U.S. patent application number 13/093578 was filed with the patent office on 2011-08-18 for golf ball.
Invention is credited to Kazuhiko ISOGAWA, Keiji Ohama.
Application Number | 20110201454 13/093578 |
Document ID | / |
Family ID | 37011075 |
Filed Date | 2011-08-18 |
United States Patent
Application |
20110201454 |
Kind Code |
A1 |
ISOGAWA; Kazuhiko ; et
al. |
August 18, 2011 |
GOLF BALL
Abstract
A golf ball having a spherical core, a mid layer covering this
core, a reinforcing layer covering this mid layer, and a cover
covering this reinforcing layer, wherein the base polymer of the
mid layer includes a styrene block-containing thermoplastic
elastomer and an ionomer resin; the mid layer has a hardness as
measured with a Shore D type hardness scale of equal to or less
than 54; the mid layer has a thickness of 0.5 mm or greater and 1.6
mm or less; and the base polymer of the reinforcing layer is a
reaction product between carboxyl group-containing polyurethane and
polycarbodiimide. The principal component of the base polymer of
the cover is an ionomer resin. The cover has a hardness as measured
with a Shore D type hardness scale hardness of equal to or greater
than 55 and the cover has a thickness of equal to or less than 1.2
mm.
Inventors: |
ISOGAWA; Kazuhiko;
(Kobe-shi, JP) ; Ohama; Keiji; (Kobe-shi,
JP) |
Family ID: |
37011075 |
Appl. No.: |
13/093578 |
Filed: |
April 25, 2011 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
11362127 |
Feb 27, 2006 |
|
|
|
13093578 |
|
|
|
|
Current U.S.
Class: |
473/373 ;
473/376 |
Current CPC
Class: |
A63B 37/0031 20130101;
A63B 37/0043 20130101; A63B 37/0076 20130101; A63B 37/0045
20130101; A63B 37/0033 20130101 |
Class at
Publication: |
473/373 ;
473/376 |
International
Class: |
A63B 37/06 20060101
A63B037/06; A63B 37/00 20060101 A63B037/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 15, 2005 |
JP |
2005-073295 |
Mar 17, 2005 |
JP |
2005-076551 |
Claims
1. A golf ball which comprises a spherical core, amid layer
positioned outside of the core, a reinforcing layer positioned
outside of the mid layer, and a cover positioned outside of the
reinforcing layer, said core having a diameter of 39.2 mm or
greater and 41.0 mm or less, said mid layer having (1) a hardness
Hm as measured with a Shore D type hardness scale of equal to or
less than 54 and (2) a thickness Tm of 0.5 mm or greater and 1.2 mm
or less, and said cover having (1) a hardness Hc as measured with a
Shore D type hardness scale of equal to or greater than 56 and (2)
a thickness Tc of 0.8 mm or less.
2. The golf ball according to claim 1, wherein said cover has a
weight Wc of equal to or less than 4.0 g.
3. The golf ball according to claim 1, wherein said cover has a
ratio (Wc/Hc) of the weight Wc to the hardness Hc of equal to or
less than 0.080.
4. The golf ball according to claim 1, wherein said mid layer has
the hardness Hm of equal to or greater than 30.
5. The golf ball according to claim 1, wherein said cover has the
thickness Tc equal to or less than 0.5 mm.
6. The golf ball according to claim 1, wherein said cover has the
hardness Hc of equal to or less than 65.
7. The golf ball according to claim 1, wherein said reinforcing
layer comprises a water-based adhesive
8. A golf ball according to claim 7, wherein said water-based
adhesive comprises a base polymer which is a reaction product
between a carboxyl group-containing polyurethane and a
polycarbodiimide.
9. The golf ball according to claim 1, wherein said reinforcing
layer has a thickness of 0.003 mm or greater and 0.050 mm or
less.
10. The golf ball according to claim 1, wherein a base polymer of
said reinforcing layer is a reaction product between carboxyl
group-containing polyurethane and polycarbodiimide.
11. The golf ball according to claim 10, wherein said carboxyl
group-containing polyurethane and said polycarbodiimide are
water-based.
12. The golf ball according to claim 1, wherein the principal
component of a base polymer of said cover is an ionomer resin.
13. The golf ball according to claim 12, wherein the base polymer
of the cover comprises a styrene block-containing thermoplastic
elastomer.
14. The golf ball according to claim 13, wherein the base polymer
of the cover comprises 10% by weight or less styrene
block-containing thermoplastic elastomer.
15. The golf ball according to claim 1, wherein a base polymer of
the mid layer comprises 10% by weight or more styrene
block-containing thermoplastic elastomer, and 40% by weight or more
ionomer resin.
16. The golf ball according to claim 15, wherein the base polymer
of the mid layer comprises 10% by weight or more and 60% by weight
or less of a styrene block-containing thermoplastic elastomer, and
40% by weight or more and 90% by weight or less of an ionomer
resin.
17. The golf ball according to claim 16, wherein the base polymer
of the mid layer comprises 30% by weight or more and 60% by weight
or less styrene block-containing thermoplastic elastomer, and 40%
by weight or more and 70% by weight or less ionomer resin.
18. The golf ball according to claim 15, wherein the styrene
block-containing thermoplastic elastomer of the mid layer is an
alloy of olefin and one or two or more selected from the group
consisting of SBS, SIS, SEBS, SEPS and SEEPS, and hydrogenated
products thereof.
19. The golf ball according to claim 1, wherein the golf ball has a
diameter greater than 42.67 mm.
Description
CROSS REFERENCE
[0001] The present application is a 37 C.F.R. .sctn.1.53(b)
continuation of, and claims priority to, U.S. application Ser. No.
11/362,127, filed Feb. 27, 2006. Priority is also claimed to
Japanese Patent Application No. 2005-073295 filed on Mar. 15, 2005
and Japanese Patent Application No. 2005-076551 filed on Mar. 17,
2005. The entire contents of these applications are hereby
incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to golf balls. More
particularly, the present invention relates to multi piece golf
balls having a core, a mid layer and a cover.
[0004] 2. Description of the Related Art
[0005] Top concern to golf players for golf balls is their flight
performances. The golf players particularly place great importance
on flight distance attained upon shots with a driver. Feel at
impact is also important to golf balls. Golf players prefer soft
feel at impact. Furthermore, durability is also important to golf
balls. Golf balls not accompanied by breakage upon repeated impacts
have been desired.
[0006] In light of flight performances and feel at impact, golf
balls having a variety of structures have been proposed. U.S. Pat.
No. 6,106,415 (JP-A No. H10-179795) discloses a golf ball in which
either one of the mid layer or the cover comprises an ionomer resin
while the other comprises polyurethane. U.S. Pat. No. 6,231,460
(JP-A No. H11-253581) discloses a golf ball having amid layer
comprising a thermoplastic polyurethane elastomer, and a cover
comprising an ionomer resin. US2003/083155 (JP-A No. 2003-52857)
discloses a golf ball having a mid layer comprising a thermoplastic
elastomer, and a cover comprising an ionomer resin. U.S. Pat. No.
6,106,415 (JP-A No. 2001-585) discloses a golf ball having amid
layer comprising an urethane resin, and a cover comprising an
ionomer resin.
[0007] Ionomer resins are inferior in compatibility with other
resins. Ionomer resins are particularly inferior in compatibility
with thermoplastic elastomers. In golf balls having a cover
comprising an ionomer resin and a mid layer comprising other resin,
adhesion between the mid layer and the cover may be insufficient.
In this type of golf ball, repeated impacts may result in
detachment of the cover from the mid layer. The detachment leads to
breakage of the golf ball. In particular, according to golf balls
having a thin mid layer or a thin cover, breakage is apt to be
caused due to insufficient adhesion. An object of the present
invention is to provide a golf ball that is excellent in the flight
performance, feel at impact and durability.
SUMMARY OF THE INVENTION
[0008] A golf ball according to one aspect of the present invention
has a spherical core, amid layer positioned outside of this core, a
reinforcing layer positioned outside of this mid layer, and a cover
positioned outside of this reinforcing layer. This mid layer has a
hardness Hm as measured with a Shore D type hardness scale of equal
to or less than 54. Principal component of the base polymer of this
cover is an ionomer resin. This cover has a hardness Hc as measured
with a Shore D type hardness scale of equal to or greater than 55.
This cover has a weight Wc of equal to or less than 5.7 g. This
cover has a ratio (Wc/Hc) of the weight Wc to the hardness Hc of
equal to or less than 0.080.
[0009] Preferably, the base polymer of the mid layer comprises 10%
by weight or more and 60% by weight or less styrene
block-containing thermoplastic elastomer, and 40% by weight or more
and 90% by weight or less ionomer resin.
[0010] Preferably, the cover has a thickness Tc of equal to or less
than 1.2 mm. Preferably, the mid layer has a thickness Tm of 0.5 mm
or greater and 1.6 mm or less.
[0011] Preferably, the reinforcing layer comprises a water-based
adhesive. Base polymer of this water-based adhesive is a reaction
product between carboxyl group-containing polyurethane and
polycarbodiimide. Preferably, the reinforcing layer has a thickness
of 0.003 mm or greater and 0.050 mm or less.
[0012] A golf ball according to another aspect of the present
invention has a spherical core, amid layer positioned outside of
this core, a reinforcing layer positioned outside of this mid
layer, and a cover positioned outside of this reinforcing layer.
This mid layer has a thickness Tm of 0.5 mm or greater and 1.7 mm
or less. Base polymer of this cover is an ionomer resin. The cover
has a hardness Hc as measured with a Shore D type hardness scale of
56 or greater and 65 or less. This cover has a thickness Tc of
equal to or less than 1.0 mm.
[0013] Preferably, the mid layer has a hardness Hm as measured with
a Shore D type hardness scale of 30 or greater and 54 or less.
Preferably, base polymer of this mid layer comprises 30% by weight
or more and 60% by weight or less styrene block-containing
thermoplastic elastomer, and 40% by weight or more and 70% by
weight or less ionomer resin.
[0014] Preferably, base polymer of the reinforcing layer is a
reaction product between carboxyl group-containing polyurethane and
polycarbodiimide. Preferably, the carboxyl group-containing
polyurethane and the polycarbodiimide are water-based.
[0015] In this golf ball, firm adhesion between the mid layer and
the cover is permitted via the reinforcing layer. According to this
golf ball, sufficient durability is achieved by virtue of the
reinforcing layer even though a thin mid layer or a thin cover is
employed. The thin mid layer can be responsible for resilience
performance of the golf ball. The thin cover can be responsible for
feel at impact of the golf ball. Also, the thin cover can optimize
launch angle of the golf ball upon impact. This golf ball is
excellent in the flight performance, feel at impact and
durability.
BRIEF DESCRIPTION OF THE DRAWING
[0016] FIG. 1 is a partially cut off cross-sectional view
illustrating a golf ball according to one embodiment of the present
invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0017] The present invention is hereinafter described in detail
with appropriate references to the accompanying drawing according
to the preferred embodiments.
[0018] A golf ball 2 illustrated in FIG. 1 has a spherical core 4,
a mid layer 6 covering this core 4, a reinforcing layer 8 covering
this mid layer 6, and a cover 10 covering this reinforcing layer 8.
Numerous dimples 12 are formed on the surface of the cover 10. Of
the surface of the cover 10, a part except for the dimples 12 is a
land 14. This golf ball 2 has a paint layer and a mark layer to the
external side of the cover 10, although these layers are not shown
in the FIGURE.
[0019] This golf ball 2 has a diameter of from 40 mm to 45 mm. From
the standpoint of conformity to a rule defined by United States
Golf Association (USGA), the diameter is preferably equal to or
greater than 42.67 mm. In light of suppression of the air
resistance, the diameter is preferably equal to or less than 44 mm,
and more preferably equal to or less than 42.80 mm. Weight of this
golf ball 2 is 40 g or greater and 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 a rule defined by
USGA, the weight is preferably equal to or less than 45.93 g.
[0020] The core 4 is usually obtained through crosslinking of a
rubber composition. Illustrative examples of preferable base rubber
include polybutadienes, polyisoprenes, styrene-butadiene
copolymers, ethylene-propylene-diene copolymers and natural
rubbers. In light of the resilience performance, polybutadienes are
preferred. When other rubber is used in combination with a
polybutadiene, it is preferred that polybutadiene is included as a
principal component. Specifically, it is preferred that percentage
of polybutadiene occupying the entire base rubber is equal to or
greater than 50% by weight, and particularly equal to or greater
than 80% by weight. Polybutadienes having a percentage of cis-1,4
bonds of equal to or greater than 40%, and particularly equal to or
greater than 80% are particularly preferred.
[0021] For crosslinking of the core 4, a co-crosslinking agent is
usually used. Preferable examples of the co-crosslinking agent in
light of the resilience performance include monovalent or bivalent
metal salts of an .alpha.,.beta.-unsaturated carboxylic acid having
2 to 8 carbon atoms. Specific examples of preferable
co-crosslinking agent include zinc acrylate, magnesium acrylate,
zinc methacrylate and magnesium methacrylate. Zinc acrylate and
zinc methacrylate are particularly preferred on the grounds that a
high resilience performance can be achieved.
[0022] As a co-crosslinking agent, an .alpha.,.beta.-unsaturated
carboxylic acid having 2 to 8 carbon atoms, and a metal oxide may
be also blended. Both components react in the rubber composition to
give a salt. This salt serves is responsible for the crosslinking
reaction. Examples of preferable .alpha.,.beta.-unsaturated
carboxylic acid include acrylic acid and methacrylic acid. Examples
of preferable metal oxide include zinc oxide and magnesium
oxide.
[0023] In light of the resilience performance of the golf ball 2,
the amount of the co-crosslinking agent to be blended is preferably
equal to or greater than 10 parts by weight, and more preferably
equal to or greater than 15 parts by weight per 100 parts by weight
of the base rubber. In light of soft feel at impact, the amount of
the co-crosslinking agent to be blended is preferably equal to or
less than 50 parts by weight, and more preferably equal to or less
than 45 parts by weight per 100 parts by weight of the base
rubber.
[0024] Into the rubber composition for use in the core 4, an
organic peroxide may be preferably blended together with the
co-crosslinking agent. The organic peroxide serves as a
crosslinking initiator. By blending the organic peroxide, the
resilience performance of the golf ball 2 may be improved. Examples
of suitable organic peroxide include dicumyl peroxide, [0025]
1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, [0026]
2,5-dimethyl-2,5-di(t-butylperoxy)hexane and di-t-butyl peroxide.
Particularly versatile organic peroxide is dicumyl peroxide.
[0027] In light of the resilience performance of the golf ball 2,
the amount of the organic peroxide to be blended is preferably
equal to or greater than 0.1 part by weight, more preferably equal
to or greater than 0.3 part by weight, and particularly preferably
equal to or greater than 0.5 part by weight per 100 parts by weight
of the base rubber. In light of soft feel at impact, the amount of
the organic peroxide to be blended is preferably equal to or less
than 3.0 parts by weight, and more preferably equal to or less than
2.5 parts by weight per 100 parts by weight of the base rubber.
[0028] Into the core 4 may be blended a filler for the purpose of
adjusting specific gravity and the like. Illustrative examples of
suitable filler include zinc oxide, barium sulfate, calcium
carbonate and magnesium carbonate. Powder of a highly dense metal
may be blended as a filler. Specific examples of the highly dense
metal include tungsten and molybdenum. The amount of the filler to
be blended is determined ad libitum so that the intended specific
gravity of the core 4 can be accomplished. Particularly preferable
filler is zinc oxide. Zinc oxide serves not only to adjust the
specific gravity but also as a crosslinking activator. Various
kinds of additives such as sulfur, a sulfur compound, an anti-aging
agent, a coloring agent, a plasticizer, a dispersant and the like
may be blended at an adequate amount to the core 4 as needed. Into
the core 4 may be also blended crosslinked rubber powder or
synthetic resin powder.
[0029] It is preferred that the core 4 has a diameter of 30.0 mm or
greater and 41.0 mm or less. Sufficient resilience performance of
the golf ball 2 is achieved by setting the diameter to be equal to
or greater than 30.0 mm. In this respect, the diameter is more
preferably equal to or greater than 32.0 mm. Feel at impact by
virtue of the mid layer 6 and the flight performance by virtue of
the cover 10 can be achieved by setting the diameter to be equal to
or less than 41.0 mm. In this respect, the diameter is more
preferably equal to or less than 40.5 mm.
[0030] It is preferred that the core 4 has an amount of compressive
deformation of 3.0 mm or greater and 6.0 mm or less. The core 4
having an amount of compressive deformation of equal to or greater
than 3.0 mm is responsible for soft feel at impact. In this
respect, the amount of compressive deformation is more preferably
equal to or greater than 3.4 mm. The core 4 having an amount of
compressive deformation of equal to or less than 6.0 mm is
responsible for the resilience performance of the golf ball 2. In
this respect, the amount of compressive deformation is more
preferably equal to or less than 5.5 mm.
[0031] Upon measurement of the amount of compressive deformation,
the core 4 is first placed on a hard plate made of metal. Next, a
cylinder made of metal gradually descends toward the core 4. The
core 4 intervened between the bottom face of the cylinder and the
hard plate is deformed. A migration distance of the cylinder,
starting from the state in which initial load of 98 N is applied to
the core 4 up to the state in which final load of 1274 N is applied
thereto is the amount of compressive deformation.
[0032] Weight of the core 4 is preferably 25 g or greater and 42 g
or less. Crosslinking temperature of the core 4 is usually
140.degree. C. or greater and 180.degree. C. or less. The
crosslinking time period of the core 4 is usually 10 minutes or
longer and 60 minutes or less. The core 4 may be formed with two or
more layers. Other layer comprising a resin composition or a rubber
composition may be provided between the core 4 and the mid layer
6.
[0033] Base polymer of the mid layer 6 comprises a styrene
block-containing thermoplastic elastomer. The styrene
block-containing thermoplastic elastomer is responsible for the
feel at impact of the golf ball 2. In light of the feel at impact,
it is preferred that proportion of the styrene block-containing
thermoplastic elastomer to total amount of the base polymer is
equal to or greater than 10% by weight, yet equal to or greater
than 25% by weight, still equal to or greater than 30% by weight,
and further equal to or greater than 40% by weight.
[0034] Examples of the styrene block-containing thermoplastic
elastomer 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. Exemplary
hydrogenated SBS may include styrene-ethylene-butylene-styrene
block copolymers (SEGS). Exemplary hydrogenated SIS may include
styrene-ethylene-propylene-styrene block copolymers (SEPS).
Exemplary hydrogenated SIBS may include
styrene-ethylene-ethylene-propylene-styrene block copolymers
(SEEPS).
[0035] In the present invention, exemplary styrene block-containing
thermoplastic elastomer may include alloys of olefin and one or two
or more selected from the group consisting of SBS, SIS, SIBS, SEGS,
SEPS and SEEPS, and hydrogenated products thereof. Olefin component
in these alloys is presumed to be responsible for the improvement
of compatibility between the thermoplastic elastomer and the
ionomer resin. Use of this alloy may improve the resilience
performance of the golf ball 2. Preferably, an olefin having 2 to
10 carbon atoms may be used.
[0036] In light of the resilience performance of the golf ball 2,
content of the styrene component in the 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 the 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.
[0037] Specific examples of the styrene block-containing
thermoplastic elastomer include "Rabalon.RTM. T3339C",
"Rabalon.RTM. SJ5400N", "Rabalon.RTM. SJ6400N", "Rabalon.RTM.
SJ7400N", "Rabalon.RTM. SJ8400N", "Rabalon.RTM. SJ9400N" and
"Rabalon.RTM. SR04", trade names by Mitsubishi Chemical
Corporation; "Epofriend.RTM. A1010", a trade name by Daicel
Chemical Industries; and "Septon HG-252", a trade name by Kuraray
Co., Ltd.
[0038] The base polymer of the mid layer 6 comprises an ionomer
resin together with the styrene block-containing thermoplastic
elastomer. Ionomer resins are highly elastic. The ionomer resin is
responsible for the resilience performance of the golf ball 2. In
light of the resilience performance, proportion of the ionomer
resin to total amount of the base polymer is preferably equal to or
greater than 40% by weight, and more preferably equal to or greater
than 50% by weight.
[0039] Examples of preferred ionomer resin include binary
copolymers formed with .alpha.-olefin and an
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 8 carbon
atoms. Examples of the other ionomer resin include ternary
copolymers formed with .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. In the binary copolymer and ternary copolymer,
preferable .alpha.-olefin may be ethylene and propylene, while
preferable .alpha.,.beta.-unsaturated carboxylic acid may be
acrylic acid and methacrylic acid. In the binary copolymer and
ternary copolymer, a part of the carboxyl group may be neutralized
with a metal ion. Illustrative examples of the metal ion 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 kinds of
metal ions. Particularly suitable metal ion in light of the
resilience performance and durability of the golf ball 2 is sodium
ion, zinc ion, lithium ion and magnesium ion.
[0040] Preferable binary copolymer comprises 80% by weight or more
and 90% by weight or less .alpha.-olefin, and 10% by weight or more
and 20% by weight or less .alpha.,.beta.-unsaturated carboxylic
acid. This binary copolymer provides excellent resilience
performance. Preferable ternary copolymer comprises 70% by weight
or more and 85% by weight or less .alpha.-olefin, 5% by weight or
more and 30% by weight or less .alpha.,.beta.-unsaturated
carboxylic acid, and 1% by weight or more and 25% by weight or less
.alpha.,.beta.-unsaturated carboxylate ester. This ternary
copolymer provides excellent resilience performance.
[0041] Particularly preferred ionomer resin is a copolymer formed
with ethylene, and acrylic acid or methacrylic acid. Preferably,
this ionomer resin has a melt index of 3 or greater and 7 or less.
This ionomer resin exhibits superior fluidity. Preferably, this
ionomer resin has a flexural rigidity of 200 MPa or greater and 400
MPa or less. This ionomer resin is highly elastic.
[0042] Specific examples of the ionomer resin include trade names
"Himilan 1555", "Himilan 1557", "Himilan 1605", "Himilan 1706",
"Himilan 1707", "Himilan AM7311", "Himilan AM7315", "Himilan
AM7317", "Himilan AM7318" and "Himilan MK7320", available from Du
Pont-MITSUI POLYCHEMICALS Co., Ltd.; trade names; "Surlyn.RTM.
7930", "Surlyn.RTM. 7940", "Surlyn.RTM. 8140", "Surlyn.RTM. 8940",
"Surlyn.RTM. 8945", "Surlyn.RTM. 9120", "Surlyn.RTM. 9910" and
"Surlyn.RTM. 9945", available from Dupont; and trade names "IOTEK
7010", "IOTEK 7030", "IOTEK 8000" and "IOTEK 8030", available from
EXXON Corporation. Two or more kinds of the ionomer resin may be
used in combination. An ionomer resin neutralized with a monovalent
metal ion, and an ionomer resin neutralized with a bivalent metal
ion may be used in combination.
[0043] Other resin may be also used in the mid layer 6 together
with the styrene block-containing thermoplastic elastomer and the
ionomer resin. Illustrative examples of the other resin include
thermoplastic polyester elastomers, thermoplastic polyamide
elastomers, thermoplastic polyurethane elastomers and thermoplastic
polyolefin elastomers.
[0044] Into the resin composition of the mid layer 6 may be blended
a filler for the purpose of adjusting specific gravity and the
like. Illustrative examples of suitable filler include zinc oxide,
barium sulfate, calcium carbonate and magnesium carbonate. Powder
of a highly dense metal may be also blended as a filler. Specific
examples of the highly dense metal include tungsten and molybdenum.
The amount of the filler to be blended is determined ad libitum so
that intended specific gravity of the mid layer 6 can be
accomplished. Into the mid layer 6 may be also blended a coloring
agent, crosslinked rubber powder or synthetic resin powder.
[0045] It is preferred that the mid layer 6 has a hardness Hm of
equal to or less than 54. The mid layer 6 having a hardness Hm of
equal to or less than 54 may be responsible for soft feel at
impact. In this respect, the hardness Hm may be equal to or less
than 53, more preferably equal to or less than 52, still preferably
equal to or less than 51, and further preferably equal to or less
than 48. In light of the resilience performance of the golf ball 2,
the hardness Hm is preferably equal to or greater than 30, more
preferably equal to or greater than 33, still more preferably equal
to or greater than 34, and further preferably equal to or greater
than 37.
[0046] In the present invention, the hardness Hm of the mid layer 6
and the hardness Hc of the cover 10 may be measured in accordance
with a standard of "ASTM-D 2240-68". For the measurement, an
automated rubber hardness scale (trade name "P1", available from
Koubunshi Keiki Co., Ltd.) which is equipped with a Shore D type
spring hardness scale is used. For the measurement, a sheet which
was formed by hot press is used having a thickness of about 2 mm
and consisting of the same material as the mid layer 6 (or the
cover 10). Prior to the measurement, the sheet is stored at a
temperature of 23.degree. C. for two weeks. When the measurement is
carried out, three sheets are overlaid.
[0047] The mid layer 6 has a thickness Tm of preferably 0.5 mm or
greater and 1.6 mm or less. The mid layer 6 having the thickness Tm
of equal to or greater than 0.5 mm may be responsible for soft feel
at impact. In this respect, the thickness Tm is more preferably
equal to or greater than 0.6 mm. By setting the thickness Tm to be
equal to or less than 1.6 mm, adverse effects of the mid layer 6 on
the resilience performance can be suppressed. In this respect, the
thickness Tm is more preferably equal to or less than 1.5 mm, and
particularly preferably equal to or less than 1.2 mm.
[0048] The surface of the mid layer 6 may be subjected to a
treatment such as brushing, grinding or the like. This treatment
can increase the roughness of the surface. Great roughness improves
adhesion between the mid layer 6 and the reinforcing layer 8 or the
cover 10.
[0049] The reinforcing layer 8 lies between the mid layer 6 and the
cover 10. The reinforcing layer 8 adheres firmly to the mid layer
6, and adheres firmly also to the cover 10. As described above,
this golf ball 2 has a thin mid layer 6. As described later, this
golf ball 2 has an extremely thin cover 10. Because the cover 10
adheres firmly to the mid layer 6 via the reinforcing layer 8, the
mid layer 6 and the cover 10 are not easily broken irrespective of
the mid layer 6 and the cover 10 being thin. This golf ball 2 is
excellent in durability. In other words, the presence of the
reinforcing layer 8 permits to provide the thin mid layer 6 and
thin cover 10.
[0050] Preferably, base polymer of the reinforcing layer 8 is a
reaction product between carboxyl group-containing polyurethane and
polycarbodiimide. This reinforcing layer 8 has a three-dimensional
structure, and is excellent in the strength. Moreover, this
reinforcing layer 8 is excellent in adhesiveness to the mid layer 6
and adhesiveness to the cover 10.
[0051] The reinforcing layer 8 preferably comprises a water-based
adhesive. The water-based adhesive is excellent in workability, and
does not adversely affect the environment. In particular, it is
preferably a reaction product between water-based carboxyl
group-containing polyurethane and water-based polycarbodiimide. A
liquid obtained by mixing an aqueous solution or a water dispersion
liquid of carboxyl group-containing polyurethane with an aqueous
solution or a water dispersion liquid of polycarbodiimide is
applied on the mid layer 6 to obtain the reinforcing layer 8
through a reaction of the carboxyl group-containing polyurethane
with the polycarbodiimide.
[0052] Anionic or nonionic carboxyl group-containing polyurethane
liquid can be used. In the anionic carboxyl group-containing
polyurethane liquid, the polyurethane is dissolved or dispersed in
water through neutralization of the carboxyl group with a base. In
the nonionic carboxyl group-containing polyurethane liquid, the
polyurethane is dispersed forcedly in water with a high shearing
force in the presence of a nonionic emulsifying agent.
[0053] Polyisocyanate component in the carboxyl group-containing
polyurethane has multiple isocyanate groups. Specific examples of
the polyisocyanate include aromatic polyisocyanates such as
2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of
2,4-toluene diisocyanate and 2,6-toluene diisocyanate (TDI),
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),
hexamethylene diisocyanate (HDI) and isophorone diisocyanate
(IPDI); and aliphatic polyisocyanates. Two or more polyisocyanates
may be used in combination. In light of the weather resistance,
TMXDI, XDI, HDI, H.sub.6XDI, IPDI and H.sub.12MDI are
preferred.
[0054] Polyol component in the carboxyl group-containing
polyurethane has multiple hydroxyl groups. A low molecular weight
polyol having a molecular weight of less than 500 and a high
molecular weight polyol having a molecular weight of equal to or
greater than 500 can be used. Examples of the low molecular weight
polyol include diol and triol. Specific examples of the diol
include ethylene glycol, diethylene glycol, triethylene glycol,
1,3-butanediol, 1,4-butanediol, neopentyl glycol and
1,6-hexanediol. Specific examples of the triol include glycerin,
trimethylolpropane and hexanetriol. Examples of the high molecular
weight polyol 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 based polyester polyols
such as poly-.epsilon.-caprolactone (PCL); polycarbonate polyols
such as polyhexamethylene carbonate; and acrylic polyols. Two or
more kinds of polyols may be used in combination. Polyols having a
weight average molecular weight of 50 or greater and 2000 or less,
particularly 100 or greater and 1000 or less are particularly
preferred.
[0055] The carboxyl group-containing polyurethane may contain a
polyamine component. Examples of the polyamine component include
aliphatic polyamines such as ethylenediamine, propylenediamine and
hexamethylenediamine; aromatic polyamines such as tolylenediamine,
xylylenediamine and diaminodiphenylmethane; alicyclic polyamines
such as diaminocyclohexylmethane, piperazine and isophoronediamine;
and hydrazines such as hydrazine, succinic acid dihydrazide, adipic
acid dihydrazide and phthalic acid dihydrazide. Alkanolamines such
as diethanolamine and monoethanolamine may be used.
[0056] The water-based polycarbodiimide has two or more
carbodiimide groups within the molecule, and is thus soluble or
dispersible in water. Suitably, a polycarbodiimide resin having a
structure represented by the following formula (I) may be used.
S1-K-(R--N.dbd.C.dbd.N).sub.n--R-K-S2 (I)
[0057] In the above formula (I), S1 and S2 represent a hydrophilic
segment; R represents a residue yielded by excluding the isocyanate
group from diisocyanate; K represents a bond formed by a reaction
of the isocyanate group with the hydrophilic segment; and n
represents an average degree of polymerization. The symbol n
represents an integer of 2 or greater and 100 or less. Illustrative
examples of the hydrophilic segment include nonionic segments
having an ethyleneoxide chain; anionic segments having a sulfonate
salt, a sulfate salt or the like; and cationic segments having a
quaternary ammonium salt. Specific examples of the polycarbodiimide
resin represented by the above formula (I) include
tetramethylxylylenecarbodiimide and
dicyclohexylmethanecarbodiimide.
[0058] Carbodiimide equivalent in the water-based polycarbodiimide
is preferably 100 or greater and 500 or less. By setting the
carbodiimide equivalent to be equal to or greater than 100, the
reinforcing layer 8 having great crosslinking density is obtained.
This reinforcing layer 8 is responsible for adhesion between the
mid layer 6 and the cover 10. In this respect, the carbodiimide
equivalent is more preferably equal to or greater than 150, and
particularly preferably equal to or greater than 250. By using the
polycarbodiimide having the carbodiimide equivalent of equal to or
less than 500, the reaction with the carboxyl group-containing
polyurethane can be completed in a short period of time. In this
respect, the carbodiimide equivalent is more preferably equal to or
less than 450, and particularly preferably equal to or less than
400. The carbodiimide equivalent refers to the chemical formula
weight of polycarbodiimide per mol of the carbodiimide group.
[0059] Solid content of the polycarbodiimide in the aqueous
solution or the water dispersion liquid is preferably equal to or
greater than 20% by weight, and more preferably equal to or greater
than 30% by weight. The solid content is preferably equal to or
less than 80% by weight, and more preferably equal to or less than
70% by weight. Illustrative examples of preferable aqueous solution
of polycarbodiimide include trade names of "Carbodilite.RTM. E-01",
"Carbodilite.RTM. E-02" and "Carbodilite.RTM. E-03A", available
from Nisshin Spinning Co., Ltd.
[0060] Amount of the polycarbodiimide to be blended is preferably
parts by weight or greater and 25 parts by weight or less per 100
parts by weight of the carboxyl group-containing polyurethane. By
setting the amount to be equal to or greater than 5 parts by
weight, a reinforcing layer 8 having great crosslinking density may
be obtained. This reinforcing layer 8 is responsible for adhesion
between the mid layer 6 and the cover 10. In this respect, the
amount is more preferably equal to or greater than 6 parts by
weight, and particularly preferably equal to or greater than 7
parts by weight. By setting the amount to be equal to or less than
25 parts by weight, the reaction with the carboxyl group-containing
polyurethane can be completed in a short period of time. In this
respect, the amount is more preferably equal to or less than 23
parts by weight, and particularly preferably equal to or less than
20 parts by weight.
[0061] The reinforcing layer 8 may comprise an oil-based adhesive.
As the base polymer of this reinforcing layer 8, a two-component
cured thermosetting resin may be typically used. Specific examples
of the two-component cured thermosetting resin include epoxy
resins, urethane resins, acrylic resins, polyester based resins and
cellulose based resins. In light of the mechanical characteristics
(e.g., strength at break) and durability of the reinforcing layer
8, two-component cured epoxy resins and two-component cured
urethane resins are preferred.
[0062] The two-component cured epoxy resin is obtained by curing an
epoxy resin with a polyamide based curing agent. Illustrative
examples of the epoxy resin for use in the two-component cured
epoxy resin include bisphenol A type epoxy resins, bisphenol F type
epoxy resins and bisphenol AD type epoxy resins. The bisphenol A
type epoxy resin is obtained by a reaction of bisphenol A with an
epoxy group-containing compound such as epichlorohydrin. The
bisphenol F type epoxy resin is obtained by a reaction of bisphenol
F with an epoxy group-containing compound. The bisphenol AD type
epoxy resin is obtained by a reaction of bisphenol AD with an epoxy
group-containing compound. In light of the balance among softness,
chemical resistance, heat resistance and toughness, the bisphenol A
type epoxy resins are preferred.
[0063] The polyamide based curing agent has multiple amino groups
and one or more amide groups. This amino group can react with an
epoxy group. Specific examples of the polyamide based curing agent
include polyamide amine curing agents and modified products of the
same. The polyamide amine curing agent is obtained by a
condensation reaction of a polymerized fatty acid with a polyamine.
Typical polymerized fatty acid may be obtained by heating naturally
occurring fatty acids containing large amounts of unsaturated fatty
acids such as linoleic acid, linolenic acid and the like in the
presence of a catalyst to perfect the synthesis. Specific examples
of the unsaturated fatty acid include tall oil, soybean oil,
linseed oil and fish oil. Polymerized fatty acids having a dimer
content of equal to or greater than 90% by weight and a trimer
content of equal to or less than 10% by weight, and being
hydrogenated are preferred. Illustrative examples of preferred
polyamine include polyethylenediamine, polyoxyalkylenediamine and
derivatives thereof.
[0064] Upon mixing of the epoxy resin and the polyamide based
curing agent, ratio of epoxy equivalent of the epoxy resin and
amine active hydrogen equivalent of the polyamide based curing
agent is preferably 1.0/1.4 or greater and 1.0/1.0 or less.
[0065] The two-component cured urethane resin is obtained by a
reaction of a base material and a curing agent. A two-component
cured urethane resin obtained by a reaction of a base material
containing a polyol component with a curing agent containing
polyisocyanate or a derivative thereof, or a two-component cured
urethane resin obtained by a reaction of a base material containing
isocyanate group-ended urethane prepolymer with a curing agent
having an active hydrogen may be used. In particular, two-component
cured urethane resins obtained by a reaction of a base material
containing a polyol component with a curing agent containing
polyisocyanate or a derivative thereof are preferred.
[0066] It is preferred that an urethane polyol is used as the
polyol component of the base material. The urethane polyol has
urethane bonds and two or more hydroxyl groups. Preferably, the
urethane polyol has a hydroxyl group at its end. The urethane
polyol may be obtained by allowing a polyol and a polyisocyanate to
react at a ratio such that an excessive molar ratio of the hydroxyl
group of the polyol component to the isocyanate group of
polyisocyanate is attained.
[0067] The polyol for use in production of the urethane polyol has
multiple hydroxyl groups. Polyol having a weight average molecular
weight of 50 or greater and 2000 or less, and particularly 100 or
greater and 1000 or less is preferred. Examples of the polyol
having a low molecular weight include diol and triol. Specific
examples of the diol include ethylene glycol, diethylene glycol,
triethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl
glycol and 1,6-hexanediol. Specific examples of the triol include
trimethylolpropane and hexanetriol. Examples of the polyol having a
high molecular weight 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 based polyester polyols
such as poly-.epsilon.-caprolactone (PCL); polycarbonate polyols
such as polyhexamethylene carbonate; and acrylic polyols. Two or
more kinds of polyols may be used in combination.
[0068] Polyisocyanate for use in production of the urethane polyol
has multiple isocyanate groups. Specific examples of the
polyisocyanate include aromatic polyisocyanates such as 2,4-toluene
diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4-toluene
diisocyanate and 2,6-toluene diisocyanate (TDI),
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),
hexamethylene diisocyanate (HDI) and isophorone diisocyanate
(IPDI); and aliphatic polyisocyanates. Two or more polyisocyanates
may be used in combination. In light of the weather resistance,
TMXDI, XDI, HDI, H.sub.6XDI, IPDI and H.sub.12MDI are
preferred.
[0069] In the reaction of the polyol with the polyisocyanate for
producing the urethane polyol, any known catalyst may be used.
Typical catalyst may be dibutyltin dilaurate.
[0070] In light of strength of the reinforcing layer 8, proportion
of urethane bonds included in the urethane polyol is preferably
equal to or greater than 0.1 mmol/g. In light of the following
capability of the reinforcing layer 8 to the cover 10, the
proportion of urethane bonds included in the urethane polyol is
preferably equal to or less than 5 mmol/g. The proportion of
urethane bonds may be adjusted by regulating the molecular weight
of the polyol to be a raw material, and by regulating compounding
ratio of the polyol and the polyisocyanate.
[0071] In light of a short time period required for the reaction of
the base material with the curing agent, the urethane polyol has a
weight average molecular weight of preferably equal to or greater
than 4000, and more preferably equal to or greater than 4500. In
light of adhesiveness of the reinforcing layer 8, the urethane
polyol has a weight average molecular weight of preferably equal to
or less than 10000, and more preferably equal to or less than
9000.
[0072] In light of adhesiveness of the reinforcing layer 8, the
urethane polyol has a hydroxyl value (mgKOH/g) of preferably equal
to or greater than 15, and more preferably equal to or greater than
73. In light of a short time period required for the reaction of
the base material with the curing agent, the urethane polyol has a
hydroxyl value of preferably equal to or less than 130, and more
preferably equal to or less than 120.
[0073] The base material may contain, in addition to the urethane
polyol, a polyol not having any urethane bond. The aforementioned
polyol that may be a raw material of the urethane polyol can be
used in the base material. Polyols that are compatible with the
urethane polyol are preferred. In light of a short time period
required for the reaction of the base material with the curing
agent, proportion of the urethane polyol in the base material is
preferably equal to or greater than 50% by weight, and more
preferably equal to or greater than 80% by weight based on the
solid content. Ideally, this proportion is 100% by weight.
[0074] The curing agent contains polyisocyanate or a derivative
thereof. The aforementioned polyisocyanate that is a raw material
of the urethane polyol may be used as the curing agent.
[0075] The reinforcing layer 8 comprises the two-component cured
thermosetting resin is obtained by applying a liquid prepared by
dissolving or dispersing the base material and the curing agent in
a solvent on the surface of the mid layer 6. In light of the
workability, application with a spray gun is preferred. Following
the application, the solvent is volatilized to permit a reaction of
the base material with the curing agent thereby forming the
reinforcing layer 8. Illustrative examples of preferred solvent
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.
[0076] In light of the durability of the golf ball 2, the
reinforcing layer 8 has a thickness of preferably equal to or
greater than 0.003 mm, and more preferably equal to or greater than
0.005 mm. In light of easy formation of the reinforcing layer 8, it
is preferred that the thickness is equal to or less than 0.30 mm,
still more, equal to or less than 0.10 mm, yet more, equal to or
less than 0.05 mm, and furthermore, equal to or less than 0.02 mm.
The thickness is measured by observation of the cross section of
the golf ball 2 with a micro scope. When the surface of the mid
layer 6 has roughness resulting from the surface roughening
treatment, the thickness is measured immediately above the
protruded portion.
[0077] Principal component of the base polymer of the cover 10 is
an ionomer resin. The aforementioned binary copolymer ionomer resin
and the ternary copolymer ionomer resin can be used in the cover
10. The ionomer resin is highly elastic. By using the ionomer resin
in the cover 10, a golf ball 2 that is excellent in resilience
performance is obtained.
[0078] As described above, the mid layer 6 comprises a styrene
block-containing thermoplastic elastomer. When this mid layer 6 and
the cover 10 comprising the ionomer resin are directly attached,
adhesiveness therebetween may become insufficient. In the present
golf ball 2, the reinforcing layer 8 lies between the mid layer 6
and the cover 10, therefore, firm adhesion between the mid layer 6
and the cover 10 is permitted via this reinforcing layer 8.
[0079] Other resin may be used in the cover 10 together with the
ionomer resin. Examples of the other resin include styrene
block-containing thermoplastic elastomers, thermoplastic
polyurethane elastomers, thermoplastic polyester elastomers,
thermoplastic polyamide elastomers and thermoplastic polyolefin
elastomers. When the other resin is used in combination with the
ionomer resin, proportion of the ionomer resin in total amount of
the base polymer is preferably equal to or greater than 50% by
weight, and more preferably equal to or greater than 70% by weight,
and particularly preferably equal to or greater than 90% by
weight.
[0080] Into the cover 10 may be blended a coloring agent such as
titanium dioxide, a filler such as barium sulfate, a dispersant, an
antioxidant, an ultraviolet absorbent, a light stabilizer, a
fluorescent agent, a fluorescent brightening agent and the like in
an appropriate amount as needed. Powder of a highly dense metal
such as tungsten, molybdenum or the like may be also blended into
the cover 10 for the purpose of adjusting the specific gravity.
[0081] The cover 10 has a hardness Hc of equal to or greater than
55. The cover 10 having a hardness Hc of equal to or greater than
55 is responsible for the resilience performance. In this respect,
the hardness Hc is preferably equal to or greater than 56, more
preferably equal to or greater than 57, and still more preferably
equal to or greater than 58. In light of soft feel at impact, the
hardness Hc is preferably equal to or less than 65, more preferably
equal to or less than 64, and still more preferably equal to or
less than 63.
[0082] The cover 10 has a thickness Tc of equal to or less than 1.2
mm. This cover 10 is extremely thin. By employing such a thin cover
10, a great launch angle can be accomplished upon impact with a
golf club. The great launch angle is responsible for great flight
distance. Moreover, by employing a thin cover 10, adverse effects
of the cover 10 on the feel at impact can be suppressed. In this
respect, the thickness Tc is preferably equal to or less than 1.0
mm, more preferably equal to or less than 0.9 mm, still more
preferably equal to or less than 0.8 mm, and even more preferably
equal to or less than 0.5 mm. Although the thin cover 10 is apt to
be broken upon repeated impacts, the reinforcing layer 8 suppresses
the breakage in this golf ball 2. This golf ball 2 is excellent in
the flight performance, feel at impact and durability. In light of
ease of production, the cover 10 has a thickness Tc of equal to or
greater than 0.1 mm, and more preferably equal to or greater than
0.3 mm. The thickness Tc is measured immediately below the land 14
where no dimple 12 exists.
[0083] The cover 10 has a weight Wc of equal to or less than 5.7 g.
By setting the weight Wc to be equal to or less than 5.7 g, a great
launch angle can be provided. The great launch angle is responsible
for great flight distance. Furthermore, by setting the weight Wc to
be equal to or less than 5.7 g, adverse effect on the feel at
impact exerted by the cover 10 may be suppressed. In this respect,
the weight Wc is more preferably equal to or less than 5.3 g, and
particularly preferably equal to or less than 4.8 g. In light of
ease of production, the cover 10 has a weight Wc of preferably
equal to or greater than 1.5 g, more preferably equal to or greater
than 1.7 g, and particularly preferably equal to or greater than
1.9 g.
[0084] Ratio (Wc/Hc) of the weight Wc to the hardness Hc in the
cover 10 is equal to or less than 0.080. By setting the ratio
(Wc/Hc) to be equal to or less than 0.080, great launch angle and
great resilience coefficient can be both achieved simultaneously.
In this respect, the ration (Wc/Hc) is more preferably equal to or
less than 0.078, and particularly preferably equal to or less than
0.075. The ratio (Wc/Hc) is preferably equal to or greater than
0.030. By setting the ratio (Wc/Hc) to be equal to or greater than
0.030, productivity and feel at impact can be both achieved
simultaneously. The ratio (Wc/Hc) is an index that represents the
degree of contribution of the cover 10 to the launch angle,
resilience coefficient, productivity and feel at impact of the golf
ball 2.
[0085] Amount of compressive deformation of the golf ball 2 is
preferably 2.0 mm or greater and 4.5 mm or less. The golf ball 2
having the amount of compressive deformation of equal to or greater
than 2.0 mm is excellent in the feel at impact. In this respect,
the amount of compressive deformation is more preferably equal to
or greater than 2.2 mm, and particularly preferably equal to or
greater than 2.3 mm. The golf ball 2 having the amount of
compressive deformation of equal to or less than 4.5 mm is
excellent in the resilience performance. In this respect, the
amount of compressive deformation is more preferably equal to or
less than 4.3 mm, and particularly preferably equal to or less than
4.0 mm. The amount of compressive deformation of the golf ball 2 is
measured in accordance with the method for measuring the amount of
compressive deformation of the core 4 as described above.
EXAMPLES
Experiment 1
Example 1
[0086] A type x rubber composition was obtained by kneading 100
parts by weight of high cis-polybutadiene (trade name "BR-730",
available from JSR Corporation), 25 parts by weight of zinc
acrylate, 10 parts of zinc oxide, an adequate amount of barium
sulfate, 0.5 part by weight of diphenyl disulfide (manufactured by
Sumitomo Seika Chemicals Co., Ltd.) and 0.8 part by weight of
dicumyl peroxide (manufactured by NOF Corporation). This rubber
composition was placed into a mold having upper and lower mold half
each having a hemispherical cavity, and heated at 170.degree. C.
for 20 minutes to obtain a core having a diameter of 39.2 mm.
[0087] In a biaxial extruder having a screw diameter of 45 mm,
which provides a rotational velocity of the screw being 200 rpm,
and having L/D of 35, a type b resin composition shown in Table 1
below was obtained. Temperature in the die during extrusion of the
resin composition was from 180.degree. C. to 230.degree. C. The
core was covered by this resin composition therearound with
injection molding to obtain a mid layer. This mid layer had a
thickness Tm of 1.0 mm, and a hardness Hm of 42.
[0088] An aqueous solution of carboxyl group-containing
polyurethane (trade name "W-615", available from Mitsui Takeda
Chemicals, Inc.) in an amount of 100 parts by weight was mixed with
10 parts by weight of a water dispersion liquid of polycarbodiimide
(trade name "Carbodilite.RTM. E-03A", supra). This aqueous solution
of carboxyl group-containing polyurethane had an acid value of 9 mg
KOH/g, and a solid content of 35% by weight. This water dispersion
liquid of polycarbodiimide had a carbodiimide equivalent of 365,
and a solid content of 40% by weight. This mixture was applied on
the mid layer by a spray gun to obtain a reinforcing layer having a
thickness of 0.008 mm.
[0089] A type e resin composition shown in Table 2 below was
obtained in the aforementioned biaxial extruder. Half shell was
obtained from this resin composition with compression molding. The
spherical body composed of the core, the mid layer and the
reinforcing layer was covered by two pieces of the half shell, and
placed into a mold having upper and lower mold half each having a
hemispherical cavity to obtain a cover by compression molding. The
cover had a thickness Tc of 0.8 mm. A paint layer was formed around
this cover to give a golf ball of Example 1. This golf ball had a
diameter of 42.8 mm.
Examples 3 to 4
[0090] In a similar manner to Example 1 except that the diameter of
the core and the thickness of the mid layer were as listed in Table
3 below, golf balls of Examples 3 to 4 were obtained.
Examples 2, 5 and 6, and Comparative Example 1
[0091] In a similar manner to Example 1 except that the type of the
resin composition of the mid layer was as listed in Table 3 below,
golf balls of Examples 2, 5 and 6, and Comparative Example 1 were
obtained. Details of the resin composition are shown in Table 2
below.
Comparative Example 2
[0092] In a similar manner to Example 1 except that the type of the
resin composition of the cover was as listed in Table 4 below, golf
ball of Comparative Example 2 was obtained. Details of the resin
composition are shown in Table 2 below.
Examples 7 to 8 and Comparative Example 3
[0093] In a similar manner to Example 1 except that the diameter of
the core and the thickness of the cover were as listed in Table 4
below, golf balls of Examples 7 to 8 were obtained. In a similar
manner to Example 1 except that the type of the rubber composition
and the diameter of the core, and the thickness of the cover were
as listed in Table 4 below, golf ball of Comparative Example 3 was
obtained. Details of the rubber composition are shown in Table 1
below.
Example 9
[0094] In a similar manner to Example 1 except that a coating
composition comprising a two-component cured epoxy resin as the
base polymer (trade name "POLIN 750LE", available from Shinto Paint
Co., Ltd.) was used for forming the reinforcing layer, golf ball of
Example 9 was obtained. This coating composition was prepared by
mixing 100 parts by weight of the base material with 100 parts by
weight of the curing agent. This base material contains a 30% by
weight bisphenol A type epoxy resin and a 70% by weight solvent.
This curing agent contains 40% by weight modified polyamide amine,
5% by weight titanium dioxide, and a 55% by weight solvent.
Comparative Example 4
[0095] In a similar manner to Example 1 except that the reinforcing
layer was not provided, golf ball of Comparative Example 4 was
obtained.
Examples 10 to 11
[0096] In a similar manner to Example 1 except that specifications
of the core, the mid layer and the cover were as listed in Table 4
below, golf balls of Examples 10 to 11 were obtained.
[0097] [Measurement of Amount of Compressive Deformation]
[0098] In a similar manner to the measurement of the amount of
compressive deformation of the core described above, amount of
compressive deformation of the golf ball was measured. The results
are shown in Table 3 and Table 4 below.
[0099] [Evaluation of Durability]
[0100] A driver with a metal head was attached to a swing machine
available from True Temper Co. Then the machine condition was set
to give the head speed of 45 m/sec, and the golf balls were hit
therewith to allow for impact on a plate for impact. Accordingly,
the number of times of the hitting until the golf ball was broken
was counted. Mean values of the measurement of six golf balls were
determined. The results are shown in Table 3 and Table 4 below in
terms of indices on the basis of the value in Comparative Example 4
being presumed as 100.
[0101] [Measurement of Flight Distance]
[0102] A driver with a metal head was attached to the swing machine
described above. Then the machine condition was set to give the
head speed of 45 m/sec, and the golf balls were hit therewith.
Accordingly, the distance from the launching point to the point
where the ball stopped was measured. Mean values of 10 times
measurement are shown in Table 3 and Table 4 below.
[0103] [Evaluation of Feel at Impact]
[0104] Using a driver, the golf balls were hit by a golf player,
and the feel at impact was rated among the following four ranks of
from "A" to "D".
[0105] A: extremely favorable
[0106] B: favorable
[0107] C: somewhat unfavorable
[0108] D: unfavorable.
The results are presented in Table 3 and Table 4 below.
TABLE-US-00001 TABLE 1 Rubber composition of core (part by weight)
Type x y BR-730 100 100 Zinc acrylate 25 24 Zinc oxide 10 10 Barium
sulfate adequate amount adequate amount Diphenyl disulfide 0.5 0.5
Dicumyl peroxide 0.8 0.8
TABLE-US-00002 TABLE 2 Resin compositions of mid layer and cover
(part by weight) Type a b c d e f g Surlyn 8945 20 26 37 40 45 50
-- Surlyn 9945 20 26 37 40 45 50 -- Rabalon SR04 60 48 26 20 10 --
-- Elastollan XNY97A* -- -- -- -- -- -- 100 Titanium dioxide 4.0
4.0 4.0 4.0 4.0 4.0 4.0 Ultra Marine Blue 0.1 0.1 0.1 0.1 0.1 0.1
0.1 Hardness (Shore D) 30 42 53 56 60 63 42 *Thermoplastic
polyurethane elastomer, available from BASF Co., Ltd.
TABLE-US-00003 TABLE 3 Results of evaluation Compara. Example 2
Example 3 Example 1 Example 4 Example 5 Example 6 Example 1 Core
Type x x x x x x x Diameter (mm) 39.2 39.8 39.2 38.8 39.2 39.2 39.2
Mid Type a b b b g c d layer Hardness Hm 30 42 42 42 42 53 56
(Shore D) Thickness Tm (mm) 1.0 0.7 1.0 1.2 1.0 1.0 1.0 Reinforcing
Base Polymer water- water- water- water- water- water- water- layer
based based based based based based based urethane urethane
urethane urethane urethane urethane urethane Cover Type e e e e e e
e Hardness Hc 60 60 60 60 60 60 60 (Shore D) Thickness Tc (mm) 0.8
0.8 0.8 0.8 0.8 0.8 0.8 Weight Wc (g) 4.0 4.0 4.0 4.0 4.0 4.0 4.0
Wc/Hc 0.067 0.067 0.067 0.067 0.067 0.067 0.067 Amount of
compressive 3.6 3.4 3.5 3.6 3.5 3.5 3.3 deformation (mm) of ball
Durability 140 143 143 144 134 144 144 Travel distance (m) 252 259
257 256 252 256 255 Feel at impact A A A A B B C
TABLE-US-00004 TABLE 4 Results of evaluation Compara. Compara.
Compara. Example Example Example 2 Example 7 Example 8 Example 3
Example 9 Example 4 10 11 Core Type x x x y x x x x Diameter (mm)
39.2 39.8 38.8 38.0 39.2 39.2 38.8 40.4 Mid Type b b b b b b b b
layer Hardness Hm 42 42 42 42 42 42 42 42 (Shore D) Thickness Tm
(mm) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 0.7 Reinforcing Base polymer
water- water- water- water- epoxy -- water- water- layer based
based based based based based urethane urethane urethane urethane
urethane urethane Cover Type c e e e e e f e Hardness Hc 53 60 60
60 60 60 63 60 (Shore D) Thickness Tc (mm) 0.8 0.5 1.0 1.4 0.8 0.8
1.0 0.5 Weight Wc (g) 4.0 2.5 4.7 6.3 4.0 4.0 4.7 2.5 Wc/Hc 0.075
0.042 0.075 0.105 0.067 0.067 0.075 0.042 Amount of compressive 3.6
3.6 3.5 3.4 3.5 3.5 3.4 3.7 deformation (mm) of ball Durability 145
142 142 142 142 100 142 130 Travel distance (m) 240 259 256 242 257
248 256 260 Feel at impact B A A B A A A A
[0109] As is clear from Table 3 and Table 4, the golf balls of
Examples are excellent in all terms of the durability, flight
performance and feel at impact. Therefore, advantages of the
present invention are clearly suggested by these results of
evaluation.
Experiment 2
Example 12
[0110] A type x rubber composition shown in Table 1 above was
obtained by kneading 100 parts by weight of high cis-polybutadiene
(trade name "BR-730", available from JSR Corporation), 25 parts by
weight of zinc acrylate, 10 parts of zinc oxide, an adequate amount
of barium sulfate, 0.5 part by weight of diphenyl disulfide and 0.8
part by weight of dicumyl peroxide. This rubber composition was
placed into a mold having upper and lower mold half each having a
hemispherical cavity, and heated at 170.degree. C. for 20 minutes
to obtain a core having a diameter of 38.8 mm.
[0111] In a biaxial extruder having a screw diameter of 45 mm,
which provides a rotational velocity of the screw being 200 rpm,
and having L/D of 35, a type B resin composition shown in Table 5
below was obtained. Temperature in the die during extrusion of the
resin composition was from 180.degree. C. to 230.degree. C. The
core was covered by this resin composition therearound with
injection molding to obtain a mid layer. This mid layer had a
thickness Tm of 1.2 mm, and a hardness Hm of 42.
[0112] An aqueous solution of carboxyl group-containing
polyurethane (trade name "W-615", available from Mitsui Takeda
Chemicals, Inc.) in an amount of 100 parts by weight was mixed with
10 parts by weight of a water dispersion liquid of polycarbodiimide
(trade name "Carbodilite.RTM. E-03A", supra). This aqueous solution
of carboxyl group-containing polyurethane had an acid value of 9 mg
KOH/g, and a solid content of 35% by weight. This water dispersion
liquid of polycarbodiimide had a carbodiimide equivalent of 365,
and a solid content of 40% by weight. This mixture was applied on
the mid layer by a spray gun to obtain a reinforcing layer having a
thickness of 0.008 mm.
[0113] A type F resin composition shown in Table 5 below was
obtained in the aforementioned biaxial extruder. Half shell was
obtained from this resin composition with compression molding. The
spherical body composed of the core, the mid layer and the
reinforcing layer was covered by two pieces of the half shell, and
placed into a mold having upper and lower mold half each having a
hemispherical cavity to obtain a cover by compression molding. The
cover had a thickness Tc of 0.8 mm. A paint layer was formed around
this cover to give a golf ball of Example 12. This golf ball had a
diameter of 42.8 mm.
Examples 14 to 15 and Comparative Example 5
[0114] In a similar manner to Example 12 except that the diameter
of the core and the thickness of the cover were as listed in Table
6 below, golf balls of Examples 14 to 15 and Comparative Example 5
were obtained.
Example 13 and Comparative Example 6
[0115] In a similar manner to Example 12 except that the diameter
of the core and the thickness of the mid layer were as listed in
Table 6 below, golf ball of Example 13 was obtained. In a similar
manner to Example 12 except that a type y rubber composition was
used for the core, and that the diameter of the core and the
thickness of the mid layer were as listed in Table 6 below, golf
ball of Comparative Example 6 was obtained. Details of the type y
rubber composition are shown in Table 1 above.
Comparative Example 7
[0116] In a similar manner to Example 1 except that the type of the
resin composition of the cover was as listed in Table 7 below, golf
ball of Comparative Example 7 was obtained. Details of the resin
composition are shown in Table 5 below.
Examples 16 to 18
[0117] In a similar manner to Example 12 except that the type of
the resin composition of the mid layer was as listed in Table 7
below, golf balls of Examples 16 to 18 were obtained. Details of
the resin composition are shown in Table 5 below.
Example 19
[0118] In a similar manner to Example 1 except that a coating
composition comprising a two-component cured epoxy resin as the
base polymer (trade name "POLIN 750LE", available from Shinto Paint
Co., Ltd.) was used for forming the reinforcing layer, golf ball of
Example 19 was obtained. This coating composition was prepared by
mixing 100 parts by weight of the base material with 100 parts by
weight of the curing agent. This base material contains a 30% by
weight bisphenol A type epoxy resin and a 70% by weight solvent.
This curing agent contains 40% by weight modified polyamide amine,
5% by weight titanium dioxide, and a 55% by weight solvent.
Comparative Example 8
[0119] In a similar manner to Example 12 except that the
reinforcing layer was not provided, golf ball of Comparative
Example 16 was obtained.
[0120] [Evaluation]
[0121] Similarly to the aforementioned Experiment 1, the amount of
compressive deformation, the durability, the flight distance and
the feel at impact of the golf balls were evaluated. The results
are presented in Table 6 and Table 7 below. In connection with the
durability, indices on the basis of the value in Comparative
Example 8 being presumed as 100 are presented in Table 6 and Table
7 below.
TABLE-US-00005 TABLE 5 Specifications of mid layer and cover (part
by weight) Type A B C D E F Surlyn 8945 18 26 33 35 40 45 Surlyn
9945 18 26 33 35 40 45 Rabalon SR04 64 48 34 30 20 10 Titanium
dioxide 4.0 4.0 4.0 4.0 4.0 4.0 Ultra Marine Blue 0.1 0.1 0.1 0.1
0.1 0.1 Hardness (Shore D) 28 42 48 50 56 60
TABLE-US-00006 TABLE 6 Results of evaluation Example Example
Example Example Compara. Compara. 13 14 12 15 Example 5 Example 6
Core Type x x x x x y Diameter (mm) 39.8 39.4 38.8 38.4 38.0 37.4
Mid Type B B B B B B layer Hardness (Shore D) 42 42 42 42 42 42
Thickness (mm) 0.7 1.2 1.2 1.2 1.2 1.9 Reinforcing Base Polymer
water- water- water- water- water- water- layer based based based
based based based urethane urethane urethane urethane urethane
urethane Cover Type F F F F F F Hardness (Shore D) 60 60 60 60 60
60 Thickness (mm) 0.8 0.5 0.8 1.0 1.2 0.8 Amount of compressive 3.3
3.4 3.4 3.4 3.3 3.3 deformation (mm) of ball Durability 133 135 138
140 139 138 Travel distance (m) 257 258 256 253 246 245 Feel at
impact A A A A C B
TABLE-US-00007 TABLE 7 Results of evaluation Compara. Example
Example Example Example Compara. Example 7 16 17 18 19 Example 8
Core Type x x x x x x Diameter (mm) 38.8 38.8 38.8 38.8 38.8 38.8
Mid Type B A C E B B layer Hardness (Shore D) 42 28 48 56 42 42
Thickness (mm) 1.2 1.2 1.2 1.2 1.2 1.2 Reinforcing Base Polymer
water- water- water- water- epoxy -- layer based based based based
urethane urethane urethane urethane Cover Type D F F F F F Hardness
(Shore D) 50 60 60 60 60 60 Thickness (mm) 0.8 0.8 0.8 0.8 0.8 0.8
Amount of compressive 3.5 3.6 3.3 3.2 3.4 3.4 deformation (mm) of
ball Durability 140 133 140 143 132 100 Travel distance (m) 240 249
254 253 254 247 Feel at impact B B B B A A
[0122] As is clear from Table 6 and Table 7, the golf balls of
Examples are excellent in all terms of the durability, flight
performance and feel at impact. Therefore, advantages of the
present invention are clearly suggested by these results of
evaluation.
[0123] The foregoing description is just for illustrative examples,
therefore, various modifications can be made in the scope without
departing from the principles of the present invention.
* * * * *