U.S. patent application number 13/461174 was filed with the patent office on 2013-11-07 for golf ball.
This patent application is currently assigned to BRIDGESTONE SPORTS CO., LTD.. The applicant listed for this patent is Hiroshi HIGUCHI, Tsuyoshi NAKAJIMA, Takashi OHIRA, Yuichiro OZAWA, Kazufumi TABATA. Invention is credited to Hiroshi HIGUCHI, Tsuyoshi NAKAJIMA, Takashi OHIRA, Yuichiro OZAWA, Kazufumi TABATA.
Application Number | 20130296074 13/461174 |
Document ID | / |
Family ID | 49512941 |
Filed Date | 2013-11-07 |
United States Patent
Application |
20130296074 |
Kind Code |
A1 |
OZAWA; Yuichiro ; et
al. |
November 7, 2013 |
GOLF BALL
Abstract
The invention provides a golf ball having a core and a cover of
at least one layer. The core is formed of a rubber composition
which includes a polybutadiene-containing base rubber, an
unsaturated carboxylic acid and/or a metal salt thereof, an organic
peroxide and sulfur, and for which the value of [sulfur
(mol)/available active oxygen content in organic peroxide] is at
least 0.01 and not more than 0.019.
Inventors: |
OZAWA; Yuichiro;
(Saitamaken, JP) ; TABATA; Kazufumi; (Saitamaken,
JP) ; NAKAJIMA; Tsuyoshi; (Saitamaken, JP) ;
OHIRA; Takashi; (Saitamaken, JP) ; HIGUCHI;
Hiroshi; (Saitamaken, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
OZAWA; Yuichiro
TABATA; Kazufumi
NAKAJIMA; Tsuyoshi
OHIRA; Takashi
HIGUCHI; Hiroshi |
Saitamaken
Saitamaken
Saitamaken
Saitamaken
Saitamaken |
|
JP
JP
JP
JP
JP |
|
|
Assignee: |
BRIDGESTONE SPORTS CO.,
LTD.
Tokyo
JP
|
Family ID: |
49512941 |
Appl. No.: |
13/461174 |
Filed: |
May 1, 2012 |
Current U.S.
Class: |
473/372 ;
473/371 |
Current CPC
Class: |
A63B 37/008 20130101;
A63B 37/0092 20130101; A63B 37/0045 20130101; C08K 5/14 20130101;
C08K 3/06 20130101; C08K 3/06 20130101; A63B 37/0043 20130101; A63B
37/0076 20130101; C08K 5/09 20130101; C08K 5/14 20130101; A63B
37/0003 20130101; A63B 37/0051 20130101; C08L 9/00 20130101; C08L
9/00 20130101; C08L 9/00 20130101; A63B 37/0096 20130101; A63B
37/0063 20130101; C08K 5/09 20130101; A63B 37/0031 20130101; A63B
37/0064 20130101; A63B 37/0033 20130101 |
Class at
Publication: |
473/372 ;
473/371 |
International
Class: |
A63B 37/06 20060101
A63B037/06 |
Claims
1. A golf ball comprising a core and a cover of at least one layer,
wherein the core is formed of a rubber composition which comprises
a polybutadiene-containing base rubber, an unsaturated carboxylic
acid and/or a metal salt thereof, an organic peroxide and sulfur,
and for which the value of [sulfur (mol)/available active oxygen
content in the organic peroxide] is at least 0.01 and not more than
0.019.
2. The golf ball of claim 1, wherein the core has a diameter of
from 32 to 41 mm.
3. The golf ball of claim 1, wherein the core is composed of a
single layer.
Description
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a golf ball having a core
and a cover composed of at least one layer. More specifically, the
invention relates to a golf ball which is capable of achieving
satisfactory distances on shots with both drivers and middle irons
used by professional golfers and skilled amateurs.
[0002] Solid golf balls have a relatively simple inner structure
composed of a core and a cover, although various golf ball
properties such as rebound, feel, spin on approach shots and
durability depend to a large degree on synergy between the core and
the cover. In numerous disclosures to date, efforts have been made
to optimize the rebound and feel of the ball, and also the spin
rate of the ball on approach shots, by closely specifying the
cross-sectional hardness of the core. Such art is described in, for
example, the following technical literature: JP-A 2011-136020 (and
the corresponding published U.S. Patent Application No.
2011/0159999), JP-A 2011-136021 (and the corresponding published
U.S. Patent Application No. 2011/0159998), JP-A 2007-152090 (and
the corresponding U.S. Pat. No. 7,273,425), JP-A 2008-194473 (and
the corresponding U.S. Pat. No. 7,481,722), and JP-A 2010-214105
(and the corresponding U.S. Pat. No. 7,909,710).
[0003] In addition, numerous disclosures have been made on art
which, in rubber compositions for golf ball cores, specifies the
hardness profile of the core from the standpoint of the rubber
formulation. For example, JP-A 2006-312044 (and the corresponding
published U.S. Pat. No. 7,278,929) discloses art in which powdered
sulfur is added so as to increase the hardness difference between
the center and surface of the core to at least a given value. In
addition, technical documents which describe rubber formulations
created in order to adjust the hardness profile of the core
include, for example, JP-A 2006-167452 (and the corresponding U.S.
Pat. No. 7,276,560), JP-A 2006-289074 (and the corresponding U.S.
Pat. No. 7,381,776), JP-A 2002-000765 (and the corresponding U.S.
Pat. No. 6,679,791), JP-A 2010-188199 (and the corresponding U.S.
Pat. No. 6,679,791, which is the same as the preceding), JP-A
2007-167257, JP-A 2008-68077 (and the corresponding U.S. Pat. No.
7,335,115), and JP-A 2008-119461 (and the corresponding U.S. Pat.
No. 7,300,362).
[0004] However, although a certain degree of improvement can be
expected for conventional rubber formulations and core hardness
profiles, even further increases in distance and improvements in
durability are desired. Lately, research and development on golf
balls has been especially intense and, in order to secure a
competitive advantage with the ball, there has existed a desire to
raise the level of the overall properties of the ball.
SUMMARY OF THE INVENTION
[0005] It is therefore an object of the invention to provide a golf
ball which is capable of achieving satisfactory distances on shots
with both drivers and middle irons used by professional golfers and
skilled amateurs.
[0006] As a result of extensive investigations aimed at achieving
the above object, the inventor has discovered that, in formulating
a rubber composition for a golf ball core, by carrying out
formulation such that the composition includes a
polybutadiene-containing base rubber, an unsaturated carboxylic
acid and/or a metal salt thereof, an organic peroxide and sulfur,
and such that the value of [sulfur (mol)/available active oxygen
content in the organic peroxide] falls in a specific range, golf
balls containing the core are capable of achieving satisfactory
distances, both on shots with drivers and on shots with middle
irons such as a number six iron (I#6).
[0007] Among recent golf balls in particular, three-piece solid
golf balls and four-piece solid golf balls featuring a urethane
cover are widely used by professional golfers and skilled amateurs.
The present invention was achieved through repeated improvements
aimed at, by optimization of the core formulation in the above
ball, increasing not only the distance achieved on shots with
drivers used by professionals and skilled amateurs, but also the
distance achieved with middle irons such as a number six iron (I#6)
used by such golfers.
[0008] Accordingly, the invention provides the following golf
ball.
[1] A golf ball comprising a core and a cover of at least one
layer, wherein the core is formed of a rubber composition which
comprises a polybutadiene-containing base rubber, an unsaturated
carboxylic acid and/or a metal salt thereof, an organic peroxide
and sulfur, and for which the value of [sulfur (mol)/available
active oxygen content in the organic peroxide] is at least 0.01 and
not more than 0.019. [2] The golf ball of [1], wherein the core has
a diameter of from 32 to 41 mm. [3] The golf ball of [1], wherein
the core is composed of a single layer.
BRIEF DESCRIPTION OF THE DIAGRAMS
[0009] FIG. 1 is a cross-sectional view showing a golf ball
according to one embodiment of the invention.
[0010] FIG. 2 is a plan view showing the dimples used in the
working examples of the invention and the comparative examples.
DETAILED DESCRIPTION OF THE INVENTION
[0011] The present invention is described more fully below.
[0012] The golf ball of the invention has a construction which
includes a core and a cover of at least one layer. As mentioned
above, the core may be composed of a single layer or may be formed
of a plurality of two or more layers, although it is preferable in
this invention for the core to be composed of a single layer. Also,
in this invention, the "cover" refers collectively to whatever
layers are formed to the outside of the core, and is composed of at
least one layer. That is, in cases where the cover is composed of a
plurality of layers, in addition to the outermost layer of the
cover, it includes also an intermediate layer interposed between
the outermost layer and the core. Accordingly, the cover may be a
two-layer cover composed of, in order from the inside: an
intermediate layer and an outermost layer. In addition, an envelope
layer may be provided between the core and the intermediate layer,
in which case the cover may be a three-layer cover composed of, in
order from the inside: an envelope layer, an intermediate layer and
an outermost layer. A large number of dimples are generally formed
on the outside surface of the outermost layer of the cover.
[0013] The core used in the invention is described. This core
includes a polybutadiene-containing base rubber, an unsaturated
carboxylic acid and/or a metal salt thereof, an organic peroxide,
and sulfur.
[0014] The polybutadiene serving as the above rubber component must
be one having a cis-1,4 bond content of at least 60% (here and
below, "%" refers to percent by weight), preferably at least 80%,
more preferably at least 90%, and most preferably at least 95%. If
the cis-1,4 bond content is too low, the resilience will decrease.
In addition, the polybutadiene has a 1,2-vinyl bond content of
preferably not more than 2%, more preferably not more than 1.7%,
and even more preferably not more than 1.5%.
[0015] The polybutadiene has a Mooney viscosity (ML.sub.1+4
(100.degree. C.)) of preferably at least 30, and more preferably at
least 35, with the upper limit being preferably not more than 100,
and more preferably not more than 90.
[0016] The term "Mooney viscosity" used herein refers to an
industrial indicator of viscosity (JIS K6300) as measured with a
Mooney viscometer, which is a type of rotary plastometer. This
value is represented by the unit symbol ML.sub.1+4 (100.degree.
C.), wherein "M" stands for Mooney viscosity, "L" stands for large
rotor (L-type), and "1+4" stands for a pre-heating time of 1 minute
and a rotor rotation time of 4 minutes. The "100.degree. C."
indicates that measurement was carried out at a temperature of
100.degree. C.
[0017] From the standpoint of obtaining a molded and vulcanized
rubber composition having a good resilience, the polybutadiene is
preferably one synthesized with a rare-earth catalyst or a group
VIII metal compound catalyst.
[0018] Such rare-earth catalysts are not subject to any particular
limitation, although preferred use may be made of a lanthanum
series rare-earth compound. Also, where necessary, an
organoaluminum compound, an alumoxane, a halogen-bearing compound
and a Lewis base may be used in combination with a lanthanum-series
rare-earth compound. Preferred use may be made of, as the various
foregoing compounds, those mentioned in JP-A 11-35633, JP-A
11-164912 and JP-A 2002-293996.
[0019] Of the above rare-earth catalysts, the use of a catalyst
which employs any of the lanthanum series rare-earth elements
neodymium, samarium and gadolinium is preferred, with the use of a
neodymium catalyst being especially recommended. In such cases, a
polybutadiene rubber having a high 1,4-cis bond content and a low
1,2-vinyl bond content can be obtained at an excellent
polymerization activity.
[0020] The polybutadiene has a molecular weight distribution Mw/Mn
(where "Mw" stands for weight-average molecular weight, and "Mn"
stands for number-average molecular weight) of preferably at least
1.0, and more preferably at least 1.3. The upper limit is
preferably not more than 6.0, and more preferably not more than
5.0. If Mw/Mn is too small, the workability may decrease, whereas
if it is too large, the resilience may decline.
[0021] The above polybutadiene is used as the base rubber, in which
case the proportion of the polybutadiene within the overall rubber
is preferably at least 40 wt %, more preferably at least 60 wt %,
even more preferably at least 80 wt %, and most preferably at least
90 wt %. The above polybutadiene may account for 100 wt %,
preferably 98 wt % or less, and even more preferably 95 wt % or
less, of the base rubber.
[0022] Examples of cis-1,4-polybutadiene rubber that may be used
include the high-cis products BR01, BR11, BR02, BR02L, BR02LL,
BR730 and BR51 available from JSR Corporation.
[0023] Rubber components other than the above-described
polybutadiene may also be included in the base rubber, insofar as
the objects of the invention can be achieved. Illustrative examples
of such other rubber components include polybutadienes other than
the above polybutadiene, and other diene rubbers, such as
styrene-butadiene rubbers, natural rubbers, isoprene rubbers and
ethylene-propylene-diene rubbers.
[0024] The unsaturated carboxylic acid and/or metal salt thereof
functions primarily as a co-crosslinking agent for the
above-described base rubber. Examples of suitable unsaturated
carboxylic acids include acrylic acid, methacrylic acid, maleic
acid and fumaric acid. The use of acrylic acid or methacrylic acid
is especially preferred. The metal salts of unsaturated carboxylic
acids are exemplified by the above unsaturated carboxylic acids
which have been neutralized with a desired metal ion. Illustrative
examples include the zinc salts and magnesium salts of methacrylic
acid and acrylic acid. The use of zinc acrylate is especially
preferred. The content of these unsaturated carboxylic acids and/or
metal salts thereof per 100 parts by weight of the base rubber is
preferably at least 10 parts by weight, more preferably at least 15
parts by weight, and even more preferably at least 20 parts by
weight. The upper limit is preferably not more than 45 parts by
weight, more preferably not more than 43 parts by weight, and even
more preferably not more than 41 parts by weight.
[0025] A known organic peroxide may be used as the organic
peroxide. Illustrative examples include dicumyl peroxide,
1,1-di(t-butylperoxy)cyclohexane, t-butylperoxy laurate, dibenzoyl
peroxide, dilauroyl peroxide and
1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane. These may be
used singly or two or more may be used in combination. Commercial
products may be used as these organic peroxides. Illustrative
examples of such commercial products include those available under
the trade names "Percumyl D," "Perhexa C-40," "Perbutyl L" (all
from NOF Corporation), the trade names "Niper BW" and "Peroyl L"
(both from NOF Corporation), and the trade name "Trigonox 29" (from
Kayaku Akzo Corporation).
[0026] The organic peroxide is included in an amount, per 100 parts
by weight of the base rubber, of preferably at least 0.1 part by
weight, more preferably at least 0.2 part by weight, and even more
preferably at least 0.3 part by weight. The upper limit is
preferably not more than 5.0 parts by weight, more preferably not
more than 4.0 parts by weight, even more preferably not more than
3.0 parts by weight, and most preferably not more than 2.0 parts by
weight. Including too much may make the core too hard, resulting in
an unpleasant feel at impact, and may markedly lower the durability
to cracking. On the other hand, if the amount included is too
small, the core may become too soft, resulting in an unpleasant
feel at impact and markedly lowering productivity.
[0027] As with the above organic peroxide, sulfur is also included
as an essential ingredient in the rubber composition. The sulfur is
exemplified by the product available from Tsurumi Chemical Industry
Co., Ltd. under the trade name "Sulfax-5." The amount of sulfur
included can be set to more than 0, and may be set to preferably at
least 0.005 part by weight, and more preferably at least 0.01 part
by weight, per 100 parts by weight of the base rubber. The upper
limit in the amount of sulfur, although not subject to any
particular limitation, may be set to preferably not more than 0.5
part by weight, more preferably not more than 0.4 part by weight,
and even more preferably not more than 0.1 part by weight. By
adding sulfur, hardness differences in the core can be increased.
However, adding too much sulfur may result in undesirable effects
during hot molding, such as explosion of the rubber composition, or
may considerably lower the rebound.
[0028] In this invention, when using both an organic peroxide and
sulfur in the above rubber composition, the value of [sulfur
(mol)/available active oxygen content in the organic peroxide] is
adjusted so as to be at least 0.01 and not more than 0.019. As used
herein, the "active oxygen content" is a numerical value indicating
the quantity of free radicals generated from the organic peroxide.
For example, as shown by the formula below, the stoichiometric
amount of active oxygen in an organic peroxide at 100%
concentration is represented for each individual organic peroxide
as the atomic weight of the active oxygens divided by the molecular
weight of the organic peroxide, expressed as a percentage.
Active oxygen content(%)=[(16.times.number of peroxide
bonds)/molecular weight].times.100
The number of moles of sulfur is calculated based on S.sub.8
sulfur.
[0029] As used herein, the "available active oxygen content" refers
to the active oxygen content (%) within the amount of organic
peroxide (number of moles) included in the rubber composition, and
is expressed as a molar quantity. In this invention, by adjusting
not the amount of organic peroxide itself, but rather the
quantitative balance between the amount of free radicals generated
from the organic peroxide and the sulfur, owing to the synergistic
effects of these compounds, a core having the desired physical
properties was discovered. Moreover, by using this core, a golf
ball can be obtained which achieves satisfactory distances on shots
with both drivers and middle irons (e.g., I#6) used by professional
golfers and skilled amateurs. In the present invention, the value
of [sulfur (mol)/available active oxygen content in the organic
peroxide] is set to at least 0.01 and not more than 0.019.
[0030] The above-described rubber composition contains the
foregoing essential ingredients of the invention, although fillers
may also be included therein as additional ingredients. Fillers
that may be preferably used include zinc oxide, barium sulfate and
calcium carbonate. These may be used singly or two or more may be
used in combination. The amount of filler included per 100 parts by
weight of the base rubber may be set to preferably at least 1 part
by weight, and more preferably at least 3 parts by weight. The
upper limit in the amount included per 100 parts by weight of the
base rubber may be set to preferably not more than 200 parts by
weight, more preferably not more than 150 parts by weight, and even
more preferably not more than 100 parts by weight. At a filler
content which is too high or too low, a proper weight and a
suitable rebound may be impossible to obtain.
[0031] In the practice of the invention, an antioxidant may be
included as an optional ingredient in the rubber composition. For
example, use may be made of a commercial product such as Nocrac
NS-6, Nocrac NS-30 or Nocrac 200 (all products of Ouchi Shinko
Chemical Industry Co., Ltd.). These may be used singly, or two or
more may be used in combination.
[0032] The amount of antioxidant included per 100 parts by weight
of the base rubber, although not subject to any particular
limitation, is preferably at least 0.05 part by weight, and more
preferably at least 0.1 part by weight. The upper limit is
preferably not more than 1.0 part by weight, more preferably not
more than 0.7 part by weight, and even more preferably not more
than 0.4 part by weight. If the antioxidant content is too high or
too low, a suitable core hardness gradient may not be obtained, as
a result of which it may not be possible to obtain a good rebound,
durability, and spin rate-lowering effect on full shots.
[0033] In addition, an organosulfur compound may be included in the
rubber composition so as to impart an excellent rebound.
Thiophenols, thionaphthols, halogenated thiophenols, and metal
salts thereof are recommended for this purpose. Illustrative
examples include pentachlorothiophenol, pentafluorothiophenol,
pentabromothiophenol, p-chlorothiophenol, and the zinc salt of
pentachlorothiophenol; and diphenylpolysulfides,
dibenzylpolysulfides, dibenzoylpolysulfides,
dibenzothiazoylpolysulfides and dithiobenzoylpolysulfides having 2
to 4 sulfurs. The use of diphenyldisulfide or the zinc salt of
pentachlorothiophenol is especially preferred.
[0034] The amount of the organosulfur compound included per 100
parts by weight of the base rubber is at least 0.05 part by weight,
preferably at least 0.07 part by weight, and more preferably at
least 0.1 part by weight. The upper limit is not more than 5 parts
by weight, preferably not more than 4 parts by weight, more
preferably not more than 3 parts by weight, and most preferably not
more than 2 parts by weight. Including too much organosulfur
compound may excessively lower the hardness, whereas including too
little is unlikely to improve the rebound.
[0035] The core can be produced by vulcanizing and curing the
rubber composition containing the various above ingredients. For
example, production may be carried out by using a mixing apparatus
such as a Banbury mixer or a roll mill to mix the ingredients,
carrying out compression molding or injection molding using a
core-forming mold, then suitably heating, and thereby curing, the
molded body at a temperature sufficient for the organic peroxide
and the co-crosslinking agent to act, such as from about
100.degree. C. to about 200.degree. C. for a period of 10 to 40
minutes.
[0036] The core diameter, although not subject to any particular
limitation, is preferably at least 32 mm, and more preferably at
least 33 mm. The upper limit is preferably not more than 41 mm, and
more preferably not more than 40 mm. At a core diameter outside of
this range, the ball's durability to cracking may dramatically
decline, or the initial velocity of the ball may decrease.
[0037] It is essential for the above core to have a cross-sectional
hardness which, letting D (mm) be a radius of the core, O be a
JIS-C hardness at a center of the core, Q be a JIS-C hardness at a
position 55% of D from the core center, and T be a JIS-C hardness
at a position 85% of D from the core center, satisfies the formulas
(1) and (2) below:
Q-O.ltoreq.5 (1)
T-Q.gtoreq.10. (2)
By adjusting the cross-sectional hardness of the core so as to
satisfy formulas (1) and (2), that is, conceptually, by finishing
the core to a hardness profile in which the cross-sectional
hardness from the core center to a position at a given distance
therefrom is relatively soft and free of large fluctuations in
hardness and in which the subsequent cross-sectional hardness up to
the core surface rises at a steep gradient, excessive deformation
of the core on full shots with a driver or with a middle iron is
suppressed, core deformation is optimized, and a loss of initial
velocity and an increase in the spin rate can be suppressed. As a
result, satisfactory distances can be obtained on shots with
drivers and on shots with middle irons such as a I#6 used by
professional golfers and skilled amateurs, in addition to which the
durability to cracking on repeated impact can be improved.
[0038] Also, in above formula (1), if the Q-O value is too large, a
sufficient spin rate-lowering effect may not be obtained, as a
result of which the desired distance may not be achieved. The Q-O
value has a lower limit of preferably at least 0.
[0039] Moreover, in above formula (2), if the T-Q value is too
small, a sufficient spin rate-lowering effect may not be obtained,
as a result of which the intended distance may not be achieved. The
T-Q value has a lower limit of preferably at least 11, and more
preferably at least 12, and an upper limit of preferably not more
than 20, and more preferably not more than 18.
[0040] The U-O value, which is the JIS-C hardness difference
between the surface of the core and the center of the core, has a
lower limit of preferably at least 10, more preferably at least 12,
and even more preferably at least 14, and an upper limit of
preferably not more than 45, more preferably not more than 40, and
even more preferably not more than 35. If the above value is too
large, a good initial velocity may not be obtained and the
durability may worsen. On the other hand, if the above value is too
small, the spin rate may rise excessively, resulting in a poor
distance, and the feel at impact may harden. The JIS-C hardness at
the core center, although not subject to any particular limitation,
has a minimum value of preferably at least 50, more preferably at
least 52, and even more preferably at least 54, and a maximum value
of preferably not more than 70, more preferably not more than 68,
and even more preferably not more than 66. The JIS-C hardness at
the core surface, although not subject to any particular
limitation, has a minimum value of preferably at least 75, more
preferably at least 77, and even more preferably at least 79, and a
maximum value of preferably not more than 100, more preferably not
more than 98, and even more preferably not more than 96.
[0041] Moreover, the U-Q value, which is the JIS-C hardness
difference between the surface of the core and a position 55% of D
from the center of the core, has a lower limit of preferably at
least 10, more preferably at least 12, and even more preferably at
least 14, and an upper limit of preferably not more than 30, more
preferably not more than 28, and even more preferably not more than
25. If the above value is too large, a good initial velocity may
not be obtained and the durability may worsen. On the other hand,
if the above value is too small, the spin rate may rise
excessively, as a result of which a good distance may not be
achieved, and the feel at impact may harden.
[0042] In the cover used in this invention, the material making up
the outermost layer, although not subject to any particular
limitation, is exemplified by ionomers and polyurethanes.
[0043] From the standpoint of controllability and scuff resistance,
it is preferable to use a polyurethane as the outermost layer
material. The use of a thermoplastic polyurethane elastomer in
particular is preferred from the standpoint of amenability to mass
production.
[0044] In cases where the outermost layer material is a
thermoplastic polyurethane elastomer, it is preferable to use one
type of resin pellet composed of a resin blend in which the main
components are (A) a thermoplastic polyurethane and (B) a
polyisocyanate compound and, when the resin pellets are charged
into an injection molding machine just prior to injection molding,
it is preferable for at least some isocyanate compound to be
present in which all the isocyanate groups on the molecule remain
in an unreacted state. Golf balls composed of such thermoplastic
polyurethane elastomers have an excellent rebound, spin performance
and scuff resistance.
[0045] To fully and effectively achieve the objects of the
invention, a necessary and sufficient amount of unreacted
isocyanate groups should be present within the outermost
layer-forming resin material. Specifically, it is recommended that
the total weight of components A and B combined be preferably at
least 60%, and more preferably at least 70%, of the overall weight
of the outermost layer. Above components A and B are described in
detail below.
[0046] In describing the thermoplastic polyurethane (A), the
structure of this thermoplastic polyurethane includes soft segments
composed of a polymeric polyol that is a long-chain polyol
(polymeric glycol), and hard segments composed of a chain extender
and a polyisocyanate compound. Here, the long-chain polyol serving
as a starting material is not subject to any particular limitation,
and may be any that is used in the prior art relating to
thermoplastic polyurethanes. Exemplary long-chain polyols include
polyester polyols, polyether polyols, polycarbonate polyols,
polyester polycarbonate polyols, polyolefin polyols, conjugated
diene polymer-based polyols, castor oil-based polyols,
silicone-based polyols and vinyl polymer-based polyols. These
long-chain polyols may be used singly or as combinations of two or
more thereof. Of the long-chain polyols mentioned here, polyether
polyols are preferred because they enable the synthesis of
thermoplastic polyurethanes having a high rebound resilience and
excellent low-temperature properties.
[0047] Illustrative examples of the above polyether polyol include
poly(ethylene glycol), poly(propylene glycol), poly(tetramethylene
glycol) and poly(methyltetramethylene glycol) obtained by the
ring-opening polymerization of cyclic ethers. The polyether polyol
may be used singly or as a combination of two or more thereof. Of
the above, poly(tetramethylene glycol) and/or
poly(methyltetramethylene glycol) are preferred.
[0048] It is preferable for these long-chain polyols to have a
number-average molecular weight in the range of 1,500 to 5,000. By
using a long-chain polyol having such a number-average molecular
weight, golf balls made with a thermoplastic polyurethane
composition having excellent properties such as resilience and
manufacturability can be reliably obtained. The number-average
molecular weight of the long-chain polyol is more preferably in the
range of 1,700 to 4,000, and even more preferably in the range of
1,900 to 3,000.
[0049] The number-average molecular weight of the long-chain polyol
refers here to the number-average molecular weight computed based
on the hydroxyl number measured in accordance with JIS K-1557.
[0050] Chain extenders that may be suitably used include those
employed in the prior art relating to thermoplastic polyurethanes.
For example, low-molecular-weight compounds which have a molecular
weight of 400 or less and bear on the molecule two or more active
hydrogen atoms capable of reacting with isocyanate groups are
preferred. Examples of the chain extender include, but are not
limited to, 1,4-butylene glycol, 1,2-ethylene glycol,
1,3-butanediol, 1,6-hexanediol and 2,2-dimethyl-1,3-propanediol. Of
these chain extenders, aliphatic diols having 2 to 12 carbons are
preferred, and 1,4-butylene glycol is more preferred.
[0051] The polyisocyanate compound is not subject to any particular
limitation; preferred use may be made of one that is used in the
prior art relating to thermoplastic polyurethanes. Specific
examples include one or more selected from the group consisting of
4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate,
2,6-toluene diisocyanate, p-phenylene diisocyanate, xylylene
diisocyanate, naphthylene-1,5-diisocyanate, tetramethylxylene
diisocyanate, hydrogenated xylylene diisocyanate,
dicyclohexylmethane diisocyanate, tetramethylene diisocyanate,
hexamethylene diisocyanate, isophorone diisocyanate, norbornene
diisocyanate, trimethylhexamethylene diisocyanate and dimer acid
diisocyanate. Depending on the type of isocyanate used, the
crosslinking reaction during injection molding may be difficult to
control. In the practice of the invention, to provide a balance
between stability at the time of production and the properties that
are manifested, it is most preferable to use 4,4'-diphenylmethane
diisocyanate, which is an aromatic diisocyanate.
[0052] It is most preferable for the thermoplastic polyurethane
serving as above component A to be a thermoplastic polyurethane
synthesized using a polyether polyol as the long-chain polyol,
using an aliphatic diol as the chain extender, and using an
aromatic diisocyanate as the polyisocyanate compound. It is
desirable, though not essential, for the polyether polyol to be a
polytetramethylene glycol having a number-average molecular weight
of at least 1,900, for the chain extender to be 1,4-butylene
glycol, and for the aromatic diisocyanate to be
4,4'-diphenylmethane diisocyanate.
[0053] The mixing ratio of active hydrogen atoms to isocyanate
groups in the above polyurethane-forming reaction may be adjusted
within a desirable range so as to make it possible to obtain a golf
ball which is composed of a thermoplastic polyurethane composition
and has various improved properties, such as rebound, spin
performance, scuff resistance and manufacturability. Specifically,
in preparing a thermoplastic polyurethane by reacting the above
long-chain polyol, polyisocyanate compound and chain extender, it
is desirable to use the respective components in proportions such
that the amount of isocyanate groups on the polyisocyanate compound
per mole of active hydrogen atoms on the long-chain polyol and the
chain extender is from 0.95 to 1.05 moles.
[0054] No particular limitation is imposed on the method of
preparing the thermoplastic polyurethane used as component A.
Production may be carried out by either a prepolymer process or a
one-shot process which uses a long-chain polyol, a chain extender
and a polyisocyanate compound and employs a known urethane-forming
reaction. Of these, a process in which melt polymerization is
carried out in a substantially solvent-free state is preferred.
Production by continuous melt polymerization using a multiple screw
extruder is especially preferred.
[0055] It is also possible to use a commercially available product
as the thermoplastic polyurethane serving as component A.
Illustrative examples include Pandex T8295, Pandex T8290, Pandex
T8283 and Pandex T8260 (all available from DIC Bayer Polymer,
Ltd.).
[0056] Next, various types of isocyanates may be employed without
particular limitation as the polyisocyanate compound serving as
component B. Illustrative examples include one or more selected
from the group consisting of 4,4'-diphenylmethane diisocyanate,
2,4-toluene diisocyanate, 2,6-toluene diisocyanate, p-phenylene
diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate,
tetramethylxylene diisocyanate, hydrogenated xylylene diisocyanate,
dicyclohexylmethane diisocyanate, tetramethylene diisocyanate,
hexamethylene diisocyanate, isophorone diisocyanate, norbornene
diisocyanate, trimethylhexamethylene diisocyanate and dimer acid
diisocyanate. Of the above group of isocyanates, the use of
4,4'-diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate
and isophorone diisocyanate is preferable in terms of the balance
between the influence on processability of, e.g., the rise in
viscosity accompanying the reaction with the thermoplastic
polyurethane serving as component A and the physical properties of
the outermost layer material of the resulting golf ball.
[0057] A thermoplastic elastomer (component C) other than the
above-described thermoplastic polyurethane may be included as an
optional component together with components A and B. By including
this component C in the above resin blend, the flow properties of
the resin blend can be further increased and improvements can be
made in various properties required of the outermost layer material
of a golf ball, such as resilience and scuff resistance.
[0058] The thermoplastic elastomer other than the above
thermoplastic polyurethane which is used as component C may be of
one, two or more types selected from among polyester elastomers,
polyamide elastomers, ionomer resins, styrene block elastomers,
hydrogenated styrene-butadiene rubbers,
styrene-ethylene/butylene-ethylene block copolymers and modified
forms thereof, ethylene-ethylene/butylene-ethylene block copolymers
and modified forms thereof, styrene-ethylene/butylene-styrene block
copolymers and modified forms thereof, ABS resins, polyacetals,
polyethylenes and nylon resins. In particular, because they
increase the resilience and scuff resistance due to reaction with
the isocyanate groups while at the same time maintaining a good
productivity, the use of polyester elastomers, polyamide elastomers
and polyacetals is especially preferred.
[0059] The above components A, B and C have a compositional ratio,
expressed as a weight ratio, which, although not subject to any
particular limitation, is preferably A:B:C=100:2 to 50:0 to 50, and
more preferably A:B:C=100:2 to 30:8 to 50.
[0060] In the present invention, the resin blend is prepared by
mixing together component A, component B and, additionally,
component C. At this time, it is essential to select conditions
such that, of the polyisocyanate compound, there exists at least
some portion in which all the isocyanate groups remain in an
unreacted state. For example, a treatment such as mixture in an
inert gas such as nitrogen or in a vacuum state must be provided.
The resin blend is then injection-molded around a core that has
been placed in a mold. For easy and trouble-free handling, it is
preferable to form the resin blend into pellets having a length of
1 to 10 mm and a diameter of 0.5 to 5 mm. Isocyanate groups in an
unreacted state remain within these resin pellets; while the resin
blend is being injection-molded about the core, or due to
post-treatment such as annealing thereafter, the unreacted
isocyanate groups react with component A and component C to form a
crosslinked material.
[0061] The outermost layer may be molded by a method which
involves, for example, feeding the above-described resin blend to
an injection-molding machine, and injecting the molten resin blend
over the core. In this case, the molding temperature varies
depending on the type of thermoplastic polyurethane, but is
preferably in the range of 150 to 250.degree. C.
[0062] When injection molding is carried out, it is desirable
though not essential to carry out molding in a low-humidity
environment such as by purging with an inert gas (e.g., nitrogen)
or a low-temperature gas (e.g., low dew-point dry air), or vacuum
treating, some or all places on the resin paths from the resin feed
area to the mold interior. Preferred, non-limiting, examples of the
medium used for transporting the resin under applied pressure
include low-humidity gases such as low dew-point dry air or
nitrogen. By carrying out molding in such a low-humidity
environment, reaction by the isocyanate groups is kept from
proceeding before the resin has been charged into the mold
interior. As a result, polyisocyanate in which the isocyanate
groups are to some degree in an unreacted state is included in the
molded resin material, thus making it possible to reduce variable
factors such as an unwanted rise in viscosity and enabling the real
crosslinking efficiency to be enhanced.
[0063] Techniques that may be used to confirm the presence of
polyisocyanate compound in an unreacted state within the resin
blend prior to injection molding about the core include those which
involve extraction with a suitable solvent that selectively
dissolves out only the polyisocyanate compound. An example of a
simple and convenient method is one in which confirmation is
carried out by simultaneous thermogravimetric and differential
thermal analysis (TG-DTA) measurement in an inert atmosphere. For
example, when the resin blend (outermost layer material) which may
be used in this invention is heated in a nitrogen atmosphere at a
temperature ramp-up rate of 10.degree. C./min, a gradual drop in
the weight of diphenylmethane diisocyanate can be observed from
about 150.degree. C. On the other hand, in a resin sample in which
the reaction between the thermoplastic polyurethane material and
the isocyanate mixture has been carried out to completion, a weight
drop is not observed from about 150.degree. C., but a weight drop
can be confirmed from about 230 to 240.degree. C.
[0064] After the resin blend has been molded as described above,
the properties as a golf ball outermost layer can be additionally
improved by carrying out annealing so as to induce the crosslinking
reaction to proceed further. "Annealing," as used herein, refers to
aging the cover in a fixed environment for a fixed length of
time.
[0065] In addition to the above-described resin components, various
additives may be optionally included in the outermost layer
material in the invention. Examples of such additives include
pigments, dispersants, antioxidants, ultraviolet absorbers,
ultraviolet stabilizers, parting agents, plasticizers, and
inorganic fillers (e.g., zinc oxide, barium sulfate, titanium
dioxide, tungsten).
[0066] Next, the thickness of the outermost layer in this
invention, although not particularly limited, is preferably at
least 0.1 mm, more preferably at least 0.3 mm, and even more
preferably at least 0.5 mm. The maximum thickness is preferably not
more than 1.4 mm, more preferably not more than 1.2 mm, and even
more preferably not more than 1.0 mm. If the outermost layer is
thicker than the above range, the rebound on W#1 shots may be
inadequate or the spin rate may increase, possibly resulting in a
poor distance. If the outermost layer is thinner than the above
range, the scuff resistance may worsen, or the controllability even
by professional golfers and skilled amateurs may be inadequate.
[0067] The material hardness of the outermost layer, expressed as
the Shore D hardness, although not particularly limited, is
preferably at least 34, more preferably at least 37, and even more
preferably at least 40. The maximum value is preferably not more
than 66, more preferably not more than 63, and even more preferably
not more than 60. At a low Shore D hardness, the ball may be too
receptive to spin on full shots, possibly resulting in a poor
distance. At a Shore D hardness which is too high, the ball may not
be receptive to spin on approach shots, which may result in a poor
controllability even by professional golfers and skilled amateurs.
It should be noted here that the material hardness of the outermost
layer refers to the hardness when the material has been molded into
a sheet of a given thickness. Below, the material hardnesses of the
intermediate layer and the envelope layer are defined in the same
way.
[0068] In the golf ball of the invention, numerous dimples are
provided on the surface of the outermost layer for the sake of
aerodynamic performance. The number of dimples formed on the
outermost layer surface is not subject to any particular
limitation. However, to enhance the aerodynamic performance of the
ball and increase the distance traveled by the ball, the number of
dimples is preferably at least 250, more preferably at least 270,
even more preferably at least 290, and most preferably at least
300. The maximum number of dimples is preferably not more than 400,
more preferably not more than 380, and even more preferably not
more than 360.
[0069] In the practice of the invention, by further increasing the
number of layers in the ball structure, it is possible to improve
the ball performance to a level desired in particular by
professional golfers and skilled amateurs. For example, an
intermediate layer may be interposed between the above-described
core and the above-described outermost layer, although the
invention is not limited to this construction.
[0070] In the above case, the material hardness of the intermediate
layer, expressed as the Shore D hardness, although not particularly
limited, is preferably at least 50, more preferably at least 55,
and even more preferably at least 60. The upper limit is preferably
not more than 70, more preferably not more than 66, and even more
preferably not more than 63. If the material hardness of the
intermediate layer is too low, the ball as a whole may be too
receptive to spin on full shots, as a result of which a good
distance may not be achieved. On the other hand, if the material
hardness of the intermediate layer is too high, the durability to
cracking when repeatedly struck may worsen or the feel at impact on
shots with a putter or on short approach shots may be too hard.
[0071] From the standpoint of lowering the spin rate both on shots
with a driver and on shots with a middle iron, it is preferable for
the JIS-C hardness at the surface of a sphere composed of the core
covered by the intermediate layer to be at least 90.
[0072] The thickness of the intermediate layer, although not
particularly limited, is preferably at least 0.5 mm, more
preferably at least 0.7 mm, and even more preferably at least 0.9
mm. The upper limit is preferably not more than 2.0 mm, and more
preferably not more than 1.7 mm. If the thickness of the
intermediate layer is larger than the above range, the spin
rate-lowering effect on shots with a W#1 may be inadequate, as a
result of which a good distance may not be obtained. If the
intermediate layer is too thin, the ball may have a poor durability
to cracking when repeatedly struck and a poor durability at low
temperatures.
[0073] The intermediate layer material is not subject to any
particular limitation. For example, advantageous use may be made of
known ionomer resins, thermoplastic elastomers and thermoset
elastomers. Illustrative examples of thermoplastic elastomers
include various types of thermoplastic elastomers, such as
polyester elastomers, polyamide elastomers, polyurethane
elastomers, olefin elastomers and styrene elastomers. It is
especially preferable to use an ionomer resin as the base resin for
the intermediate layer material. In this case, it is desirable that
formulation of the ionomer resin composition involve using a
mixture of a zinc ion (Zn.sup.2+)-neutralized ionomer resin and a
sodium ion (Na.sup.+)-neutralized ionomer resin. The mixing ratio
therebetween, or zinc ion (Zn.sup.2+)-neutralized ionomer resin
(I)/sodium ion (Na.sup.+)-neutralized ionomer resin (II), expressed
in terms of weight percent, is preferably from 25/75 to 75/25, more
preferably from 35/65 to 65/35, and even more preferably from 45/55
to 55/45. If the (I)/(II) resin ratio does not satisfy the above
range, there is a possibility that the rebound of the overall ball
will become smaller, which may make it impossible to obtain the
desired flight performance. Moreover, the durability to cracking
when repeatedly struck at ordinary temperatures may worsen, and the
durability to cracking at low temperatures (sub-zero Celsius) may
also worsen.
[0074] It is preferable to subject the surface of the intermediate
layer to abrasion treatment so as to increase adhesion with the
outermost layer located on the outside thereof. In addition,
following such abrasion treatment, a primer may be applied to the
surface. It is also possible to increase adhesion by adding an
adhesion reinforcing agent to the intermediate layer material.
[0075] In the practice of the invention, in addition to the above
intermediate layer, an envelope layer may be provided between the
core and the intermediate layer. In such a case, there is obtained
a multi-piece solid golf ball G having a four-layer construction
which, as shown in FIG. 1, is composed of, in order from the
inside: a core 1, an envelope layer 2, an intermediate layer 3, and
an outermost layer 4 having numerous dimples D on the surface
thereof.
[0076] In the above case, the envelope layer has a material
hardness, expressed as the Shore D hardness, which is not
particularly limited, but is preferably at least 40, more
preferably at least 42, and even more preferably at least 44. The
upper limit is preferably not more than 61, more preferably not
more than 59, and even more preferably not more than 57. If the
material hardness of the envelope layer is too low, the overall
ball may be too receptive to spin on full shots, as a result of
which a good distance may not be achieved. On the other hand, if
the material hardness of the envelope layer is too high, the
durability to cracking when repeatedly struck may worsen, or the
ball may have a hard feel at impact.
[0077] The thickness of the envelope layer, although not
particularly limited, is preferably at least 1.0 mm, more
preferably at least 1.2 mm, and even more preferably at least 1.4
mm. The upper limit is preferably not more than 4.0 mm, more
preferably not more than 3.0 mm, and even more preferably not more
than 2.0 mm. At an envelope layer thickness greater than the above
range, the initial velocity of the ball may be inadequate even when
struck with a driver, as a result of which the desired distance may
not be achieved. On the other hand, if the envelope layer is too
thin, the spin rate-lowering effect may be inadequate, as a result
of which the desired distance may not be achieved.
[0078] Although no particular limitation is imposed on the envelope
layer material, preferred use may be made of, for example, a known
ionomer resin, a thermoplastic elastomer, or a thermoset elastomer.
Illustrative examples of thermoplastic elastomers include various
types of thermoplastic elastomers, such as polyester elastomers,
polyamide elastomers, polyurethane elastomers, olefin elastomers
and styrene elastomers.
[0079] It is especially preferable to use, as the envelope layer
material, a mixture obtained by compounding (f) a base resin of (a)
an olefin-unsaturated carboxylic acid random copolymer and/or a
metal ion neutralization product of an olefin-unsaturated
carboxylic acid random copolymer blended with (b) an
olefin-unsaturated carboxylic acid-unsaturated carboxylic acid
ester random terpolymer and/or a metal ion neutralization product
of an olefin-unsaturated carboxylic acid-unsaturated carboxylic
acid ester random terpolymer in a weight ratio of from 100:0 to
0:100, (e) a non-ionomeric thermoplastic elastomer, (c) from 5 to
80 parts by weight of a fatty acid and/or fatty acid derivative
having a molecular weight of from 228 to 1500, and (d) from 0.1 to
17 parts by weight of a basic metal compound capable of
neutralizing un-neutralized acid groups in the above base resin and
component (c). In this case, it is preferable for the weight ratio
of the base resin (f) to the non-ionomeric thermoplastic elastomer
(e) to be adjusted within the range of 100:0 to 100:100, and for a
mixture of component (f), component (c) and component (d) to be
prepared, and it is also preferable to use all of above components
(c), (d), (e) and (f). In this way, the ball rebound and flight
performance can be further improved.
[0080] In this invention, commercially available products may be
used as the base resins of components (a) and (b). Examples of
commercial products which may be used as the random copolymer in
component (a) include Nucrel 1560, Nucrel 1214 and Nucrel 1035 (all
products of DuPont-Mitsui Polychemicals Co., Ltd.), and Escor 5200,
Escor 5100 and Escor 5000 (all products of ExxonMobil Chemical).
Examples of commercial products which may be used as the random
copolymer in component (b) include Nucrel AN4311, Nucrel AN4318
(both products of DuPont-Mitsui Polychemicals Co., Ltd.), and Escor
ATX325, Escor ATX320 and Escor ATX310 (all products of ExxonMobil
Chemical).
[0081] Examples of commercial products which may be used as the
metal ion neutralization product of the random copolymer in
component (a) include Himilan 1554, Himilan 1557, Himilan 1601,
Himilan 1605, Himilan 1706 and Himilan AM7311 (all products of
DuPont-Mitsui Polychemicals Co., Ltd.), Surlyn 7930 (E.I. DuPont de
Nemours & Co.), and Iotek 3110 and Iotek 4200 (ExxonMobil
Chemical). Examples of commercial products which may be used as the
metal ion neutralization product of the random copolymer in
component (b) include Himilan 1855, Himilan 1856 and Himilan AM7316
(all products of DuPont-Mitsui Polychemicals Co., Ltd.), Surlyn
6320, Surlyn 8320, Surlyn 9320 and Surlyn 8120 (all products of
E.I. DuPont de Nemours & Co.), and Iotek 7510 and Iotek 7520
(both products of ExxonMobil Chemical). Examples of
zinc-neutralized ionomer resins which are preferred as the metal
ion neutralization product of the above random copolymers include
Himilan 1706, Himilan 1557 and Himilan AM7316.
[0082] Above component (c) is a fatty acid and/or fatty acid
derivative having a molecular weight of at least 228 but not more
than 1500. This component has a very small molecular weight
compared with the base resin. It suitably adjusts the melt
viscosity of the mixture, and thus helps in particular to improve
the flow properties. Component (c) of this invention includes a
relatively high content of acid groups (or derivatives thereof),
and is able to suppress an excessive loss of resilience.
Illustrative examples of the fatty acid of component (c) include
myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid,
behenic acid, oleic acid, linoleic acid, linolenic acid, arachidic
acid and lignoceric acid. Of these, stearic acid, arachidic acid,
behenic acid and lignoceric acid are preferred. Behenic acid is
especially preferred.
[0083] Preferred use may be made of a basic inorganic metal
compound as the basic metal compound of component (d). Illustrative
examples of the metal ion therein include Li.sup.+, Na.sup.+,
K.sup.+, Ca.sup.++, Mg.sup.++, Zn.sup.++, Al.sup.+++, Ni.sup.++,
Fe.sup.++, Fe.sup.+++, Cu.sup.++, Mn.sup.++, Sn.sup.++, Pb.sup.++
and Co.sup.++. Known basic inorganic fillers containing these metal
ions may be used as the basic inorganic metal compound. Specific
examples include magnesium oxide, magnesium hydroxide, magnesium
carbonate, zinc oxide, sodium hydroxide, sodium carbonate, calcium
oxide, calcium hydroxide, lithium hydroxide and lithium carbonate.
In particular, a hydroxide or a monoxide is recommended. Calcium
hydroxide and magnesium oxide, each of which has a high reactivity
with the base resin, are more preferred. Calcium hydroxide is
especially preferred.
[0084] Illustrative examples of component (e) include olefin
elastomers, styrene elastomers, polyester elastomers, urethane
elastomers and polyamide elastomers. From the standpoint of further
increasing rebound, the use of an olefin elastomer or a polyester
elastomer is especially preferred. A commercially available product
may be used as component (e). Examples include olefin elastomers
such as Dynaron (JSR Corporation), and polyester elastomers such as
Hytrel (DuPont-Toray Co., Ltd.).
[0085] Various additives such as pigments, dispersants,
antioxidants, ultraviolet absorbers and light stabilizers may be
optionally included in the thermoplastic resin. Specific examples
of such additives include inorganic fillers such as zinc oxide,
barium sulfate and titanium dioxide.
[0086] The above material may be obtained by mixing the various
above-described components under applied heat. For example, the
material may be obtained by using a known mixing apparatus such as
a kneading-type twin-screw extruder, a Banbury mixer or a kneader
to knead the ingredients at a heating temperature of from 150 to
250.degree. C. Alternatively, direct use may be made of a
commercial product, specific examples of which include those having
the trade names HPF 1000, HPF 2000 and HPF AD1027, as well as the
experimental material HPF SEP1264-3, all produced by E.I. DuPont de
Nemours & Co.
[0087] The method of manufacturing multi-piece solid golf balls in
which the above-described core, envelope layer, intermediate layer
and outermost layer are each formed as successive layers is not
subject to any particular limitation. Production may be carried out
by an ordinary method such as a known injection molding process. By
way of illustration, first a core is placed within a given
injection mold, following which the envelope layer material is
injection-molded over the core to form a first intermediate sphere,
which sphere is then placed in another injection mold and the
intermediate layer material is injection-molded over the sphere to
form a second intermediate sphere. Next, this second intermediate
sphere is placed in yet another injection mold and the outermost
layer material is injection-molded over the second intermediate
sphere, concurrent with which dimples are molded in the outermost
layer surface, thereby giving a multi-piece golf ball.
Alternatively, instead of the above method in which the materials
for the respective layers are injection-molded, use may made of a
method in which each of the respective intermediate spheres is
enclosed by two half-cups that have been molded beforehand into
hemispherical shapes, and the resulting assembly is molded under
applied heat and pressure.
[0088] The golf ball of the invention has a diameter of not less
than 42 mm, preferably not less than 42.3 mm, and more preferably
not less than 42.6. The upper limit in the diameter is not more
than 44 mm, preferably not more than 43.8 mm, more preferably not
more than 43.5 mm, and even more preferably not more than 43
mm.
[0089] The weight of the golf ball is preferably not less than 44.5
g, more preferably not less than 44.7 g, even more preferably not
less than 45.1 g, and most preferably not less than 45.2 g. The
upper limit in the weight is not more than 47.0 g, more preferably
not more than 46.5 g, and even more preferably not more than 46.0
g.
[0090] As explained above, the golf ball of this invention is
capable of achieving satisfactory distances on shots with both
drivers and middle irons (e.g., I#6) used by professional golfers
and skilled amateurs.
EXAMPLES
[0091] Examples of the invention and Comparative Examples are given
below by way of illustration, and not by way of limitation.
Examples 1 to 3, Comparative Examples 1 to 3
[0092] Golf ball cores were produced by using the rubber
formulations in the respective examples of the invention and
comparative examples as shown in Table 1 below to prepare core
compositions, then molding and vulcanizing the core compositions at
a vulcanization temperature of 155.degree. C. and for a
vulcanization time of 25 minutes.
TABLE-US-00001 TABLE 1 Example Comparative Example 1 2 3 1 2 3
Polybutadiene 100 100 100 100 100 100 Zinc oxide 5 5 5 5 5 5 Barium
sulfate 15 15 15 15 15 15 Antioxidant 0.1 0.1 0.1 0.1 0.1 0.1 Zinc
stearate 5 5 5 5 5 5 Zinc salt of 1 1 1 1 1 1 pentachlorothiophenol
Zinc acrylate 30 30 30 30 30 30 Sulfur 0.085 0.08 0.06 0.12 0.1
Peroxide (1) 1.05 0.75 1.05 3 0.3 Peroxide (2) 3 0.3 Molar quantity
Sulfur 0.0003 0.0003 0.0002 0.0004 0.0004 (mol) Peroxide (1) 0.004
0.003 0.004 0.011 0.001 Peroxide (2) 0.005 0.0005 Available active
Peroxide (1) 0.023 0.016 0.023 0.064 0.006 oxygen content Peroxide
(2) 0.023 0.002 Sulfur (mol) + Available 0.014 0.018 0.010 0.020
0.006 -- active oxygen content Numbers of ingredient in the table
indicate parts by weight.
[0093] Details on the above materials are given below. [0094]
Polybutadiene: Available under the trade name "BR730" from JSR
Corporation [0095] Antioxidant:
2,2-Methylenebis(4-methyl-6-butylphenol), available under the trade
name "Nocrac NS-6" from Ouchi Shinko Chemical Industry Co., Ltd.
[0096] Zinc stearate: Available under the trade name "Zinc Stearate
G" from NOF Corporation [0097] Sulfur: Available under the trade
name "Sulfax-5" from Tsurumi Chemical Industry Co., Ltd. (sulfur
concentration, 95%) [0098] Peroxide (1): Dicumyl peroxide,
available under the trade name "Percumyl D" from NOF Corporation;
active oxygen content, 5.80% [0099] Peroxide (2): A mixture of
1,1-di(t-butylperoxy)-cyclohexane and silica, available under the
trade name "Perhexa C-40" from NOF Corporation; active oxygen
content, 4.92% [Sulfur (mol)/Available Active Oxygen Content in
Organic Peroxide]
[0100] "Available active oxygen content" refers to the active
oxygen content (%) in the amount (number of moles) of organic
peroxide included in the rubber composition. The active oxygen
content is a characteristic value for each compound among organic
peroxides. In addition, the values obtained by dividing sulfur
(mol) by the available active oxygen contents of the organic
peroxides are shown in the above table. The number of moles of
sulfur is calculated based on S.sub.8 sulfur. In the table, the
numerical values for molar quantity (mol), available active oxygen
content, and [sulfur (mol)/available active oxygen content] are
shown as values which have been rounded off.
[0101] Next, using the respective resin materials shown in Table 2,
an envelope layer, an intermediate layer and an outermost layer
were formed in this order over the core by injection molding,
thereby forming a three-layer cover. A common dimple configuration
I (338 dimples; a plan view of the dimple pattern is shown in FIG.
2) was used for the dimples. The dimples were formed, during
injection molding of the outermost layer, by impression with
numerous outermost layer-forming protrusions provided on the
spherical surface of the mold cavity.
TABLE-US-00002 TABLE 2 I II III HPF 1000 100 Himilan 1605 50
Himilan 1557 15 Himilan 1706 35 Trimethylolpropane 1.1 T8290 37.5
T8283 62.5 Titanium oxide 3.8 Polyethylene wax 1.4 Isocyanate
compound 7.5 Numbers in the table indicate parts by weight.
[0102] Details on the above materials are given below. [0103] HPF
1000: An ionomer available from E.I. DuPont de Nemours & Co.
[0104] Himilan: Ionomers available from DuPont-Mitsui Polychemicals
Co., Ltd. [0105] T8290, T8283: MDI-PTMG type thermoplastic
polyurethanes available under the trade name "Pandex" from DIC
Bayer Polymer [0106] Polyethylene wax: Available as "Sanwax 161P"
from Sanyo Chemical Industries, Ltd. [0107] Isocyanate compound:
4,4'-Diphenylmethane diisocyanate
[0108] Physical properties such as hardness of the individual
layers and the ball, and the flight performance (carry) on shots
with an I#6 were evaluated according to the criteria described
below for the golf balls obtained in each of Examples 1 to 3 and
Comparative Examples 1 to 3. The results are presented in Table 3.
In (1) to (6) below, measurements were carried out in a
23.+-.1.degree. C. environment.
(1) Center Hardness of Core
[0109] The core was cut into hemispheres and the cut face was
rendered into a flat plane, following which a durometer indenter
was pressed perpendicularly against the center thereof and
measurement was carried out. The JIS-C (JIS K6301-1975 standard,
defined similarly below) hardness value is indicated.
(2) Surface Hardness of Core
[0110] A durometer was set perpendicular on a surface portion of
the spherical core, and the hardness was measured based on the
JIS-C hardness standard. The result was indicated as a JIS-C
hardness value. "U" represents the JIS-C hardness at a position
100% of D from the center of the core; i.e., at the core
surface.
(3) Cross-Sectional Hardness of Core
[0111] The core was cut with a fine cutter and, letting D (mm) be
the radius of the core, O be the JIS-C hardness at a center of the
core, Q be the JIS-C hardness at a position 55% of D from the core
center, and T be the JIS-C hardness at a position 85% of D from the
core center, the JIS-C hardness value at each of these places was
measured.
(4) Material Hardnesses of Envelope Layer and Intermediate
Layer
[0112] The resin material for the envelope layer was formed into a
sheet having a thickness of 2 mm, and the hardness was measured
with a type D durometer in accordance with ASTM-D2240.
(5) Surface Hardness of Intermediate Layer-Covered Sphere
[0113] The indenter of a durometer was set substantially
perpendicular to the spherical surface of the intermediate layer,
and the JIS-C hardness was measured.
(6) Material Hardness of Outermost Layer
[0114] The measurement method was the same as in (4) above.
(7) Flight Test Using a Middle Iron (I#6)
[0115] The carry (m) of the ball when struck at a head speed of 44
m/s with, as the middle iron, an X-BLADE CB (a number six iron
manufactured by Bridgestone Sports Co., Ltd.) was measured. The
results were rated according to the following criteria.
[0116] Good: Carry was 150 m or more
[0117] NG: Carry was less than 150 m
TABLE-US-00003 TABLE 3 Comparative Example Example 1 2 3 1 2 3 Core
Diameter (mm) 35.4 35.4 35.4 35.4 35.4 35.4 O 0% of radius D 63 64
62 57 55 62 (core center) Q 55% of radius D 68 69 66 70 72 71 T 85%
of radius D 84 82 82 74 76 80 U 100% of radius 92 84 90 88 80 81
(core surface) Q-O (55%-0%) 5 5 4 13 17 9 hardness difference T-Q
(85%-55%) 16 13 16 4 4 9 hardness difference Cover Envelope layer
Material I I I I I I Thickness (mm) 1.7 1.7 1.7 1.7 1.7 1.7 Sheet D
hardness 51 51 51 51 51 51 Intermediate Material II II II II II II
layer Thickness (mm) 1.1 1.1 1.1 1.1 1.1 1.1 Sheet D hardness 62 62
62 62 62 62 JIS-C hardness at 98 98 98 98 98 98 surface of
intermediate layer Outermost Material III III III III III III layer
Thickness (mm) 0.8 0.8 0.8 0.8 0.8 0.8 Sheet D hardness 44 44 44 44
44 44 Flight performance Carry (m) 151 150 153 148 148 148 (I#6)
Rating good good good NG NG NG
[0118] As shown in Table 3 above, the golf balls obtained in the
examples of the invention had an excellent flight performance when
struck using an I#6. By contrast, the balls obtained in Comparative
Examples 1 to 3 all had a poor flight performance when an I#6 was
used.
* * * * *