover, and the golf ball further comprises a reinforcing layer
between the outer mid layer and the cover.
69. The golf ball according to claim 57, wherein the rubber
composition further includes an organic sulfur compound (e).
70. The golf ball according to claim 69, wherein the organic sulfur
compound (e) is at least one member selected from the group
consisting of thiophenols, diphenyl disulfides, thionaphthols,
thiuram disulfides, and metal salts thereof.
71. The golf ball according to claim 69, wherein the organic sulfur
compound (e) is 2-thionaphthol.
72. The golf ball according to claim 69, wherein the rubber
composition includes 100 parts by weight of the base rubber (a) and
0.05 parts by weight or greater but 5.0 parts by weight or less of
the organic sulfur compound (e).
73. 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 the core comprises a center and an envelope layer
positioned outside the center, when distances (%) from a boundary
between the center and the envelope layer to nine points and JIS-C
hardnesses at the nine points, which nine points are obtained by
dividing a distance from the boundary between the center and the
envelope layer to a surface of the core at intervals of 12.5% of
the distance, 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 Shore D hardness Hm1 of the inner mid layer
is greater than a Shore D hardness Hm2 of the outer mid layer, the
hardness Hm1 is greater than a Shore D hardness Hc of the cover,
and a thickness Tm2 of the outer mid layer is equal to or greater
than 0.5 mm but equal to or less than 1.5 mm.
74. The golf ball according to claim 73, wherein a JIS-C hardness
Ho at a central point of the core is equal to or greater than 40
but equal to or less than 70, and a JIS-C hardness Hs at the
surface of the core is equal to or greater than 80 but equal to or
less than 96.
75. The golf ball according to claim 73, wherein a JIS-C hardness
Hs at the surface of the core is greater than a JIS-C hardness Ho
at a central point of the core, and a difference (Hs-Ho) between
the hardness Hs and the hardness Ho is equal to or greater than
20.
76. The golf ball according to claim 73, wherein a difference
(Hm1-Hm2) between the hardness Hm1 and the hardness Hm2 is equal to
or greater than 8, and a difference (Hm1-Hc) between the hardness
Hm1 and the hardness Hc is equal to or greater than 30.
77. The golf ball according to claim 73, wherein a sum (Tm1+Tm2) of
a thickness Tm1 of the inner mid layer and the thickness Tm2 is
equal to or greater than 1.0 mm but equal to or less than 3.0 mm,
and a thickness Tc of the cover is equal to or less than 0.8
mm.
78. The golf ball according to claim 73, wherein a diameter of the
center is equal to or greater than 10 mm but equal to or less than
25 mm.
79. The golf ball according to claim 73, wherein the envelope layer
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) an acid and/or a salt,
and 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.
80. The golf ball according to claim 79, wherein the acid and/or
the salt (d) is a carboxylic acid and/or a salt thereof (d1).
81. The golf ball according to claim 80, wherein a carbon number of
a carboxylic acid component of the carboxylic acid and/or the salt
thereof (d1) is equal to or greater than 1 but equal to or less
than 30.
82. The golf ball according to claim 80, wherein the carboxylic
acid and/or the salt thereof (d1) is a fatty acid and/or a salt
thereof.
83. The golf ball according to claim 80, wherein the carboxylic
acid and/or the salt thereof (d1) is a zinc salt of a carboxylic
acid.
84. The golf ball according to claim 80, wherein the carboxylic
acid and/or the salt thereof (d1) is one or more members selected
from the group consisting of zinc octoate, zinc laurate, zinc
myristate, and zinc stearate.
85. The golf ball according to claim 79, wherein the rubber
composition includes 100 parts by weight of the base rubber (a) and
1.0 parts by weight or greater but 40 parts by weight or less of
the acid and/or the salt (d).
86. The golf ball according to claim 79, wherein the rubber
composition includes the .alpha.,.beta.-unsaturated carboxylic acid
(b1), and the rubber composition further includes a metal compound
(f).
87. The golf ball according to claim 79, 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).
88. The golf ball according to claim 79, wherein the rubber
composition includes 100 parts by weight of the base rubber (a) and
0.2 parts by weight or greater but 5 parts by weight or less of the
crosslinking initiator (c).
89. The golf ball according to claim 79, wherein the rubber
composition includes the metal salt (b2) of the
.alpha.,.beta.-unsaturated carboxylic acid.
90. The golf ball according to claim 73, wherein the outer mid
layer is formed from a resin composition, the cover is formed from
another resin composition, a principal component of a base resin of
the resin composition of the outer mid layer is different from a
principal component of a base resin of the resin composition of the
cover, and the golf ball further comprises a reinforcing layer
between the outer mid layer and the cover.
91. The golf ball according to claim 79, wherein the rubber
composition further includes an organic sulfur compound (e).
92. The golf ball according to claim 91, wherein the organic sulfur
compound (e) is at least one member selected from the group
consisting of thiophenols, diphenyl disulfides, thionaphthols,
thiuram disulfides, and metal salts thereof.
93. The golf ball according to claim 91, wherein the organic sulfur
compound (e) is 2-thionaphthol.
94. The golf ball according to claim 91, wherein the rubber
composition includes 100 parts by weight of the base rubber (a) and
0.05 parts by weight or greater but 5.0 parts by weight or less of
the organic sulfur compound (e).
Description
[0001] This application claims priority on Patent Application No.
2012-122531 filed in JAPAN on May 29, 2012, Patent Application No.
2012-122543 filed in JAPAN on May 29, 2012, Patent Application No.
2012-122578 filed in JAPAN on May 30, 2012, and Patent Application
No. 2012-122961 filed in JAPAN on May 30, 2012. The entire contents
of these Japanese Patent Applications 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 core, a
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,
US2008/0194358, US2008/0194359, and US2008/0214325), JP2008-194473
(US2008/0194357 and US2008/0312008), and JP2010-253268
(US2010/0273575).
[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 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 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 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] Golf players are also interested in durability of golf
balls. When being hit with a driver or the like, a golf ball
receives great shock and deforms. When a local load is applied to a
part of the ball due to the deformation, the golf ball is broken. A
golf ball that is resistant to deformation caused by hitting can be
continuously used over a long period of time.
[0017] Skilled golf players further desire appropriate feel at
impact when hitting a golf ball. A hard cover deteriorates feel at
impact. Golf players prefer soft feel at impact.
[0018] 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. 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.
[0019] Golf players' requirements for flight distance have been
escalated more than ever. Golf players further desire golf balls
that have excellent durability against hitting and can be
continuously used. Another object of the present invention is to
provide a golf ball that has desired flight performance upon a shot
with a driver and desired controllability upon a shot with a short
iron and has excellent durability.
[0020] Golf players further desire favorable feel at impact upon a
shot. Still another object of the present invention is to provide a
golf ball that has desired flight performance upon a shot with a
driver, excellent controllability upon an approach shot, and
excellent durability and provides satisfactory feel at impact.
SUMMARY OF THE INVENTION
[0021] A golf ball according to the present invention includes a
core, amid layer positioned outside the core, an inner cover
positioned outside the mid layer, and an outer cover positioned
outside the inner cover. The core includes a center and an envelope
layer positioned outside the center. The envelope layer is formed
by a rubber composition being crosslinked. The rubber composition
includes:
[0022] (a) a base rubber;
[0023] (b) a co-crosslinking agent;
[0024] (c) a crosslinking initiator; and
[0025] (d) an acid and/or a salt.
The co-crosslinking agent (b) is:
[0026] (b1) an .alpha.,62 -unsaturated carboxylic acid having 3 to
8 carbon atoms; and/or
[0027] (b2) a metal salt of an .alpha.,.beta.-unsaturated
carboxylic acid having 3 to 8 carbon atoms.
A Shore D hardness Hc1 of the inner cover is greater than a Shore D
hardness Hc2 of the outer cover. A thickness T1 of the inner cover
is equal to or greater than 0.1 mm but equal to or less than 0.8
mm. In the golf ball according to the present invention, a hardness
distribution is appropriate. In the golf ball, the energy loss is
low when the golf ball is hit. When the golf ball is hit with a
driver, the spin rate is low. The low spin rate achieves 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.
[0028] According to another aspect, a golf ball according to the
present invention includes a core, a mid layer positioned outside
the core, an inner cover positioned outside the mid layer, and an
outer cover positioned outside the inner cover. The core includes a
center and an envelope layer positioned outside the center. The
envelope layer is formed by a rubber composition being crosslinked.
The rubber composition includes:
[0029] (a) a base rubber;
[0030] (b) a co-crosslinking agent;
[0031] (c) a crosslinking initiator; and
[0032] (d) an acid and/or a salt.
The co-crosslinking agent (b) is:
[0033] (b1) an .alpha.,.beta.-unsaturated carboxylic acid having 3
to 8 carbon atoms; and/or
[0034] (b2) a metal salt of an .alpha.,.beta.-unsaturated
carboxylic acid having 3 to 8 carbon atoms.
A Shore D hardness Hm of the mid layer is greater than a Shore D
hardness Hc1 of the inner cover. The Shore D hardness Hc1 of the
inner cover is less than a Shore D hardness Hc2 of the outer cover.
In the golf ball according to the present invention, a hardness
distribution is appropriate. In the golf ball, the energy loss is
low when the golf ball is hit. When the golf ball is hit with a
driver, the spin rate is low. The low spin rate achieves 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. In
addition, the golf ball also has excellent durability.
[0035] According to still another aspect, a golf ball according to
the present invention includes 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. The core includes a center and an envelope layer positioned
outside the center. When distances (%) from a boundary between the
center and the envelope layer to nine points and JIS-C hardnesses
at the nine points, which nine points are obtained by dividing a
distance from the boundary between the center and the envelope
layer to a surface of the core at intervals of 12.5% of the
distance, 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 Shore D hardness Hm1 of the inner mid layer is less than a
Shore D hardness Hm2 of the outer mid layer. The hardness Hm2 is
greater than a Shore D hardness Hc of the cover. In the golf ball
according to the present invention, a hardness distribution of the
core is appropriate. In the golf ball, the energy loss is low when
the golf ball is hit. When the golf ball is hit with a driver, the
spin rate is low. The low spin rate achieves a large flight
distance. In the golf ball, a hardness distribution of the entire
ball is also appropriate. When the golf ball is hit with a short
iron, the spin rate is high. The golf ball has excellent
controllability. When the golf ball is hit, the local load applied
to the golf ball is low. The golf ball has excellent
durability.
[0036] According to still another aspect, a golf ball according to
the present invention includes 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. The core includes a center and an envelope layer positioned
outside the center. When distances (%) from a boundary between the
center and the envelope layer to nine points and JIS-C hardnesses
at the nine points, which nine points are obtained by dividing a
distance from the boundary between the center and the envelope
layer to a surface of the core at intervals of 12.5% of the
distance, 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 Shore D hardness Hm1 of the inner mid layer is greater than
a Shore D hardness Hm2 of the outer mid layer. The hardness Hm1 is
greater than a Shore D hardness Hc of the cover. A thickness Tm2 of
the outer mid layer is equal to or greater than 0.5 mm but equal to
or less than 1.5 mm. In the golf ball according to the present
invention, a hardness distribution of the core is appropriate. When
the golf ball is hit with a driver, the spin rate is low. The low
spin rate achieves a large flight distance. In the golf ball, a
hardness distribution of the entire ball is also appropriate. When
the golf ball is hit with a short iron, the spin rate is high. The
golf ball has excellent controllability. When the golf ball is hit,
the local load applied to the golf ball is low. The golf ball has
excellent durability. In addition, with the golf ball, soft feel at
impact is obtained.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037] FIG. 1 is a partially cutaway cross-sectional view of a golf
ball according to a first embodiment of the present invention;
[0038] FIG. 2 is a line graph showing a hardness distribution of a
core of the golf ball in FIG. 1;
[0039] FIG. 3 is a partially cutaway cross-sectional view of a golf
ball according to a second embodiment of the present invention;
[0040] FIG. 4 is a line graph showing a hardness distribution of a
core of the golf ball in FIG. 3;
[0041] FIG. 5 is a partially cutaway cross-sectional view of a golf
ball according to a third embodiment of the present invention;
[0042] FIG. 6 is a line graph showing a hardness distribution of an
envelope layer of the golf ball in FIG. 5;
[0043] FIG. 7 is a partially cutaway cross-sectional view of a golf
ball according to a fourth embodiment of the present invention;
and
[0044] FIG. 8 is a line graph showing a hardness distribution of an
envelope layer of the golf ball in FIG. 7.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0045] The following will describe in detail the present invention,
based on preferred embodiments with reference to the accompanying
drawings.
First Embodiment
[0046] A golf ball 2 shown in FIG. 1 includes a spherical core 4, a
mid layer 6 positioned outside the core 4, a reinforcing layer 8
positioned outside the mid layer 6, an inner cover 10 positioned
outside the reinforcing layer 8, and an outer cover 12 positioned
outside the inner cover 10. On the surface of the outer 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 outer cover 12, but these layers are not shown in the
drawing.
[0047] 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.
[0048] In the golf ball 2, the core 4 includes a spherical center
18 and an envelope layer 20. The envelope layer 20 is positioned
outside the center 18.
[0049] In the golf ball 2, the center 18 is more flexible than the
envelope layer 20. The center 18 can suppress spin. The center 18
preferably has a diameter of 10 mm or greater but 20 mm or less. In
the golf ball 2 that includes the center 18 having a diameter of 10
mm or greater, spin can be suppressed. In this respect, the
diameter is more preferably equal to or greater than 12 mm and
particularly preferably equal to or greater than 14 mm. The golf
ball 2 that includes the center 18 having a diameter of 20 mm or
less has excellent resilience performance. In this respect, the
diameter is more preferably equal to or less than 18 mm and
particularly preferably equal to or less than 16 mm.
[0050] The envelope layer 20 is harder than the center 18. When the
golf ball 2 is hit with a driver, the energy loss is low in the
envelope layer 20. The envelope layer 20 can contribute to the
resilience performance of the golf ball 2. When the golf ball 2 is
hit with a driver, the flight distance is large. When the golf ball
2 is hit with a golf club, stress concentration does not occur.
Thus, the golf ball 2 has excellent durability.
[0051] In the golf ball 2, the ratio of the radius of the center 18
to the radius of the core 4 is preferably less than 40%. Thus, the
envelope layer 20 can effectively contribute to the resilience
performance of the golf ball 2. In this respect, the ratio is more
preferably equal to or less than 39%. The ratio is preferably equal
to or greater than 20%. Thus, the center 18 can effectively
contribute to suppression of spin. In this respect, the ratio is
more preferably equal to or greater than 25%. When the golf ball 2
is hit with a driver, the flight distance is large.
[0052] In the present invention, JIS-C hardnesses are measured at
nine measuring points obtained by dividing a region from the
central point of the core 4 to the surface of the core 4 into eight
sections. 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. In the golf ball 2, the first to third points are
included in the center 18. The fourth to ninth points are included
in the envelope layer 20.
[0053] First point: 0.0% (central point)
[0054] Second point: 12.5%
[0055] Third point: 25.0%
[0056] Fourth point: 40.0%
[0057] Fifth point: 50.0%
[0058] Sixth point: 62.5%
[0059] Seventh point: 75.0%
[0060] Eighth point: 87.5%
[0061] Ninth point: 100.0% (surface)
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 spherical 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.
[0062] FIG. 2 is a line graph showing a hardness distribution of
the envelope layer 20 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. In the
graph, among the first to ninth points, points included in the
envelope layer 20 are plotted. In the present embodiment, six
points including the fourth to ninth points are plotted in the
graph.
[0063] FIG. 2 also shows a linear approximation curve obtained by a
least-square method on the basis of the ratios and the hardnesses
of the six measuring points. The linear approximation curve is
indicated by a dotted line. In FIG. 2, the broken line does not
greatly deviate from the linear approximation curve. In other
words, the broken line has a shape close to the linear
approximation curve. In the envelope layer 20, the hardness
linearly increases from its inside toward its outside. When the
golf ball 2 is hit with a driver, the energy loss is low in the
envelope layer 20. The golf ball 2 has excellent resilience
performance. When the golf ball 2 is hit with a driver, the flight
distance is large. When the golf ball 2 is hit with a golf club,
stress concentration does not occur. Thus, the golf ball 2 has
excellent durability.
[0064] R.sup.2 of the linear approximation curve for the envelope
layer 20 which is obtained by the least-square method is preferably
equal to or greater than 0.95. R.sup.2 is an index indicating the
linearity of the broken line. For the envelope layer 20 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
golf ball 2 that includes the envelope layer 20 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).
[0065] 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 preferably equal to or
greater than 15. The core 4 in which the difference (H(100)-H(0))
is equal to or greater than 15 has an outer-hard/inner-soft
structure. When the golf ball 2 is hit with a driver, the recoil
(torsional return) in the core 4 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 23 and
particularly preferably equal to or greater than 24. 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. In the core
4, the hardness gradually increases from its central point toward
its surface.
[0066] The center 18 is formed by crosslinking a rubber
composition. Examples of base rubbers for use in the rubber
composition include polybutadienes, polyisoprenes,
styrene-butadiene copolymers, ethylene-propylene-diene copolymers,
and natural rubbers. Two or more rubbers may be used in
combination. In light of resilience performance, polybutadienes are
preferred, and high-cis polybutadienes are particularly
preferred.
[0067] Preferably, the rubber composition of the center 18 includes
a co-crosslinking agent. Examples of preferable co-crosslinking
agents in light of resilience performance include zinc acrylate,
magnesium acrylate, zinc methacrylate, and magnesium methacrylate.
Preferably, the rubber composition includes an organic peroxide
together with a co-crosslinking agent. 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.
Preferably, the rubber composition includes a sulfur compound.
[0068] According to need, various additives such as a filler,
sulfur, a vulcanization accelerator, an anti-aging agent, a
coloring agent, a plasticizer, a dispersant, and the like are
included in the rubber composition of the center 18 in an adequate
amount. Synthetic resin powder or crosslinked rubber powder may
also be included in the rubber composition.
[0069] The envelope layer 20 is formed by crosslinking a rubber
composition. The rubber composition includes:
[0070] (a) a base rubber;
[0071] (b) a co-crosslinking agent;
[0072] (c) a crosslinking initiator; and
[0073] (d) an acid and/or a salt.
[0074] 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.
[0075] 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
golf ball 2. 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.
[0076] From the standpoint that a polybutadiene having a low
proportion of 1,2-vinyl bonds and excellent polymerization activity
is obtained, a rare-earth-element-containing catalyst is preferably
used for synthesis of a polybutadiene. In particular, a
polybutadiene synthesized with a catalyst containing neodymium,
which is a lanthanum-series rare earth element compound, is
preferred.
[0077] 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.
[0078] Rotor: L rotor
[0079] Preheating time: 1 minute
[0080] Rotating time of rotor: 4 minutes
[0081] Temperature: 100.degree. C.
[0082] 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.
[0083] The molecular weight distribution is measured by gel
permeation chromatography ("HLC-8120GPC" manufactured by Tosoh
Corporation). The measurement conditions are as follows.
[0084] Detector: differential refractometer
[0085] Column: GMHHXL (manufactured by Tosoh Corporation)
[0086] Column temperature: 40.degree. C.
[0087] Mobile phase: tetrahydrofuran
The molecular weight distribution is calculated as a value obtained
by conversion using polystyrene standard.
[0088] The co-crosslinking agent (b) is:
[0089] (b1) an .alpha.,.beta.-unsaturated carboxylic acid having 3
to 8 carbon atoms; and
[0090] (b2) a metal salt of an .alpha.,.beta.-unsaturated
carboxylic acid having 3 to 8 carbon atoms.
[0091] 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).
[0092] 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 (f). The metal compound (f) 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.
[0093] Examples of the metal compound (f) 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 (f) is
particularly preferably a zinc compound. Two or more metal
compounds may be used in combination.
[0094] 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.
[0095] 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.
[0096] 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.
[0097] 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.
[0098] In the present invention, the co-crosslinking agent (b) is
not included in the concept of the acid and/or the salt (d). It is
inferred that as described later, during heating and forming of the
core 4, the acid and/or the salt (d) breaks the metal crosslinks by
the co-crosslinking agent (b) in the envelope layer 20, which is a
part of the core 4.
[0099] Examples of the acid and/or the salt (d) include oxo acids,
such as carboxylic acids, sulfonic acids, and phosphoric acid, and
salts thereof; and hydroacids, such as hydrochloric acid and
hydrofluoric acid, and salts thereof. Oxo acids and salts thereof
are preferred. A carboxylic acid and/or a salt thereof (d1) is
preferred. Carboxylates are particularly preferred.
[0100] The carboxylic acid component in the carboxylic acid and/or
the salt thereof (d1) has a carboxyl group. The carboxylic acid
component reacts with the co-crosslinking agent (b). It is inferred
that by this reaction, metal crosslinks are broken.
[0101] The carbon number of the carboxylic acid component of the
carboxylic acid and/or the salt thereof (d1) is preferably equal to
or greater than 1 but equal to or less than 30, more preferably
equal to or greater than 3 but equal to or less than 30, and even
more preferably equal to or greater than 5 but equal to or less
than 28. Examples of the carboxylic acid include aliphatic
carboxylic acids (fatty acids) and aromatic carboxylic acids. As
the carboxylic acid and/or the salt thereof (d1), a fatty acid
and/or a salt thereof is preferred. The carbon number of the fatty
acid component in the fatty acid and/or the salt thereof is
preferably equal to or greater than 1 but equal to or less than
30.
[0102] The rubber composition may include a saturated fatty acid
and/or a salt thereof, or may include an unsaturated fatty acid
and/or a salt thereof. The saturated fatty acid and/or the salt
thereof is preferred.
[0103] 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. Octanoic acid, lauric acid,
myristic acid, palmitic acid, stearic acid, oleic acid, and behenic
acid are preferred.
[0104] 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).
[0105] The rubber composition may include an aromatic carboxylate
substituted with a hydroxyl group, an alkoxy group, or an oxo
group. 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), .beta.-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).
[0106] 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.
[0107] The organic cation is a cation having 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.
[0108] 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, or
oleic acid. Zinc salts of carboxylic acids are particularly
preferred. Examples of preferable zinc salts of carboxylic acids
include zinc octoate, zinc laurate, zinc myristate, and zinc
stearate. A particularly preferable zinc salt of a carboxylic acid
is zinc octoate.
[0109] In light of linearity of the hardness distribution of the
envelope layer 20, the amount of the acid and/or the salt (d) is
preferably equal to or greater than 0.5 parts by weight, more
preferably equal to or greater than 1.0 parts by weight, and
particularly preferably equal to or greater than 2.0 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 45 parts by weight, more preferably equal to or less than 40
parts by weight, and particularly preferably equal to or less than
30 parts by weight, per 100 parts by weight of the base rubber.
[0110] The weight ratio of the co-crosslinking agent (b) and the
acid and/or the salt (d) in the rubber composition is preferably
equal to or greater than 3/7 but equal to or less than 9/1. From
the rubber composition in which this weight ratio is within the
above range, the envelope layer 20 whose hardness linearly
increases from its inside toward its outside can be obtained.
[0111] 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. In the present invention, when the rubber
composition includes this zinc acrylate, this coating material is
not included in the concept of the acid and/or the salt (d).
[0112] Preferably, the rubber composition further includes an
organic sulfur compound (e). The organic sulfur compound (e)
increases the linearity of the hardness distribution of the
envelope layer 20. In addition, the organic sulfur compound (e)
increases the degree of the outer-hard/inner-soft structure.
[0113] An example of the organic sulfur compound (e) 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 (e). Examples of the
organic sulfur compound (e) 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 (e) include thiophenols,
thionaphthols, polysulfides, thiocarboxylic acids, dithiocarboxylic
acids, sulfenamides, thiurams, dithiocarbamates, and thiazoles.
Preferable organic sulfur compounds (e) are thiophenols, diphenyl
disulfides, thionaphthols, thiuram disulfides, and metal salts
thereof.
[0114] Specific examples of the organic sulfur compound (e) are
represented by the following chemical formulas (1) to (4).
##STR00001##
[0115] In the chemical formula (1), R1 to R5 each represent H or a
substituent.
##STR00002##
[0116] In the chemical formula (2), R1 to R10 each represent H or a
substituent.
##STR00003##
[0117] In the chemical formula (3), R1 to R5 each represent H or a
substituent, and M1 represents a monovalent metal atom.
##STR00004##
[0118] In the chemical formula (4), R1 to R10 each represent H or a
substituent, and M2 represents a bivalent metal atom.
[0119] 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).
[0120] 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.
[0121] 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 [0122] 4-chloro-2-nitrothiophenol,
4-chloro-2-aminothiophenol, [0123] 4-chloro-2-hydroxythiophenol,
[0124] 4-chloro-2-phenylthiothiophenol, [0125]
4-methyl-2-nitrothiophenol, 4-methyl-2-aminothiophenol, [0126]
4-methyl-2-hydroxythiophenol, [0127]
4-methyl-2-phenylthiothiophenol, [0128]
4-carboxy-2-nitrothiophenol, 4-carboxy-2-aminothiophenol, [0129]
4-carboxy-2-hydroxythiophenol, [0130]
4-carboxy-2-phenylthiothiophenol, [0131]
4-methoxycarbonyl-2-nitrothiophenol, [0132]
4-methoxycarbonyl-2-aminothiophenol, [0133]
4-methoxycarbonyl-2-hydroxythiophenol, [0134]
4-methoxycarbonyl-2-phenylthiothiophenol, [0135]
4-formyl-2-nitrothiophenol, 4-formyl-2-aminothiophenol, [0136]
4-formyl-2-hydroxythiophenol, [0137]
4-formyl-2-phenylthiothiophenol, [0138] 4-acetyl-2-nitrothiophenol,
4-acetyl-2-aminothiophenol, [0139] 4-acetyl-2-hydroxythiophenol,
[0140] 4-acetyl-2-phenylthiothiophenol, [0141]
4-chlorocarbonyl-2-nitrothiophenol, [0142]
4-chlorocarbonyl-2-aminothiophenol, [0143]
4-chlorocarbonyl-2-hydroxythiophenol, [0144]
4-chlorocarbonyl-2-phenylthiothiophenol, [0145]
4-sulfo-2-nitrothiophenol, 4-sulfo-2-aminothiophenol, [0146]
4-sulfo-2-hydroxythiophenol, [0147] 4-sulfo-2-phenylthiothiophenol,
[0148] 4-methoxysulfonyl-2-nitrothiophenol, [0149]
4-methoxysulfonyl-2-aminothiophenol, [0150]
4-methoxysulfonyl-2-hydroxythiophenol, [0151]
4-methoxysulfonyl-2-phenylthiothiophenol, [0152]
4-chlorosulfonyl-2-nitrothiophenol, [0153]
4-chlorosulfonyl-2-aminothiophenol, [0154]
4-chlorosulfonyl-2-hydroxythiophenol, [0155]
4-chlorosulfonyl-2-phenylthiothiophenol, [0156]
4-sulfino-2-nitrothiophenol, 4-sulfino-2-aminothiophenol, [0157]
4-sulfino-2-hydroxythiophenol, [0158]
4-sulfino-2-phenylthiothiophenol, [0159]
4-methylsulfinyl-2-nitrothiophenol, [0160]
4-methylsulfinyl-2-aminothiophenol, [0161]
4-methylsulfinyl-2-hydroxythiophenol, [0162]
4-methylsulfinyl-2-phenylthiothiophenol, [0163]
4-carbamoyl-2-nitrothiophenol, [0164]
4-carbamoyl-2-aminothiophenol, [0165]
4-carbamoyl-2-hydroxythiophenol, [0166]
4-carbamoyl-2-phenylthiothiophenol, [0167]
4-trichloromethyl-2-nitrothiophenol, [0168]
4-trichloromethyl-2-aminothiophenol, [0169]
4-trichloromethyl-2-hydroxythiophenol, [0170]
4-trichloromethyl-2-phenylthiothiophenol, [0171]
4-cyano-2-nitrothiophenol, 4-cyano-2-aminothiophenol, [0172]
4-cyano-2-hydroxythiophenol, [0173] 4-cyano-2-phenylthiothiophenol,
[0174] 4-methoxy-2-nitrothiophenol, 4-methoxy-2-aminothiophenol,
[0175] 4-methoxy-2-hydroxythiophenol, and [0176]
4-methoxy-2-phenylthiothiophenol.
[0177] 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, [0178]
4-acetyl-2-methylthiophenol, 4-acetyl-2-carboxythiophenol, [0179]
4-acetyl-2-methoxycarbonylthiophenol, [0180]
4-acetyl-2-formylthiophenol, [0181]
4-acetyl-2-chlorocarbonylthiophenol, [0182]
4-acetyl-2-sulfothiophenol, [0183]
4-acetyl-2-methoxysulfonylthiophenol, [0184]
4-acetyl-2-chlorosulfonylthiophenol, [0185]
4-acetyl-2-sulfinothiophenol, [0186]
4-acetyl-2-methylsulfinylthiophenol, [0187]
4-acetyl-2-carbamoylthiophenol, [0188]
4-acetyl-2-trichloromethylthiophenol, [0189]
4-acetyl-2-cyanothiophenol, and [0190]
4-acetyl-2-methoxythiophenol.
[0191] Examples of the organic sulfur compound represented by the
chemical formula (2) include diphenyl disulfide; diphenyl
disulfides substituted with halogen groups, such as [0192]
bis(4-fluorophenyl)disulfide, [0193]
bis(2,5-difluorophenyl)disulfide, [0194]
bis(2,4,5-trifluorophenyl)disulfide, [0195]
bis(2,4,5,6-tetrafluorophenyl)disulfide, [0196]
bis(pentafluorophenyl)disulfide, [0197]
bis(4-chlorophenyl)disulfide, [0198]
bis(2,5-dichlorophenyl)disulfide, [0199]
bis(2,4,5-trichlorophenyl)disulfide, [0200]
bis(2,4,5,6-tetrachlorophenyl)disulfide, [0201]
bis(pentachlorophenyl)disulfide, [0202]
bis(4-bromophenyl)disulfide, [0203]
bis(2,5-dibromophenyl)disulfide, [0204]
bis(2,4,5-tribromophenyl)disulfide, [0205]
bis(2,4,5,6-tetrabromophenyl)disulfide, [0206]
bis(pentabromophenyl)disulfide, bis(4-iodophenyl)disulfide, [0207]
bis(2,5-diiodophenyl)disulfide, [0208]
bis(2,4,5-triiodophenyl)disulfide, [0209]
bis(2,4,5,6-tetraiodophenyl)disulfide, and [0210]
bis(pentaiodophenyl)disulfide; diphenyl disulfides substituted with
alkyl groups, such as [0211] bis(4-methylphenyl)disulfide, [0212]
bis(2,4,5-trimethylphenyl)disulfide, [0213]
bis(pentamethylphenyl)disulfide, [0214]
bis(4-t-butylphenyl)disulfide, [0215]
bis(2,4,5-tri-t-butylphenyl)disulfide, and [0216]
bis(penta-t-butylphenyl)disulfide; diphenyl disulfides substituted
with carboxyl groups, such as [0217] bis(4-carboxyphenyl)disulfide,
[0218] bis(2,4,6-tricarboxyphenyl)disulfide, and [0219]
bis(pentacarboxyphenyl)disulfide; diphenyl disulfides substituted
with alkoxycarbonyl groups, such as [0220]
bis(4-methoxycarbonylphenyl)disulfide, [0221]
bis(2,4,6-trimethoxycarbonylphenyl)disulfide, and [0222]
bis(pentamethoxycarbonylphenyl)disulfide; diphenyl disulfides
substituted with formyl groups, such as [0223]
bis(4-formylphenyl)disulfide, [0224]
bis(2,4,6-triformylphenyl)disulfide, and [0225]
bis(pentaformylphenyl)disulfide; diphenyl disulfides substituted
with acyl groups, such as [0226] bis(4-acetylphenyl)disulfide,
[0227] bis(2,4,6-triacetylphenyl)disulfide, and [0228]
bis(pentaacetylphenyl)disulfide; diphenyl disulfides substituted
with carbonyl halide groups, such as [0229]
bis(4-chlorocarbonylphenyl)disulfide, [0230]
bis(2,4,6-tri(chlorocarbonyl)phenyl)disulfide, and [0231]
bis(penta(chlorocarbonyl)phenyl)disulfide; diphenyl disulfides
substituted with sulfo groups, such as [0232]
bis(4-sulfophenyl)disulfide, [0233]
bis(2,4,6-trisulfophenyl)disulfide, and [0234]
bis(pentasulfophenyl)disulfide; diphenyl disulfides substituted
with alkoxysulfonyl groups, such as [0235]
bis(4-methoxysulfonylphenyl)disulfide, [0236]
bis(2,4,6-trimethoxysulfonylphenyl)disulfide, and [0237]
bis(pentamethoxysulfonylphenyl)disulfide; diphenyl disulfides
substituted with sulfonyl halide groups, such as [0238]
bis(4-chlorosulfonylphenyl)disulfide, [0239]
bis(2,4,6-tri(chlorosulfonyl)phenyl)disulfide, and [0240]
bis(penta(chlorosulfonyl)phenyl)disulfide; diphenyl disulfides
substituted with sulfino groups, such as [0241]
bis(4-sulfinophenyl)disulfide, [0242]
bis(2,4,6-trisulfinophenyl)disulfide, and [0243]
bis(pentasulfinophenyl)disulfide; diphenyl disulfides substituted
with alkylsulfinyl groups, such as [0244]
bis(4-methylsulfinylphenyl)disulfide, [0245]
bis(2,4,6-tri(methylsulfinyl)phenyl)disulfide, and [0246]
bis(penta(methylsulfinyl)phenyl)disulfide; diphenyl disulfides
substituted with carbamoyl groups, such as [0247]
bis(4-carbamoylphenyl)disulfide, [0248]
bis(2,4,6-tricarbamoylphenyl)disulfide, and [0249]
bis(pentacarbamoylphenyl)disulfide; diphenyl disulfides substituted
with alkyl halide groups, such as [0250]
bis(4-trichloromethylphenyl)disulfide, [0251]
bis(2,4,6-tri(trichloromethyl)phenyl)disulfide, and [0252]
bis(penta(trichloromethyl)phenyl)disulfide; diphenyl disulfides
substituted with cyano groups, such as [0253]
bis(4-cyanophenyl)disulfide, [0254]
bis(2,4,6-tricyanophenyl)disulfide, and [0255]
bis(pentacyanophenyl)disulfide; and diphenyl disulfides substituted
with alkoxy groups, such as [0256] bis(4-methoxyphenyl)disulfide,
[0257] bis(2,4,6-trimethoxyphenyl)disulfide, and [0258]
bis(pentamethoxyphenyl)disulfide. Each of these diphenyl disulfides
is substituted with one type of substituent.
[0259] 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 [0260] bis(4-chloro-2-nitrophenyl)disulfide, [0261]
bis(4-chloro-2-aminophenyl)disulfide, [0262]
bis(4-chloro-2-hydroxyphenyl)disulfide, [0263]
bis(4-chloro-2-phenylthiophenyl)disulfide, [0264]
bis(4-methyl-2-nitrophenyl)disulfide, [0265]
bis(4-methyl-2-aminophenyl)disulfide, [0266]
bis(4-methyl-2-hydroxyphenyl)disulfide, [0267]
bis(4-methyl-2-phenylthiophenyl)disulfide, [0268]
bis(4-carboxy-2-nitrophenyl)disulfide, [0269]
bis(4-carboxy-2-aminophenyl)disulfide, [0270]
bis(4-carboxy-2-hydroxyphenyl)disulfide, [0271]
bis(4-carboxy-2-phenylthiophenyl)disulfide, [0272]
bis(4-methoxycarbonyl-2-nitrophenyl)disulfide, [0273]
bis(4-methoxycarbonyl-2-aminophenyl)disulfide, [0274]
bis(4-methoxycarbonyl-2-hydroxyphenyl)disulfide, [0275]
bis(4-methoxycarbonyl-2-phenylthiophenyl)disulfide, [0276]
bis(4-formyl-2-nitrophenyl)disulfide, [0277]
bis(4-formyl-2-aminophenyl)disulfide, [0278]
bis(4-formyl-2-hydroxyphenyl)disulfide, [0279]
bis(4-formyl-2-phenylthiophenyl)disulfide, [0280]
bis(4-acetyl-2-nitrophenyl)disulfide, [0281]
bis(4-acetyl-2-aminophenyl)disulfide, [0282]
bis(4-acetyl-2-hydroxyphenyl)disulfide, [0283]
bis(4-acetyl-2-phenylthiophenyl)disulfide, [0284]
bis(4-chlorocarbonyl-2-nitrophenyl)disulfide, [0285]
bis(4-chlorocarbonyl-2-aminophenyl)disulfide, [0286]
bis(4-chlorocarbonyl-2-hydroxyphenyl)disulfide, [0287]
bis(4-chlorocarbonyl-2-phenylthiophenyl)disulfide, [0288]
bis(4-sulfo-2-nitrophenyl)disulfide, [0289]
bis(4-sulfo-2-aminophenyl)disulfide, [0290]
bis(4-sulfo-2-hydroxyphenyl)disulfide, [0291]
bis(4-sulfo-2-phenylthiophenyl)disulfide, [0292]
bis(4-methoxysulfonyl-2-nitrophenyl)disulfide, [0293]
bis(4-methoxysulfonyl-2-aminophenyl)disulfide, [0294]
bis(4-methoxysulfonyl-2-hydroxyphenyl)disulfide, [0295]
bis(4-methoxysulfonyl-2-phenylthiophenyl)disulfide, [0296]
bis(4-chlorosulfonyl-2-nitrophenyl)disulfide, [0297]
bis(4-chlorosulfonyl-2-aminophenyl)disulfide, [0298]
bis(4-chlorosulfonyl-2-hydroxyphenyl)disulfide, [0299]
bis(4-chlorosulfonyl-2-phenylthiophenyl)disulfide, [0300]
bis(4-sulfino-2-nitrophenyl)disulfide, [0301]
bis(4-sulfino-2-aminophenyl)disulfide, [0302]
bis(4-sulfino-2-hydroxyphenyl)disulfide, [0303]
bis(4-sulfino-2-phenylthiophenyl)disulfide, [0304]
bis(4-methylsulfinyl-2-nitrophenyl)disulfide, [0305]
bis(4-methylsulfinyl-2-aminophenyl)disulfide, [0306]
bis(4-methylsulfinyl-2-hydroxyphenyl)disulfide, [0307]
bis(4-methylsulfinyl-2-phenylthiophenyl)disulfide, [0308]
bis(4-carbamoyl-2-nitrophenyl)disulfide, [0309]
bis(4-carbamoyl-2-aminophenyl)disulfide, [0310]
bis(4-carbamoyl-2-hydroxyphenyl)disulfide, [0311]
bis(4-carbamoyl-2-phenylthiophenyl)disulfide, [0312]
bis(4-trichloromethyl-2-nitrophenyl)disulfide, [0313]
bis(4-trichloromethyl-2-aminophenyl)disulfide, [0314]
bis(4-trichloromethyl-2-hydroxyphenyl)disulfide, [0315]
bis(4-trichloromethyl-2-phenylthiophenyl)disulfide, [0316]
bis(4-cyano-2-nitrophenyl)disulfide, [0317]
bis(4-cyano-2-aminophenyl)disulfide, [0318]
bis(4-cyano-2-hydroxyphenyl)disulfide, [0319]
bis(4-cyano-2-phenylthiophenyl)disulfide, [0320]
bis(4-methoxy-2-nitrophenyl)disulfide, [0321]
bis(4-methoxy-2-aminophenyl)disulfide, [0322]
bis(4-methoxy-2-hydroxyphenyl)disulfide, and [0323]
bis(4-methoxy-2-phenylthiophenyl)disulfide.
[0324] 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, [0325]
bis(4-acetyl-2-methylphenyl)disulfide, [0326]
bis(4-acetyl-2-carboxyphenyl)disulfide, [0327]
bis(4-acetyl-2-methoxycarbonylphenyl)disulfide, [0328]
bis(4-acetyl-2-formylphenyl)disulfide, [0329]
bis(4-acetyl-2-chlorocarbonylphenyl)disulfide, [0330]
bis(4-acetyl-2-sulfophenyl)disulfide, [0331]
bis(4-acetyl-2-methoxysulfonylphenyl)disulfide, [0332]
bis(4-acetyl-2-chlorosulfonylphenyl)disulfide, [0333]
bis(4-acetyl-2-sulfinophenyl)disulfide, [0334]
bis(4-acetyl-2-methylsulfinylphenyl)disulfide, [0335]
bis(4-acetyl-2-carbamoylphenyl)disulfide, [0336]
bis(4-acetyl-2-trichloromethylphenyl)disulfide, [0337]
bis(4-acetyl-2-cyanophenyl)disulfide, and [0338]
bis(4-acetyl-2-methoxyphenyl)disulfide.
[0339] 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-difluorothiophenol sodium 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.
[0340] 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.
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 [0341] 4-chloro-2-nitrothiophenol sodium salt, [0342]
4-chloro-2-aminothiophenol sodium salt, [0343]
4-chloro-2-hydroxythiophenol sodium salt, [0344]
4-chloro-2-phenylthiothiophenol sodium salt, [0345]
4-methyl-2-nitrothiophenol sodium salt, [0346]
4-methyl-2-aminothiophenol sodium salt, [0347]
4-methyl-2-hydroxythiophenol sodium salt, [0348]
4-methyl-2-phenylthiothiophenol sodium salt, [0349]
4-carboxy-2-nitrothiophenol sodium salt, [0350]
4-carboxy-2-aminothiophenol sodium salt, [0351]
4-carboxy-2-hydroxythiophenol sodium salt, [0352]
4-carboxy-2-phenylthiothiophenol sodium salt, [0353]
4-methoxycarbonyl-2-nitrothiophenol sodium salt, [0354]
4-methoxycarbonyl-2-aminothiophenol sodium salt, [0355]
4-methoxycarbonyl-2-hydroxythiophenol sodium salt, [0356]
4-methoxycarbonyl-2-phenylthiothiophenol sodium salt, [0357]
4-formyl-2-nitrothiophenol sodium salt, [0358]
4-formyl-2-aminothiophenol sodium salt, [0359]
4-formyl-2-hydroxythiophenol sodium salt, [0360]
4-formyl-2-phenylthiothiophenol sodium salt, [0361]
4-acetyl-2-nitrothiophenol sodium salt, [0362]
4-acetyl-2-aminothiophenol sodium salt, [0363]
4-acetyl-2-hydroxythiophenol sodium salt, [0364]
4-acetyl-2-phenylthiothiophenol sodium salt, [0365]
4-chlorocarbonyl-2-nitrothiophenol sodium salt, [0366]
4-chlorocarbonyl-2-aminothiophenol sodium salt, [0367]
4-chlorocarbonyl-2-hydroxythiophenol sodium salt, [0368]
4-chlorocarbonyl-2-phenylthiothiophenol sodium salt, [0369]
4-sulfo-2-nitrothiophenol sodium salt, [0370]
4-sulfo-2-aminothiophenol sodium salt, [0371]
4-sulfo-2-hydroxythiophenol sodium salt, [0372]
4-sulfo-2-phenylthiothiophenol sodium salt, [0373]
4-methoxysulfonyl-2-nitrothiophenol sodium salt, [0374]
4-methoxysulfonyl-2-aminothiophenol sodium salt, [0375]
4-methoxysulfonyl-2-hydroxythiophenol sodium salt, [0376]
4-methoxysulfonyl-2-phenylthiothiophenol sodium salt, [0377]
4-chlorosulfonyl-2-nitrothiophenol sodium salt, [0378]
4-chlorosulfonyl-2-aminothiophenol sodium salt, [0379]
4-chlorosulfonyl-2-hydroxythiophenol sodium salt, [0380]
4-chlorosulfonyl-2-phenylthiothiophenol sodium salt, [0381]
4-sulfino-2-nitrothiophenol sodium salt, [0382]
4-sulfino-2-aminothiophenol sodium salt, [0383]
4-sulfino-2-hydroxythiophenol sodium salt, [0384]
4-sulfino-2-phenylthiothiophenol sodium salt, [0385]
4-methylsulfinyl-2-nitrothiophenol sodium salt, [0386]
4-methylsulfinyl-2-aminothiophenol sodium salt, [0387]
4-methylsulfinyl-2-hydroxythiophenol sodium salt, [0388]
4-methylsulfinyl-2-phenylthiothiophenol sodium salt, [0389]
4-carbamoyl-2-nitrothiophenol sodium salt, [0390]
4-carbamoyl-2-aminothiophenol sodium salt, [0391]
4-carbamoyl-2-hydroxythiophenol sodium salt, [0392]
4-carbamoyl-2-phenylthiothiophenol sodium salt, [0393]
4-trichloromethyl-2-nitrothiophenol sodium salt, [0394]
4-trichloromethyl-2-aminothiophenol sodium salt, [0395]
4-trichloromethyl-2-hydroxythiophenol sodium salt, [0396]
4-trichloromethyl-2-phenylthiothiophenol sodium salt, [0397]
4-cyano-2-nitrothiophenol sodium salt, [0398]
4-cyano-2-aminothiophenol sodium salt, [0399]
4-cyano-2-hydroxythiophenol sodium salt, [0400]
4-cyano-2-phenylthiothiophenol sodium salt, [0401]
4-methoxy-2-nitrothiophenol sodium salt, [0402]
4-methoxy-2-aminothiophenol sodium salt, [0403]
4-methoxy-2-hydroxythiophenol sodium salt, and [0404]
4-methoxy-2-phenylthiothiophenol sodium salt.
[0405] 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, [0406]
4-acetyl-2-methylthiophenol sodium salt, [0407]
4-acetyl-2-carboxythiophenol sodium salt, [0408]
4-acetyl-2-methoxycarbonylthiophenol sodium salt, [0409]
4-acetyl-2-formylthiophenol sodium salt, [0410]
4-acetyl-2-chlorocarbonylthiophenol sodium salt, [0411]
4-acetyl-2-sulfothiophenol sodium salt, [0412]
4-acetyl-2-methoxysulfonylthiophenol sodium salt, [0413]
4-acetyl-2-chlorosulfonylthiophenol sodium salt, [0414]
4-acetyl-2-sulfinothiophenol sodium salt, [0415]
4-acetyl-2-methylsulfinylthiophenol sodium salt, [0416]
4-acetyl-2-carbamoylthiophenol sodium salt, [0417]
4-acetyl-2-trichloromethylthiophenol sodium salt, [0418]
4-acetyl-2-cyanothiophenol sodium salt, and [0419]
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).
[0420] 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.
[0421] 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 [0422] 4-chloro-2-nitrothiophenol zinc salt, [0423]
4-chloro-2-aminothiophenol zinc salt, [0424]
4-chloro-2-hydroxythiophenol zinc salt, [0425]
4-chloro-2-phenylthiothiophenol zinc salt, [0426]
4-methyl-2-nitrothiophenol zinc salt, [0427]
4-methyl-2-aminothiophenol zinc salt, [0428]
4-methyl-2-hydroxythiophenol zinc salt, [0429]
4-methyl-2-phenylthiothiophenol zinc salt, [0430]
4-carboxy-2-nitrothiophenol zinc salt, [0431]
4-carboxy-2-aminothiophenol zinc salt, [0432]
4-carboxy-2-hydroxythiophenol zinc salt, [0433]
4-carboxy-2-phenylthiothiophenol zinc salt, [0434]
4-methoxycarbonyl-2-nitrothiophenol zinc salt, [0435]
4-methoxycarbonyl-2-aminothiophenol zinc salt, [0436]
4-methoxycarbonyl-2-hydroxythiophenol zinc salt, [0437]
4-methoxycarbonyl-2-phenylthiothiophenol zinc salt, [0438]
4-formyl-2-nitrothiophenol zinc salt, [0439]
4-formyl-2-aminothiophenol zinc salt, [0440]
4-formyl-2-hydroxythiophenol zinc salt, [0441]
4-formyl-2-phenylthiothiophenol zinc salt, [0442]
4-acetyl-2-nitrothiophenol zinc salt, [0443]
4-acetyl-2-aminothiophenol zinc salt, [0444]
4-acetyl-2-hydroxythiophenol zinc salt, [0445]
4-acetyl-2-phenylthiothiophenol zinc salt, [0446]
4-chlorocarbonyl-2-nitrothiophenol zinc salt, [0447]
4-chlorocarbonyl-2-aminothiophenol zinc salt, [0448]
4-chlorocarbonyl-2-hydroxythiophenol zinc salt, [0449]
4-chlorocarbonyl-2-phenylthiothiophenol zinc salt, [0450]
4-sulfo-2-nitrothiophenol zinc salt, [0451]
4-sulfo-2-aminothiophenol zinc salt, [0452]
4-sulfo-2-hydroxythiophenol zinc salt, [0453]
4-sulfo-2-phenylthiothiophenol zinc salt, [0454]
4-methoxysulfonyl-2-nitrothiophenol zinc salt, [0455]
4-methoxysulfonyl-2-aminothiophenol zinc salt, [0456]
4-methoxysulfonyl-2-hydroxythiophenol zinc salt, [0457]
4-methoxysulfonyl-2-phenylthiothiophenol zinc salt, [0458]
4-chlorosulfonyl-2-nitrothiophenol zinc salt, [0459]
4-chlorosulfonyl-2-aminothiophenol zinc salt, [0460]
4-chlorosulfonyl-2-hydroxythiophenol zinc salt, [0461]
4-chlorosulfonyl-2-phenylthiothiophenol zinc salt, [0462]
4-sulfino-2-nitrothiophenol zinc salt, [0463]
4-sulfino-2-aminothiophenol zinc salt, [0464]
4-sulfino-2-hydroxythiophenol zinc salt, [0465]
4-sulfino-2-phenylthiothiophenol zinc salt, [0466]
4-methylsulfinyl-2-nitrothiophenol zinc salt, [0467]
4-methylsulfinyl-2-aminothiophenol zinc salt, [0468]
4-methylsulfinyl-2-hydroxythiophenol zinc salt, [0469]
4-methylsulfinyl-2-phenylthiothiophenol zinc salt, [0470]
4-carbamoyl-2-nitrothiophenol zinc salt, [0471]
4-carbamoyl-2-aminothiophenol zinc salt, [0472]
4-carbamoyl-2-hydroxythiophenol zinc salt, [0473]
4-carbamoyl-2-phenylthiothiophenol zinc salt, [0474]
4-trichloromethyl-2-nitrothiophenol zinc salt, [0475]
4-trichloromethyl-2-aminothiophenol zinc salt, [0476]
4-trichloromethyl-2-hydroxythiophenol zinc salt, [0477]
4-trichloromethyl-2-phenylthiothiophenol zinc salt, [0478]
4-cyano-2-nitrothiophenol zinc salt, [0479]
4-cyano-2-aminothiophenol zinc salt, [0480]
4-cyano-2-hydroxythiophenol zinc salt, [0481]
4-cyano-2-phenylthiothiophenol zinc salt, [0482]
4-methoxy-2-nitrothiophenol zinc salt, [0483]
4-methoxy-2-aminothiophenol zinc salt, [0484]
4-methoxy-2-hydroxythiophenol zinc salt, and [0485]
4-methoxy-2-phenylthiothiophenol zinc salt.
[0486] 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, [0487]
4-acetyl-2-methylthiophenol zinc salt, [0488]
4-acetyl-2-carboxythiophenol zinc salt, [0489]
4-acetyl-2-methoxycarbonylthiophenol zinc salt, [0490]
4-acetyl-2-formylthiophenol zinc salt, [0491]
4-acetyl-2-chlorocarbonylthiophenol zinc salt, [0492]
4-acetyl-2-sulfothiophenol zinc salt, [0493]
4-acetyl-2-methoxysulfonylthiophenol zinc salt, [0494]
4-acetyl-2-chlorosulfonylthiophenol zinc salt, [0495]
4-acetyl-2-sulfinothiophenol zinc salt, [0496]
4-acetyl-2-methylsulfinylthiophenol zinc salt, [0497]
4-acetyl-2-carbamoylthiophenol zinc salt, [0498]
4-acetyl-2-trichloromethylthiophenol zinc salt, [0499]
4-acetyl-2-cyanothiophenol zinc salt, and [0500]
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).
[0501] Examples of thionaphthols include 2-thionaphthol,
1-thionaphthol, 2-chloro-1-thionaphthol, 2-bromo-1-thionaphthol,
2-fluoro-1-thionaphthol, 2-cyano-1-thionaphthol,
2-acetyl-1-thionaphthol, 1-chloro-2-thionaphthol,
1-bromo-2-thionaphthol, 1-fluoro-2-thionaphthol,
1-cyano-2-thionaphthol, 1-acetyl-2-thionaphthol, and metal salts
thereof. 1-thionaphthol, 2-thionaphthol, and zinc salts thereof are
preferred.
[0502] 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 (MBTS); 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.
[0503] From the standpoint that an outer-hard/inner-soft structure
is easily obtained, particularly preferable organic sulfur
compounds (e) are 2-thionaphthol, bis(pentabromophenyl)disulfide,
and 2,6-dichlorothiophenol.
[0504] From the standpoint that an outer-hard/inner-soft structure
is easily obtained, the amount of the organic sulfur compound (e)
is preferably equal to or greater than 0.05 parts by weight, more
preferably equal to or greater than 0.1 parts by weight, and
particularly preferably equal to or greater than 0.2 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, more preferably equal to or less than 3.0
parts by weight, and particularly preferably equal to or less than
1.0 parts by weight, per 100 parts by weight of the base
rubber.
[0505] For the purpose of adjusting specific gravity and the like,
a filler may be included in the envelope layer 20. 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.
[0506] 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 envelope layer
20. Crosslinked rubber powder or synthetic resin powder may also be
dispersed in the rubber composition.
[0507] During heating and forming of the core 4, the base rubber
(a) is crosslinked by the co-crosslinking agent (b). 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. In the rubber composition, the acid reacts with the metal
salt of the co-crosslinking agent (b) to bond to cation. In the
rubber composition, the salt reacts with the metal salt of the
co-crosslinking agent (b) to exchange cation. By the bonding and
the exchange, metal crosslinks are broken. The bonding and the
exchange are likely to occur near the innermost portion of the
envelope layer 20 where the temperature is high, and are unlikely
to occur near the surface of the envelope layer 20. In other words,
breaking of metal crosslinks is likely to occur near the innermost
portion of the envelope layer 20 and is unlikely to occur near the
surface of the envelope layer 20. As a result, the crosslinking
density of the envelope layer 20 increases from its inside toward
its outside. In the envelope layer 20, the hardness linearly
increases from its inside toward its outside. Further, since the
rubber composition includes the organic sulfur compound (e)
together with the acid and/or the salt (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.
When the golf ball 2 that includes the core 4 is hit with a driver,
the spin rate is low. In the golf ball 2, excellent flight
performance is achieved upon a shot with a driver.
[0508] The hardness H(0) at the central point of the core 4 is
preferably equal to or greater than 40 but equal to or less than
70. The golf ball 2 having a hardness H(0) of 40 or greater has
excellent resilience performance. In this respect, the hardness
H(0) is more preferably equal to or greater than 45 and
particularly preferably equal to or greater than 47. The core 4
having a hardness H(0) of 70 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 68 and particularly
preferably equal to or less than 65.
[0509] The hardness H(100) at the surface of the core 4 is
preferably equal to or greater than 78 but equal to or less than
96. The core 4 having a hardness H(100) of 78 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 and
particularly preferably equal to or greater than 82. The golf ball
2 having a hardness H(100) of 96 or less has excellent durability.
In this respect, the hardness H(100) is more preferably equal to or
less than 94 and particularly preferably equal to or less than
92.
[0510] The core 4 preferably has a diameter of 38.0 mm or greater
but 42.0 mm or less. The core 4 having a diameter of 38.0 mm or
greater can achieve excellent resilience performance of the golf
ball 2. In this respect, the diameter is more preferably equal to
or greater than 39.0 mm and particularly preferably equal to or
greater than 39.5 mm. In the golf ball 2 that includes the core 4
having a diameter of 42.0 mm or less, the mid layer 6, the inner
cover 10, and the outer cover 12 can have sufficient thicknesses.
The golf ball 2 that includes the mid layer 6, the inner cover 10,
and the outer cover 12 which have large thicknesses has excellent
durability. In this respect, the diameter is more preferably equal
to or less than 41 mm and particularly preferably equal to or less
than 40 mm.
[0511] For the 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.
[0512] Particularly preferable base polymers are ionomer resins.
The golf ball 2 that includes the mid layer 6 including an ionomer
resin has excellent resilience performance. An ionomer resin and
another resin may be used in combination for the 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.
[0513] 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
greater but 90% by weight or less of an .alpha.-olefin, and 10% by
weight or greater but 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 greater but 85% by weight or
less of an .alpha.-olefin, 5% by weight or greater but 30% by
weight or less of an .alpha.,.beta.-unsaturated carboxylic acid,
and 1% by weight or greater but 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.
[0514] 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.
[0515] 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", "Surlyn AD8546", "HPF1000", and
"HPF2000", manufactured by E.I. du Pont de Nemours and Company; and
trade names "IOTEK 7010", "IOTEK 7030", "IOTEK 7510", "IOTEK 7520",
"IOTEK 8000", and "IOTEK 8030", manufactured by ExxonMobil Chemical
Company.
[0516] Two or more ionomer resins may be used in combination for
the 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.
[0517] 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.
[0518] 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.
[0519] 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).
[0520] 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.
[0521] In the present invention, styrene block-containing
thermoplastic elastomers include an alloy of an olefin and one or
more members selected from the group consisting of SBS, SIS, SIBS,
and hydrogenated products thereof. 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.
[0522] Specific examples of polymer alloys include trade names
"Rabalon T3221C", "Rabalon T3339C", "Rabalon SJ4400N", "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.
[0523] The mid layer 6 may include a highly elastic resin as the
base polymer. The highly elastic resin contributes to high rigidity
of the mid layer 6. Specific examples of the highly elastic resin
include polyamides.
[0524] 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 mid layer 6 in an adequate
amount.
[0525] From the standpoint that an outer-hard/inner-soft structure
can be achieved in the sphere consisting of the core 4 and the mid
layer 6, the mid layer 6 has a hardness Hm of preferably 45 or
greater and particularly preferably 55 or greater. In light of feel
at impact of the golf ball 2, the hardness Hm is preferably equal
to or less than 72 and particularly preferably equal to or less
than 70. The hardness Hm 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 mid layer 6 is used.
[0526] The mid layer 6 preferably has a thickness Tm of 0.5 mm or
greater but 1.6 mm or less. In the sphere that includes the mid
layer 6 having a thickness Tm of 0.5 mm or greater, the spin
suppression effect provided by the outer-hard/inner-soft structure
is great. In this respect, the thickness Tm is particularly
preferably equal to or greater than 0.7 mm. The golf ball 2 that
includes the mid layer 6 having a thickness Tm 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 Tm is particularly preferably equal to or less than 1.2
mm.
[0527] For forming the mid layer 6, known methods such as injection
molding, compression molding, and the like can be used.
[0528] For the inner cover 10, a resin composition is suitably
used. A preferable base polymer of the resin composition is a
polyurethane. The polyurethane is flexible. When the golf ball 2
that includes the inner cover 10 formed from the resin composition
that includes the polyurethane is hit with a short iron, the spin
rate is high. The inner cover 10 formed from this resin composition
contributes to controllability upon a shot with a short iron.
Furthermore, the polyurethane can also contribute to excellent feel
at impact when the golf ball 2 is hit with a putter or a short
iron.
[0529] In light of ease of forming the inner cover 10, 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.
[0530] 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.
[0531] Examples of aromatic diisocyanates include
4,4'-diphenylmethane diisocyanate (MDI) and toluene diisocyanate
(TDI). Examples of aliphatic diisocyanates include hexamethylene
diisocyanate (HDI).
[0532] 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", and
"Elastollan XKP016N", manufactured by BASF Japan Ltd.; and trade
names "RESAMINE P4585LS" and "RESAMINE PS62490", manufactured by
Dainichiseika Color & Chemicals Mfg. Co., Ltd.
[0533] 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. 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.
[0534] According to need, a coloring agent such as titanium dioxide
and a fluorescent pigment, 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 inner cover 10 in an adequate
amount.
[0535] The inner cover 10 preferably has a Shore D hardness Hc1 of
60 or less. The golf ball 2 that includes the inner cover 10 having
a hardness Hc1 of 60 or less has excellent controllability. In this
respect, the hardness Hc1 is more preferably equal to or less than
55 and particularly preferably equal to or less than 50. In light
of flight distance upon a shot with a driver, the hardness Hc1 is
preferably equal to or greater than 40. The hardness Hc1 is
measured by the same measurement method as that for the hardness
Hm.
[0536] The inner cover 10 has a thickness T1 of 0.1 mm or greater
but 0.8 mm or less. The golf ball 2 having a thickness T1 of 0.1 mm
or greater has excellent controllability. In this respect, the
thickness T1 is more preferably equal to or greater than 0.2 mm and
particularly preferably equal to or greater than 0.3 mm. The golf
ball 2 having a thickness T1 of 0.8 mm or less has excellent
resilience performance. In this respect, the thickness T1 is more
preferably equal to or less than 0.6 mm and particularly preferably
equal to or less than 0.5 mm.
[0537] For forming the inner cover 10, known methods such as
injection molding, compression molding, and the like can be
used.
[0538] For the outer cover 12, a resin composition is suitably
used. A preferable base polymer of the resin composition is a
polyurethane. The polyurethane is flexible. When the golf ball 2
that includes the outer cover 12 formed from the resin composition
that includes the polyurethane is hit with a short iron, the spin
rate is high. The outer 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 outer
cover 12. Furthermore, the polyurethane can contribute to excellent
feel at impact when the golf ball 2 is hit with a putter or a short
iron.
[0539] In light of ease of forming the outer cover 12, a preferable
base polymer is a thermoplastic polyurethane elastomer. The
thermoplastic polyurethane elastomer described above for the inner
cover 10 can be used for the outer cover 12. Particularly, an
elastomer including a polyurethane component obtained by a reaction
of a polyol and an alicyclic diisocyanate is preferred. Since the
alicyclic diisocyanate does not have any double bond in the main
chain, the alicyclic diisocyanate suppresses yellowing of the outer
cover 12. In addition, since the alicyclic diisocyanate has
excellent strength, the alicyclic diisocyanate suppresses a scuff
on the outer cover 12.
[0540] From the standpoint that a low hardness of the outer cover
12 can be achieved, particularly preferable thermoplastic
polyurethane elastomers are "Elastollan NY80A", "Elastollan NY82A",
"Elastollan NY84A", "Elastollan NY85A", and "Elastollan NY90A".
[0541] A thermoplastic polyurethane elastomer and another resin may
be used in combination. The outer cover 12 can include the resin
described above for the inner cover 10. 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.
[0542] According to need, a coloring agent such as titanium dioxide
and a fluorescent pigment, 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 outer cover 12 in an adequate
amount.
[0543] The outer cover 12 preferably has a Shore D hardness Hc2 of
48 or less. The golf ball 2 that includes the outer cover 12 having
a hardness Hc2 of 48 or less has excellent controllability. In this
respect, the hardness Hc2 is more preferably equal to or less than
40 and particularly preferably equal to or less than 32. In light
of flight distance upon a shot with a driver, the hardness Hc2 is
preferably equal to or greater than 10. The hardness Hc2 is
measured by the same measurement method as that for the hardness
Hm.
[0544] The outer cover 12 preferably has a thickness T2 of 0.1 mm
or greater but 0.8 mm or less. The golf ball 2 having a thickness
T2 of 0.1 mm or greater has excellent controllability. In this
respect, the thickness T2 is more preferably equal to or greater
than 0.2 mm and particularly preferably equal to or greater than
0.3 mm. The golf ball 2 having a thickness T2 of 0.8 mm or less has
excellent resilience performance. In this respect, the thickness T2
is more preferably equal to or less than 0.6 mm and particularly
preferably equal to or less than 0.5 mm.
[0545] For forming the outer cover 12, known methods such as
injection molding, compression molding, and the like can be used.
When forming the outer cover 12, the dimples 14 are formed by
pimples formed on the cavity face of a mold.
[0546] Preferably, the hardness Hm of the mid layer 6, the hardness
Hc1 of the inner cover 10, and the hardness Hc2 of the outer cover
12 meet the relationships of the following mathematical
formulas.
Hm>Hc1
Hm>Hc2
When the golf ball 2 is hit with a driver, the sphere consisting of
the core 4 and the mid layer 6 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 inner cover 10 and the
outer cover 12. Since the inner cover 10 and the outer cover 12 are
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.
[0547] When the golf ball 2 is hit, the inner cover 10 and the
outer cover 12 absorb 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 inner cover 10 and the outer cover 12 achieve
excellent feel at impact.
[0548] In light of achievement of both desired flight performance
and desired controllability, the difference (Hm-Hc1) between the
hardness Hm and the hardness Hc1 is preferably equal to or greater
than 15 and more preferably equal to or greater than 18. The
difference (Hm-Hc1) is preferably equal to or less than 40.
[0549] In light of achievement of both desired flight performance
and desired controllability, the difference (Hm-Hc2) between the
hardness Hm and the hardness Hc2 is preferably equal to or greater
than 20 and more preferably equal to or greater than 36. The
difference (Hm-Hc2) is preferably equal to or less than 60.
[0550] In the golf ball 2, the hardness Hc1 and the hardness Hc2
meet the relationship of the following mathematical formula.
Hc1>Hc2
In the golf ball 2, the hardness is lower in order of the mid layer
6, the inner cover 10, and the outer cover 12. The golf ball 2 has
excellent feel at impact.
[0551] In light of feel at impact, the difference (Hc1-Hc2) between
the hardness Hc1 and the hardness Hc2 is preferably equal to or
greater than 5 and particularly preferably equal to or greater than
10. The difference (Hc1-Hc2) is preferably equal to or less than
30.
[0552] The difference (T1-T2) between the thickness T1 of the inner
cover 10 and the thickness T2 of the outer cover 12 is preferably
equal to or greater than -0.4 mm but equal to or less than 0.4 mm.
In the golf ball 2 in which the difference (T1-T2) is within the
above range, the inner cover 10 and the outer cover 12 are easily
formed. In this respect, the difference (T1-T2) is more preferably
equal to or greater than -0.3 mm but equal to or less than 0.3 mm,
and is particularly preferably equal to or greater than -0.2 mm but
equal to or less than 0.2 mm.
[0553] In light of flight performance, the sum (T1+T2) of the
thickness T1 of the inner cover 10 and the thickness T2 of the
outer cover 12 is preferably equal to or less than 1.0 mm and
particularly preferably equal to or less than 0.8 mm. In light of
controllability, the sum (T1+T2) is preferably equal to or greater
than 0.2 mm and particularly preferably equal to or greater than
0.4 mm.
[0554] The reinforcing layer 8 is positioned between the mid layer
6 and the inner cover 10. The reinforcing layer 8 firmly adheres to
the mid layer 6 and also to the inner cover 10. The reinforcing
layer 8 suppresses separation of the inner cover 10 from the mid
layer 6. In the golf ball 2, when the mid layer 6 is formed from a
resin composition and the inner cover 10 is formed from a resin
composition whose base resin is different from the base resin of
the mid layer 6, the reinforcing layer 8 effectively suppresses
separation of the inner cover 10 from the mid layer 6.
[0555] As the base polymer of the reinforcing layer 8, 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 8, two-component curing type epoxy resins
and two-component curing type urethane resins are preferred.
[0556] 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.
[0557] 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.
[0558] 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.
[0559] 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.
[0560] 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.
[0561] 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.
[0562] 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-toluene diisocyanate 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.
[0563] 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.
[0564] In light of strength of the reinforcing layer 8, 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 8 to the inner cover 10, 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.
[0565] From the standpoint that the 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 8, 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.
[0566] In light of adhesion of the reinforcing layer 8, 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 the 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.
[0567] 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 the 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.
[0568] 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.
[0569] The reinforcing layer 8 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.
[0570] The reinforcing layer 8 is obtained by applying, to the
surface of the mid layer 6, 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 8. 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.
[0571] In light of feel at impact, the golf ball 2 has an amount of
compressive deformation (comp'n) of preferably 2.3 mm or greater
and more preferably 2.5 mm or greater. In light of resilience
performance, the amount of compressive deformation is preferably
equal to or less than 3.5 mm, more preferably equal to or less than
3.3 mm, and particularly preferably equal to or less than 3.1
mm.
[0572] For measurement of the amount of compressive deformation, a
YAMADA type compression tester is used. In the tester, the golf
ball 2 is placed on a hard plate made of metal. Next, a cylinder
made of metal gradually descends toward the golf ball 2. The golf
ball 2, 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 golf ball 2 up to the state in which a final load of 1274 N
is applied thereto, is measured.
Second Embodiment
[0573] A golf ball 102 shown in FIG. 3 includes a spherical core
104, amid layer 106 positioned outside the core 104, a reinforcing
layer 108 positioned outside the mid layer 106, an inner cover 110
positioned outside the reinforcing layer 108, and an outer cover
112 positioned outside the inner cover 110. On the surface of the
outer cover 112, a large number of dimples 114 are formed. Of the
surface of the golf ball 102, a part other than the dimples 114 is
a land 116. The golf ball 102 includes a paint layer and a mark
layer on the external side of the outer cover 112, but these layers
are not shown in the drawing.
[0574] The golf ball 102 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 102 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.
[0575] In the golf ball 102, the core 104 includes a spherical
center 118 and an envelope layer 120. The envelope layer 120 is
positioned outside the center 118.
[0576] In the golf ball 102, the center 118 is more flexible than
the envelope layer 120. The center 118 can suppress spin. The
center 118 preferably has a diameter of 10 mm or greater but 20 mm
or less. In the golf ball 102 that includes the center 118 having a
diameter of 10 mm or greater, spin can be suppressed. In this
respect, the diameter is more preferably equal to or greater than
12 mm and particularly preferably equal to or greater than 14 mm.
The golf ball 102 that includes the center 118 having a diameter of
20 mm or less has excellent resilience performance. In this
respect, the diameter is more preferably equal to or less than 18
mm and particularly preferably equal to or less than 16 mm.
[0577] The envelope layer 120 is harder than the center 118. When
the golf ball 102 is hit with a driver, the energy loss is low in
the envelope layer 120. The envelope layer 120 can contribute to
the resilience performance of the golf ball 102. When the golf ball
102 is hit with a driver, the flight distance is large. When the
golf ball 102 is hit with a golf club, stress concentration does
not occur. Thus, the golf ball 102 has excellent durability.
[0578] In the golf ball 102, the ratio of the radius of the center
118 to the radius of the core 104 is preferably less than 40%.
Thus, the envelope layer 120 can effectively contribute to the
resilience performance of the golf ball 102. In this respect, the
ratio is more preferably equal to or less than 39%. The ratio is
preferably equal to or greater than 20%. Thus, the center 118 can
effectively contribute to suppression of spin. In this respect, the
ratio is more preferably equal to or greater than 25%. When the
golf ball 102 is hit with a driver, the flight distance is
large.
[0579] In the present invention, JIS-C hardnesses are measured at
nine measuring points obtained by dividing a region from the
central point of the core 104 to the surface of the core 104 into
eight sections. The ratio of the distance from the central point of
the core 104 to each of these measuring points to the radius of the
core 104 is as follows. In the golf ball 102, the first to third
points are included in the center 118. The fourth to ninth points
are included in the envelope layer 120.
[0580] First point: 0.0% (central point)
[0581] Second point: 12.5%
[0582] Third point: 25.0%
[0583] Fourth point: 40.0%
[0584] Fifth point: 50.0%
[0585] Sixth point: 62.5%
[0586] Seventh point: 75.0%
[0587] Eighth point: 87.5%
[0588] Ninth point: 100.0% (surface)
Hardnesses at the first to eighth points are measured by pressing a
JIS-C type hardness scale against a cut plane of the core 104 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 spherical core 104. 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.
[0589] FIG. 4 is a line graph showing a hardness distribution of
the envelope layer 120 of the golf ball 102 in FIG. 3. The
horizontal axis of the graph indicates the ratio (%) of a distance
from the central point of the core 104 to the radius of the core
104. The vertical axis of the graph indicates a JIS-C hardness. In
the graph, among the first to ninth points, points included in the
envelope layer 120 are plotted. In the present embodiment, six
points including the fourth to ninth points are plotted in the
graph.
[0590] FIG. 4 also shows a linear approximation curve obtained by a
least-square method on the basis of the ratios and the hardnesses
of the six measuring points. The linear approximation curve is
indicated by a dotted line. In FIG. 4, the broken line does not
greatly deviate from the linear approximation curve. In other
words, the broken line has a shape close to the linear
approximation curve. In the envelope layer 120, the hardness
linearly increases from its inside toward its outside. When the
golf ball 102 is hit with a driver, the energy loss is low in the
envelope layer 120. The golf ball 102 has excellent resilience
performance. When the golf ball 102 is hit with a driver, the
flight distance is large. When the golf ball 102 is hit with a golf
club, stress concentration does not occur. Thus, the golf ball 102
has excellent durability.
[0591] R.sup.2 of the linear approximation curve for the envelope
layer 120 which is obtained by the least-square method is
preferably equal to or greater than 0.95. R.sup.2 is an index
indicating the linearity of the broken line. For the envelope layer
120 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 golf ball 102 that includes the envelope layer
120 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).
[0592] In light of suppression of spin, the gradient a of the
linear approximation curve is preferably equal to or greater than
0.30, more preferably equal to or greater than 0.33, and
particularly preferably equal to or greater than 0.35.
[0593] In the present invention, a JIS-C hardness at a measuring
point whose ratio of the distance from the central point of the
core 104 to the radius of the core 104 is x % is represented by
H(x). The hardness at the central point of the core 104 is
represented by H(0), and the surface hardness of the core 104 is
represented by H(100). The difference (H(100)-H(0)) between the
surface hardness H(100) and the central hardness H(0) is preferably
equal to or greater than 15. The core 104 in which the difference
(H(100)-H(0)) is equal to or greater than 15 has an
outer-hard/inner-soft structure. When the golf ball 102 is hit with
a driver, the recoil (torsional return) in the core 104 is great,
and thus spin is suppressed. The core 104 contributes to the flight
performance of the golf ball 102. In light of flight performance,
the difference (H(100)-H(0)) is more preferably equal to or greater
than 23 and particularly preferably equal to or greater than 24.
From the standpoint that the core 104 can easily be formed, the
difference (H(100)-H(0)) is preferably equal to or less than 50. In
the core 104, the hardness gradually increases from its central
point toward its surface.
[0594] The center 118 is formed by crosslinking a rubber
composition. Examples of base rubbers for use in the rubber
composition include polybutadienes, polyisoprenes,
styrene-butadiene copolymers, ethylene-propylene-diene copolymers,
and natural rubbers. Two or more rubbers may be used in
combination. In light of resilience performance, polybutadienes are
preferred, and high-cis polybutadienes are particularly
preferred.
[0595] Preferably, the rubber composition of the center 118
includes a co-crosslinking agent. Examples of preferable
co-crosslinking agents in light of resilience performance include
zinc acrylate, magnesium acrylate, zinc methacrylate, and magnesium
methacrylate. Preferably, the rubber composition includes an
organic peroxide together with a co-crosslinking agent. 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.
Preferably, the rubber composition includes a sulfur compound.
[0596] According to need, various additives such as a filler,
sulfur, a vulcanization accelerator, an anti-aging agent, a
coloring agent, a plasticizer, a dispersant, and the like are
included in the rubber composition of the center 118 in an adequate
amount. Synthetic resin powder or crosslinked rubber powder may
also be included in the rubber composition.
[0597] The envelope layer 120 is formed by crosslinking a rubber
composition. The rubber composition includes:
[0598] (a) a base rubber;
[0599] (b) a co-crosslinking agent;
[0600] (c) a crosslinking initiator; and
[0601] (d) an acid and/or a salt.
[0602] The rubber composition of the envelope layer 120 can include
the base rubber (a) described above for the envelope layer 20 of
the first embodiment.
[0603] The co-crosslinking agent (b) is:
[0604] (b1) an .alpha.,.beta.-unsaturated carboxylic acid having 3
to 8 carbon atoms; and
[0605] (b2) a metal salt of an .alpha.,.beta.-unsaturated
carboxylic acid having 3 to 8 carbon atoms.
The rubber composition of the envelope layer 120 can include the
co-crosslinking agent (b) described above for the envelope layer 20
of the first embodiment.
[0606] When the rubber composition of the envelope layer 120
includes the .alpha.,.beta.-unsaturated carboxylic acid (b1), the
rubber composition preferably further includes a metal compound
(f). The rubber composition of the envelope layer 120 can include
the metal compound (f) described above for the envelope layer 20 of
the first embodiment.
[0607] In light of resilience performance of the golf ball 102, 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.
[0608] The rubber composition of the envelope layer 120 can include
the crosslinking initiator (c) described above for the envelope
layer 20 of the first embodiment. In light of resilience
performance of the golf ball 102, 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 102, 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.
[0609] The rubber composition of the envelope layer 120 can include
the acid and/or the salt (d) described above for the envelope layer
20 of the first embodiment. It is inferred that as described later,
during heating and forming of the core 104, the acid and/or the
salt (d) breaks the metal crosslinks by the co-crosslinking agent
(b) in the envelope layer 120, which is a part of the core 104. In
the present invention, the co-crosslinking agent (b) is not
included in the concept of the acid and/or the salt (d).
[0610] In light of linearity of the hardness distribution of the
envelope layer 120, the amount of the acid and/or the salt (d) is
preferably equal to or greater than 0.5 parts by weight, more
preferably equal to or greater than 1.0 parts by weight, and
particularly preferably equal to or greater than 2.0 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 45 parts by weight, more preferably equal to or less than 40
parts by weight, and particularly preferably equal to or less than
30 parts by weight, per 100 parts by weight of the base rubber.
[0611] The weight ratio of the co-crosslinking agent (b) and the
acid and/or the salt (d) in the rubber composition is preferably
equal to or greater than 3/7 but equal to or less than 9/1. From
the rubber composition in which this weight ratio is within the
above range, the envelope layer 120 whose hardness linearly
increases from its inside toward its outside can be obtained.
[0612] 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. In the present invention, when the rubber
composition includes this zinc acrylate, this coating material is
not included in the concept of the acid and/or the salt (d).
[0613] Preferably, the rubber composition of the envelope layer 120
further includes the organic sulfur compound (e) described above
for the envelope layer 20 of the first embodiment. The organic
sulfur compound (e) increases the linearity of the hardness
distribution of the envelope layer 120. In addition, the organic
sulfur compound (e) increases the degree of the
outer-hard/inner-soft structure.
[0614] From the standpoint that an outer-hard/inner-soft structure
is easily obtained, particularly preferable organic sulfur
compounds (e) are 2-thionaphthol, bis(pentabromophenyl)disulfide,
and 2,6-dichlorothiophenol.
[0615] From the standpoint that an outer-hard/inner-soft structure
is easily obtained, the amount of the organic sulfur compound (e)
is preferably equal to or greater than 0.05 parts by weight, more
preferably equal to or greater than 0.1 parts by weight, and
particularly preferably equal to or greater than 0.2 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, more preferably equal to or less than 3.0
parts by weight, and particularly preferably equal to or less than
1.0 parts by weight, per 100 parts by weight of the base
rubber.
[0616] For the purpose of adjusting specific gravity and the like,
a filler may be included in the envelope layer 120. 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 104 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.
[0617] 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 envelope layer
120. Crosslinked rubber powder or synthetic resin powder may also
be dispersed in the rubber composition.
[0618] During heating and forming of the core 104, the base rubber
(a) is crosslinked by the co-crosslinking agent (b). The heat of
the crosslinking reaction of the base rubber remains near the
central point of the core 104. Thus, during heating and forming of
the core 104, the temperature at the central portion is high. The
temperature gradually decreases from the central point toward the
surface. In the rubber composition, the acid reacts with the metal
salt of the co-crosslinking agent (b) to bond to cation. In the
rubber composition, the salt reacts with the metal salt of the
co-crosslinking agent (b) to exchange cation. By the bonding and
the exchange, metal crosslinks are broken. The bonding and the
exchange are likely to occur near the innermost portion of the
envelope layer 120 where the temperature is high, and are unlikely
to occur near the surface of the envelope layer 120. In other
words, breaking of metal crosslinks is likely to occur near the
innermost portion of the envelope layer 120 and is unlikely to
occur near the surface of the envelope layer 120. As a result, the
crosslinking density of the envelope layer 120 increases from its
inside toward its outside. In the envelope layer 120, the hardness
linearly increases from its inside toward its outside. Further,
since the rubber composition includes the organic sulfur compound
(e) together with the acid and/or the salt (d), the gradient of the
hardness distribution can be controlled, and the degree of the
outer-hard/inner-soft structure of the core 104 can be increased.
When the golf ball 102 that includes the core 104 is hit with a
driver, the spin rate is low. In the golf ball 102, excellent
flight performance is achieved upon a shot with a driver.
[0619] The hardness H(0) at the central point of the core 104 is
preferably equal to or greater than 40 but equal to or less than
70. The golf ball 102 having a hardness H(0) of 40 or greater has
excellent resilience performance. In this respect, the hardness
H(0) is more preferably equal to or greater than 45 and
particularly preferably equal to or greater than 47. The core 104
having a hardness H(0) of 70 or less can achieve an
outer-hard/inner-soft structure. In the golf ball 102 that includes
the core 104, spin can be suppressed. In this respect, the hardness
H(0) is more preferably equal to or less than 68 and particularly
preferably equal to or less than 65.
[0620] The hardness H(100) at the surface of the core 104 is
preferably equal to or greater than 78 but equal to or less than
96. The core 104 having a hardness H(100) of 78 or greater can
achieve an outer-hard/inner-soft structure. In the golf ball 102
that includes the core 104, spin can be suppressed. In this
respect, the hardness H(100) is more preferably equal to or greater
than 80 and particularly preferably equal to or greater than 82.
The golf ball 102 having a hardness H(100) of 96 or less has
excellent durability. In this respect, the hardness H(100) is more
preferably equal to or less than 94 and particularly preferably
equal to or less than 92.
[0621] The core 104 preferably has a diameter of 38.0 mm or greater
but 42.0 mm or less. The core 104 having a diameter of 38.0 mm or
greater can achieve excellent resilience performance of the golf
ball 102. In this respect, the diameter is more preferably equal to
or greater than 39.0 mm and particularly preferably equal to or
greater than 39.5 mm. In the golf ball 102 that includes the core
104 having a diameter of 42.0 mm or less, the mid layer 106, the
inner cover 110, and the outer cover 112 can have sufficient
thicknesses. The golf ball 102 that includes the mid layer 106, the
inner cover 110, and the outer cover 112 which have large
thicknesses has excellent durability. In this respect, the diameter
is more preferably equal to or less than 41 mm and particularly
preferably equal to or less than 40 mm.
[0622] For the mid layer 106, a resin composition is suitably used.
Examples of the base polymer of the resin composition include
ionomer resins, polystyrenes, polyesters, polyamides, and
polyolefins.
[0623] Particularly preferable base polymers are ionomer resins.
The golf ball 102 that includes the mid layer 106 including an
ionomer resin has excellent resilience performance. An ionomer
resin and another resin may be used in combination for the mid
layer 106. 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.
[0624] The mid layer 106 can include the ionomer resin described
above for the golf ball 2 of the first embodiment. The mid layer
106 can include the styrene block-containing thermoplastic
elastomer described above for the golf ball 2 of the first
embodiment.
[0625] The mid layer 106 may include a highly elastic resin as the
base polymer. The highly elastic resin contributes to high rigidity
of the mid layer 106. Specific examples of the highly elastic resin
include polyamides.
[0626] 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 mid layer 106 in an
adequate amount.
[0627] From the standpoint that an outer-hard/inner-soft structure
can be achieved in the sphere consisting of the core 104 and the
mid layer 106, the mid layer 106 has a hardness Hm 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 102, the hardness Hm is preferably equal to or less than 75,
more preferably equal to or less than 72, and particularly
preferably equal to or less than 70. The hardness Hm is measured by
the method described above for the golf ball 2 of the first
embodiment.
[0628] The mid layer 106 preferably has a thickness Tm of 0.5 mm or
greater but 1.6 mm or less. In the sphere that includes the mid
layer 106 having a thickness Tm of 0.5 mm or greater, the spin
suppression effect provided by the outer-hard/inner-soft structure
is great. In this respect, the thickness Tm is particularly
preferably equal to or greater than 0.7 mm. The golf ball 102 that
includes the mid layer 106 having a thickness Tm of 1.6 mm or less
can include a large core 104. The large core 104 can contribute to
the resilience performance of the golf ball 102. In this respect,
the thickness Tm is particularly preferably equal to or less than
1.2 mm.
[0629] For forming the mid layer 106, known methods such as
injection molding, compression molding, and the like can be
used.
[0630] For the inner cover 110, a resin composition is suitably
used. A preferable base polymer of the resin composition is a
polyurethane. The polyurethane is flexible. When the golf ball 102
that includes the inner cover 110 formed from the resin composition
that includes the polyurethane is hit with a short iron, the spin
rate is high. The inner cover 110 formed from this resin
composition contributes to controllability upon a shot with a short
iron. Furthermore, the polyurethane can also contribute to
excellent feel at impact when the golf ball 102 is hit with a
putter or a short iron.
[0631] In light of ease of forming the inner cover 110, a
preferable base polymer is a thermoplastic polyurethane elastomer.
The inner cover 110 can include the thermoplastic polyurethane
elastomer described above for the golf ball 2 of the first
embodiment.
[0632] 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. 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.
[0633] According to need, a coloring agent such as titanium dioxide
and a fluorescent pigment, 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 inner cover 110 in an adequate
amount.
[0634] The inner cover 110 preferably has a Shore D hardness Hc1 of
48 or less. The golf ball 102 that includes the inner cover 110
having a hardness Hc1 of 48 or less has excellent controllability.
In this respect, the hardness Hc1 is more preferably equal to or
less than 40 and particularly preferably equal to or less than 32.
In light of flight distance upon a shot with a driver, the hardness
Hc1 is preferably equal to or greater than 10. The hardness Hc1 is
measured by the same measurement method as that for the hardness
Hm.
[0635] The inner cover 110 has a thickness T1 of 0.1 mm or greater
but 0.8 mm or less. The golf ball 102 having a thickness T1of 0.1
mm or greater has excellent controllability. In this respect, the
thickness T1 is more preferably equal to or greater than 0.2 mm and
particularly preferably equal to or greater than 0.3 mm. The golf
ball 102 having a thickness T1 of 0.8 mm or less has excellent
resilience performance. In this respect, the thickness T1 is more
preferably equal to or less than 0.6 mm and particularly preferably
equal to or less than 0.5 mm.
[0636] For forming the inner cover 110, known methods such as
injection molding, compression molding, and the like can be
used.
[0637] For the outer cover 112, a resin composition is suitably
used. A preferable base polymer of the resin composition is a
polyurethane. The polyurethane is flexible. When the golf ball 102
that includes the outer cover 112 formed from the resin composition
that includes the polyurethane is hit with a short iron, the spin
rate is high. The outer cover 112 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 outer cover 112. Furthermore, the polyurethane can contribute
to excellent feel at impact when the golf ball 102 is hit with a
putter or a short iron.
[0638] In light of ease of forming the outer cover 112, a
preferable base polymer is a thermoplastic polyurethane elastomer.
The thermoplastic polyurethane elastomer described above for the
inner cover 110 can be used for the outer cover 112. Particularly,
an elastomer including a polyurethane component obtained by a
reaction of a polyol and an alicyclic diisocyanate is preferred.
Since the alicyclic diisocyanate does not have any double bond in
the main chain, the alicyclic diisocyanate suppresses yellowing of
the outer cover 112. In addition, since the alicyclic diisocyanate
has excellent strength, the alicyclic diisocyanate suppresses a
scuff on the outer cover 112.
[0639] A thermoplastic polyurethane elastomer and another resin may
be used in combination. The outer cover 112 can include the resin
described above for the inner cover 110. 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.
[0640] According to need, a coloring agent such as titanium dioxide
and a fluorescent pigment, 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 outer cover 112 in an adequate
amount.
[0641] The outer cover 112 preferably has a Shore D hardness Hc2 of
60 or less. The golf ball 102 that includes the outer cover 112
having a hardness Hc2 of 60 or less has excellent controllability.
In this respect, the hardness Hc2 is more preferably equal to or
less than 55 and particularly preferably equal to or less than 50.
In light of flight distance upon a shot with a driver, the hardness
Hc2 is preferably equal to or greater than 40. The hardness Hc2 is
measured by the same measurement method as that for the hardness
Hm.
[0642] The outer cover 112 preferably has a thickness T2 of 0.1 mm
or greater but 0.8 mm or less. The golf ball 102 having a thickness
T2 of 0.1 mm or greater has excellent controllability. In this
respect, the thickness T2 is more preferably equal to or greater
than 0.2 mm and particularly preferably equal to or greater than
0.3 mm. The golf ball 102 having a thickness T2 of 0.8 mm or less
has excellent resilience performance. In this respect, the
thickness T2 is more preferably equal to or less than 0.6 mm and
particularly preferably equal to or less than 0.5 mm.
[0643] For forming the outer cover 112, known methods such as
injection molding, compression molding, and the like can be used.
When forming the outer cover 112, the dimples 114 are formed by
pimples formed on the cavity face of a mold.
[0644] In the golf ball 102, the hardness Hm of the mid layer 106
and the hardness Hc1 of the inner cover 110 meet the relationship
of the following mathematical formula.
Hm>Hc1
When the golf ball 102 is hit with a driver, the sphere consisting
of the core 104 and the mid layer 106 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 104 linearly changes. Thus, the golf ball 102
is launched at a high speed due to deformation and restoration of
the core 104. The suppression of the spin rate and the high launch
speed achieve a large flight distance. When the golf ball 102 is
hit with a short iron, this sphere becomes less distorted since the
head speed is low. When the golf ball 102 is hit with a short iron,
the behavior of the golf ball 102 depends on the inner cover 110.
Since the inner cover 110 is flexible, a slip between the golf ball
102 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 102, both desired
flight performance upon a shot with a driver and desired
controllability upon a shot with a short iron are achieved.
[0645] When the golf ball 102 is hit, the inner cover 110 absorbs
the shock. This absorption achieves soft feel at impact.
Particularly, when the golf ball 102 is hit with a short iron or a
putter, the inner cover 110 achieves excellent feel at impact.
[0646] In light of achievement of both desired flight performance
and desired controllability, the difference (Hm-Hc1) between the
hardness Hm and the hardness Hc1 is preferably equal to or greater
than 20 and more preferably equal to or greater than 36. The
difference (Hm-Hc1) is preferably equal to or less than 60.
[0647] Preferably, the hardness Hm of the mid layer 106 and the
hardness Hc2 of the outer cover 112 meet the relationship of the
following mathematical formula.
Hm>Hc2
When the golf ball 102 is hit with a driver, the sphere consisting
of the core 104 and the mid layer 106 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 104 linearly changes. Thus, the golf ball 102
is launched at a high speed due to deformation and restoration of
the core 104. The suppression of the spin rate and the high launch
speed achieve a large flight distance. When the golf ball 102 is
hit with a short iron, this sphere becomes less distorted since the
head speed is low. When the golf ball 102 is hit with a short iron,
the behavior of the golf ball 102 depends also on the outer cover
112 in addition to the aforementioned inner cover 110. Since the
inner cover 110 and the outer cover 112 are flexible, a slip
between the golf ball 102 and a clubface is effectively 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 102, both desired flight performance upon a shot with a driver
and desired controllability upon a shot with a short iron are
achieved.
[0648] When the golf ball 102 is hit, the inner cover 110 and the
outer cover 112 absorb the shock. This absorption achieves soft
feel at impact. Particularly, when the golf ball 102 is hit with a
short iron or a putter, the inner cover 110 and the outer cover 112
achieve excellent feel at impact.
[0649] In light of achievement of both desired flight performance
and desired controllability, the difference (Hm-Hc2) between the
hardness Hm and the hardness Hc2 is preferably equal to or greater
than 15 and more preferably equal to or greater than 18. The
difference (Hm-Hc2) is preferably equal to or less than 40.
[0650] In the golf ball 102, the hardness Hc1 of the inner cover
110 and the hardness Hc2 of the outer cover 112 meet the
relationship of the following mathematical formula.
Hc1<Hc2
In the golf ball 102, the outer cover 112 can contribute to
suppression of spin. In the golf ball 102, further improvement of
flight performance upon a shot with driver is achieved without
impairing controllability upon a shot with a short iron.
[0651] In light of flight performance, the difference (Hc2-Hc1)
between the hardness Hc2 and the hardness Hc1 is preferably equal
to or greater than 5 and more preferably equal to or greater than
10. In light of controllability, the difference (Hc2-Hc1) is
preferably equal to or less than 20.
[0652] The difference (T1-T2) between the thickness T1 of the inner
cover 110 and the thickness T2 of the outer cover 112 is preferably
equal to or greater than -0.4 mm but equal to or less than 0.4 mm.
In the golf ball 102 in which the difference (T1-T2) is within the
above range, the inner cover 110 and the outer cover 112 are easily
formed. In this respect, the difference (T1-T2) is more preferably
equal to or greater than -0.3 mm but equal to or less than 0.3 mm,
and is particularly preferably equal to or greater than -0.2 mm but
equal to or less than 0.2 mm.
[0653] In light of flight performance, the sum (T1+T2) of the
thickness T1 of the inner cover 110 and the thickness T2 of the
outer cover 112 is preferably equal to or less than 1.0 mm and
particularly preferably equal to or less than 0.8 mm. In light of
controllability, the sum (T1+T2) is preferably equal to or greater
than 0.2 mm and particularly preferably equal to or greater than
0.4 mm.
[0654] The reinforcing layer 108 is positioned between the mid
layer 106 and the inner cover 110. The reinforcing layer 108 firmly
adheres to the mid layer 106 and also to the inner cover 110. The
reinforcing layer 108 suppresses separation of the inner cover 110
from the mid layer 106. In the golf ball 102, when the mid layer
106 is formed from a resin composition and the inner cover 110 is
formed from a resin composition whose base resin is different from
the base resin of the mid layer 106, the reinforcing layer 108
effectively suppresses separation of the inner cover 110 from the
mid layer 106.
[0655] As the base polymer of the reinforcing layer 108, 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 108, two-component curing type epoxy
resins and two-component curing type urethane resins are
preferred.
[0656] The reinforcing layer 108 can include the two-component
curing type epoxy resin described above for the golf ball 2 of the
first embodiment. The reinforcing layer 108 can include the
two-component curing type urethane resin described above for the
golf ball 2 of the first embodiment.
[0657] The reinforcing layer 108 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.
[0658] In light of feel at impact, the golf ball 102 has an amount
of compressive deformation (comp'n) of preferably 2.3 mm or
greater, more preferably 2.5 mm or greater, and particularly
preferably 2.7 mm or greater. In light of resilience performance,
the amount of compressive deformation is preferably equal to or
less than 3.5 mm, more preferably equal to or less than 3.3 mm, and
particularly preferably equal to or less than 3.1 mm. The amount of
compressive deformation is measured by the method described above
for the golf ball 2 of the first embodiment.
Third Embodiment
[0659] A golf ball 202 shown in FIG. 5 includes a spherical core
204, an inner mid layer 206 positioned outside the core 204, an
outer mid layer 208 positioned outside the inner mid layer 206, a
reinforcing layer 210 positioned outside the outer mid layer 208,
and a cover 212 positioned outside the reinforcing layer 210. The
core 204 includes a spherical center 214 and an envelope layer 216
positioned outside the center 214. On the surface of the cover 212,
a large number of dimples 217 are formed. Of the surface of the
golf ball 202, a part other than the dimples 217 is a land 218. The
golf ball 202 includes a paint layer and a mark layer on the
external side of the cover 212, but these layers are not shown in
the drawing.
[0660] The golf ball 202 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 202 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.
[0661] The center 214 is formed by crosslinking a rubber
composition. Examples of base rubbers for use in the rubber
composition include polybutadienes, polyisoprenes,
styrene-butadiene copolymers, ethylene-propylene-diene copolymers,
and natural rubbers. Two or more rubbers may be used in
combination. In light of resilience performance, polybutadienes are
preferred, and high-cis polybutadienes are particularly
preferred.
[0662] Preferably, the rubber composition of the center 214
includes a co-crosslinking agent. Examples of preferable
co-crosslinking agents in light of resilience performance include
acrylic acid, methacrylic acid, zinc acrylate, magnesium acrylate,
zinc methacrylate, and magnesium methacrylate. Preferably, the
rubber composition further include a metal compound. Examples of
the metal compound include magnesium oxide and zinc oxide.
Preferably, the rubber composition includes an organic peroxide
with a co-crosslinking agent. 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.
Preferably, the rubber composition includes a sulfur compound. The
rubber composition may include a carboxylic acid or a salt
thereof.
[0663] According to need, various additives such as a filler,
sulfur, a vulcanization accelerator, an anti-aging agent, a
coloring agent, a plasticizer, a dispersant, and the like are
included in the rubber composition of the center 214 in an adequate
amount. Synthetic resin powder or crosslinked rubber powder may
also be included in the rubber composition.
[0664] In the present embodiment, the center 214 is preferably more
flexible than the envelope layer 216. In light of resilience
performance, the JIS-C hardness at the central point of the center
214 is preferably equal to or greater than 40.0, more preferably
equal to or greater than 45.0, and particularly preferably equal to
or greater than 50.0. In light of suppression of spin, the JIS-C
hardness at the central point of the center 214 is preferably equal
to or less than 70.0, more preferably equal to or less than 65.0,
and particularly preferably equal to or less than 60.0.
[0665] In light of achievement of an outer-hard/inner-soft
structure of the center 214, the JIS-C hardness at the surface of
the center 214 is preferably equal to or greater than 50.0 and more
preferably equal to or greater than 60.0. In light of durability
and feel at impact, the JIS-Chardness is preferably equal to or
less than 70.0. In the center 214, the hardness continuously
increases from the central point to the surface of the center
214.
[0666] The JIS-C hardness at the central point of the center 214 is
measured by pressing a JIS-C type hardness scale against a cut
plane of the spherical center 214 that has been cut into two
halves. The hardness at the surface of the center 214 is measured
by pressing the JIS-C type hardness scale against the surface of
the center 214. 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.
[0667] The center 214 preferably has a diameter of 10 mm or greater
but 25 mm or less. In the golf ball 202 that includes the center
214 having a diameter of 10 mm or greater, spin can be suppressed.
In this respect, the diameter is more preferably equal to or
greater than 12 mm and particularly preferably equal to or greater
than 14 mm. The golf ball 202 that includes the center 214 having a
diameter of 25 mm or less has excellent resilience performance,
even though the center 214 is flexible. In this respect, the
diameter is more preferably equal to or less than 22 mm and
particularly preferably equal to or less than 19 mm.
[0668] FIG. 6 is a line graph showing a hardness distribution of
the envelope layer 216 of the golf ball 202 in FIG. 5. In the
present invention, JIS-C hardnesses are measured at nine points
obtained by dividing the distance from the boundary between the
center 214 and the envelope layer 216 to the surface of the core
204 (the thickness of the envelope layer 216) at intervals of 12.5%
of the distance. The horizontal axis of the graph indicates a
distance from the boundary between the center 214 and the envelope
layer 216 as a ratio (%) to the thickness of the envelope layer
216. The vertical axis of the graph indicates the JIS-C hardness at
each measuring point. The ratio (%) of the distance from the
boundary between the center 214 and the envelope layer 216 to each
of these measuring points to the thickness of the envelope layer
216 is as follows.
[0669] First point: 0.0% (the boundary between the center 214 and
the envelope layer 216)
[0670] Second point: 12.5%
[0671] Third point: 25.0%
[0672] Fourth point: 37.5%
[0673] Fifth point: 50.0%
[0674] Sixth point: 62.5%
[0675] Seventh point: 75.0%
[0676] Eighth point: 87.5%
[0677] Ninth point: 100.0% (the surface of the core 204)
[0678] Hardnesses at the first to eighth points are measured by
pressing a JIS-C type hardness scale against a cut plane of the
core 204, consisting of the center 214 and the envelope layer 216,
which 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 spherical core 204. 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.
[0679] FIG. 6 also shows a linear approximation curve obtained by a
least-square method on the basis of the hardness at each measuring
point and the distance (%) from the boundary between the center 214
and the envelope layer 216 to each measuring point. The linear
approximation curve is indicated by a dotted line. In FIG. 6, the
broken line does not greatly deviate from the linear approximation
curve. In other words, the broken line has a shape close to the
linear approximation curve. In the envelope layer 216, the hardness
linearly increases from its inside toward its outside. When the
golf ball 202 is hit with a driver, the energy loss is low in the
envelope layer 216. In the envelope layer 216, the hardness
continuously increases from the boundary with the center 214 toward
its surface. In the envelope layer 216, there is no discontinuous
point caused by a multilayer structure. When the golf ball 202 that
includes the envelope layer 216 deforms by being hit, no local load
is applied thereto. The golf ball 202 has resistance to breakage
caused by deformation of the envelope layer 216.
[0680] R.sup.2 of the linear approximation curve for the envelope
layer 216 which is obtained by the least-square method is
preferably equal to or greater than 0.95. R.sup.2 is an index
indicating the linearity of the broken line. For the envelope layer
216 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 golf ball 202 that includes the envelope layer
216 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 0.97 and particularly preferably equal to or
greater than 0.99. 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 boundary
between the center 214 and the envelope layer 216 and the hardness
(JIS-C) by the standard deviation of the distance (%) from the
boundary between the center 214 and the envelope layer 216 and the
standard deviation of the hardness (JIS-C).
[0681] In light of suppression of spin, the gradient a of the
linear approximation curve is preferably equal to or greater than
0.20, more preferably equal to or greater than 0.23, and
particularly preferably equal to or greater than 0.26.
[0682] In the present invention, a JIS-C hardness at a measuring
point whose distance from the boundary between the center 214 and
the envelope layer 216 is x (%) is represented by H(x). The
hardness at the boundary between the center 214 and the envelope
layer 216 is represented by H(0.0). In the present invention, the
JIS-C hardness at the surface of the core 204 is represented by Hs.
The difference (Hs-H(0.0)) between the hardness Hs and the hardness
H(0.0) is preferably equal to or greater than 22. The envelope
layer 216 in which the difference (Hs-H(0.0)) is equal to or
greater than 22 contributes to suppression of spin. In this
respect, the difference (Hs-H(0.0)) is more preferably equal to or
greater than 26 and particularly preferably equal to or greater
than 30. From the standpoint that the core 204 can easily be
formed, the difference (Hs-H(0.0)) is preferably equal to or less
than 50.
[0683] The envelope layer 216 is formed by crosslinking a rubber
composition. The rubber composition includes:
[0684] (a) a base rubber;
[0685] (b) a co-crosslinking agent;
[0686] (c) a crosslinking initiator; and
[0687] (d) an acid and/or a salt.
[0688] The rubber composition of the envelope layer 216 can include
the base rubber (a) described above for the envelope layer 20 of
the first embodiment.
[0689] Examples of preferable co-crosslinking agents (b)
include:
[0690] (b1) an .alpha.,.beta.-unsaturated carboxylic acid having 3
to 8 carbon atoms; and
[0691] (b2) a metal salt of an .alpha.,.beta.-unsaturated
carboxylic acid having 3 to 8 carbon atoms.
The rubber composition of the envelope layer 216 can include the
co-crosslinking agent (b) described above for the envelope layer 20
of the first embodiment.
[0692] When the rubber composition of the envelope layer 216
includes the .alpha.,.beta.-unsaturated carboxylic acid (b1), the
rubber composition preferably further includes a metal compound
(f). The rubber composition of the envelope layer 216 can include
the metal compound (f) described above for the envelope layer 20 of
the first embodiment.
[0693] In light of resilience performance of the golf ball 202, 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 per 100 parts
by weight of the base rubber.
[0694] The rubber composition of the envelope layer 216 can include
the crosslinking initiator (c) described above for the envelope
layer 20 of the first embodiment. The crosslinking initiator (c) is
preferably an organic peroxide. The organic peroxide contributes to
the resilience performance of the golf ball 202.
[0695] In light of resilience performance of the golf ball 202, 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 202, the amount is preferably equal to or less than 5
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.
[0696] The rubber composition of the envelope layer 216 can include
the acid and/or the salt (d) described above for the envelope layer
20 of the first embodiment. The acid component included in the acid
and/or the salt (d) has reactivity with a cationic component.
During heating and forming of the envelope layer 216, the acid
dissociates and reacts with the cationic component of the
co-crosslinking agent (b). It is thought that the acid inhibits
formation of the metal crosslinks by the co-crosslinking agent (b)
within the envelope layer 216. The acid component included in the
salt exchanges the cationic component with the co-crosslinking
agent (b). It is inferred that during heating and forming of the
envelope layer 216, the salt breaks the metal crosslinks by the
co-crosslinking agent (b). In the present invention, the
co-crosslinking agent (b) is not included in the concept of the
acid and/or the salt (d).
[0697] In light of linearity of the hardness distribution of the
envelope layer 216, the amount of the acid and/or the salt (d) is
preferably equal to or greater than 1.0 parts by weight, more
preferably equal to or greater than 2.0 parts by weight, and
particularly preferably equal to or greater than 3.0 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.
[0698] The weight ratio of the co-crosslinking agent (b) and the
acid and/or the salt (d) in the rubber composition is preferably
equal to or greater than 3/7 but equal to or less than 9/1, and is
particularly preferably equal to or greater than 4/6 but equal to
or less than 8/2. From the rubber composition in which this weight
ratio is within the above range, the envelope layer 216 having an
appropriate hardness distribution can be obtained.
[0699] 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. In the present invention, when the rubber
composition includes this zinc acrylate, the stearic acid or zinc
stearate coating the zinc acrylate is not included in the concept
of the acid and/or the salt (d).
[0700] Preferably, the rubber composition of the envelope layer 216
further includes the organic sulfur compound (e) described above
for the envelope layer 20 of the first embodiment. The organic
sulfur compound (e) can contribute to control of: the linearity of
the hardness distribution of the envelope layer 216; and the degree
of an outer-hard/inner-soft structure.
[0701] From the standpoint that an outer-hard/inner-soft structure
is easily obtained, more preferable organic sulfur compounds (e)
are 2-thionaphthol, bis(pentabromophenyl)disulfide, and
2,6-dichlorothiophenol. A particularly preferable organic sulfur
compound (e) is 2-thionaphthol.
[0702] From the standpoint that an outer-hard/inner-soft structure
is easily obtained, the amount of the organic sulfur compound (e)
is preferably equal to or greater than 0.05 parts by weight, more
preferably equal to or greater than 0.1 parts by weight, and
particularly preferably equal to or greater than 0.2 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, more preferably equal to or less than 3.0
parts by weight, and particularly preferably equal to or less than
1.0 parts by weight, per 100 parts by weight of the base
rubber.
[0703] For the purpose of adjusting specific gravity and the like,
a filler may be included in the envelope layer 216. 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 204 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.
[0704] 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 envelope layer
216. Crosslinked rubber powder or synthetic resin powder may also
be dispersed in the rubber composition.
[0705] During heating of the envelope layer 216, the heat of a
crosslinking reaction of the base rubber (a) remains within the
envelope layer 216. Thus, during heating of the envelope layer 216,
the internal temperature of the envelope layer 216 is high as
compared to the surface temperature of the envelope layer 216. The
temperature gradually decreases from the boundary between the
center 214 and the envelope layer 216 toward the surface of the
envelope layer 216. The acid and/or the salt (d) reacts with the
metal salt of the co-crosslinking agent (b) to inhibit formation of
or break metal crosslinks. This reaction is accelerated in a region
where the temperature is high. In other words, breaking of metal
crosslinks is likely to occur near the innermost portion of the
envelope layer 216 where the temperature is high, and is unlikely
to occur near the surface of the envelope layer 216. As a result,
the crosslinking density of the envelope layer 216 continuously
increases from its inside toward its outside. In the envelope layer
216, the hardness linearly increases from its inside toward its
outside. Furthermore, since the rubber composition includes the
organic sulfur compound (e) together with the acid and/or the salt
(d), the gradient of the hardness distribution can be controlled,
and the degree of the outer-hard/inner-soft structure of the
envelope layer 216 can be increased.
[0706] The envelope layer 216 preferably has a thickness Te of 5 mm
or greater but 16 mm or less. The golf ball 202 that includes the
envelope layer 216 having a thickness Te of 5 mm or greater has
excellent resilience performance. In this respect, the thickness Te
is more preferably equal to or greater than 6 mm and particularly
preferably equal to or greater than 7 mm. In the golf ball 202 that
includes the envelope layer 216 having a thickness Te of 16 mm or
less, spin is suppressed upon a shot with a driver. In this
respect, the thickness Te is more preferably equal to or less than
15 mm and particularly preferably equal to or less than 14 mm.
[0707] In light of the resilience performance, the hardness H(0.0)
at the innermost portion of the envelope layer 216 is preferably
equal to or greater than 60.0 and more preferably equal to or
greater than 63.0. In light of appropriate hardness distribution,
the hardness H(0.0) is preferably equal to or less than 70.0 and
more preferably equal to or less than 65.0. In light of durability,
the difference between the hardness H(0.0) and the surface hardness
of the center 214 is preferably less than 10. When the golf ball
202 that includes the center 214 and the envelope layer 216 deforms
by being hit, the local load is low even though the golf ball 202
has a multilayer structure.
[0708] The JIS-C hardness Hs at the surface of the core 204 is
preferably equal to or greater than 80.0 but equal to or less than
96.0. When the golf ball 202 that includes the core 204 having a
hardness Hs of 80.0 or greater is hit with a driver, the spin is
small. The flight distance of the golf ball 202 is large. In this
respect, the hardness Hs is more preferably equal to or greater
than 82.0 and particularly preferably equal to or greater than
84.0. The golf ball 202 having a hardness Hs of 96.0 or less has
excellent durability. In this respect, the hardness Hs is more
preferably equal to or less than 94.0 and particularly preferably
equal to or less than 92.0.
[0709] The JIS-C hardness Ho at the central point of the core 204
is equal to the JIS-C hardness at the central point of the center
214. As described above, in light of resilience performance, the
hardness Ho is preferably equal to or greater than 40.0 but equal
to or less than 70.0. The hardness Hs is preferably greater than
the hardness Ho. The difference (Hs-Ho) between the hardness Hs and
the hardness Ho is preferably equal to or greater than 30 and more
preferably equal to or greater than 34. In the golf ball 202 that
includes the core 204, spin is suppressed upon a shot with a
driver. In light of ease of producing the core 204, the difference
(Hs-Ho) is preferably equal to or less than 50.
[0710] The core 204 preferably has a diameter of 36.0 mm or
greater. The core 204 having a diameter of 36.0 mm or greater can
achieve excellent resilience performance of the golf ball 202. In
light of durability, the diameter of the core 204 is preferably
equal to or less than 39.0 mm and more preferably equal to or less
than 38.0 mm.
[0711] In light of feel at impact, the core 204 has an amount of
compressive deformation Dc of preferably 3.5 mm or greater and
particularly preferably 3.8 mm or greater. In light of resilience
performance of the core 204, the amount of compressive deformation
Dc is preferably equal to or less than 4.5 mm and particularly
preferably equal to or less than 4.0 mm.
[0712] For the inner mid layer 206, a resin composition is suitably
used. Examples of the base resin of the resin composition include
ionomer resins, polystyrenes, polyesters, polyamides, and
polyolefins.
[0713] Particularly preferable base resins are ionomer resins. The
golf ball 202 that includes the inner mid layer 206 including an
ionomer resin has excellent resilience performance. An ionomer
resin and another resin may be used in combination for the inner
mid layer 206. In this case, the principal component of the base
resin is preferably the ionomer resin. Specifically, the proportion
of the ionomer resin to the entire base resin is preferably equal
to or greater than 45% by weight and more preferably equal to or
greater than 60% by weight.
[0714] The inner mid layer 206 can include the ionomer resin
described above for the golf ball 2 of the first embodiment. The
inner mid layer 206 can include the styrene block-containing
thermoplastic elastomer described above for the golf ball 2 of the
first embodiment.
[0715] 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 206 in an
adequate amount.
[0716] From the standpoint that an outer-hard/inner-soft structure
can be achieved in the sphere consisting of the core 204 and the
inner mid layer 206, the inner mid layer 206 has a Shore D hardness
Hm1 of preferably 30 or greater and more preferably 40 or greater.
In the golf ball 202 that includes the inner mid layer 206 having a
hardness Hm1 in this range, a spin rate is sufficiently suppressed
upon a shot with a driver. The flight distance of the golf ball 202
is large. In light of controllability of the golf ball 202, the
hardness Hm1 is preferably equal to or less than 60 and
particularly preferably equal to or less than 54. When the golf
ball 202 is hit with a short iron, the spin rate is high. The golf
ball 202 has excellent controllability. The hardness Hm1 is
measured by the method described above for the golf ball 2 of the
first embodiment.
[0717] The inner mid layer 206 preferably has a thickness Tm1 of
0.5 mm or greater but 1.6 mm or less. In light of durability, the
thickness Tm1 is more preferably equal to or greater than 0.7 mm.
In light of resilience performance, the thickness Tm1 is more
preferably equal to or less than 1.2 mm.
[0718] For the outer mid layer 208, a resin composition is suitably
used. Examples of the base resin of the resin composition include
ionomer resins, polystyrenes, polyesters, polyamides, and
polyolefins.
[0719] Particularly preferable base resins are ionomer resins. The
golf ball 202 that includes the outer mid layer 208 including an
ionomer resin has excellent resilience performance. An ionomer
resin and another resin may be used in combination for the outer
mid layer 208. In this case, the principal component of the base
resin is preferably the ionomer resin. Specifically, the proportion
of the ionomer resin to the entire base resin is preferably equal
to or greater than 80% by weight and more preferably equal to or
greater than 90% by weight. The ionomer resin described above for
the inner mid layer 206 can also be used for the outer mid layer
208. The styrene block-containing thermoplastic elastomer described
above for the inner mid layer 206 may be used in combination for
the outer mid layer 208.
[0720] The outer mid layer 208 may include a highly elastic resin.
Specific examples of the highly elastic resin include
polyamides.
[0721] 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 208 in an
adequate amount.
[0722] In light of a spin suppression effect upon a shot with a
driver, the outer mid layer 208 has a Shore D hardness Hm2 of
preferably 55 or greater and more preferably 60 or greater. The
flight distance of the golf ball 202 is large. In light of
controllability of the golf ball 202, the hardness Hm2 is
preferably equal to or less than 70 and more preferably equal to or
less than 68. When the golf ball 202 is hit with a short iron, the
spin rate is high. The hardness Hm2 is measured by the same method
as that for the hardness Hm1.
[0723] In light of achievement of an outer-hard/inner-soft
structure, the hardness Hm1 of the inner mid layer 206 is
preferably less than the hardness Hm2 of the outer mid layer 208.
When the golf ball 202 is hit with a driver, the spin rate is low.
The flight distance of the golf ball 202 is large.
[0724] In light of resilience performance and controllability, the
difference (Hm2-Hm1) between the hardness Hm2 of the outer mid
layer 208 and the hardness Hm1 of the inner mid layer 206 is
preferably equal to or greater than 8 and particularly preferably
equal to or greater than 14. In light of feel at impact, the
difference (Hm2-Hm1) is preferably equal to or less than 30. When
the golf ball 202 that includes the outer mid layer 208 having a
hardness Hm2 in this range is hit with a driver, the spin rate is
low. When the golf ball 202 is hit with a short iron, the spin rate
is high.
[0725] The outer mid layer 208 preferably has a thickness Tm2 of
0.5 mm or greater. In the golf ball 202 that includes the outer mid
layer 208 having a thickness Tm2 of 0.5 mm or greater, the shock by
a hit is alleviated. Thus, the golf ball 202 has excellent
durability. In this respect, the thickness Tm2 is more preferably
equal to or greater than 0.7 mm. The thickness Tm2 is preferably
equal to or less than 1.6 mm. The golf ball 202 that includes the
outer mid layer 208 having a thickness Tm2 of 1.6 mm or less
includes a relatively large core 204. The golf ball 202 has
sufficient resilience performance. In this respect, the thickness
Tm2 is particularly preferably equal to or less than 1.2 mm.
[0726] The sum (Tm1+Tm2) of the thickness Tm1 and the thickness Tm2
is preferably equal to or greater than 1.0 mm. In the golf ball
202, the shock by a hit is alleviated. Thus, the golf ball 202 has
excellent durability. In this respect, the sum (Tm1+Tm2) is more
preferably equal to or greater than 1.3 mm. The sum (Tm1+Tm2) is
preferably equal to or less than 3.0 mm. The golf ball 202 includes
a relatively large core 204. The golf ball 202 has sufficient
resilience performance. In this respect, the sum (Tm1+Tm2) is more
preferably equal to or less than 2.0 mm.
[0727] For forming the outer mid layer 208, known methods such as
injection molding, compression molding, and the like can be
used.
[0728] For the cover 212, a resin composition is suitably used. A
preferable base resin of the resin composition is a urethane resin
or a urea resin. The principal component of the urethane resin is a
polyurethane. The polyurethane is flexible. When the golf ball 202
that includes the cover 212 formed from the resin composition that
includes the polyurethane is hit with a short iron, the spin rate
is high. The cover 212 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
212. Furthermore, the polyurethane can also contribute to excellent
feel at impact when the golf ball 202 is hit with a putter or a
short iron.
[0729] In light of ease of forming the cover 212, a preferable base
resin is a thermoplastic polyurethane elastomer. The cover 212 can
include the thermoplastic polyurethane elastomer described above
for the golf ball 2 of the first embodiment.
[0730] 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.
[0731] 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 212 in an adequate amount.
[0732] The cover 212 preferably has a Shore D hardness Hc of 48 or
less. The golf ball 202 that includes the cover 212 having a
hardness Hc of 48 or less has excellent controllability. In this
respect, the hardness Hc is more preferably equal to or less than
40 and particularly preferably equal to or less than 32. In light
of flight distance upon a shot with a driver, the hardness Hc is
preferably equal to or greater than 10 and more preferably equal to
or greater than 15. The hardness Hc is measured by the same
measurement method as that for the hardness Hm1 and the hardness
Hm2.
[0733] The hardness Hm2 of the outer mid layer 208 is greater than
the hardness Hc of the cover 212. When the golf ball 202 is hit
with a driver, the sphere consisting of the core 204, the inner mid
layer 206, and the outer mid layer 208 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 204 linearly changes. Thus, the golf ball 202
is launched at a high speed due to deformation and restoration of
the core 204. The suppression of the spin rate and the high launch
speed achieve a large flight distance. When the golf ball 202 is
hit with a short iron, this sphere becomes less distorted since the
head speed is low. When the golf ball 202 is hit with a short iron,
the behavior of the golf ball 202 mainly depends on the cover 212.
Since the cover 212 is flexible, a slip between the golf ball 202
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 202, both desired flight
performance upon a shot with a driver and desired controllability
upon a shot with a short iron are achieved. In this respect, the
hardness Hc is more preferably less than the hardness Hm1 of the
inner mid layer 206.
[0734] When the golf ball 202 is hit, the cover 212 including the
polyurethane absorbs the shock. This absorption achieves soft feel
at impact. Particularly, when the golf ball 202 is hit with a short
iron or a putter, the flexible cover 212 achieves excellent feel at
impact.
[0735] In light of achievement of both desired flight performance
and desired controllability, the difference (Hm2-Hc) between the
hardness Hm2 of the outer mid layer 208 and the hardness Hc of the
cover 212 is preferably equal to or greater than 30 and more
preferably equal to or greater than 34. In the golf ball 202 in
which the hardness of the outer mid layer 208 and the hardness of
the cover 212 meet this condition, a backspin rate is suppressed
upon a shot with a driver. In the golf ball 202, a backspin rate
upon an approach shot is increased. In light of durability, the
difference (Hm2-Hc) is preferably equal to or less than 45 and more
preferably equal to or less than 40.
[0736] In light of achievement of both desired flight performance
and desired controllability, the difference (Hm1-Hc) between the
hardness Hm1 of the inner mid layer 206 and the hardness Hc of the
cover 212 is preferably equal to or greater than 13 but equal to or
less than 28.
[0737] In light of flight performance upon a shot with a driver,
the cover 212 has a thickness Tc of preferably 0.8 mm or less, more
preferably 0.6 mm or less, and particularly preferably 0.5 mm or
less. In light of durability and controllability, the thickness Tc
is preferably equal to or greater than 0.3 mm and more preferably
equal to or greater than 0.4 mm.
[0738] For forming the cover 212, known methods such as injection
molding, compression molding, and the like can be used. When
forming the cover 212, the dimples 217 are formed by pimples formed
on the cavity face of a mold.
[0739] In light of achievement of both desired flight performance
and desired controllability, the principal component of the base
resin of the resin composition of the cover 212 is preferably a
urethane resin or a urea resin, and the principal component of the
base resin of the resin composition of the outer mid layer 208 is
preferably an ionomer resin. In other words, the principal
component of the base resin of the outer mid layer 208 is different
from the principal component of the base resin of the cover
212.
[0740] In light of durability, the golf ball 202 that further
includes the reinforcing layer 210 between the outer mid layer 208
and the cover 212 is preferred. The reinforcing layer 210 is
positioned between the outer mid layer 208 and the cover 212. The
reinforcing layer 210 firmly adheres to the outer mid layer 208 and
also to the cover 212. The reinforcing layer 210 suppresses
separation of the cover 212 from the outer mid layer 208. As
described above, the cover 212 of the golf ball 202 is thin. When
the golf ball 202 is hit by the edge of a clubface, a wrinkle is
likely to occur. The reinforcing layer 210 suppresses occurrence of
a wrinkle to improve the durability of the golf ball 202.
[0741] As the base polymer of the reinforcing layer 210, 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 210, two-component curing type epoxy
resins and two-component curing type urethane resins are
preferred.
[0742] The reinforcing layer 210 can include the two-component
curing type epoxy resin described above for the golf ball 2 of the
first embodiment. The reinforcing layer 210 can include the
two-component curing type urethane resin described above for the
golf ball 2 of the first embodiment.
[0743] The reinforcing layer 210 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.
[0744] In light of feel at impact, the golf ball 202 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. The amount of compressive
deformation is measured by the method described above for the golf
ball 2 of the first embodiment.
Fourth Embodiment
[0745] A golf ball 302 shown in FIG. 7 includes a spherical core
304, an inner mid layer 306 positioned outside the core 304, an
outer mid layer 308 positioned outside the inner mid layer 306, a
reinforcing layer 310 positioned outside the outer mid layer 308,
and a cover 312 positioned outside the reinforcing layer 310. The
core 304 includes a spherical center 314 and an envelope layer 316
positioned outside the center 314. On the surface of the cover 312,
a large number of dimples 317 are formed. Of the surface of the
golf ball 302, a part other than the dimples 317 is a land 318. The
golf ball 302 includes a paint layer and a mark layer on the
external side of the cover 312, but these layers are not shown in
the drawing.
[0746] The golf ball 302 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 302 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 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.
[0747] The center 314 is formed by crosslinking a rubber
composition. Examples of base rubbers for use in the rubber
composition include polybutadienes, polyisoprenes,
styrene-butadiene copolymers, ethylene-propylene-diene copolymers,
and natural rubbers. Two or more rubbers may be used in
combination. In light of resilience performance, polybutadienes are
preferred, and high-cis polybutadienes are particularly
preferred.
[0748] Preferably, the rubber composition of the center 314
includes a co-crosslinking agent. Examples of preferable
co-crosslinking agents in light of resilience performance include
acrylic acid, methacrylic acid, zinc acrylate, magnesium acrylate,
zinc methacrylate, and magnesium methacrylate. Preferably, the
rubber composition further include a metal compound. Examples of
the metal compound include magnesium oxide and zinc oxide.
Preferably, the rubber composition includes an organic peroxide
with a co-crosslinking agent. 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.
Preferably, the rubber composition includes a sulfur compound. The
rubber composition may include a carboxylic acid and/or a salt
thereof.
[0749] According to need, various additives such as a filler,
sulfur, a vulcanization accelerator, an anti-aging agent, a
coloring agent, a plasticizer, a dispersant, and the like are
included in the rubber composition of the center 314 in an adequate
amount. Synthetic resin powder or crosslinked rubber powder may
also be included in the rubber composition.
[0750] In the present embodiment, the center 314 is preferably more
flexible than the envelope layer 316. In light of resilience
performance, the JIS-C hardness at the central point of the center
314 is preferably equal to or greater than 40, more preferably
equal to or greater than 45, and particularly preferably equal to
or greater than 50. In light of suppression of spin, the JIS-C
hardness at the central point of the center 314 is preferably equal
to or less than 70, more preferably equal to or less than 65, and
particularly preferably equal to or less than 60.
[0751] In light of achievement of an outer-hard/inner-soft
structure of the center 314, the JIS-C hardness at the surface of
the center 314 is preferably equal to or greater than 50 and more
preferably equal to or greater than 60. In light of durability and
feel at impact, the JIS-C hardness is preferably equal to or less
than 75. In the center 314, the hardness continuously increases
from the central point to the surface of the center 314.
[0752] The JIS-C hardness at the central point of the center 314 is
measured by pressing a JIS-C type hardness scale against a cut
plane of the spherical center 314 that has been cut into two
halves. The hardness at the surface of the center 314 is measured
by pressing the JIS-C type hardness scale against the surface of
the center 314. 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.
[0753] The center 314 preferably has a diameter of 10 mm or greater
but 25 mm or less. In the golf ball 302 that includes the center
314 having a diameter of 10 mm or greater, spin can be suppressed.
In this respect, the diameter is more preferably equal to or
greater than 12 mm and particularly preferably equal to or greater
than 14 mm. The golf ball 302 that includes the center 314 having a
diameter of 25 mm or less has excellent resilience performance,
even though the center 314 is flexible. In this respect, the
diameter is more preferably equal to or less than 22 mm and
particularly preferably equal to or less than 19 mm.
[0754] FIG. 8 is a line graph showing a hardness distribution of
the envelope layer 316 of the golf ball 302 in FIG. 7. In the
present invention, JIS-C hardnesses are measured at nine points
obtained by dividing the distance from the boundary between the
center 314 and the envelope layer 316 to the surface of the core
304 (the thickness of the envelope layer 316) at intervals of 12.5%
of the distance. The horizontal axis of the graph indicates a
distance from the boundary between the center 314 and the envelope
layer 316 as a ratio (%) to the thickness of the envelope layer
316. The vertical axis of the graph indicates the JIS-C hardness at
each measuring point. The ratio (%) of the distance from the
boundary between the center 314 and the envelope layer 316 to each
of these measuring points to the thickness of the envelope layer
316 is as follows.
[0755] First point: 0.0% (the boundary between the center 314 and
the envelope layer 316)
[0756] Second point: 12.5%
[0757] Third point: 25.0%
[0758] Fourth point: 37.5%
[0759] Fifth point: 50.0%
[0760] Sixth point: 62.5%
[0761] Seventh point: 75.0%
[0762] Eighth point: 87.5%
[0763] Ninth point: 100.0% (the surface of the core 304)
[0764] Hardnesses at the first to eighth points are measured by
pressing a JIS-C type hardness scale against a cut plane of the
core 304, consisting of the center 314 and the envelope layer 316,
which 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 spherical core 304. 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.
[0765] FIG. 8 also shows a linear approximation curve obtained by a
least-square method on the basis of the hardness at each measuring
point and the distance (%) from the boundary between the center 314
and the envelope layer 316 to each measuring point. The linear
approximation curve is indicated by a dotted line. In FIG. 8, the
broken line does not greatly deviate from the linear approximation
curve. In other words, the broken line has a shape close to the
linear approximation curve. In the envelope layer 316, the hardness
linearly increases from its inside toward its outside. When the
golf ball 302 is hit with a driver, the energy loss is low in the
envelope layer 316. In the envelope layer 316, the hardness
continuously increases from the boundary with the center 314 toward
its surface. In the envelope layer 316, there is no discontinuous
point caused by a multilayer structure. When the golf ball 302 that
includes the envelope layer 316 deforms by being hit, no local load
is applied thereto. The golf ball 302 has resistance to breakage
caused by deformation of the envelope layer 316.
[0766] R.sup.2 of the linear approximation curve for the envelope
layer 316 which is obtained by the least-square method is
preferably equal to or greater than 0.95. R.sup.2 is an index
indicating the linearity of the broken line. For the envelope layer
316 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 golf ball 302 that includes the envelope layer
316 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 0.97 and particularly preferably equal to or
greater than 0.99. 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 boundary
between the center 314 and the envelope layer 316 and the hardness
(JIS-C) by the standard deviation of the distance (%) from the
boundary between the center 314 and the envelope layer 316 and the
standard deviation of the hardness (JIS-C).
[0767] In light of suppression of spin, the gradient a of the
linear approximation curve is preferably equal to or greater than
0.20, more preferably equal to or greater than 0.23, and
particularly preferably equal to or greater than 0.26.
[0768] In the present invention, a JIS-C hardness at a measuring
point whose distance from the boundary between the center 314 and
the envelope layer 316 is x (%) is represented by H(x). The
hardness at the boundary between the center 314 and the envelope
layer 316 is represented by H(0.0). In the present invention, the
JIS-C hardness at the surface of the core 304 is represented by Hs.
The difference (Hs-H(0.0)) between the hardness Hs and the hardness
H(0.0) is preferably equal to or greater than 22. The envelope
layer 316 in which the difference (Hs-H(0.0)) is equal to or
greater than 22 contributes to suppression of spin. In this
respect, the difference (Hs-H(0.0)) is more preferably equal to or
greater than 26 and particularly preferably equal to or greater
than 30. From the standpoint that the core 304 can easily be
formed, the difference (Hs-H(0.0)) is preferably equal to or less
than 50.
[0769] The envelope layer 316 is formed by crosslinking a rubber
composition. The rubber composition includes:
[0770] (a) a base rubber;
[0771] (b) a co-crosslinking agent;
[0772] (c) a crosslinking initiator; and
[0773] (d) an acid and/or a salt.
[0774] The rubber composition of the envelope layer 316 can include
the base rubber (a) described above for the envelope layer 20 of
the first embodiment.
[0775] Examples of preferable co-crosslinking agents (b)
include:
[0776] (b1) an .alpha.,.beta.-unsaturated carboxylic acid having 3
to 8 carbon atoms; and
[0777] (b2) a metal salt of an .alpha.,.beta.-unsaturated
carboxylic acid having 3 to 8 carbon atoms.
The rubber composition of the envelope layer 316 can include the
co-crosslinking agent (b) described above for the envelope layer 20
of the first embodiment.
[0778] When the rubber composition of the envelope layer 316
includes the .alpha.,.beta.-unsaturated carboxylic acid (b1), the
rubber composition preferably further includes a metal compound
(f). The rubber composition of the envelope layer 316 can include
the metal compound (f) described above for the envelope layer 20 of
the first embodiment.
[0779] In light of resilience performance of the golf ball 302, 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 per 100 parts
by weight of the base rubber.
[0780] The rubber composition of the envelope layer 316 can include
the crosslinking initiator (c) described above for the envelope
layer 20 of the first embodiment. The crosslinking initiator (c) is
preferably an organic peroxide. The organic peroxide contributes to
the resilience performance of the golf ball 302.
[0781] In light of resilience performance of the golf ball 302, 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 302, the amount is preferably equal to or less than 5
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.
[0782] The rubber composition of the envelope layer 316 can include
the acid and/or the salt (d) described above for the envelope layer
20 of the first embodiment. The acid component included in the acid
and/or the salt (d) has reactivity with a cationic component.
During heating and forming of the envelope layer 316, the acid
dissociates and reacts with the cationic component of the
co-crosslinking agent (b). It is thought that the acid inhibits
formation of the metal crosslinks by the co-crosslinking agent (b)
within the envelope layer 316. The acid component included in the
salt exchanges the cationic component with the co-crosslinking
agent (b). It is inferred that during heating and forming of the
envelope layer 316, the salt breaks the metal crosslinks by the
co-crosslinking agent (b). In the present invention, the
co-crosslinking agent (b) is not included in the concept of the
acid and/or the salt (d).
[0783] In light of linearity of the hardness distribution of the
envelope layer 316, the amount of the acid and/or the salt (d) is
preferably equal to or greater than 1.0 parts by weight, more
preferably equal to or greater than 2.0 parts by weight, and
particularly preferably equal to or greater than 3.0 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.
[0784] The weight ratio of the co-crosslinking agent (b) and the
acid and/or the salt (d) in the rubber composition is preferably
equal to or greater than 3/7 but equal to or less than 9/1, and is
particularly preferably equal to or greater than 4/6 but equal to
or less than 8/2. From the rubber composition in which this weight
ratio is within the above range, the envelope layer 316 having an
appropriate hardness distribution can be obtained.
[0785] 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. In the present invention, when the rubber
composition includes this zinc acrylate, the stearic acid or zinc
stearate coating the zinc acrylate is not included in the concept
of the acid and/or the salt (d).
[0786] Preferably, the rubber composition of the envelope layer 316
further includes the organic sulfur compound (e) described above
for the envelope layer 20 of the first embodiment. The organic
sulfur compound (e) can contribute to control of: the linearity of
the hardness distribution of the envelope layer 316; and the degree
of an outer-hard/inner-soft structure.
[0787] From the standpoint that an outer-hard/inner-soft structure
is easily obtained, more preferable organic sulfur compounds (e)
are 2-thionaphthol, bis(pentabromophenyl)disulfide, and
2,6-dichlorothiophenol. A particularly preferable organic sulfur
compound (e) is 2-thionaphthol.
[0788] From the standpoint that an outer-hard/inner-soft structure
is easily obtained, the amount of the organic sulfur compound (e)
is preferably equal to or greater than 0.05 parts by weight, more
preferably equal to or greater than 0.1 parts by weight, and
particularly preferably equal to or greater than 0.2 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, more preferably equal to or less than 3.0
parts by weight, and particularly preferably equal to or less than
1.0 parts by weight, per 100 parts by weight of the base
rubber.
[0789] For the purpose of adjusting specific gravity and the like,
a filler may be included in the envelope layer 316. 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 304 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.
[0790] 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 envelope layer
316. Crosslinked rubber powder or synthetic resin powder may also
be dispersed in the rubber composition.
[0791] During heating of the envelope layer 316, the heat of a
crosslinking reaction of the base rubber (a) remains within the
envelope layer 316. Thus, during heating of the envelope layer 316,
the internal temperature of the envelope layer 316 is high as
compared to the surface temperature of the envelope layer 316. The
temperature gradually decreases from the boundary between the
center 314 and the envelope layer 316 toward the surface of the
envelope layer 316. The acid and/or the salt (d) reacts with the
metal salt of the co-crosslinking agent (b) to inhibit formation of
or break metal crosslinks. This reaction is accelerated in a region
where the temperature is high. In other words, breaking of metal
crosslinks is likely to occur near the innermost portion of the
envelope layer 316 where the temperature is high, and is unlikely
to occur near the surface of the envelope layer 316. As a result,
the crosslinking density of the envelope layer 316 continuously
increases from its inside toward its outside. In the envelope layer
316, the hardness linearly increases from its inside toward its
outside. Furthermore, since the rubber composition includes the
organic sulfur compound (e) together with the acid and/or the salt
(d), the gradient of the hardness distribution can be controlled,
and the degree of the outer-hard/inner-soft structure of the
envelope layer 316 can be increased.
[0792] The envelope layer 316 preferably has a thickness Te of 5 mm
or greater but 16 mm or less. The golf ball 302 that includes the
envelope layer 316 having a thickness Te of 5 mm or greater has
excellent resilience performance. In this respect, the thickness Te
is more preferably equal to or greater than 6 mm and particularly
preferably equal to or greater than 7 mm. In the golf ball 302 that
includes the envelope layer 316 having a thickness Te of 16 mm or
less, spin is suppressed upon a shot with a driver. In this
respect, the thickness Te is more preferably equal to or less than
15 mm and particularly preferably equal to or less than 14 mm.
[0793] In light of the resilience performance, the hardness H(0.0)
at the innermost portion of the envelope layer 316 is preferably
equal to or greater than 60 and more preferably equal to or greater
than 63. In light of appropriate hardness distribution, the
hardness H(0.0) is preferably equal to or less than 70 and more
preferably equal to or less than 65. In light of durability, the
difference between the hardness H(0.0) and the surface hardness of
the center 314 is preferably less than 10. When the golf ball 302
that includes the center 314 and the envelope layer 316 deforms by
being hit, the local load is low even though the golf ball 302 has
a multilayer structure.
[0794] The JIS-C hardness Hs at the surface of the core 304 is
preferably equal to or greater than 80 but equal to or less than
96. When the golf ball 302 that includes the core 304 having a
hardness Hs of 80 or greater is hit with a driver, the spin is
small. The flight distance of the golf ball 302 is large. In this
respect, the hardness Hs is more preferably equal to or greater
than 82 and particularly preferably equal to or greater than 84.
The golf ball 302 having a hardness Hs of 96 or less has excellent
durability. In this respect, the hardness Hs is more preferably
equal to or less than 94 and particularly preferably equal to or
less than 92.
[0795] The JIS-C hardness Ho at the central point of the core 304
is equal to the JIS-C hardness at the central point of the center
314. As described above, in light of resilience performance, the
hardness Ho is preferably equal to or greater than 40 but equal to
or less than 70. The hardness Hs is preferably greater than the
hardness Ho. The difference (Hs-Ho) between the hardness Hs and the
hardness Ho is preferably equal to or greater than 20 and more
preferably equal to or greater than 25. In the golf ball 302 that
includes the core 304, spin is suppressed upon a shot with a
driver. In light of ease of producing the core 304, the difference
(Hs-Ho) is preferably equal to or less than 50.
[0796] The core 304 preferably has a diameter of 36.0 mm or
greater. The core 304 having a diameter of 36.0 mm or greater can
achieve excellent resilience performance of the golf ball 302. In
light of durability, the diameter of the core 304 is preferably
equal to or less than 39.0 mm and more preferably equal to or less
than 38.0 mm.
[0797] In light of feel at impact, the core 304 has an amount of
compressive deformation Dc of preferably 3.0 mm or greater and
particularly preferably 3.5 mm or greater. In light of resilience
performance of the core 304, the amount of compressive deformation
Dc is preferably equal to or less than 4.5 mm and particularly
preferably equal to or less than 4.0 mm.
[0798] For the inner mid layer 306, a resin composition is suitably
used. Examples of the base resin of the resin composition include
ionomer resins, polystyrenes, polyesters, polyamides, and
polyolefins.
[0799] Particularly preferable base resins are ionomer resins. The
golf ball 302 that includes the inner mid layer 306 including an
ionomer resin has excellent resilience performance. An ionomer
resin and another resin may be used in combination for the inner
mid layer 306. In this case, the principal component of the base
resin is preferably the ionomer resin. Specifically, the proportion
of the ionomer resin to the entire base resin is preferably equal
to or greater than 80% by weight and more preferably equal to or
greater than 90% by weight.
[0800] The inner mid layer 306 can include the ionomer resin
described above for the golf ball 2 of the first embodiment. Two or
more ionomer resins may be used in combination for the inner mid
layer 306. An ionomer resin neutralized with a monovalent metal ion
and an ionomer resin neutralized with a bivalent metal ion may be
used in combination.
[0801] The inner mid layer 306 may include a highly elastic resin.
Specific examples of the highly elastic resin include
polyamides.
[0802] 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 306 in an
adequate amount.
[0803] From the standpoint that an outer-hard/inner-soft structure
can be achieved in the sphere consisting of the core 304 and the
inner mid layer 306, the inner mid layer 306 has a Shore D hardness
Hm1 of preferably 55 or greater and more preferably 60 or greater.
In the golf ball 302 that includes the inner mid layer 306 having a
hardness Hm1 in this range, a spin rate is sufficiently suppressed
upon a shot with a driver. The flight distance of the golf ball 302
is large. In light of controllability of the golf ball 302, the
hardness Hm1 is preferably equal to or less than 70 and
particularly preferably equal to or less than 68. When the golf
ball 302 is hit with a short iron, the spin rate is high. The golf
ball 302 has excellent controllability. The hardness Hm1 is
measured by the method described above for the golf ball 2 of the
first embodiment.
[0804] The inner mid layer 306 preferably has a thickness Tm1 of
0.5 mm or greater but 1.5 mm or less. In light of durability, the
thickness Tm1 is more preferably equal to or greater than 0.7 mm.
In light of resilience performance, the thickness Tm1 is more
preferably equal to or less than 1.2 mm.
[0805] For the outer mid layer 308, a resin composition is suitably
used. Examples of the base resin of the resin composition include
ionomer resins, polystyrenes, polyesters, polyamides, and
polyolefins.
[0806] Particularly preferable base resins are ionomer resins. The
ionomer resin described above for the inner mid layer 306 can also
be used for the outer mid layer 308. The golf ball 302 that
includes the outer mid layer 308 including an ionomer resin has
excellent resilience performance. An ionomer resin and another
resin may be used in combination for the outer mid layer 308. In
this case, the principal component of the base resin is preferably
the ionomer resin. Specifically, the proportion of the ionomer
resin to the entire base resin is preferably equal to or greater
than 45% by weight and more preferably equal to or greater than 60%
by weight.
[0807] 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. The outer mid layer 308 can include the styrene
block-containing thermoplastic elastomer described above for the
golf ball 2 of the first embodiment.
[0808] 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 308 in an
adequate amount.
[0809] In light of a spin suppression effect upon a shot with a
driver, the outer mid layer 308 has a Shore D hardness Hm2 of
preferably 30 or greater and more preferably 40 or greater. The
flight distance of the golf ball 302 is large. In light of
controllability of the golf ball 302, the hardness Hm2 is
preferably equal to or less than 60 and more preferably equal to or
less than 54. When the golf ball 302 is hit with a short iron, the
spin rate is high. The hardness Hm2 is measured by the same method
as that for the hardness Hm1.
[0810] In light of durability and feel at impact, the hardness Hm1
of the inner mid layer 306 is preferably greater than the hardness
Hm2 of the outer mid layer 308. When the golf ball 302 in which the
hardness Hm1 is greater than the hardness Hm2 is hit with a driver,
the shock provided to the golf ball 302 by the driver is
alleviated. The golf ball 302 has excellent durability. The golf
ball 302 has soft feel at impact.
[0811] In light of achievement of both desired resilience
performance and desired controllability, the difference (Hm1-Hm2)
between the hardness Hm2 of the outer mid layer 308 and the
hardness Hm1 of the inner mid layer 306 is preferably equal to or
greater than 8 and particularly preferably equal to or greater than
14. In light of durability, the difference (Hm1-Hm2) is preferably
equal to or less than 35.
[0812] The outer mid layer 308 preferably has a thickness Tm2 of
0.5 mm or greater. In the golf ball 302 that includes the outer mid
layer 308 having a thickness Tm2 of 0.5 mm or greater, the shock by
a hit is alleviated. Thus, the golf ball 302 has excellent
durability. In this respect, the thickness Tm2 is more preferably
equal to or greater than 0.7 mm. The thickness Tm2 is preferably
equal to or less than 1.5 mm. The golf ball 302 that includes the
outer mid layer 308 having a thickness Tm2 of 1.5 mm or less
includes a relatively large core 304. The golf ball 302 has
sufficient resilience performance. The golf ball 302 has soft feel
at impact. In this respect, the thickness Tm2 is particularly
preferably equal to or less than 1.2 mm.
[0813] The sum (Tm1+Tm2) of the thickness Tm1 and the thickness Tm2
is preferably equal to or greater than 1.0 mm. In the golf ball
302, the shock by a hit is alleviated. Thus, the golf ball 302 has
excellent durability. In this respect, the sum (Tm1+Tm2) is more
preferably equal to or greater than 1.3 mm. The sum (Tm1+Tm2) is
preferably equal to or less than 3.0 mm. The golf ball 302 includes
a relatively large core 304. The golf ball 302 has sufficient
resilience performance. In this respect, the sum (Tm1+Tm2) is more
preferably equal to or less than 2.0 mm.
[0814] For forming the outer mid layer 308, known methods such as
injection molding, compression molding, and the like can be
used.
[0815] For the cover 312, a resin composition is suitably used. A
preferable base resin of the resin composition is a urethane resin
or a urea resin. The principal component of the urethane resin is a
polyurethane. The polyurethane is flexible. When the golf ball 302
that includes the cover 312 formed from the resin composition that
includes the polyurethane is hit with a short iron, the spin rate
is high. The cover 312 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
312. Furthermore, the polyurethane can also contribute to excellent
feel at impact when the golf ball 302 is hit with a putter or a
short iron.
[0816] In light of ease of forming the cover 312, a preferable base
resin is a thermoplastic polyurethane elastomer. The cover 312 can
include the thermoplastic polyurethane elastomer described above
for the golf ball 2 of the first embodiment.
[0817] 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 312 in an adequate amount.
[0818] The cover 312 preferably has a Shore D hardness Hc of 48 or
less. The golf ball 302 that includes the cover 312 having a
hardness Hc of 48 or less has excellent controllability. In this
respect, the hardness Hc is more preferably equal to or less than
40 and particularly preferably equal to or less than 32. In light
of flight distance upon a shot with a driver, the hardness Hc is
preferably equal to or greater than 10 and more preferably equal to
or greater than 15. The hardness Hc is measured by the same
measurement method as that for the hardness Hm1 and the hardness
Hm2.
[0819] The hardness Hm1 of the inner mid layer 306 is greater than
the hardness Hc of the cover 312. When the golf ball 302 is hit
with a driver, the sphere consisting of the core 304, the inner mid
layer 306, and the outer mid layer 308 becomes significantly
distorted since the head speed is high. The hardness of the
envelope layer 316 included in the core 304 linearly changes. Thus,
the golf ball 302 is launched at a high speed due to deformation
and restoration of the envelope layer 316. The high launch speed
achieves a large flight distance. When the golf ball 302 is hit
with a short iron, this sphere becomes less distorted since the
head speed is low. When the golf ball 302 is hit with a short iron,
the behavior of the golf ball 302 mainly depends on the cover 312.
Since the cover 312 is flexible, a slip between the golf ball 302
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 302, both desired flight
performance upon a shot with a driver and desired controllability
upon a shot with a short iron are achieved. In this respect, the
hardness Hc is more preferably less than the hardness Hm2 of the
outer mid layer 308.
[0820] When the golf ball 302 is hit, the cover 312 including the
polyurethane absorbs the shock. This absorption achieves soft feel
at impact. Particularly, when the golf ball 302 is hit with a short
iron or a putter, the cover 312 achieves excellent feel at
impact.
[0821] In light of achievement of both desired flight performance
and desired controllability, the difference (Hm1-Hc) between the
hardness Hm1 of the inner mid layer 306 and the hardness Hc of the
cover 312 is preferably equal to or greater than 30 and more
preferably equal to or greater than 34. In the golf ball 302 in
which the hardness of the inner mid layer 306 and the hardness of
the cover 312 meet this condition, a backspin rate is suppressed
upon a shot with a driver. In the golf ball 302, a backspin rate
upon an approach shot is increased. In light of durability, the
difference (Hm1-Hc) is preferably equal to or less than 45 and more
preferably equal to or less than 38.
[0822] In light of achievement of both desired flight performance
and desired controllability, the difference (Hm2-Hc) between the
hardness Hm2 of the outer mid layer 308 and the hardness Hc of the
cover 312 is preferably equal to or greater than 13 but equal to or
less than 30.
[0823] In light of flight performance upon a shot with a driver,
the cover 312 has a thickness Tc of preferably 0.8 mm or less, more
preferably 0.6 ram or less, and particularly preferably 0.5 mm or
less. In light of durability and controllability, the thickness Tc
is preferably equal to or greater than 0.3 mm and more preferably
equal to or greater than 0.5 mm.
[0824] For forming the cover 312, known methods such as injection
molding, compression molding, and the like can be used. When
forming the cover 312, the dimples 317 are formed by pimples formed
on the cavity face of a mold.
[0825] In light of achievement of both desired flight performance
and desired controllability, the principal component of the base
resin of the resin composition of the cover 312 is preferably a
urethane resin or a urea resin, and the principal component of the
base resin of the resin composition of the outer mid layer 308 is
preferably an ionomer resin. In other words, the principal
component of the base resin of the outer mid layer 308 is different
from the principal component of the base resin of the cover
312.
[0826] In light of durability, the golf ball 302 that further
includes the reinforcing layer 310 between the outer mid layer 308
and the cover 312 is preferred. The reinforcing layer 310 is
positioned between the outer mid layer 308 and the cover 312. The
reinforcing layer 310 firmly adheres to the outer mid layer 308 and
also to the cover 312. The reinforcing layer 310 suppresses
separation of the cover 312 from the outer mid layer 308. As
described above, the cover 312 of the golf ball 302 is thin. When
the golf ball 302 is hit by the edge of a clubface, a wrinkle is
likely to occur. The reinforcing layer 310 suppresses occurrence of
a wrinkle to improve the durability of the golf ball 302.
[0827] As the base polymer of the reinforcing layer 310, 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 310, two-component curing type epoxy
resins and two-component curing type urethane resins are
preferred.
[0828] The reinforcing layer 310 can include the two-component
curing type epoxy resin described above for the golf ball 2 of the
first embodiment. The reinforcing layer 310 can include the
two-component curing type urethane resin described above for the
golf ball 2 of the first embodiment.
[0829] The reinforcing layer 310 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.
[0830] In light of feel at impact, the golf ball 302 has an amount
of compressive deformation Db of preferably 2.0 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. The amount of compressive
deformation is measured by the method described above for the golf
ball 2 of the first embodiment.
EXAMPLES
Experiment 1
Example I-1
[0831] A rubber composition was obtained by kneading 100 parts by
weight of a high-cis polybutadiene (trade name "BR-730",
manufactured by JSR Corporation), 23 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, 0.3 parts by weight of
bis(pentabromophenyl)disulfide, 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 center with a
diameter of 15 mm.
[0832] A rubber composition was obtained by kneading 100 parts by
weight of a high-cis polybutadiene (the aforementioned "BR-730"),
35 parts by weight of zinc diacrylate (the aforementioned "Sanceler
SR"), 5 parts by weight of zinc oxide, an appropriate amount of
barium sulfate, 0.2 parts by weight of 2-thionaphthol, 0.8 parts by
weight of dicumyl peroxide, and 5.0 parts by weight of zinc
octoate. Half shells were formed from this rubber composition. The
center was covered with two of these half shells. The center and
the half shells were placed into a mold including upper and lower
mold halves each having a hemispherical cavity, and heated at
150.degree. C. for 20 minutes to obtain a core with a diameter of
39.5 mm. An envelope layer was formed from the rubber composition.
The amount of barium sulfate was adjusted such that the specific
gravity of the envelope layer coincides with the specific gravity
of the center and the weight of a golf ball is 45.4 g.
[0833] A resin composition was obtained by kneading 55 parts by
weight of an ionomer resin (the aforementioned "Surlyn 8945"), 45
parts by weight of another ionomer resin (the aforementioned
"Himilan AM7329"), and 3 parts by weight of titanium dioxide with a
twin-screw kneading extruder. The core was placed into a mold. The
resin composition was injected around the core by injection molding
to form a mid layer with a thickness of 1.0 mm.
[0834] 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 dioxide. 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
mid layer with a spray gun, and kept at 23.degree. C. for 12 hours
to obtain a reinforcing layer with a thickness of 10 .mu.m.
[0835] A resin composition was obtained by kneading 100 parts by
weight of a thermoplastic polyurethane elastomer (the
aforementioned "Elastollan NY97A"), 0.2 parts by weight of a
hindered amine light stabilizer (trade name "TINUVIN 770",
manufactured by Ciba Japan K.K.), 4 parts by weight of titanium
dioxide, and 0.04 parts by weight of ultramarine blue 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 mold including upper and lower mold halves each
having a hemispherical cavity. An inner cover was obtained from the
half shells by compression molding. The thickness of the inner
cover was 0.3 mm.
[0836] A resin composition was obtained by kneading 100 parts by
weight of a thermoplastic polyurethane elastomer (the
aforementioned "Elastollan NY82A"), 0.2 parts by weight of a
hindered amine light stabilizer (trade name "TINUVIN 770",
manufactured by Ciba Japan K. K.), 4 parts by weight of titanium
dioxide, and 0.04 parts by weight of ultramarine blue 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, the reinforcing layer, and the inner cover
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. An outer cover was obtained
from the half shells by compression molding. The thickness of the
outer cover was 0.3 mm. Dimples having a shape that is the inverted
shape of the pimples were formed on the outer cover. A clear paint
including a two-component curing type polyurethane as a base
material was applied to this outer cover to obtain a golf ball of
Example I-1 with a diameter of 42.7 mm.
Examples I-2 to I-23 and Comparative Examples I-1 to I-5
[0837] Golf balls of Examples I-2 to I-23 and Comparative Examples
I-1 to I-5 were obtained in the same manner as Example I-1, except
the specifications of the core, the mid layer, the inner cover, and
the outer cover were as shown in Tables I-13 to I-18 below. The
composition of the core is shown in detail in Tables I-1 to I-4
below. A hardness distribution of the core is shown in Tables I-7
to I-12 below. The composition of the mid layer is shown in detail
in Table I-5 below. The compositions of the inner cover and the
outer cover are shown in detail in Table I-6 below.
[0838] [Hit with Driver (W#1)]
[0839] A driver with a titanium head (trade name "XXIO",
manufactured by DUNLOP SPORTS CO. LTD., shaft hardness: S, loft
angle: 10.0.degree.) was attached to a swing machine manufactured
by True Temper Co. A golf ball was hit under the condition of a
head speed of 45 m/sec. The spin rate was measured immediately
after the hit. Furthermore, the distance from the launch point to
the stop point was measured. The average value of data obtained by
10 measurements is shown in Tables I-13 to I-18 below.
[0840] [Hit with Sand Wedge (SW)]
[0841] A sand wedge (SW) was attached to the above swing machine. A
golf ball was hit under the condition of a head speed of 21 m/sec.
The backspin rate was measured immediately after the hit. The
average value of data obtained by 10 measurements is shown in
Tables I-13 to I-18 below.
[0842] [Durability]
[0843] A golf ball was kept at 23.degree. C. for 12 hours. The
above driver was attached to the above swing machine. The golf ball
was repeatedly hit under the condition of a head speed of 45 m/sec.
The number of hits required to break the golf ball was counted. The
average value of numbers of hits obtained by 12 measurements is
shown as an index in Tables I-13 to I-18 below.
TABLE-US-00001 TABLE I-1 Compositions of Center and Envelope Layer
(parts by weight) A B C D BR-730 100 100 100 100 Sanceler SR 23.0
35.0 32.0 33.0 ZN-DA90S -- -- -- -- Zinc oxide 5 5 5 5 Barium
sulfate * * * * 2-thionaphthol -- 0.2 0.2 0.2
Bis(pentabromophenyl)disulfide 0.3 -- -- -- 2,6-dichlorothiophenol
-- -- -- -- Dicumyl peroxide 0.8 0.8 0.8 0.8 Zinc octoate -- 5.0 --
0.5 Zinc stearate -- -- -- -- Acid and/or salt 0.0 5.0 0.0 0.5 *
Appropriate amount
TABLE-US-00002 TABLE I-2 Compositions of Center and Envelope Layer
(parts by weight) E F G H BR-730 100 100 100 100 Sanceler SR 34.0
37.0 40.0 34.0 ZN-DA90S -- -- -- -- Zinc oxide 5 5 5 5 Barium
sulfate * * * * 2-thionaphthol 0.2 0.2 0.2 0.2
Bis(pentabromophenyl)disulfide -- -- -- -- 2,6-dichlorothiophenol
-- -- -- -- Dicumyl peroxide 0.8 0.8 0.8 0.8 Zinc octoate 2.0 12.0
45.0 -- Zinc stearate -- -- -- 5 Acid and/or salt 2.0 12.0 45.0 5.0
* Appropriate amount
TABLE-US-00003 TABLE I-3 Compositions of Center and Envelope Layer
(parts by weight) I J K L BR-730 100 100 100 100 Sanceler SR 38.0
36.0 -- 36.0 ZN-DA90S -- -- 35 -- Zinc oxide 5 5 5 5 Barium sulfate
* * * * 2-thionaphthol -- -- 0.2 0.2 Bis(pentabromophenyl)disulfide
0.3 -- -- -- 2,6-dichlorothiophenol -- 0.1 -- -- Dicumyl peroxide
0.8 0.8 0.8 0.8 Zinc octoate 5.0 5.0 5.0 5.0 Zinc stearate -- -- --
-- Acid and/or salt 5.0 5.0 5.0 5.0 * Appropriate amount
TABLE-US-00004 TABLE I-4 Compositions of Center and Envelope Layer
(parts by weight) M N O BR-730 100 100 100 Sanceler SR 34.5 35.0
36.5 ZN-DA90S -- -- -- Zinc oxide 5 5 5 Barium sulfate * * *
2-thionaphthol 0.2 0.2 0.2 Bis(pentabromophenyl)disulfide -- -- --
2,6-dichlorothiophenol -- -- -- Dicumyl peroxide 0.8 0.8 0.8 Zinc
octoate 20.0 30.0 40.0 Zinc stearate -- -- -- Acid and/or salt 20.0
30.0 40.0 * Appropriate amount
[0844] The details of the compounds listed in Tables I-1 to I-4 are
as follows.
[0845] BR-730: 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)
[0846] Sanceler SR: zinc diacrylate manufactured by SANSHIN
CHEMICAL INDUSTRY CO., LTD. (a product coated with 10% by weight of
stearic acid)
[0847] ZN-DA90S: zinc diacrylate manufactured by Nihon Jyoryu Kogyo
Co., Ltd. (a product coated with 10% by weight of zinc
stearate)
[0848] Zinc oxide: trade name "Ginrei R" manufactured by Toho Zinc
Co., Ltd.
[0849] Barium sulfate: trade name "Barium Sulfate BD" manufactured
by Sakai Chemical Industry Co., Ltd.
[0850] 2-thionaphthol: a product of Tokyo Chemical Industry Co.,
Ltd.
[0851] Bis(pentabromophenyl)disulfide: a product of Kawaguchi
Chemical Industry Co., LTD.
[0852] 2,6-dichlorothiophenol: a product of Tokyo Chemical Industry
Co., Ltd.
[0853] Dicumyl peroxide: trade name "Percumyl D" manufactured by
NOF Corporation
[0854] Zinc octoate: a product of Mitsuwa Chemicals Co., Ltd.
[0855] Zinc stearate: a product of Wako Pure Chemical Industries,
Ltd.
TABLE-US-00005 TABLE I-5 Composition of Mid Layer (parts by weight)
M1 M2 M3 Surlyn 55 47 25 8945 Himilan 45 45 45 AM7329 Rabalon -- 8
30 T3221C Titanium 3 3 3 dioxide Hardness 65 58 47 (Shore D)
TABLE-US-00006 TABLE I-6 Composition of Cover (parts by weight) C1
C2 C3 C4 C5 C6 Elastollan NY82A 100 60 Elastollan NY85A 50 40
Elastollan NY90A 50 5 Elastollan NY97A 100 95 Surlyn 8945 40
Himilan AM7329 55 Rabalon T3221C 5 TINUVIN 770 0.2 0.2 0.2 0.2 0.2
0.2 Titanium dioxide 4 4 4 4 4 4 Ultramarine blue 0.04 0.04 0.04
0.04 0.04 0.04 Hardness (Shore D) 29 36 47 60 46 30
TABLE-US-00007 TABLE I-7 Hardness Distribution of Core Ex. Ex. Ex.
Ex. Ex. I-1 I-2 I-3 I-4 I-5 center A A A A A envelope layer B D E F
G H(0) 62.0 62.0 62.0 62.0 62.0 H(12.5) 63.0 63.0 63.0 63.0 63.0
H(25) 63.5 63.5 63.5 63.5 63.5 H(40) 64.0 70.0 67.5 65.0 70.0 H(50)
68.5 71.5 70.0 68.5 72.0 H(62.5) 71.0 73.5 73.0 72.0 74.0 H(75)
81.0 81.5 81.5 80.5 77.5 H(87.5) 84.5 84.0 84.0 84.0 78.5 H(100)
87.5 86.0 86.5 85.0 79.0
TABLE-US-00008 TABLE I-8 Hardness Distribution of Core Ex. Ex. Ex.
Ex. Ex. I-6 I-7 I-8 I-9 I-10 center A A A A A envelope layer H I J
K L H(0) 62.0 62.0 62.0 62.0 62.0 H(12.5) 63.0 63.0 63.0 63.0 63.0
H(25) 63.5 63.5 63.5 63.5 63.5 H(40) 64.5 65.0 64.0 63.5 64.5 H(50)
69.0 69.0 68.5 68.0 69.0 H(62.5) 71.0 70.0 71.0 71.0 71.5 H(75)
81.0 80.0 81.0 81.0 81.5 H(87.5) 84.5 84.0 84.5 84.5 85.0 H(100)
87.0 87.5 87.5 87.5 88.0
TABLE-US-00009 TABLE I-9 Hardness Distribution of Core Ex. Ex. Ex.
Ex. Ex. I-11 I-12 I-13 I-14 I-15 center A A A A A envelope layer L
B B B B H(0) 62.0 62.0 62.0 62.0 62.0 H(12.5) 63.0 63.0 63.0 63.0
63.0 H(25) 63.5 63.5 63.5 63.5 63.5 H(40) 64.5 64.0 64.0 64.0 64.0
H(50) 69.0 68.5 68.5 68.5 68.5 H(62.5) 71.5 71.0 71.0 71.0 71.0
H(75) 81.5 81.0 81.0 81.0 81.0 H(87.5) 85.0 84.5 84.5 84.5 84.5
H(100) 88.0 87.5 87.5 87.5 87.5
TABLE-US-00010 TABLE I-10 Hardness Distribution of Core Ex. Ex. Ex.
Ex. Ex. I-16 I-17 I-18 I-19 I-20 center A A A A A envelope layer B
B B B B H(0) 62.0 62.0 62.0 62.0 62.0 H(12.5) 63.0 63.0 63.0 63.0
63.0 H(25) 63.5 63.5 63.5 63.5 63.5 H(40) 64.0 64.0 64.0 64.0 64.0
H(50) 68.5 68.5 68.5 68.5 68.5 H(62.5) 71.0 71.0 71.0 71.0 71.0
H(75) 81.0 81.0 81.0 81.0 81.0 H(87.5) 84.5 84.5 84.5 84.5 84.5
H(100) 87.5 87.5 87.5 87.5 87.5
TABLE-US-00011 TABLE I-11 Hardness Distribution of Core Ex. Ex. Ex.
I-21 I-22 I-23 center A A A envelope layer M N O H(0) 62.0 62.0
62.0 H(12.5) 63.0 63.0 63.0 H(25) 63.5 63.5 63.5 H(40) 66.0 67.0
69.0 H(50) 69.5 70.0 71.0 H(62.5) 73.0 73.0 73.0 H(75) 79.0 77.0
76.0 H(87.5) 82.0 80.0 79.0 H(100) 84.0 82.0 80.5
TABLE-US-00012 TABLE I-12 Hardness Distribution of Core Comp. Comp.
Comp. Comp. Comp. Ex. Ex. Ex. Ex. Ex. I-1 I-2 I-3 I-4 I-5 center A
A A A A envelope layer B B B C B H(0) 62.0 62.0 62.0 62.0 62.0
H(12.5) 63.0 63.0 63.0 63.0 63.0 H(25) 63.5 63.5 63.5 63.5 63.5
H(40) 64.0 64.0 64.0 70.5 64.0 H(50) 68.5 68.5 68.5 71.5 68.5
H(62.5) 71.0 71.0 71.0 73.5 71.0 H(75) 81.0 81.0 81.0 82.0 81.0
H(87.5) 84.5 84.5 84.5 84.0 84.5 H(100) 87.5 87.5 87.5 86.0
87.5
TABLE-US-00013 TABLE I-13 Results of Evaluation Ex. Ex. Ex. Ex. Ex.
I-1 I-2 I-3 I-4 I-5 Center Diameter (mm) 15.0 15.0 15.0 15.0 15.0
Enve- Acid/salt(phr) 5.0 0.5 2.0 12.0 45.0 lope H(100) - 23.5 16.0
19.0 20.0 9.0 layer H(40) R.sup.2 0.97 0.95 0.96 0.96 0.95 Gradient
.alpha. 0.41 0.30 0.34 0.36 0.16 Core Diameter (mm) 39.5 39.5 39.5
39.5 39.5 H(100) - 25.5 24.0 24.5 23.0 17.0 H(0) Mid Composition M1
M1 M1 M1 M1 layer Hm (Shore D) 65.0 65.0 65.0 65.0 65.0 Diameter
(mm) 41.5 41.5 41.5 41.5 41.5 Tm (mm) 1.0 1.0 1.0 1.0 1.0 Inner
Composition C3 C3 C3 C3 C3 cover Hc1 (Shore D) 47.0 47.0 47.0 47.0
47.0 T1 (mm) 0.3 0.3 0.3 0.3 0.3 Outer Composition C1 C1 C1 C1 C1
cover Hc2 (Shore D) 29.0 29.0 29.0 29.0 29.0 T2 (mm) 0.3 0.3 0.3
0.3 0.3 Ball Hm - Hc1 18.0 18.0 18.0 18.0 18.0 Hm - Hc2 36.0 36.0
36.0 36.0 36.0 Hc1 - Hc2 18.0 18.0 18.0 18.0 18.0 T1 + T2 (mm) 0.6
0.6 0.6 0.6 0.6 T1 - T2 (mm) 0.0 0.0 0.0 0.0 0.0 Db (mm) 2.6 2.6
2.6 2.6 2.6 W#1 spin (rpm) 3000 3150 3050 3050 3400 W#1 flight (m)
242 237 241 241 234 SW spin (rpm) 6850 6900 6850 6850 6950
Durability 112 102 108 107 103
TABLE-US-00014 TABLE I-14 Results of Evaluation Ex. Ex. Ex. Ex. Ex.
I-6 I-7 I-8 I-9 I-10 Center Diameter (mm) 15.0 15.0 15.0 15.0 15.0
Enve- Acid/salt(phr) 5.0 5.0 5.0 5.0 5.0 lope H(100) - 22.5 22.5
23.5 24.0 23.5 layer H(40) R.sup.2 0.96 0.96 0.97 0.97 0.97
Gradient .alpha. 0.40 0.39 0.41 0.42 0.41 Core Diameter (mm) 39.5
39.5 39.5 39.5 39.5 H(100) - 25.0 25.5 25.5 25.5 26.0 H(0) Mid
Composition M1 M1 M1 M1 M2 layer Hm (Shore D) 65.0 65.0 65.0 65.0
58.0 Diameter (mm) 41.5 41.5 41.5 41.5 41.5 Tm (mm) 1.0 1.0 1.0 1.0
1.0 Inner Composition C3 C3 C3 C3 C3 cover Hc1 (Shore D) 47.0 47.0
47.0 47.0 47.0 T1 (mm) 0.3 0.3 0.3 0.3 0.3 Outer Composition C1 C1
C1 C1 C1 cover Hc2 (Shore D) 29.0 29.0 29.0 29.0 29.0 T2 (mm) 0.3
0.3 0.3 0.3 0.3 Ball Hm - Hc1 18.0 18.0 18.0 18.0 11.0 Hm - Hc2
36.0 36.0 36.0 36.0 29.0 Hc1 - Hc2 18.0 18.0 18.0 18.0 18.0 T1 + T2
(mm) 0.6 0.6 0.6 0.6 0.6 T1 - T2 (mm) 0.0 0.0 0.0 0.0 0.0 Db (mm)
2.6 2.6 2.6 2.6 2.6 W#1 spin(rpm) 3050 3050 3000 2950 3050 W#1
flight (m) 241 241 242 243 241 SW spin (rpm) 6850 6850 6850 6850
7000 Durability 111 111 112 114 120
TABLE-US-00015 TABLE I-15 Results of Evaluation Ex. Ex. Ex. Ex. Ex.
I-11 I-12 I-13 I-14 I-15 Center Diameter (mm) 15.0 15.0 15.0 15.0
15.0 Enve- Acid/salt(phr) 5.0 5.0 5.0 5.0 5.0 lope H(100) - 23.5
23.5 23.5 23.5 23.5 layer H(40) R.sup.2 0.97 0.97 0.97 0.97 0.97
Gradient .alpha. 0.41 0.41 0.41 0.41 0.41 Core Diameter (mm) 39.5
39.1 39.1 39.1 39.5 H(100) - 26.0 25.5 25.5 25.5 25.5 H(0) Mid
Composition M3 M1 M1 M1 M1 layer Hm (Shore D) 47.0 65.0 65.0 65.0
65.0 Diameter (mm) 41.5 41.5 41.5 41.5 41.5 Tm (mm) 1.0 1.0 1.0 1.0
1.0 Inner Composition C3 C3 C3 C3 C3 cover Hc1 (Shore D) 47.0 47.0
47.0 47.0 47.0 T1 (mm) 0.3 0.4 0.5 0.3 0.3 Outer Composition C1 C1
C1 C1 C5 cover Hc2 (Shore D) 29.0 29.0 29.0 29.0 46.0 T2 (mm) 0.3
0.4 0.3 0.5 0.3 Ball Hm - Hc1 0.0 18.0 18.0 18.0 18.0 Hm - Hc2 18.0
36.0 36.0 36.0 19.0 Hc1 - Hc2 18.0 18.0 18.0 18.0 1.0 T1 + T2 (mm)
0.6 0.8 0.8 0.8 0.6 T1 - T2 (mm) 0.0 0.0 0.2 -0.2 0.0 Db (mm) 2.7
2.6 2.6 2.6 2.6 W#1 spin (rpm) 3100 3100 3050 3150 3000 W#1 flight
(m) 239 240 242 242 242 SW spin (rpm) 7050 6950 6900 7000 6700
Durability 130 115 112 112 112
TABLE-US-00016 TABLE I-16 Results of Evaluation Ex. Ex. Ex. Ex. Ex.
I-16 I-17 I-18 I-19 I-20 Center Diameter (mm) 15.0 15.0 15.0 15.0
15.0 Enve- Acid/salt(phr) 5.0 5.0 5.0 5.0 5.0 lope H(100) - 23.5
23.5 23.5 23.5 23.5 layer H(40) R.sup.2 0.97 0.97 0.97 0.97 0.97
Gradient .alpha. 0.41 0.41 0.41 0.41 0.41 Core Diameter (mm) 39.5
38.3 40.3 39.1 39.1 H(100) - 25.5 25.5 25.5 25.5 25.5 H(0) Mid
Composition M1 M1 M1 M1 M1 layer Hardness Hm 65.0 65.0 65.0 65.0
65.0 (Shore D) Diameter (mm) 41.5 40.3 42.3 41.1 41.1 Tm (mm) 1.0
1.0 1.0 1.0 1.0 Inner Composition C6 C3 C3 C3 C3 cover Hc1 (Shore
D) 30.0 47.0 47.0 47.0 47.0 T1 (mm) 0.3 0.6 0.1 0.65 0.15 Outer
Composition C1 C1 C1 C1 C1 cover Hc2 (Shore D) 29.0 29.0 29.0 29.0
29.0 T2 (mm) 0.3 0.6 0.1 0.15 0.65 Ball Hm - Hc1 35.0 18.0 18.0
18.0 18.0 Hm - Hc2 36.0 36.0 36.0 36.0 36.0 Hc1 - Hc2 1.0 18.0 18.0
18.0 18.0 T1 + T2 (mm) 0.6 1.2 0.2 0.8 0.8 T1 - T2 (mm) 0.0 0.0 0.0
0.5 -0.5 Db (mm) 2.6 2.6 2.6 2.6 2.6 W#1 spin (rpm) 3200 3250 2850
3100 3100 W#1 flight (m) 238 237 244 240 240 SW spin (rpm) 6850
7050 6550 6950 6950 Durability 112 120 100 115 115
TABLE-US-00017 TABLE I-17 Results of Evaluation Ex. Ex. Ex. I-21
I-22 I-23 Center Diameter (mm) 15.0 15.0 15.0 Envelope Acid/salt
(phr) 20.0 30.0 40.0 layer H(100) - H(40) 18.0 15.0 11.5 R.sup.2
0.98 0.99 0.99 Gradient .alpha. 0.31 0.26 0.20 Core Diameter (mm)
39.5 39.5 39.5 H(100) - H(0) 22.0 20.0 18.5 Mid Composition M1 M1
M1 layer Hm (Shore D) 65.0 65.0 65.0 Diameter (mm) 41.5 41.5 41.5
Tm (mm) 1.0 1.0 1.0 Inner Composition C3 C3 C3 cover Hc1 (Shore D)
47.0 47.0 47.0 T1 (mm) 0.3 0.3 0.3 Outer Composition C1 C1 C1 cover
Hc2 (Shore D) 29.0 29.0 29.0 T2 (mm) 0.3 0.3 0.3 Ball Hm - Hc1 18.0
18.0 18.0 Hm - Hc2 36.0 36.0 36.0 Hc1 - Hc2 18.0 18.0 18.0 T1 + T2
(mm) 0.6 0.6 0.6 T1 - T2 (mm) 0.0 0.0 0.0 Db (mm) 2.6 2.6 2.6 W#1
spin(rpm) 3100 3200 3350 W#1 flight (m) 240 238 236 SW spin (rpm)
6910 6920 6930 Durability 110 106 105
TABLE-US-00018 TABLE I-18 Results of Evaluation Comp. Comp. Comp.
Comp. Comp. Ex. Ex. Ex. Ex. Ex. I-1 I-2 I-3 I-4 I-5 Center Diameter
(mm) 15.0 15.0 15.0 15.0 15.0 Enve- Acid/salt(phr) 5.0 5.0 5.0 0.0
5.0 lope H(100) - 23.5 23.5 23.5 15.5 23.5 layer H(40) R.sup.2 0.97
0.97 0.97 0.94 0.97 Gradient .alpha. 0.41 0.41 0.41 0.29 0.41 Core
Diameter (mm) 39.5 39.5 39.5 39.5 39.5 H(100) - 25.5 25.5 25.5 24.0
25.5 H(0) Mid Composition M1 M1 M1 M1 M1 layer Hm (Shore D) 65.0
65.0 65.0 65.0 65.0 Diameter (mm) 41.5 41.5 41.5 41.5 41.5 Tm (mm)
1.0 1.0 1.0 1.0 1.0 Inner Composition C1 C2 C3 C3 C1 cover Hc1
(Shore D) 29.0 36.0 47.0 47.0 29.0 T1 (mm) 0.6 0.6 0.6 0.3 0.3
Outer Composition -- -- -- C1 C3 cover Hc2 (Shore D) -- -- -- 29.0
47.0 T2 (mm) -- -- -- 0.3 0.3 Ball Hm - Hc1 -- -- -- 18.0 36.0 Hm -
Hc2 -- -- -- 36.0 18.0 Hc1 - Hc2 -- -- -- 18.0 -18.0 T1 + T2 (mm)
-- -- -- 0.6 0.6 T1 - T2 (mm) -- -- -- 0.0 0.0 Db (mm) 2.6 2.6 2.6
2.6 2.6 W#1 spin (rpm) 3150 3050 2950 3200 2950 W#1 flight (m) 240
240 243 235 243 SW spin (rpm) 6900 6750 6700 6900 6650 Durability
112 112 112 100 112
[0856] As shown in Tables I-13 to I-18, the golf balls according to
Examples are excellent in various performance characteristics. From
the results of evaluation, advantages of the present invention are
clear.
Experiment 2
Example II-1
[0857] A rubber composition was obtained by kneading 100 parts by
weight of a high-cis polybutadiene (trade name "BR-730",
manufactured by JSR Corporation), 23 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, 0.3 parts by weight of
bis(pentabromophenyl)disulfide, 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 center with a
diameter of 15.0 mm.
[0858] A rubber composition was obtained by kneading 100 parts by
weight of a high-cis polybutadiene (the aforementioned "BR-730"),
35 parts by weight of zinc diacrylate (the aforementioned "Sanceler
SR"), 5 parts by weight of zinc oxide, an appropriate amount of
barium sulfate, 0.2 parts by weight of 2-thionaphthol, 0.8 parts by
weight of dicumyl peroxide, and 5.0 parts by weight of zinc
octoate. Half shells were formed from this rubber composition. The
center was covered with two of these half shells. The center and
the half shells were placed into a mold including upper and lower
mold halves each having a hemispherical cavity, and heated at
150.degree. C. for 20 minutes to obtain a core with a diameter of
39.5 mm. An envelope layer was formed from the rubber composition.
The amount of barium sulfate was adjusted such that the specific
gravity of the envelope layer coincides with the specific gravity
of the center and the weight of a golf ball is 45.4 g.
[0859] A resin composition was obtained by kneading 55 parts by
weight of an ionomer resin (the aforementioned "Surlyn 8945"), 45
parts by weight of another ionomer resin (the aforementioned
"Himilan AM7329"), and 3 parts by weight of titanium dioxide with a
twin-screw kneading extruder. The core was placed into a mold. The
resin composition was injected around the core by injection molding
to form a mid layer with a thickness of 1.0 mm.
[0860] 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 dioxide. 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
mid layer with a spray gun, and kept at 23.degree. C. for 12 hours
to obtain a reinforcing layer with a thickness of 10 .mu.m.
[0861] A resin composition was obtained by kneading 100 parts by
weight of a thermoplastic polyurethane elastomer (the
aforementioned "Elastollan NY82A"), 0.2 parts by weight of a
hindered amine light stabilizer (trade name "TINUVIN 770",
manufactured by Ciba Japan K.K.), 4 parts by weight of titanium
dioxide, and 0.04 parts by weight of ultramarine blue 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 mold including upper and lower mold halves each
having a hemispherical cavity. An inner cover was obtained from the
half shells by compression molding. The thickness of the inner
cover was 0.3 mm.
[0862] A resin composition was obtained by kneading 100 parts by
weight of a thermoplastic polyurethane elastomer (the
aforementioned "Elastollan NY97A"), 0.2 parts by weight of a
hindered amine light stabilizer (trade name "TINUVIN 770",
manufactured by Ciba Japan K.K.), 4 parts by weight of titanium
dioxide, and 0.04 parts by weight of ultramarine blue 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, the reinforcing layer, and the inner cover
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. An outer cover was obtained
from the half shells by compression molding. The thickness of the
outer cover was 0.3 mm. Dimples having a shape that is the inverted
shape of the pimples were formed on the outer cover. A clear paint
including a two-component curing type polyurethane as a base
material was applied to this outer cover to obtain a golf ball of
Example II-1 with a diameter of 42.7 mm.
Examples II-2 to II-23 and Comparative Examples II-1 to II-8
[0863] Golf balls of Examples II-2 to II-23 and Comparative
Examples II-1 to II-8 were obtained in the same manner as Example
II-1, except the specifications of the core, the mid layer, the
inner cover, and the outer cover were as shown in Tables II-15 to
II-22 below. The composition of the core is shown in detail in
Tables II-1 to II-4 below. A hardness distribution of the core is
shown in Tables II-7 to II-14 below. The composition of the mid
layer is shown in detail in Table II-5 below. The compositions of
the inner cover and the outer cover are shown in detail in Table
II-6 below.
[0864] [Hit with Driver (W#1)]
[0865] A driver with a titanium head (trade name "XXIO",
manufactured by DUNLOP SPORTS CO. LTD., shaft hardness: S, loft
angle: 10.0.degree.) was attached to a swing machine manufactured
by True Temper Co. A golf ball was hit under the condition of a
head speed of 45 m/sec. The spin rate was measured immediately
after the hit. Furthermore, the distance from the launch point to
the stop point was measured. The average value of data obtained by
10 measurements is shown in Tables II-15 to II-22 below.
[0866] [Hit with Sand Wedge (SW)]
[0867] A sand wedge (SW) was attached to the above swing machine. A
golf ball was hit under the condition of a head speed of 21 m/sec.
The backspin rate was measured immediately after the hit. The
average value of data obtained by 10 measurements is shown in
Tables II-15 to II-22 below.
[0868] [Durability]
[0869] A golf ball was kept at 23.degree. C. for 12 hours. The
above driver was attached to the above swing machine. The golf ball
was repeatedly hit under the condition of a head speed of 45 m/sec.
The number of hits required to break the golf ball was counted. The
average value of numbers of hits obtained by 12 measurements is
shown as an index in Tables II-15 to II-22 below.
TABLE-US-00019 TABLE II-1 Compositions of Center and Envelope Layer
(parts by weight) A B C D BR-730 100 100 100 100 Sanceler SR 23.0
35.0 32.0 33.0 ZN-DA90S -- -- -- -- Zinc oxide 5 5 5 5 Barium
sulfate * * * * 2-thionaphthol -- 0.2 0.2 0.2
Bis(pentabromophenyl)disulfide** 0.3 -- -- --
2,6-dichlorothiophenol -- -- -- -- Dicumyl peroxide 0.8 0.8 0.8 0.8
Zinc octoate -- 5.0 -- 0.5 Zinc stearate -- -- -- -- Acid and/or
salt 0.0 5.0 0.0 0.5 * Appropriate amount
TABLE-US-00020 TABLE II-2 Compositions of Center and Envelope Layer
(parts by weight) E F G H BR-730 100 100 100 100 Sanceler SR 34.0
37.0 40.0 34.0 ZN-DA90S -- -- -- -- Zinc oxide 5 5 5 5 Barium
sulfate * * * * 2-thionaphthol 0.2 0.2 0.2 0.2
Bis(pentabromophenyl)disulfide -- -- -- -- 2,6-dichlorothiophenol
-- -- -- -- Dicumyl peroxide 0.8 0.8 0.8 0.8 Zinc octoate 2.0 12.0
45.0 -- Zinc stearate -- -- -- 5 Acid and/or salt 2.0 12.0 45.0 5.0
* Appropriate amount
TABLE-US-00021 TABLE II-3 Compositions of Center and Envelope Layer
(parts by weight) I J K L BR-730 100 100 100 100 Sanceler SR 38.0
36.0 -- 36.0 ZN-DA90S -- -- 35 -- Zinc oxide 5 5 5 5 Barium sulfate
* * * * 2-thionaphthol -- -- 0.2 0.2 Bis(pentabromophenyl)disulfide
0.3 -- -- -- 2,6-dichlorothiophenol -- 0.1 -- -- Dicumyl peroxide
0.8 0.8 0.8 0.8 Zinc octoate 5.0 5.0 5.0 5.0 Zinc stearate -- -- --
-- Acid and/or salt 5.0 5.0 5.0 5.0 * Appropriate amount
TABLE-US-00022 TABLE II-4 Compositions of Center and Envelope Layer
(parts by weight) M N O BR-730 100 100 100 Sanceler SR 34.5 35.0
36.5 ZN-DA90S -- -- -- Zinc oxide 5 5 5 Barium sulfate * * *
2-thionaphthol 0.2 0.2 0.2 Bis(pentabromophenyl)disulfide -- -- --
2,6-dichlorothiophenol -- -- -- Dicumyl peroxide 0.8 0.8 0.8 Zinc
octoate 20.0 30.0 40.0 Zinc stearate -- -- -- Acid and/or salt 20.0
30.0 40.0 * Appropriate amount
[0870] The details of the compounds listed in Tables II-1 to II-4
are as follows.
[0871] BR-730: 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)
[0872] Sanceler SR: zinc diacrylate manufactured by SANSHIN
CHEMICAL INDUSTRY CO., LTD. (a product coated with 10% by weight of
stearic acid)
[0873] ZN-DA90S: zinc diacrylate manufactured by Nihon Jyoryu Kogyo
Co., Ltd. (a product coated with 10% by weight of zinc
stearate)
[0874] Zinc oxide: trade name "Ginrei R" manufactured by Toho Zinc
Co., Ltd.
[0875] Barium sulfate: trade name "Barium Sulfate BD" manufactured
by Sakai Chemical Industry Co., Ltd.
[0876] 2-thionaphthol: a product of Tokyo Chemical Industry Co.,
Ltd.
[0877] Bis(pentabromophenyl)disulfide: a product of Kawaguchi
Chemical Industry Co., LTD.
[0878] 2,6-dichlorothiophenol: a product of Tokyo Chemical Industry
Co., Ltd.
[0879] Dicumyl peroxide: trade name "Percumyl D" manufactured by
NOF Corporation
[0880] Zinc octoate: a product of Mitsuwa Chemicals Co., Ltd.
[0881] Zinc stearate: a product of Wako Pure Chemical Industries,
Ltd.
TABLE-US-00023 TABLE II-5 Composition of Mid Layer (parts by
weight) M1 M2 M3 M4 Surlyn 55 47 25 15 8945 Himilan 45 45 45 45
AM7329 Rabalon -- 8 30 40 T3221C Titanium 3 3 3 3 dioxide Hardness
65 58 47 40 (Shore D)
TABLE-US-00024 TABLE II-6 Composition of Cover (parts by weight) C1
C2 C3 C4 C5 C6 Elastollan NY82A 100 60 Elastollan NY85A 50 40
Elastollan NY90A 50 5 Elastollan NY97A 100 95 Surlyn 8945 40
Himilan AM7329 55 Rabalon T3221C 5 TINUVIN 770 0.2 0.2 0.2 0.2 0.2
0.2 Titanium dioxide 4 4 4 4 4 4 Ultramarine blue 0.04 0.04 0.04
0.04 0.04 0.04 Hardness (Shore D) 29 36 47 60 46 30
TABLE-US-00025 TABLE II-7 Hardness Distribution of Core Comp. Comp.
Comp. Ex. Ex. Ex. Ex. II-1 II-1 II-2 II-3 center A A A A envelope
layer B B B B H(0) 62.0 62.0 62.0 62.0 H(12.5) 63.0 63.0 63.0 63.0
H(25) 63.5 63.5 63.5 63.5 H(40) 64.0 64.0 64.0 64.0 H(50) 68.5 68.5
68.5 68.5 H(62.5) 71.0 71.0 71.0 71.0 H(75) 81.0 81.0 81.0 81.0
H(87.5) 84.5 84.5 84.5 84.5 H(100) 87.5 87.5 87.5 87.5
TABLE-US-00026 TABLE II-8 Hardness Distribution of Core Comp. Ex.
Ex. Ex. Ex. II-2 II-3 II-4 II-4 center A A A A envelope layer B B C
D H(0) 62.0 62.0 62.0 62.0 H(12.5) 63.0 63.0 63.0 63.0 H(25) 63.5
63.5 63.5 63.5 H(40) 64.0 64.0 70.5 70.0 H(50) 68.5 68.5 71.5 71.5
H(62.5) 71.0 71.0 73.5 73.5 H(75) 81.0 81.0 82.0 81.5 H(87.5) 84.5
84.5 84.0 84.0 H(100) 87.5 87.5 86.0 86.0
TABLE-US-00027 TABLE II-9 Hardness Distribution of Core Comp. Comp.
Comp. Ex. Ex. Ex. Ex. II-5 II-6 II-5 II-7 center A A A A envelope
layer B B B B H(0) 62.0 62.0 62.0 62.0 H(12.5) 63.0 63.0 63.0 63.0
H(25) 63.5 63.5 63.5 63.5 H(40) 64.0 64.0 64.0 64.0 H(50) 68.5 68.5
68.5 68.5 H(62.5) 71.0 71.0 71.0 71.0 H(75) 81.0 81.0 81.0 81.0
H(87.5) 84.5 84.5 84.5 84.5 H(100) 87.5 87.5 87.5 87.5
TABLE-US-00028 TABLE II-10 Hardness Distribution of Core Ex. Ex.
Ex. Ex. II-6 II-7 II-8 II-9 center A A A A envelope layer B E F G
H(0) 62.0 62.0 62.0 62.0 H(12.5) 63.0 63.0 63.0 63.0 H(25) 63.5
63.5 63.5 63.5 H(40) 64.0 67.5 65.0 70.0 H(50) 68.5 70.0 68.5 72.0
H(62.5) 71.0 73.0 72.0 74.0 H(75) 81.0 81.5 80.5 77.5 H(87.5) 84.5
84.0 84.0 78.5 H(100) 87.5 86.5 85.0 79.0
TABLE-US-00029 TABLE II-11 Hardness Distribution of Core Ex. Ex.
Ex. Ex. II-10 II-11 II-12 II-13 center A A A A envelope layer H I J
K H(0) 62.0 62.0 62.0 62.0 H(12.5) 63.0 63.0 63.0 63.0 H(25) 63.5
63.5 63.5 63.5 H(40) 64.5 65.0 64.0 63.5 H(50) 69.0 69.0 68.5 68.0
H(62.5) 71.0 70.0 71.0 71.0 H(75) 81.0 80.0 81.0 81.0 H(87.5) 84.5
84.0 84.5 84.5 H(100) 87.0 87.5 87.5 87.5
TABLE-US-00030 TABLE II-12 Hardness Distribution of Core Ex. Ex.
Ex. Ex. II-14 II-15 II-16 II-17 center A A A A envelope layer L L B
B H(0) 62.0 62.0 62.0 62.0 H(12.5) 63.0 63.0 63.0 63.0 H(25) 63.5
63.5 63.5 63.5 H(40) 64.5 64.5 64.0 64.0 H(50) 69.0 69.0 68.5 68.5
H(62.5) 71.5 71.5 71.0 71.0 H(75) 81.5 81.5 81.0 81.0 H(87.5) 85.0
85.0 84.5 84.5 H(100) 88.0 88.0 87.5 87.5
TABLE-US-00031 TABLE II-13 Hardness Distribution of Core Comp. Ex.
Ex. Ex. Ex. II-18 II-19 II-20 II-8 center A A A A envelope layer B
B B B H(0) 62.0 62.0 62.0 62.0 H(12.5) 63.0 63.0 63.0 63.0 H(25)
63.5 63.5 63.5 63.5 H(40) 64.0 64.0 64.0 64.0 H(50) 68.5 68.5 68.5
68.5 H(62.5) 71.0 71.0 71.0 71.0 H(75) 81.0 81.0 81.0 81.0 H(87.5)
84.5 84.5 84.5 84.5 H(100) 87.5 87.5 87.5 87.5
TABLE-US-00032 TABLE II-14 Hardness Distribution of Core Ex. Ex.
Ex. II-21 II-22 II-23 center A A A envelope layer M N O H(0) 62.0
62.0 62.0 H(12.5) 63.0 63.0 63.0 H(25) 63.5 63.5 63.5 H(40) 66.0
67.0 69.0 H(50) 69.5 70.0 71.0 H(62.5) 73.0 73.0 73.0 H(75) 79.0
77.0 76.0 H(87.5) 82.0 80.0 79.0 H(100) 84.0 82.0 80.5
TABLE-US-00033 TABLE II-15 Results of Evaluation Comp. Comp. Comp.
Ex. Ex. Ex. Ex. II-1 II-1 II-2 II-3 Center Diameter (mm) 15.0 15.0
15.0 15.0 Envelope Acid/salt (phr) 5.0 5.0 5.0 5.0 layer H(100) -
H(40) 23.5 23.5 23.5 23.5 R.sup.2 0.97 0.97 0.97 0.97 Core Diameter
(mm) 39.5 39.5 39.5 39.5 H(100) - H(0) 25.5 25.5 25.5 25.5 Mid
Composition M1 M1 M1 M1 layer Hm (Shore D) 65.0 65.0 65.0 65.0 Tm
(mm) 1.0 1.0 1.0 1.0 Inner Composition C1 C1 C2 C3 cover Hc1 (Shore
D) 29.0 29.0 36.0 47.0 T1 (mm) 0.30 0.30 0.30 0.30 Outer
Composition C3 C1 C2 C3 cover Hc2 (Shore D) 47.0 29.0 36.0 47.0 T2
(mm) 0.30 0.30 0.30 0.30 Ball Hm - Hc1 36.0 36.0 29.0 18.0 Hm - Hc2
18.0 36.0 29.0 18.0 Hc2 - Hc1 18.0 0.0 0.0 0.0 T1 + T2 (mm) 0.60
0.60 0.60 0.60 T1 - T2 (mm) 0.00 0.00 0.00 0.00 Db (mm) 2.6 2.6 2.6
2.6 W#1 spin (rpm) 3000 3150 3050 2950 W#1 flight (m) 242 240 240
243 SW spin (rpm) 6850 6900 6750 6700 Durability 112 112 112
112
TABLE-US-00034 TABLE II-16 Results of Evaluation Comp. Ex. Ex. Ex.
Ex. II-2 II-3 II-4 II-4 Center Diameter (mm) 15.0 15.0 15.0 15.0
Envelope Acid/salt (phr) 5.0 5.0 0.0 0.5 layer H(100) - H(40) 23.5
23.5 15.5 16.0 R.sup.2 0.97 0.97 0.94 0.95 Core Diameter (mm) 39.5
39.5 39.5 39.5 H(100) - H(0) 25.5 25.5 24.0 24.0 Mid Composition M1
M1 M1 M1 layer Hm (Shore D) 65.0 65.0 65.0 65.0 Tm (mm) 1.0 1.0 1.0
1.0 Inner Composition C5 C1 C1 C1 cover Hc1 (Shore D) 46.0 29.0
29.0 29.0 T1 (mm) 0.30 0.30 0.30 0.30 Outer Composition C3 C6 C3 C3
cover Hc2 (Shore D) 47.0 30.0 47.0 47.0 T2 (mm) 0.30 0.30 0.30 0.30
Ball Hm - Hc1 19.0 36.0 36.0 36.0 Hm - Hc2 18.0 35.0 18.0 18.0 Hc2
- Hc1 1.0 1.0 18.0 18.0 T1 + T2 (mm) 0.60 0.60 0.60 0.60 T1 - T2
(mm) 0.00 0.00 0.00 0.00 Db (mm) 2.6 2.6 2.6 2.6 W#1 spin (rpm)
2950 3150 3200 3100 W#1 flight (m) 243 240 235 241 SW spin (rpm)
6800 7000 6900 6900 Durability 112 112 100 102
TABLE-US-00035 TABLE II-17 Results of Evaluation Comp. Comp. Comp.
Ex. Ex. Ex. Ex. II-5 II-6 II-5 II-7 Center Diameter (mm) 15.0 15.0
15.0 15.0 Envelope Acid/salt (phr) 5.0 5.0 5.0 5.0 layer H(100) -
H(40) 23.5 23.5 23.5 23.5 R.sup.2 0.97 0.97 0.97 0.97 Core Diameter
(mm) 39.5 38.3 38.3 40.3 H(100) - H(0) 25.5 25.5 25.5 25.5 Mid
Composition M1 M1 M1 M1 layer Hm (Shore D) 65.0 65.0 65.0 65.0 Tm
(mm) 1.0 1.0 1.0 1.0 Inner Composition C3 C3 C1 C3 cover Hc1 (Shore
D) 47.0 47.0 29.0 47.0 T1 (mm) 0.30 0.60 0.60 0.10 Outer
Composition C1 C3 C3 C3 cover Hc2 (Shore D) 29.0 47.0 47.0 47.0 T2
(mm) 0.30 0.60 0.60 0.10 Ball Hm - Hc1 18.0 18.0 36.0 18.0 Hm - Hc2
36.0 18.0 18.0 18.0 Hc2 - Hc1 -18.0 0.0 18.0 0.0 T1 + T2 (mm) 0.60
1.20 1.20 0.20 T1 - T2 (mm) 0.00 0.00 0.00 0.00 Db (mm) 2.6 2.6 2.6
2.6 W#1 spin (rpm) 3200 3250 3250 2800 W#1 flight (m) 239 237 237
245 SW spin (rpm) 7000 6850 7050 6500 Durability 112 120 120
105
TABLE-US-00036 TABLE II-18 Results of Evaluation Ex. Ex. Ex. Ex.
II-6 II-7 II-8 II-9 Center Diameter (mm) 15.0 15.0 15.0 15.0
Envelope Acid/salt (phr) 5.0 2.0 12.0 45.0 layer H(100) - H(40)
23.5 19.0 20.0 9.0 R.sup.2 0.97 0.96 0.96 0.95 Core Diameter (mm)
38.3 39.5 39.5 39.5 H(100) - H(0) 25.5 24.5 23.0 17.0 Mid
Composition M1 M1 M1 M1 layer Hm (Shore D) 65.0 65.0 65.0 65.0 Tm
(mm) 1.0 1.0 1.0 1.0 Inner Composition C1 C1 C1 C1 cover Hc1 (Shore
D) 29.0 29.0 29.0 29.0 T1 (mm) 0.60 0.30 0.30 0.30 Outer
Composition C3 C3 C3 C3 cover Hc2 (Shore D) 47.0 47.0 47.0 47.0 T2
(mm) 0.60 0.30 0.30 0.30 Ball Hm - Hc1 36.0 36.0 36.0 36.0 Hm - Hc2
18.0 18.0 18.0 18.0 Hc2 - Hc1 18.0 18.0 18.0 18.0 T1 + T2 (mm) 0.20
0.60 0.60 0.60 T1 - T2 (mm) 0.00 0.00 0.00 0.00 Db (mm) 2.6 2.6 2.6
2.6 W#1 spin (rpm) 2850 3050 3050 3100 W#1 flight (m) 245 241 241
240 SW spin (rpm) 6700 6850 6850 6950 Durability 105 108 107
103
TABLE-US-00037 TABLE II-19 Results of Evaluation Ex. Ex. Ex. Ex.
II-10 II-11 II-12 II-13 Center Diameter (mm) 15.0 15.0 15.0 15.0
Envelope Acid/salt (phr) 5.0 5.0 5.0 5.0 layer H(100) - H(40) 22.5
22.5 23.5 24.0 R.sup.2 0.96 0.96 0.97 0.97 Core Diameter (mm) 39.5
39.5 39.5 39.5 H(100) - H(0) 25.0 25.5 25.5 25.5 Mid Composition M1
M1 M1 M1 layer Hm (Shore D) 65.0 65.0 65.0 65.0 Tm (mm) 1.0 1.0 1.0
1.0 Inner Composition C1 C1 C1 C1 cover Hc1 (Shore D) 29.0 29.0
29.0 29.0 T1 (mm) 0.30 0.30 0.30 0.30 Outer Composition C3 C3 C3 C3
cover Hc2 (Shore D) 47.0 47.0 47.0 47.0 T2 (mm) 0.30 0.30 0.30 0.30
Ball Hm - Hc1 36.0 36.0 36.0 36.0 Hm - Hc2 18.0 18.0 18.0 18.0 Hc2
- Hc1 18.0 18.0 18.0 18.0 T1 + T2 (mm) 0.60 0.60 0.60 0.60 T1 - T2
(mm) 0.00 0.00 0.00 0.00 Db (mm) 2.6 2.6 2.6 2.6 W#1 spin (rpm)
3050 3050 3000 2950 W#1 flight (m) 241 241 242 243 SW spin (rpm)
6850 6850 6850 6850 Durability 111 111 112 114
TABLE-US-00038 TABLE II-20 Results of Evaluation Ex. Ex. Ex. Ex.
II-14 II-15 II-16 II-17 Center Diameter (mm) 15.0 15.0 15.0 15.0
Envelope Acid/salt (phr) 5.0 5.0 5.0 5.0 layer H (100) - H (40)
23.5 23.5 23.5 23.5 R.sup.2 0.97 0.97 0.97 0.97 Core Diameter (mm)
39.5 39.5 39.1 39.1 H(100) - H(0) 26.0 26.0 25.5 25.5 Mid
Composition M2 M3 M1 M1 layer Hm (Shore D) 58.0 47.0 65.0 65.0 Tm
(mm) 1.0 1.0 1.0 1.0 Inner Composition C1 C1 C1 C1 cover Hc1 (Shore
D) 29.0 29.0 29.0 29.0 T1 (mm) 0.30 0.30 0.40 0.50 Outer
Composition C3 C3 C3 C3 cover Hc2 (Shore D) 47.0 47.0 47.0 47.0 T2
(mm) 0.30 0.30 0.40 0.30 Ball Hm - Hc1 29.0 18.0 36.0 36.0 Hm - Hc2
11.0 0.0 18.0 18.0 Hc2 - Hc1 18.0 18.0 18.0 18.0 T1 + T2 (mm) 0.60
0.60 0.80 0.80 T1 - T2 (mm) 0.00 0.00 0.00 0.20 Db (mm) 2.6 2.7 2.6
2.6 W#1 spin (rpm) 3050 3100 3100 3150 W#1 flight (m) 241 239 240
239 SW spin (rpm) 7000 7050 6950 7000 Durability 120 130 115
112
TABLE-US-00039 TABLE II-21 Results of Evaluation Comp. Ex. Ex. Ex.
Ex. II-18 II-19 II-20 II-8 Center Diameter (mm) 15.0 15.0 15.0 15.0
Envelope Acid/salt (phr) 5.0 5.0 5.0 5.0 layer H(100) - H(40) 23.5
23.5 23.5 23.5 R.sup.2 0.97 0.97 0.97 0.97 Core Diameter (mm) 39.1
39.1 39.1 39.5 H(100) - H(0) 25.5 25.5 25.5 25.5 Mid Composition M1
M1 M1 M4 layer Hm (Shore D) 65.0 65.0 65.0 40.0 Tm (mm) 1.0 1.0 1.0
1.0 Inner Composition C1 C1 C1 C5 cover Hc1 (Shore D) 29.0 29.0
29.0 46.0 T1 (mm) 0.30 0.65 0.2 0.3 Outer Composition C3 C3 C3 C3
cover Hc2 (Shore D) 47.0 47.0 47.0 47.0 T2 (mm) 0.50 0.15 0.7 0.3
Ball Hm - Hc1 36.0 36.0 36.0 -6.0 Hm - Hc2 18.0 18.0 18.0 -7.0 Hc2
- Hc1 18.0 18.0 18.0 1.0 T1 + T2 (mm) 0.80 0.80 0.8 0.6 T1 - T2
(mm) 0.20 0.50 -0.5 0.0 Db (mm) 2.6 2.6 2.6 2.6 W#1 spin (rpm) 3050
3200 3000 3200 W#1 flight (m) 241 238 242 239 SW spin (rpm) 6900
7100 6800 7000 Durability 112 115 115 108
TABLE-US-00040 TABLE II-22 Results of Evaluation Ex. Ex. Ex. II-21
II-22 II-23 Center Diameter (mm) 15.0 15.0 15.0 Envelope Acid/salt
(phr) 20.0 30.0 40.0 layer H(100) - H(40) 18.0 15.0 11.5 R.sup.2
0.98 0.99 0.99 Core Diameter (mm) 39.5 39.5 39.5 H(100) - H(0) 22.0
20.0 18.5 Mid Composition M1 M1 M1 layer Hm (Shore D) 65.0 65.0
65.0 Tm (mm) 1.0 1.0 1.0 Inner Composition C1 C1 C1 cover Hc1
(Shore D) 29.0 29.0 29.0 T1 (mm) 0.30 0.30 0.30 Outer Composition
C3 C3 C3 cover Hc2 (Shore D) 47.0 47.0 47.0 T2 (mm) 0.30 0.30 0.30
Ball Hm - Hc1 36.0 36.0 36.0 Hm - Hc2 18.0 18.0 18.0 Hc2 - Hc1 18.0
18.0 18.0 T1 + T2 (mm) 0.60 0.60 0.60 T1 - T2 (mm) 0.00 0.00 0.00
Db (mm) 2.6 2.6 2.6 W#1 spin (rpm) 3060 3070 3090 W#1 flight (m)
241 240 240 SW spin (rpm) 6880 6900 6930 Durability 106 105 103
[0882] As shown in Tables II-15 to II-22, the golf balls according
to Examples are excellent in various performance characteristics.
From the results of evaluation, advantages of the present invention
are clear.
Experiment 3
Example III-1
[0883] A rubber composition was obtained by kneading 100 parts by
weight of a high-cis polybutadiene (trade name "BR-730",
manufactured by JSR Corporation), 18 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, 0.3 parts by weight of
bis(pentabromophenyl)disulfide (a product of Kawaguchi Chemical
Industry Co., LTD.), and 0.9 parts by weight of dicumyl peroxide
(trade name "Percumyl D", manufactured by NOF Corporation). 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 spherical center with a
diameter of 15.0 mm.
[0884] A rubber composition was obtained by kneading 100 parts by
weight of a high-cis polybutadiene (the aforementioned "BR-730"),
42 parts by weight of zinc diacrylate (the aforementioned "Sanceler
SR"), 5 parts by weight of zinc oxide, an appropriate amount of
barium sulfate, 0.2 parts by weight of 2-thionaphthol, 0.9 parts by
weight of dicumyl peroxide, and 30 parts by weight of zinc octoate.
Half shells were formed from this rubber composition. The center
was covered with two of these half shells. The center and the half
shells were 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
38.5 mm. An envelope layer was formed from the rubber composition.
The amount of barium sulfate was adjusted such that the specific
gravity of the envelope layer coincides with the specific gravity
of the center and the weight of a golf ball is 45.4 g.
[0885] A resin composition was obtained by kneading 25 parts by
weight of an ionomer resin (the aforementioned "Surlyn 8945"), 45
parts by weight of another ionomer resin (the aforementioned
"Himilan AM7329"), 30 parts by weight of a styrene block-containing
thermoplastic elastomer (the aforementioned "Rabalon T3221C"), and
3 parts by weight of titanium dioxide with a twin-screw kneading
extruder. The extruding conditions were a screw diameter of 45 mm,
a screw rotational speed of 200 rpm, screw L/D of 35, and a die
temperature of 160.degree. C. to 230.degree. C. The core was placed
into a mold. The resin composition was injected around the core by
injection molding to form an inner mid layer with a thickness of
0.8 mm.
[0886] A resin composition was obtained by kneading 55 parts by
weight of an ionomer resin (the aforementioned "Surlyn 8945"), 45
parts by weight of another ionomer resin (the aforementioned
"Himilan AM7329"), and 3 parts by weight of titanium dioxide with a
twin-screw kneading extruder under the above extruding conditions.
The sphere consisting of the core and the inner mid layer was
placed into a mold. The resin composition was injected around the
sphere by injection molding to form an outer mid layer with a
thickness of 0.8 mm.
[0887] 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 dioxide. 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 an air gun, and kept at 23.degree. C. for 12
hours to obtain a reinforcing layer with a thickness of 10
.mu.m.
[0888] A resin composition was obtained by kneading 100 parts by
weight of a thermoplastic polyurethane elastomer (the
aforementioned "Elastollan NY82A"), 0.2 parts by weight of a
hindered amine light stabilizer (trade name "TINUVIN 770",
manufactured by Ciba Japan K.K.), 4 parts by weight of titanium
dioxide, and 0.04 parts by weight of ultramarine blue with a
twin-screw kneading extruder under the above extruding conditions.
Half shells were formed from this resin composition by compression
molding. The sphere consisting of the core, the inner mid layer,
the outer 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 0.5 mm. Dimples having a
shape that is the inverted shape of the pimples were formed on the
cover. The surface of the cover was polished. A clear paint
including a two-component curing type polyurethane as a base
material was applied to this cover with an air gun, and was dried
and cured to obtain a golf ball of Example III-1 with a diameter of
42.7 mm and a weight of 45.6 g.
Examples III-2 to III-19 and Comparative Examples III-1 to
III-7
[0889] Golf balls of Examples III-2 to III-19 and Comparative
Examples III-1 to III-7 were obtained in the same manner as Example
III-1, except the specifications of the center and the envelope
layer were as shown in Tables III-7 to III-12 below and the
specifications of the inner mid layer, the outer mid layer, and the
cover were as shown in Tables III-13 to III-18 below. The
composition and the vulcanization conditions of the center are
shown in Table III-1 below. The composition and the vulcanization
conditions of the envelope layer are shown in Tables III-2 to III-4
below. The compositions and the hardnesses of the inner mid layer
and the outer mid layer are shown in Table III-5 below. The
composition and the hardness of the cover are shown in Table III-6
below.
[0890] [Hit with Driver (W#1)]
[0891] A driver with a titanium head (trade name "XXIO",
manufactured by DUNLOP SPORTS CO. LTD., shaft hardness: S, loft
angle: 10.0.degree.) was attached to a swing machine manufactured
by True Temper Co. A golf ball was hit under the condition of a
head speed of 45 m/sec. The spin rate was measured immediately
after the hit. Furthermore, the flight distance from the launch
point to the stop point was measured. The average value of data
obtained by 10 measurements is shown in Tables III-13 to III-18
below.
[0892] [Hit with Sand Wedge (SW)]
[0893] A sand wedge (trade name "XXIO", manufactured by DUNLOP
SPORTS CO. LTD., shaft hardness: R, loft angle: 56.0.degree.) was
attached to a swing machine manufactured by True Temper Co. A golf
ball was hit under the condition of a head speed of 21 m/sec. The
backspin rate was measured immediately after the hit. The average
value of data obtained by 10 measurements is shown in Tables III-13
to III-18 below.
[0894] [Durability]
[0895] A driver with a titanium head (trade name "XXIO",
manufactured by DUNLOP SPORTS CO. LTD., shaft hardness: S, loft
angle: 10.0.degree.) was attached to a swing robot M/C manufactured
by True Temper Co. A golf ball having been kept at 23.degree. C.
for 12 hours was used for the measurement. The golf ball was
repeatedly hit under the condition of a head speed of 45 m/sec. The
number of hits required to break the golf ball was measured. An
index of the average value of data obtained for 12 golf balls is
shown in Tables III-13 to III-18 below. The higher the index is,
the more excellent the durability of the golf ball is.
TABLE-US-00041 TABLE III-1 Composition and Vulcanization Conditions
of Center (parts by weight) Type (1) (2) (3) BR-730 100 100 100
Sanceler SR 18 14 20 Zinc oxide 5 5 5 Barium sulfate * * *
Bis(pentabromophenyl)disulfide 0.3 0.3 0.3 Dicumyl peroxide 0.9 0.9
0.9 Vulcanization conditions Temperature (.degree. C.) 170 170 170
Time (min) 25 25 25 * Appropriate amount
TABLE-US-00042 TABLE III-2 Composition and Vulcanization Conditions
of Envelope Layer (parts by weight) Type E1 E2 E3 E4 E5 BR-730 100
100 100 100 100 Sanceler SR 36 40 40 40 41 ZN-DA90S -- -- -- -- --
Zinc oxide 5 5 5 5 5 Barium sulfate * * * * * 2-thionaphthol 0.2
0.2 0.2 0.2 0.2 Bis(pentabromophenyl)disulfide -- -- -- -- --
Dicumyl peroxide 0.9 0.9 0.9 0.9 0.9 Zinc octoate -- 0.5 2 5 10
Zinc stearate -- -- -- -- -- Zinc myristate -- -- -- -- -- Amount
of acid/salt 0 0.5 2 5 10 Vulcanization conditions Temperature
(.degree. C.) 170 170 170 170 170 Time (min) 25 25 25 25 25 *
Appropriate amount
TABLE-US-00043 TABLE III-3 Composition and Vulcanization Conditions
of Envelope Layer (parts by weight) Type E6 E7 E8 E9 E10 BR-730 100
100 100 100 100 Sanceler SR 42 43 37 38 40 ZN-DA90S -- -- -- -- --
Zinc oxide 5 5 5 5 5 Barium sulfate * * * * * 2-thionaphthol 0.2
0.2 0.2 0.2 0.2 Bis(pentabromophenyl)disulfide -- -- -- -- --
Dicumyl peroxide 0.9 0.9 0.9 0.9 0.9 Zinc octoate 30 45 -- -- --
Zinc stearate -- -- 10 20 -- Zinc myristate -- -- -- -- 5 Amount of
acid/salt 30 45 10 20 5 Vulcanization conditions Temperature
(.degree. C.) 170 170 170 170 170 Time (min) 25 25 25 25 25 *
Appropriate amount
TABLE-US-00044 TABLE III-4 Composition and Vulcanization Conditions
of Envelope Layer (parts by weight) Type E11 E12 E13 E14 E15 BR-730
100 100 100 100 100 Sanceler SR 41 42 -- 41 39 ZN-DA90S -- -- 40 --
-- Zinc oxide 5 5 5 5 5 Barium sulfate * * * * * 2-thionaphthol 0.2
-- 0.2 0.2 0.2 Bis(pentabromophenyl)disulfide -- 0.3 -- -- --
Dicumyl peroxide 0.9 0.9 0.9 0.9 0.9 Zinc octoate -- 5 5 5 5 Zinc
stearate -- -- -- -- -- Zinc myristate 10 -- -- -- -- Amount of
acid/salt 10 5 5 5 5 Vulcanization conditions Temperature (.degree.
C.) 170 170 170 170 170 Time (min) 25 25 25 25 25 * Appropriate
amount
[0896] The details of the compounds listed in Tables III-1 to III-4
are as follows.
[0897] BR-730: 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)
[0898] Sanceler SR: zinc diacrylate manufactured by SANSHIN
CHEMICAL INDUSTRY CO., LTD. (a product coated with 10% by weight of
stearic acid)
[0899] ZN-DA90S: zinc diacrylate manufactured by Nihon Jyoryu Kogyo
Co., Ltd. (a product coated with 10% by weight of zinc
stearate)
[0900] Zinc oxide: trade name "Ginrei R" manufactured by Toho Zinc
Co., Ltd.
[0901] Barium sulfate: trade name "Barium Sulfate BD" manufactured
by Sakai Chemical Industry Co., Ltd.
[0902] Bis(pentabromophenyl)disulfide: a product of Kawaguchi
Chemical Industry Co., LTD.
[0903] Dicumyl peroxide: trade name "Percumyl D" manufactured by
NOF Corporation
[0904] 2-thionaphthol: a product of Tokyo Chemical Industry Co.,
Ltd.
[0905] Zinc octoate: a product of Mitsuwa Chemicals Co., Ltd.
(purity: 99% or greater)
[0906] Zinc stearate: a product of Wako Pure Chemical Industries,
Ltd. (purity: 99% or greater)
[0907] Zinc myristate: a product of NOF Corporation (purity: 90% or
greater)
TABLE-US-00045 TABLE III-5 Compositions and Hardnesses of Inner Mid
Layer and Outer Mid Layer (parts by weight) Type a b c D Surlyn
8945 55 45 25 20 Himilan AM7329 45 45 45 25 Rabalon T3221C -- 10 30
55 Titanium dioxide 3 3 3 3 Hardness (Shore D) 65 56 47 29
TABLE-US-00046 TABLE III-6 Composition and Hardness of Cover (parts
by weight) Type A B C D Elastollan NY82A 100 -- -- -- Elastollan
NY85A -- 50 -- -- Elastollan NY90A -- 50 -- -- Elastollan NY97A --
-- 100 -- Surlyn 8945 -- -- -- 40 Himilan AM7329 -- -- -- 55
Rabalon T3221C -- -- -- 5 TINUVIN 770 0.2 0.2 0.2 0.2 Titanium
dioxide 4 4 4 4 Ultramarine blue 0.04 0.04 0.04 0.04 Hardness Hc 29
36 47 60 (Shore D)
TABLE-US-00047 TABLE III-7 Physical Properties and Hardness
Distribution of Core (JIS-C hardness) Ex. Ex. Ex. Ex. Ex. III-1
III-2 III-3 III-4 III-5 Center Composition (1) (1) (1) (1) (1)
Diameter (mm) 15 15 15 15 15 Ho (JIS-C) 57 57 57 57 57 Surface
hardness 61 61 61 61 61 (JIS-C) Envelope layer Composition E6 E5 E4
E3 E8 Te (mm) 11.75 11.75 11.75 11.75 11.75 H(0.0) 60.5 62.5 63.5
62.0 64.5 H(12.5) 64.5 65.0 66.0 68.0 67.0 H(25.0) 66.5 69.0 69.5
71.0 70.5 H(37.5) 69.0 71.0 71.0 73.5 72.0 H(50.0) 71.0 72.5 73.0
74.5 73.5 H(62.5) 73.0 74.5 76.5 75.0 75.0 H(75.0) 75.5 82.0 82.5
79.5 83.0 H(87.5) 78.0 86.0 87.0 84.5 87.0 Hs 83.0 89.0 91.0 88.5
91.0 Hs - H(0.0) 22.5 26.5 27.5 26.5 26.5 R.sup.2 0.98 0.97 0.97
0.95 0.95 Gradient 0.20 0.26 0.27 0.23 0.26
TABLE-US-00048 TABLE III-8 Physical Properties and Hardness
Distribution of Core (JIS-C hardness) Ex. Ex. Ex. Ex. Ex. III-6
III-7 III-8 III-9 III-10 Center Composition (1) (1) (1) (1) (1)
Diameter (mm) 15 15 15 15 15 Ho (JIS-C) 57 57 57 57 57 Surface
hardness 61 61 61 61 61 (JIS-C) Envelope layer Composition E9 E10
E11 E12 E13 Te (mm) 11.75 11.75 11.75 11.75 11.75 H(0.0) 63.0 64.0
63.0 63.5 63.5 H(12.5) 65.0 66.5 65.5 65.5 66.0 H(25.0) 67.0 70.0
69.5 70.0 69.5 H(37.5) 69.5 72.0 71.5 71.0 71.0 H(50.0) 72.0 73.0
72.5 73.0 74.0 H(62.5) 73.5 74.5 74.5 76.5 76.5 H(75.0) 82.0 82.5
82.5 82.0 82.5 H(87.5) 84.0 87.0 86.5 87.0 87.0 Hs 88.0 91.0 89.5
91.0 91.0 Hs - H(0.0) 25.0 27.0 26.5 27.5 27.5 R.sup.2 0.96 0.95
0.96 0.97 0.97 Gradient 0.25 0.26 0.26 0.27 0.27
TABLE-US-00049 TABLE III-9 Physical Properties and Hardness
Distribution of Core (JIS-C hardness) Ex. Ex. Ex. Ex. Ex. III-11
III-12 III-13 III-14 III-15 Center Composition (1) (1) (1) (1) (1)
Diameter (mm) 15 15 15 15 15 Ho (JIS-C) 57 57 57 57 57 Surface
hardness 61 61 61 61 61 (JIS-C) Envelope layer Composition E4 E4 E4
E14 E4 Te (mm) 11.75 11.75 11.75 11.75 11.35 H(0.0) 63.5 63.5 63.5
64.0 63.5 H(12.5) 66.0 66.0 66.0 66.0 66.0 H(25.0) 69.5 69.5 69.5
70.0 69.5 H(37.5) 71.0 71.0 71.0 71.5 71.0 H(50.0) 73.0 73.0 73.0
73.5 73.0 H(62.5) 76.5 76.5 76.5 77.0 76.5 H(75.0) 82.5 82.5 82.5
83.0 82.5 H(87.5) 87.0 87.0 87.0 87.5 87.0 Hs 91.0 91.0 91.0 91.5
91.0 Hs - H(0.0) 27.5 27.5 27.5 27.5 27.5 R.sup.2 0.97 0.97 0.97
0.97 0.97 Gradient 0.27 0.27 0.27 0.27 0.27
TABLE-US-00050 TABLE III-10 Physical Properties and Hardness
Distribution of Core (JIS-C hardness) Ex. Ex. Ex. Ex. III-16 III-17
III-18 III-19 Center Composition (1) (2) (3) (3) Diameter (mm) 15 9
21 26 Ho (JIS-C) 57 49 62 62 Surface hardness 61 53 66 66 (JIS-C)
Envelope layer Composition E15 E4 E4 E4 Te (mm) 10.15 14.75 8.75
6.25 H(0.0) 63.0 63.0 64.0 64.0 H(12.5) 65.0 65.5 66.5 66.5 H(25.0)
69.0 69.5 69.5 69.5 H(37.5) 70.5 71.0 71.0 71.0 H(50.0) 72.5 73.0
73.0 73.0 H(62.5) 76.0 76.5 76.5 76.5 H(75.0) 82.0 82.5 82.5 82.0
H(87.5) 86.5 87.0 86.5 86.5 Hs 90.5 91.0 90.0 89.0 Hs - H(0.0) 27.5
28.0 26.0 25.0 R.sup.2 0.97 0.97 0.97 0.97 Gradient 0.27 0.28 0.26
0.25
TABLE-US-00051 TABLE III-11 Physical Properties and Hardness
Distribution of Core (JIS-C hardness) Comp. Comp. Comp. Comp. Comp.
Ex. Ex. Ex. Ex. Ex. III-1 III-2 III-3 III-4 III-5 Center
Composition (1) (1) (1) (1) (1) Diameter (mm) 15 15 15 15 15 Ho
(JIS-C) 57 57 57 57 57 Surface hardness 61 61 61 61 61 (JIS-C)
Envelope layer Composition E1 E4 E15 E15 E14 Te (mm) 11.75 11.75
11.75 11.75 11.75 H(0.0) 64.0 63.5 63.0 63.0 64.0 H(12.5) 74.0 66.0
65.0 65.0 66.0 H(25.0) 78.0 69.5 69.0 69.0 70.0 H(37.5) 78.0 71.0
70.5 70.5 71.5 H(50.0) 78.0 73.0 72.5 72.5 73.5 H(62.5) 79.0 76.5
76.0 76.0 77.0 H(75.0) 80.0 82.5 82.0 82.0 83.0 H(87.5) 84.0 87.0
86.5 86.5 87.5 Hs 89.0 91.0 90.5 90.5 91.5 Hs - H(0.0) 25.0 27.5
27.5 27.5 27.5 R.sup.2 0.81 0.97 0.97 0.97 0.97 Gradient 0.18 0.27
0.27 0.27 0.27
TABLE-US-00052 TABLE III-12 Physical Properties and Hardness
Distribution of Core (JIS-C hardness) Comp. Comp. Ex. Ex. III-6
III-7 Center Composition (1) (1) Diameter (mm) 15 15 Ho (JIS-C) 57
57 Surface hardness 61 61 (JIS-C) Envelope layer Composition E2 E7
Te (mm) 11.75 11.75 H(0.0) 62.0 71.0 H(12.5) 71.5 74.0 H(25.0) 75.5
74.5 H(37.5) 76.0 75.0 H(50.0) 76.5 75.0 H(62.5) 77.5 75.0 H(75.0)
78.5 75.5 H(87.5) 83.5 78.0 Hs 88.0 79.0 Hs - H(0.0) 26.0 8.0
R.sup.2 0.86 0.84 Gradient 0.20 0.06
TABLE-US-00053 TABLE III-13 Results of Evaluation Ex. Ex. Ex. Ex.
Ex. III-1 III-2 III-3 III-4 III-5 Core Diameter (mm) 38.5 38.5 38.5
38.5 38.5 Hs - Ho 26.0 32.0 34.0 31.5 34.0 Inner mid layer
Composition c c c c c Hm1 (Shore D) 47 47 47 47 47 Diameter (mm)
40.1 40.1 40.1 40.1 40.1 Tm1 (mm) 0.8 0.8 0.8 0.8 0.8 outer mid
layer Composition a a a a Hm2 (Shore D) 65 5 65 65 65 Diameter (mm)
41.7 41.7 41.7 41.7 41.7 Tm2 (mm) 0.8 0.8 0.8 0.8 0.8 Cover
Composition A A A A A Hc (Shore D) 29 29 29 29 29 Tc (mm) 0.5 0.5
0.5 0.5 0.5 Tm1 + Tm2 (mm) 1.6 1.6 1.6 1.6 1.6 Hm2 - Hm1 (Shore D)
18 18 18 18 18 Hm2 - Hc (Shore D) 36 36 36 36 36 Db (mm) 2.4 2.4
2.4 2.4 2.4 W#1 spin (rpm) 3050 3000 2950 3050 3050 W#1 flight (m)
243 245 246 243 243 SW spin (rpm) 6700 6700 6700 6750 6750 W#1
durability 108 110 112 108 107
TABLE-US-00054 TABLE III-14 Results of Evaluation Ex. Ex. Ex. Ex.
Ex. III-6 III-7 III-8 III-9 III-10 Core Diameter (mm) 38.5 38.5
38.5 38.5 38.5 Hs - Ho 31.0 34.0 32.5 34.0 34.0 Inner mid layer
Composition c c c c c Hm1 (Shore D) 47 47 47 47 47 Diameter (mm)
40.1 40.1 40.1 40.1 40.1 Tm1 (mm) 0.8 0.8 0.8 0.8 0.8 outer mid
layer Composition a a a a a Hm2 (Shore D) 65 65 65 65 65 Diameter
(mm) 41.7 41.7 41.7 41.7 41.7 Tm2 (mm) 0.8 0.8 0.8 0.8 0.8 Cover
Composition A A A A A Hc (Shore D) 29 29 29 29 29 Tc (mm) 0.5 0.5
0.5 0.5 0.5 Tm1 + Tm2 (mm) 1.6 1.6 1.6 1.6 1.6 Hm2 - Hm1 (Shore D)
18 18 18 18 18 Hm2 - Hc (Shore D) 36 36 36 36 36 Db (mm) 2.4 2.4
2.4 2.4 2.4 W#1 spin (rpm) 3000 3050 3000 3000 2950 W#1 flight (m)
245 242 244 245 246 SW spin (rpm) 6700 6750 6700 6700 6700 W#1
durability 109 107 109 108 112
TABLE-US-00055 TABLE III-15 Results of Evaluation Ex. Ex. Ex. Ex.
Ex. III-11 III-12 III-13 III-14 III-15 Core Diameter (mm) 38.5 38.5
38.5 38.5 37.7 Hs - Ho 34.0 34.0 34.0 34.5 34.0 Inner mid layer
Composition b c c d c Hm1 (Shore D) 56 47 47 29 47 Diameter (mm)
40.1 40.1 40.1 40.1 39.3 Tm1 (mm) 0.8 0.8 0.8 0.8 0.8 outer mid
layer Composition a a a a a Hm2 (Shore D) 65 65 65 65 65 Diameter
(mm) 41.7 41.7 41.7 41.7 40.9 Tm2 (mm) 0.8 0.8 0.8 0.8 0.8 Cover
Composition A B C A A Hc (Shore D) 29 36 47 29 29 Tc (mm) 0.5 0.5
0.5 0.5 0.9 Tm1 + Tm2 (mm) 1.6 1.6 1.6 1.6 1.6 Hm2 - Hm1 (Shore D)
9 18 18 36 18 Hm2 - Hc (Shore D) 36 29 18 36 36 Db (mm) 2.3 2.4 2.4
2.4 2.4 W#1 spin (rpm) 2900 2850 2800 3050 3100 W#1 flight (m) 247
248 249 241 242 SW spin (rpm) 6550 6550 6400 6750 6900 W#1
durability 109 108 106 115 110
TABLE-US-00056 TABLE III-16 Results of Evaluation Ex. Ex. Ex. Ex.
III-16 III-17 III-18 III-19 Core Diameter (mm) 35.3 38.5 38.5 38.5
Hs - Ho 33.5 42.0 28.0 27.0 Inner mid layer Composition c c c c Hm1
(Shore D) 47 47 47 47 Diameter (mm) 38.5 40.1 40.1 40.1 Tm1 (mm)
1.6 0.8 0.8 0.8 outer mid layer Composition a a a a Hm2 (Shore D)
65 65 65 65 Diameter (mm) 41.7 41.7 41.7 41.7 Tm2 (mm) 1.6 0.8 0.8
0.8 Cover Composition A A A A Hc (Shore D) 29 29 29 29 Tc (mm) 0.5
0.5 0.5 0.5 Tm1 + Tm2 (mm) 3.2 1.6 1.6 1.6 Hm2 - Hm1 (Shore D) 18
18 18 18 Hm2 - Hc (Shore D) 36 36 36 36 Db (mm) 2.3 2.4 2.4 2.5 W#1
spin (rpm) 3000 3050 2850 2800 W#1 flight (m) 242 243 243 242 SW
spin rate (rpm) 6600 6750 6650 6650 W#1 durability 115 114 108
106
TABLE-US-00057 TABLE III-17 Results of Evaluation Comp. Comp. Comp.
Comp. Comp. Ex. Ex. Ex. Ex. Ex. III-1 III-2 III-3 III-4 III-5 Core
Diameter (mm) 38.5 38.5 38.5 38.5 38.5 Hs - Ho 32.0 34.0 33.5 33.5
34.5 Inner mid layer Composition c a c a c Hm1 (Shore D) 47 65 47
65 47 Diameter (mm) 40.1 40.1 40.1 40.1 40.1 Tm1 (mm) 0.8 0.8 0.8
0.8 0.8 outer mid layer Composition a c b a c Hm2 (Shore D) 65 47
56 65 47 Diameter (mm) 41.7 41.7 41.7 41.7 41.7 Tm2 (mm) 0.8 0.8
0.8 0.8 0.8 Cover Composition A A D A A Hc (Shore D) 29 29 60 29 29
Tc (mm) 0.5 0.5 0.5 0.5 0.5 Tm1 + Tm2 (mm) 1.6 1.6 1.6 1.6 1.6 Hm2
- Hm1 (Shore D) 18 -18 9 0 0 Hm2 - Hc (Shore D) 36 18 -4 36 18 Db
(mm) 2.4 2.4 2.4 2.4 2.4 W#1 spin (rpm) 3200 3050 2700 2850 3300
W#1 flight (m) 237 243 251 248 235 SW spin (rpm) 6750 6800 5700
6400 6950 W#1 durability 100 120 103 80 130
TABLE-US-00058 TABLE III-18 Results of Evaluation Comp. Comp. Ex.
Ex. III-6 III-7 Core Diameter (mm) 38.5 38.5 Hs - Ho 31.0 22.0
Inner mid layer Composition c c Hm1 (Shore D) 47 47 Diameter (mm)
40.1 40.1 Tm1 (mm) 0.8 0.8 outer mid layer Composition a a Hm2
(Shore D) 65 65 Diameter (mm) 41.7 41.7 Tm2 (mm) 0.8 0.8 Cover
Composition A A Hc (Shore D) 29 29 Tc (mm) 0.5 0.5 Tm1 + Tm2 (mm)
1.6 1.6 Hm2 - Hm1 (Shore D) 18 18 Hm2 - Hc (Shore D) 36 36 Db (mm)
2.4 2.4 W#1 spin (rpm) 3100 3100 W#1 flight (m) 240 240 SW spin
(rpm) 6750 6750 W#1 durability 106 107
[0908] As shown in Tables III-13 to III-18, the golf balls
according to Examples are excellent in various performance
characteristics. From the results of evaluation, advantages of the
present invention are clear.
Experiment 4
Example IV-1
[0909] A rubber composition was obtained by kneading 100 parts by
weight of a high-cis polybutadiene (trade name "BR-730",
manufactured by JSR Corporation), 18 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, 0.3 parts by weight of
bis(pentabromophenyl)disulfide (a product of Kawaguchi Chemical
Industry Co., LTD.), and 0.9 parts by weight of dicumyl peroxide
(trade name "Percumyl D", manufactured by NOF Corporation). 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 spherical center with a
diameter of 15.0 mm.
[0910] A rubber composition was obtained by kneading 100 parts by
weight of a high-cis polybutadiene (the aforementioned "BR-730"),
42 parts by weight of zinc diacrylate (the aforementioned "Sanceler
SR"), 5 parts by weight of zinc oxide, an appropriate amount of
barium sulfate, 0.2 parts by weight of 2-thionaphthol, 0.9 parts by
weight of dicumyl peroxide, and 30 parts by weight of zinc octoate.
Half shells were formed from this rubber composition. The center
was covered with two of these half shells. The center and the half
shells were 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
38.5 mm. An envelope layer was formed from the rubber composition.
The amount of barium sulfate was adjusted such that the specific
gravity of the envelope layer coincides with the specific gravity
of the center and the weight of a golf ball is 45.4 g.
[0911] A resin composition was obtained by kneading 55 parts by
weight of an ionomer resin (the aforementioned "Surlyn 8945"), 45
parts by weight of another ionomer resin (the aforementioned
"Himilan AM7329"), and 3 parts by weight of titanium dioxide with a
twin-screw kneading extruder. The extruding conditions were a screw
diameter of 45 mm, a screw rotational speed of 200 rpm, screw L/D
of 35, and a die temperature of 160.degree. C. to 230.degree. C.
The core was placed into a mold. The resin composition was injected
around the core by injection molding to form an inner mid layer
with a thickness of 0.8 mm.
[0912] A resin composition was obtained by kneading 27 parts by
weight of an ionomer resin (the aforementioned "Surlyn 8945"), 45
parts by weight of another ionomer resin (the aforementioned
"Himilan AM7329"), 28 parts by weight of a styrene block-containing
thermoplastic elastomer (the aforementioned "Rabalon T3221C"), and
3 parts by weight of titanium dioxide with a twin-screw kneading
extruder under the above extruding conditions. The sphere
consisting of the core and the inner mid layer was placed into a
mold. The resin composition was injected around the sphere by
injection molding to form an outer mid layer with a thickness of
0.8 mm.
[0913] 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 dioxide. 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 an air gun, and kept at 23.degree. C. for 12
hours to obtain a reinforcing layer with a thickness of 10
.mu.m.
[0914] A resin composition was obtained by kneading 100 parts by
weight of a thermoplastic polyurethane elastomer (the
aforementioned "Elastollan NY82A"), 0.2 parts by weight of a
hindered amine light stabilizer (trade name "TINUVIN 770",
manufactured by Ciba Japan K. K.), 4 parts by weight of titanium
dioxide, and 0.04 parts by weight of ultramarine blue with a
twin-screw kneading extruder under the above extruding conditions.
Half shells were formed from this resin composition by compression
molding. The sphere consisting of the core, the inner mid layer,
the outer 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 0.5 mm. Dimples having a
shape that is the inverted shape of the pimples were formed on the
cover. The surface of the cover was polished. A clear paint
including a two-component curing type polyurethane as a base
material was applied to this cover with an air gun, and was dried
and cured to obtain a golf ball of Example IV-1 with a diameter of
42.7 mm and a weight of 45.6 g.
Examples IV-2 to IV-18 and Comparative Examples IV-1 to IV-9
[0915] Golf balls of Examples IV-2 to IV-18 and Comparative
Examples IV-1 to IV-9 were obtained in the same manner as Example
IV-1, except the specifications of the center and the envelope
layer were as shown in Tables IV-7 to IV-12 below and the
specifications of the inner mid layer, the outer mid layer, and the
cover were as shown in Tables IV-13 to IV-18 below. The composition
and the vulcanization conditions of the center are shown in Table
IV-1 below. The composition and the vulcanization conditions of the
envelope layer are shown in Tables IV-2 to IV-4 below. The
compositions and the hardnesses of the inner mid layer and the
outer mid layer are shown in Table IV-5 below. The composition and
the hardness of the cover are shown in Table IV-6 below.
[0916] [Hit with Driver (W#1)]
[0917] A driver with a titanium head (trade name "XXIO",
manufactured by DUNLOP SPORTS CO. LTD., shaft hardness: S, loft
angle: 10.0.degree.) was attached to a swing machine manufactured
by True Temper Co. A golf ball was hit under the condition of a
head speed of 45 m/sec. The spin rate was measured immediately
after the hit. Furthermore, the flight distance from the launch
point to the stop point was measured. The average value of data
obtained by 10 measurements is shown in Tables IV-13 to IV-18
below.
[0918] [Hit with Sand Wedge (SW)]
[0919] A sand wedge (trade name "XXIO", manufactured by DUNLOP
SPORTS CO. LTD., shaft hardness: R, loft angle: 56.0.degree.) was
attached to a swing machine manufactured by True Temper Co. A golf
ball was hit under the condition of a head speed of 21 m/sec. The
backspin rate was measured immediately after the hit. The average
value of data obtained by 10 measurements is shown in Tables IV-13
to IV-18 below.
[0920] [Durability]
[0921] A driver with a titanium head (trade name "XXIO",
manufactured by DUNLOP SPORTS CO. LTD., shaft hardness: S, loft
angle: 10.0.degree.) was attached to a swing robot M/C manufactured
by True Temper Co. A golf ball having been kept at 23.degree. C.
for 12 hours was used for the measurement. The golf ball was
repeatedly hit under the condition of a head speed of 45 m/sec. The
number of hits required to break the golf ball was measured. An
index of the average value of data obtained for 12 golf balls is
shown in Tables IV-13 to IV-18 below. The higher the index is, the
more excellent the durability of the golf ball is.
[0922] [Feel at Impact]
[0923] Golf players hit golf balls with drivers with titanium heads
(trade name "XXIO", manufactured by DUNLOP SPORTS CO. LTD., shaft
hardness: S, loft angle: 10.0.degree.). The feel at impact was
evaluated on the basis of the following criteria.
[0924] A: very favorable (soft)
[0925] B: favorable (soft)
[0926] C: slightly poor (slightly hard)
[0927] D: poor (hard)
TABLE-US-00059 TABLE IV-1 Composition and Vulcanization Conditions
of Center (parts by weight) Type (1) (2) (3) BR-730 100 100 100
Sanceler SR 18 14 20 Zinc oxide 5 5 5 Barium sulfate * * *
Bis(pentabromophenyl)disulfide 0.3 0.3 0.3 Dicumyl peroxide 0.9 0.9
0.9 Vulcanization conditions Temperature (.degree. C.) 170 170 170
Time (min) 25 25 25 * Appropriate amount
TABLE-US-00060 TABLE IV-2 Composition and Vulcanization Conditions
of Envelope Layer (parts by weight) Type E1 E2 E3 E4 E5 BR-730 100
100 100 100 100 Sanceler SR 36 40 40 40 41 ZN-DA90S -- -- -- -- --
Zinc oxide 5 5 5 5 5 Barium sulfate * * * * * 2-thionaphthol 0.2
0.2 0.2 0.2 0.2 Bis(pentabromophenyl)disulfide -- -- -- -- --
Dicumyl peroxide 0.9 0.9 0.9 0.9 0.9 Zinc octoate -- 0.5 2 5 10
Zinc stearate -- -- -- -- -- Zinc myristate -- -- -- -- --
Vulcanization conditions Temperature (.degree. C.) 170 170 170 170
170 Time (min) 25 25 25 25 25 * Appropriate amount
TABLE-US-00061 TABLE IV-3 Composition and Vulcanization Conditions
of Envelope Layer (parts by weight) Type E6 E7 E8 E9 E10 BR-730 100
100 100 100 100 Sanceler SR 42 43 37 38 40 ZN-DA90S -- -- -- -- --
Zinc oxide 5 5 5 5 5 Barium sulfate * * * * * 2-thionaphthol 0.2
0.2 0.2 0.2 0.2 Bis(pentabromophenyl)disulfide -- -- -- -- --
Dicumyl peroxide 0.9 0.9 0.9 0.9 0.9 Zinc octoate 30 45 -- -- --
Zinc stearate -- -- 10 20 -- Zinc myristate -- -- -- -- 5
Vulcanization conditions Temperature (.degree. C.) 170 170 170 170
170 Time (min) 25 25 25 25 25 * Appropriate amount
TABLE-US-00062 TABLE IV-4 Composition and Vulcanization Conditions
of Envelope Layer (parts by weight) Type E11 E12 E13 E14 E15 BR-730
100 100 100 100 100 Sanceler SR 41 42 -- 41 39 ZN-DA90S -- -- 40 --
-- Zinc oxide 5 5 5 5 5 Barium sulfate * * * * * 2-thionaphthol 0.2
-- 0.2 0.2 0.2 Bis(pentabromophenyl)disulfide -- 0.3 -- -- --
Dicumyl peroxide 0.9 0.9 0.9 0.9 0.9 Zinc octoate -- 5 5 5 5 Zinc
stearate -- -- -- -- -- Zinc myristate 10 -- -- -- -- Vulcanization
conditions Temperature (.degree. C.) 170 170 170 170 170 Time (min)
25 25 25 25 25 * Appropriate amount
[0928] The details of the compounds listed in Tables IV-1 to IV-4
are as follows.
[0929] BR-730: 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)
[0930] Sanceler SR: zinc diacrylate manufactured by SANSHIN
CHEMICAL INDUSTRY CO., LTD. (a product coated with 10% by weight of
stearic acid)
[0931] ZN-DA90S: zinc diacrylate manufactured by Nihon Jyoryu Kogyo
Co., Ltd. (a product coated with 10% by weight of zinc
stearate)
[0932] Zinc oxide: trade name "Ginrei R" manufactured by Toho Zinc
Co., Ltd.
[0933] Barium sulfate: trade name "Barium Sulfate BD" manufactured
by Sakai Chemical Industry Co., Ltd.
[0934] 2-thionaphthol: a product of Tokyo Chemical Industry Co.,
Ltd.
[0935] Bis(pentabromophenyl)disulfide: a product of Kawaguchi
Chemical Industry Co., LTD.
[0936] Dicumyl peroxide: trade name "Percumyl D" manufactured by
NOF Corporation
[0937] Zinc octoate: a product of Mitsuwa Chemicals Co., Ltd.
(purity: 99% or greater)
[0938] Zinc stearate: a product of Wako Pure Chemical Industries,
Ltd. (purity: 99% or greater)
[0939] Zinc myristate: a product of NOF Corporation (purity: 90% or
greater)
TABLE-US-00063 TABLE IV-5 Compositions and Hardnesses of Inner Mid
Layer and Outer Mid Layer (parts by weight) Type a b c d Surlyn
8945 55 45 27 20 Himilan AM7329 45 45 45 25 Rabalon T3221C -- 10 28
55 Titanium dioxide 3 3 3 3 Hardness (Shore D) 65 56 48 29
TABLE-US-00064 TABLE IV-6 Composition and Hardness of Cover (parts
by weight) Type C1 C2 C3 C4 Elastollan NY82A 100 -- -- --
Elastollan NY85A -- 50 -- -- Elastollan NY90A -- 50 -- --
Elastollan NY97A -- -- 100 -- Surlyn 8945 -- -- -- 40 Himilan
AM7329 -- -- -- 55 Rabalon T3221C -- -- -- 5 TINUVIN 770 0.2 0.2
0.2 0.2 Titanium dioxide 4 4 4 4 Ultramarine blue 0.04 0.04 0.04
0.04 Hardness 29 36 47 60 Hc (Shore D)
TABLE-US-00065 TABLE IV-7 Physical Properties and Hardness
Distribution of Core (JIS-C hardness) Ex. Ex. Ex. Ex. Ex. IV-1 IV-2
IV-3 IV-4 IV-5 Center Composition (1) (1) (1) (1) (1) Diameter (mm)
15 15 15 15 15 Ho (JIS-C) 57 57 57 57 57 Surface hardness 61 61 61
61 61 (JIS-C) Envelope layer Composition E6 E5 E4 E3 E8 Thickness
(mm) 11.75 11.75 11.75 11.75 11.75 H(0.0) 60.5 62.5 63.5 62.0 64.5
H(12.5) 64.5 65.0 66.0 68.0 67.0 H(25.0) 66.5 69.0 69.5 71.0 70.5
H(37.5) 69.0 71.0 71.0 73.5 72.0 H(50.0) 71.0 72.5 73.0 74.5 73.5
H(62.5) 73.0 74.5 76.5 75.0 75.0 H(75.0) 75.5 82.0 82.5 79.5 83.0
H(87.5) 78.0 86.0 87.0 84.5 87.0 Hs 83.0 89.0 91.0 88.5 91.0 Hs -
H(0.0) 22.5 26.5 27.5 26.5 26.5 R.sup.2 0.98 0.97 0.97 0.95 0.95
Gradient 0.20 0.26 0.27 0.23 0.26
TABLE-US-00066 TABLE IV-8 Physical Properties and Hardness
Distribution of Core (JIS-C hardness) Ex. Ex. Ex. Ex. Ex. IV-6 IV-7
IV-8 IV-9 IV-10 Center Composition (1) (1) (1) (1) (1) Diameter
(mm) 15 15 15 15 15 Ho (JIS-C) 57 57 57 57 57 Surface hardness 61
61 61 61 61 (JIS-C) Envelope layer Composition E9 E10 E11 E12 E13
Thickness (mm) 11.75 11.75 11.75 11.75 11.75 H(0.0) 63.0 64.0 63.0
63.5 63.5 H(12.5) 65.0 66.5 65.5 65.5 66.0 H(25.0) 67.0 70.0 69.5
70.0 69.5 H(37.5) 69.5 72.0 71.5 71.0 71.0 H(50.0) 72.0 73.0 72.5
73.0 74.0 H(62.5) 73.5 74.5 74.5 76.5 76.5 H(75.0) 82.0 82.5 82.5
82.0 82.5 H(87.5) 84.0 87.0 86.5 87.0 87.0 Hs 88.0 91.0 89.5 91.0
91.0 Hs - H(0.0) 25.0 27.0 26.5 27.5 27.5 R.sup.2 0.96 0.95 0.96
0.97 0.97 Gradient 0.25 0.26 0.26 0.27 0.27
TABLE-US-00067 TABLE IV-9 Physical Properties and Hardness
Distribution of Core (JIS-C hardness) Ex. Ex. Ex. Ex. Ex. IV-11
IV-12 IV-13 IV-14 IV-15 Center Composition (1) (1) (1) (1) (1)
Diameter (mm) 15 15 15 15 15 Ho (JIS-C) 57 57 57 57 57 Surface
hardness 61 61 61 61 61 (JIS-C) Envelope layer Composition E4 E4 E4
E14 E4 Thickness (mm) 11.75 11.75 11.75 11.75 11.35 H(0.0) 63.5
63.5 63.5 64.0 63.5 H(12.5) 66.0 66.0 66.0 66.0 66.0 H(25.0) 69.5
69.5 69.5 70.0 69.5 H(37.5) 71.0 71.0 71.0 71.5 71.0 H(50.0) 73.0
73.0 73.0 73.5 73.0 H(62.5) 76.5 76.5 76.5 77.0 76.5 H(75.0) 82.5
82.5 82.5 83.0 82.5 H(87.5) 87.0 87.0 87.0 87.5 87.0 Hs 91.0 91.0
91.0 91.5 91.0 Hs - H(0.0) 27.5 27.5 27.5 27.5 27.5 R.sup.2 0.97
0.97 0.97 0.97 0.97 Gradient 0.27 0.27 0.27 0.27 0.27
TABLE-US-00068 TABLE IV-10 Physical Properties and Hardness
Distribution of Core (JIS-C hardness) Ex. Ex. Ex. IV-16 IV-17 IV-18
Center Composition (2) (3) (3) Diameter (mm) 9 21 26 Ho (JIS-C) 49
62 62 Surface hardness 53 66 66 (JIS-C) Envelope layer Composition
E4 E4 E4 Thickness (mm) 14.75 8.75 6.25 H(0.0) 63.0 64.0 64.0
H(12.5) 65.5 66.5 66.5 H(25.0) 69.5 69.5 69.5 H(37.5) 71.0 71.0
71.0 H(50.0) 73.0 73.0 73.0 H(62.5) 76.5 76.5 76.5 H(75.0) 82.5
82.5 82.0 H(87.5) 87.0 86.5 86.5 Hs 91.0 90.0 89.0 Hs - H(0.0) 28.0
26.0 25.0 R.sup.2 0.97 0.97 0.97 Gradient 0.27 0.26 0.25
TABLE-US-00069 TABLE IV-11 Physical Properties and Hardness
Distribution of Core (JIS-C hardness) Comp. Comp. Comp. Comp. Comp.
Ex. Ex. Ex. Ex. Ex. IV-1 IV-2 IV-3 IV-4 IV-5 Center Composition (1)
(1) (1) (1) (1) Diameter (mm) 15 15 15 15 15 Ho (JIS-C) 57 57 57 57
57 Surface hardness 61 61 61 61 61 (JIS-C) Envelope layer
Composition E1 E4 E15 E15 E14 Thickness (mm) 11.75 11.75 11.75
11.75 11.75 H(0.0) 64.0 63.5 63.0 63.0 64.0 H(12.5) 74.0 66.0 65.0
65.0 66.0 H(25.0) 78.0 69.5 69.0 69.0 70.0 H(37.5) 78.0 71.0 70.5
70.5 71.5 H(50.0) 78.0 73.0 72.5 72.5 73.5 H(62.5) 79.0 76.5 76.0
76.0 77.0 H(75.0) 80.0 82.5 82.0 82.0 83.0 H(87.5) 84.0 87.0 86.5
86.5 87.5 Hs 89.0 91.0 90.5 90.5 91.5 Hs - H(0.0) 25.0 27.5 27.5
27.5 27.5 R.sup.2 0.81 0.97 0.97 0.97 0.97 Gradient 0.18 0.27 0.27
0.27 0.27
TABLE-US-00070 TABLE IV-12 Physical Properties and Hardness
Distribution of Core (JIS-C hardness) Comp. Comp. Comp. Comp. Ex.
Ex. Ex. Ex. IV-6 IV-7 IV-8 IV-9 Center Composition (1) (1) (1) (1)
Diameter (mm) 15 15 15 15 Ho (JIS-C) 57 57 57 57 Surface hardness
61 61 61 61 (JIS-C) Envelope layer Composition E15 E15 E2 E7
Thickness (mm) 10.15 11.75 11.75 11.75 H(0.0) 63.0 63.0 62.0 71.0
H(12.5) 65.0 65.0 71.5 74.0 H(25.0) 69.0 69.0 75.5 74.5 H(37.5)
70.5 70.5 76.0 75.0 H(50.0) 72.5 72.5 76.5 75.0 H(62.5) 76.0 76.0
77.5 75.0 H(75.0) 82.0 82.0 78.5 75.5 H(87.5) 86.5 86.5 83.5 78.0
Hs 90.5 90.5 88.0 79.0 Hs - H(0.0) 27.5 27.5 26.0 8.0 R.sup.2 0.97
0.97 0.86 0.84 Gradient 0.27 0.27 0.20 0.06
TABLE-US-00071 TABLE IV-13 Results of Evaluation Ex. Ex. Ex. Ex.
Ex. IV-1 IV-2 IV-3 IV-4 IV-5 Core Diameter (mm) 38.5 38.5 38.5 38.5
38.5 Hs - Ho 26.0 32.0 34.0 31.5 34.0 Inner mid layer Composition a
a a a a Hm1 (Shore D) 65 65 65 65 65 Diameter (mm) 40.1 40.1 40.1
40.1 40.1 Tm1 (mm) 0.8 0.8 0.8 0.8 0.8 Outer mid layer Composition
c c c c c Hm2 (Shore D) 48 48 48 48 48 Diameter (mm) 41.7 41.7 41.7
41.7 41.7 Tm2 (mm) 0.8 0.8 0.8 0.8 0.8 Cover Composition C1 C1 C1
C1 C1 Hc (Shore D) 29 29 29 29 29 Tc (mm) 0.5 0.5 0.5 0.5 0.5 Tm1 +
Tm2 (mm) 1.6 1.6 1.6 1.6 1.6 Hm1 - Hm2 (Shore D) 17 17 17 17 17 Hm1
- Hc (Shore D) 36 36 36 36 36 Db (mm) 2.4 2.4 2.4 2.4 2.4 W#1 spin
(rpm) 3150 3100 3050 3150 3150 W#1 flight (m) 241 242 243 241 241
SW spin (rpm) 6800 6800 6800 6850 6850 W#1 durability 112 116 118
112 116 W#1 feel at impact A A A A A
TABLE-US-00072 TABLE IV-14 Results of Evaluation Ex. Ex. Ex. Ex.
Ex. IV-6 IV-7 IV-8 IV-9 IV-10 Core Diameter (mm) 38.5 38.5 38.5
38.5 38.5 Hs - Ho 31.0 34.0 32.5 34.0 34.0 Inner mid layer
Composition a a a a a Hm1 (Shore D) 65 65 65 65 65 Diameter (mm)
40.1 40.1 40.1 40.1 40.1 Tm1 (mm) 0.8 0.8 0.8 0.8 0.8 Outer mid
layer Composition c c c c c Hm2 (Shore D) 48 48 48 48 48 Diameter
(mm) 41.7 41.7 41.7 41.7 41.7 Tm2 (mm) 0.8 0.8 0.8 0.8 0.8 Cover
Composition C1 C1 C1 C1 C1 Hc (Shore D) 29 29 29 29 29 Tc (mm) 0.5
0.5 0.5 0.5 0.5 Tm1 + Tm2 (mm) 1.6 1.6 1.6 1.6 1.6 Hm1 - Hm2 (Shore
D) 17 17 17 17 17 Hm1 - Hc (Shore D) 36 36 36 36 36 Db (mm) 2.4 2.4
2.4 2.4 2.4 W#1 spin (rpm) 3100 3150 3100 3100 3050 W#1 flight (m)
242 240 241 242 243 SW spin (rpm) 6800 6850 6800 6800 6800 W#1
durability 115 115 114 115 118 W#1 feel at impact A A A A A
TABLE-US-00073 TABLE IV-15 Results of Evaluation Ex. Ex. Ex. Ex.
Ex. IV-11 IV-12 IV-13 IV-14 IV-15 Core Diameter (mm) 38.5 38.5 38.5
38.5 37.7 Hs - Ho 34.0 34.0 34.0 34.5 34.0 Inner mid layer
Composition a a a a a Hm1 (Shore D) 65 65 65 65 65 Diameter (mm)
40.1 40.1 40.1 40.1 39.3 Tm1 (mm) 0.8 0.8 0.8 0.8 0.8 Outer mid
layer Composition b c c d c Hm2 (Shore D) 56 48 48 29 48 Diameter
(mm) 41.7 41.7 41.7 41.7 40.9 Tm2 (mm) 0.8 0.8 0.8 0.8 0.8 Cover
Composition C1 C2 C3 C1 C1 Hc (Shore D) 29 36 47 29 29 Tc (mm) 0.5
0.5 0.5 0.5 0.9 Tm1 + Tm2 (mm) 1.6 1.6 1.6 1.6 1.6 Hm1 - Hm2 (Shore
D) 9 17 17 36 18 Hm1 - Hc (Shore D) 36 29 18 36 36 n Db (mm) 2.4
2.4 2.4 2.4 2.4 W#1 spin (rpm) 3000 2950 2900 3150 3200 W#1 flight
(m) 244 246 247 240 239 SW spin (rpm) 6650 6650 6500 6850 7000 W#1
durability 112 114 107 120 120 W#1 feel at impact B A B A A
TABLE-US-00074 TABLE IV-16 Results of Evaluation Ex. Ex. Ex. IV-16
IV-17 IV-18 Core Diameter (mm) 38.5 38.5 38.5 Hs - Ho 42.0 29.0
29.0 Inner mid layer Composition a a a Hm1 (Shore D) 65 65 65
Diameter (mm) 40.1 40.1 40.1 Tm1 (mm) 0.8 0.8 0.8 Outer mid layer
Composition c c c Hm2 (Shore D) 48 48 48 Diameter (mm) 41.7 41.7
41.7 Tm2 (mm) 0.8 0.8 0.8 Cover Composition C1 C1 C1 Hc (Shore D)
29 29 29 Tc (mm) 0.5 0.5 0.5 Tm1 + Tm2 (mm) 1.6 1.6 1.6 Hm1 - Hm2
(Shore D) 17 17 17 Hm1 - Hc (Shore D) 36 36 36 Db (mm) 2.4 2.4 2.4
W#1 spin (rpm) 3150 2950 2900 W#1 flight (m) 241 241 240 SW spin
(rpm) 6850 6750 6750 W#1 durability 120 110 108 W#1 feel at impact
A A A
TABLE-US-00075 TABLE IV-17 Results of Evaluation Comp. Comp. Comp.
Comp. Comp. Ex. Ex. Ex. Ex. Ex. IV-1 IV-2 IV-3 IV-4 IV-5 Core
Diameter (mm) 38.5 38.5 38.5 38.5 38.5 Hs - Ho 32.0 34.0 33.5 33.5
34.5 Inner mid layer Composition a c b a c Hm1 (Shore D) 65 48 56
65 48 Diameter (mm) 40.1 40.1 40.1 40.1 40.1 Tm1 (mm) 0.8 0.8 0.8
0.8 0.8 Outer mid layer Composition c a c a c Hm2 (Shore D) 48 65
48 65 47 Diameter (mm) 41.7 41.7 41.7 41.7 41.7 Tm2 (mm) 0.8 0.8
0.8 0.8 0.8 Cover Composition C1 C1 C4 C1 C1 Hc (Shore D) 29 29 60
29 29 Tc (mm) 0.5 0.5 0.5 0.5 0.5 Tm1 + Tm2 (mm) 1.6 1.6 1.6 1.6
1.6 Hm1 - Hm2 (Shore D) 17 -17 8 -- -- Hm1 - Hc (Shore D) 36 19 -4
36 19 Db (mm) 2.4 2.4 2.4 2.4 2.4 W#1 spin (rpm) 3300 2950 2800
2850 3250 W#1 flight (m) 235 246 249 248 236 SW spin (rpm) 6850
6700 5800 6400 6900 W#1 durability 100 75 102 70 136 W#1 feel at
impact B C C D B
TABLE-US-00076 TABLE IV-18 Results of Evaluation Comp. Comp. Comp.
Comp. Ex. Ex. Ex. Ex. IV-6 IV-7 IV-8 IV-9 Core Diameter (mm) 35.3
38.5 38.5 38.5 Hs - Ho 33.5 33.5 31.0 22.0 Inner mid layer
Composition a a a a Hm1 (Shore D) 65 65 65 65 Diameter (mm) 38.5
40.9 40.1 40.1 Tm1 (mm) 1.6 1.2 0.8 0.8 Outer mid layer Composition
c c c c Hm2 (Shore D) 48 48 48 48 Diameter (mm) 41.7 41.7 41.7 41.7
Tm2 (mm) 1.6 0.4 0.8 0.8 Cover Composition C1 C1 C1 C1 Hc (Shore D)
29 29 29 29 Tc (mm) 0.5 0.5 0.5 0.5 Tm1 + Tm2 (mm) 3.2 1.6 1.6 1.6
Hm1 - Hm2 (Shore D) 17 17 17 17 Hm1 - Hc (Shore D) 36 36 36 36 Db
(mm) 2.3 2.4 2.4 2.4 W#1 spin (rpm) 3150 3100 3200 3200 W#1 flight
(m) 238 242 239 239 SW spin (rpm) 6850 6700 6850 6800 W#1
durability 118 78 108 109 W#1 feel at impact C C A A
[0940] As shown in Tables IV-13 to IV-18, the golf balls according
to Examples are excellent in various performance characteristics.
From the results of evaluation, advantages of the present invention
are clear.
[0941] The golf ball according to the present invention can be used
for playing golf on golf courses and practicing at driving ranges.
The above descriptions are merely for illustrative examples, and
various modifications can be made without departing from the
principles of the present invention.
* * * * *