# Patent

## Title
Golf ball

## Abstract

Golf ball 2 has a spherical core 4, a reinforcing layer 6 positioned outside of the core 4 and a cover 8 positioned outside of the reinforcing layer 6. The core 4 has a inner sphere 10, a first mid layer 12 positioned outside of the inner sphere 10, and a second mid layer 14 positioned outside of the first mid layer 12. The principal component of the first mid layer 12 and the second mid layer 14 is an ionomer resin. The principal component of the cover 8 is a thermoplastic polyurethane elastomer. The second mid layer 14 has a hardness Hs which is greater than a hardness Hf of the first mid layer 12 and a hardness Hc of the cover 8. The hardness Hc of the cover 8 is equal to or less than 50. A product (Tc·Hc) of a thickness Tc (mm) and a hardness Hc of the cover 8 is equal to or less than 25.

## Background
This application claims priority on Patent Application No. 2006-155949 filed in JAPAN on Jun. 5, 2006. The entire contents of this Japanese Patent Application are hereby incorporated by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to golf balls. More particularly, the present invention relates to golf balls having an inner sphere, a first mid layer, a second mid layer and a cover.
2. Description of the Related Art
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. The golf players also place great importance on flight distance upon shots with a long iron and a middle iron. The flight performance greatly depends on resilience performances.
The golf players place great importance also on spin performances of the golf balls. Great back spin rate results in small run. For golf players, golf balls which are liable to be spun backwards are apt to be rendered to stop at a targeted position. Great side spin rate results in easily curved trajectory of the golf ball. For golf players, golf balls which are liable to be spun sidewise are apt to allow their trajectory to curve intentionally. The golf balls that are excellent in spin performances are excellent in control performances. High-level golf players particularly place great importance on control performances upon shots with a short iron.
For golf players, stability of spin rate is also important. With a golf ball having variance of the spin rate, it is not easy to obtain the intended trajectory by the golf players.
Upon shots with an iron, the golf ball is rubbed with the face of the club. Due to this rubbing, the surface of the golf ball may be scuffed. Greatly scuffed golf balls can be no longer used. Scuff resistance performances are also important for golf balls.
In light of improvement of performances, a variety of proposals have been made with respect to golf balls. U.S. Pat. No. 6,123,630 (JP-A-10-328325) discloses a four-piece golf ball comprising a core having two-layer structure and a cover having two-layer structure. The core is formed by an inner sphere and a first mid layer. U.S. Pat. No. 6,248,027 (JP-A-10-328328) discloses a four-piece golf ball comprising a core having two-layer structure and a cover having two-layer structure. The core is formed by an inner sphere and a first mid layer.
Requirements for golf balls by golf players have been increasingly escalated in recent years. Balance of a higher order among the performances has been desired. An object of the present invention is to provide a golf ball that is excellent in the resilience performance, the spin performance, the spin stability and the scuff resistance performance.
SUMMARY OF THE INVENTION
A golf ball according to the present invention has a spherical core and a cover positioned outside of this core and formed by a thermoplastic resin composition. The core has an inner sphere, a first mid layer positioned outside of this inner sphere and formed by a thermoplastic resin composition and a second mid layer positioned outside of this first mid layer and formed by a thermoplastic resin composition. This second mid layer has a hardness Hs which is greater than a hardness Hf of the first mid layer and hardness Hc of the cover. The hardness Hc of the cover is equal to or less than 50. A product (Tc·Hc) of a thickness Tc (mm) of the cover and the hardness Hc of the cover is equal to or less than 25.
In this golf ball, the thickness Tc and the hardness Hc are small. According to conventional golf balls having a soft cover, this cover is responsible for the spin performance. This soft cover is likely to deteriorate the resilience performance. In conventional golf balls, deterioration of the resilience performance due to the cover is suppressed by employing a thin cover. However, too thin cover cannot be responsible for the spin performance enough. In the golf ball according to the present invention, the cover is responsible for spin performance irrespective of being thin, by employing the cover with a product (Tc·Hc) of being equal to or less than 25. Further, this cover can also be responsible for the spin stability and the scuff resistance performance. A thin cover does not deteriorate the resilience performance. The golf ball is excellent in all terms of the resilience performance, the spin performance, the spin stability and the scuff resistance performance.
Preferably, a sum (Tf+Ts+Tc) of a thickness Tf of the first mid layer, a thickness Ts of the second mid layer and a thickness Tc of the cover is 0.5 mm or greater and 3.7 mm or less.
Preferably, a ratio (Hs/Hc) of a hardness Hs of the second mid layer to a hardness Hc of the cover is 1.4 or greater and 3.7 or less. Preferably, a difference (Hs−Hf) of the hardness Hs of the second mid layer and the hardness Hf of the first mid layer is 3 or greater.
Preferably, the principal component of the base polymer of the first mid layer is an ionomer resin, the principal component of the base polymer of the second mid layer is an ionomer resin, and the principal component of the base polymer of the cover is a thermoplastic polyurethane elastomer.
Preferably, the hardness Hc of the cover is smaller than a central hardness Hi of the inner sphere. Preferably, the golf ball further has a reinforcing layer with a thickness of 3 μm or greater and 50 μm or less and positioned between the second mid layer and the cover. Preferably, the thickness Tc of the cover is equal to or less than 1.0 mm.



BRIEF DESCRIPTION OF THE DRAWINGS
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
The present invention will be hereinafter described in detail with appropriate references to the accompanying drawing according to preferred embodiments.
Golf ball 2 illustrated in FIG. 1 has a spherical core 4, a reinforcing layer 6 positioned outside of this core 4, and a cover 8 positioned outside of this reinforcing layer 6. The core 4 has an inner sphere 10, a first mid layer 12 positioned outside of this inner sphere 10, and a second mid layer 14 positioned outside of this first mid layer 12. Numerous dimples 16 are formed on the surface of the cover 8. Of the surface of the cover 8, a part other than the dimples 16 is a land 18. This golf ball 2 has a paint layer and a mark layer on the external side of the cover 8, although these layers are not shown in the Figure.
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. The 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.
The inner sphere 10 is formed by a composition including a thermosetting polymer as a base. Specifically, the inner sphere 10 is obtained through crosslinking of a rubber composition. 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 polybutadiene, it is preferred that the polybutadiene is included as a principal component. Specifically, it is preferred that percentage of polybutadiene to 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.
For crosslinking of the inner sphere 10, a co-crosslinking agent is used. Preferable examples of the co-crosslinking agent in light of the resilience performance include monovalent or bivalent metal salts of an α,β-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.
As a co-crosslinking agent, an α,β-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 is responsible for the crosslinking reaction. Examples of preferable α,β-unsaturated carboxylic acid include acrylic acid and methacrylic acid. Examples of preferable metal oxide include zinc oxide and magnesium oxide.
The amount of the co-crosslinking agent to be blended is preferably 10 parts by weight or greater and 40 parts by weight or less per 100 parts by weight of the base rubber. By setting the amount to be equal to or greater than 10 parts by weight, excellent resilience performance can be achieved. In this respect, the amount is more preferably equal to or greater than 15 parts by weight. By setting the amount to be equal to or less than 40 parts by weight, excellent feel at impact can be achieved. In this respect, the amount is more preferably equal to or less than 35 parts by weight.
Preferably, the rubber composition of the inner sphere 10 includes an organic peroxide together with the co-crosslinking agent. The organic peroxide serves as a crosslinking initiator. The organic peroxide is responsible for the resilience performance. Examples of suitable organic peroxide include dicumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di (t-butylperoxy)hexane and di-t-butyl peroxide. Particularly versatile organic peroxide is dicumyl peroxide.
The amount of the organic peroxide to be blended is preferably 0.1 part by weight or greater and 3.0 parts by weight or less per 100 parts by weight of the base rubber. By setting the amount to be equal to or greater than 0.1 parts by weight, excellent resilience performance can be achieved. In this respect, the amount is 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. By setting the amount to be equal to or less than 3.0 parts by weight, excellent feel at impact can be achieved. In this respect, the amount is more preferably equal to or less than 2.5 parts by weight.
Preferably, the rubber composition of the inner sphere 10 includes an organic sulfur compound. Illustrative examples of preferable organic sulfur compound include monosubstitution such as diphenyl disulfide, bis(4-chlorophenyl)disulfide, bis(3-chlorophenyl)disulfide, bis(4-bromophenyl)disulfide, bis(3-bromophenyl)disulfide, bis(4-fluorophenyl)disulfide, bis(4-iodophenyl)disulfide and bis(4-cyanophenyl)disulfide; disubstitution such as bis(2,5-dichlorophenyl)disulfide, bis(3,5-dichlorophenyl)disulfide, bis(2,6-dichlorophenyl)disulfide, bis(2,5-dibromophenyl)disulfide, bis(3,5-dibromophenyl)disulfide, bis(2-chloro-5-bromophenyl)disulfide and bis(2-cyano-5-bromophenyl)disulfide; trisubstitution such as bis(2,4,6-trichlorophenyl)disulfide and bis(2-cyano-4-chloro-6-bromophenyl)disulfide; tetrasubstitution such as bis(2,3,5,6-tetrachlorophenyl)disulfide; and pentasubstitution such as bis(2,3,4,5,6-pentachlorophenyl)disulfide and bis(2,3,4,5,6-pentabromophenyl)disulfide. The organic sulfur compound contributes to resilience performance. Particularly preferable organic sulfur compound is diphenyl disulfide and bis(pentabromophenyl)disulfide.
In light of resilience performance of the golf ball 2, the amount of the organic sulfur compound to be blended is preferably equal to or greater than 0.1 part by weight and more preferably equal to or greater than 0.2 part by weight per 100 parts by weight of the base rubber. In light of the soft feel at impact, the amount of the organic sulfur compound to be blended is preferably equal to or less than 1.5 parts by weight, more preferably equal to or less than 1.0 part by weight, and particularly preferably equal to or less than 0.8 part by weight per 100 parts by weight of the base rubber.
Into the inner sphere 10 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 inner sphere 10 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, an anti-aging agent, a coloring agent, a plasticizer, a dispersant and the like may be blended at an adequate amount to the inner sphere 10 as needed. Into the inner sphere 10 may be also blended crosslinked rubber powder or synthetic resin powder.
The inner sphere 10 has a central hardness Hi of preferably 20 or greater and 50 or less. By the inner sphere 10 having the central hardness Hi of equal to or greater than 20, excellent resilience performance and light feel at impact can be achieved. In this respect, the central hardness Hi is more preferably equal to or greater than 25, and particularly preferably equal to or greater than 30. By the inner sphere 10 having the central hardness Hi of equal to or less than 50, excessive spin upon a shot with a driver can be suppressed. In this respect, the central hardness Hi is more preferably equal to or less than 46, and particularly preferably equal to or less than 43. The central hardness Hi is measured by pressing a Shore D type hardness scale at a central point of a hemisphere obtained by cutting the inner sphere 10. For the measurement, an automated rubber hardness machine (trade name “LA1”, available from Koubunshi Keiki Co., Ltd.) which is equipped with this hardness scale is used.
The inner sphere 10 has a surface hardness SHi of preferably 30 or greater and 70 or less. By the inner sphere 10 having the surface hardness SHi of equal to or greater than 30, excellent resilience performance can be achieved. In this respect, the surface hardness SHi is more preferably equal to or greater than 40, and particularly preferably equal to or greater than 50. By the inner sphere 10 having the surface hardness SHi of equal to or less than 70, excellent feel at impact can be achieved. In this respect, the surface hardness SHi is more preferably equal to or less than 65, and particularly preferably equal to or less than 60. The surface hardness is measured by pressing the Shore D type hardness scale against the surface of the spherical body (inner sphere 10, core 4, golf ball 2 and the like). For the measurement, the automated rubber hardness machine (trade name “LA1”, available from Koubunshi Keiki Co., Ltd.) which is equipped with this hardness scale is used.
In light of achievement of both feel at impact and resilience performance, a difference (SHi−Hi) between the surface hardness SHi and the central hardness Hi is preferably equal to or greater than 10, and more preferably equal to or greater than 15. The difference (SHi−Hi) is preferably equal to or less than 30.
The amount of compressive deformation Di of the inner sphere 10 is preferably 2.5 mm or greater and 6.0 mm or less. By the inner sphere 10 having the amount of compressive deformation Di of equal to or greater than 2.5 mm, excellent feel at impact can be achieved. In this respect, the amount of compressive deformation Di is more preferably equal to or greater than 2.8 mm and particularly preferably equal to or greater than 3.0 mm. As described later, this golf ball 2 has a thin cover 8. Upon hitting of this golf ball 2, the inner sphere 10 is greatly deformed resulting from the cover 8 being thin. Owing to the inner sphere 10 having the amount of compressive deformation Di of equal to or less than 6.0 mm, excellent resilience performance can be achieved. In this respect, the amount of compressive deformation Di is more preferably equal to or less than 5.0 mm, and particularly preferably equal to or less than 4.5 mm.
Upon measurement of the amount of compressive deformation, the spherical body (inner sphere 10, core 4, golf ball 2 and the like) is first placed on a hard plate made of metal. Next, a cylinder made of metal gradually descends toward the spherical body. The spherical body 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 spherical body up to the state in which final load of 1274 N is applied thereto is the amount of compressive deformation.
A diameter of the inner sphere 10 is preferably equal to or greater than 30 mm, more preferably equal to or greater than 33 mm, and particularly preferably equal to or greater than 35 mm. The diameter of the inner sphere 10 is preferably equal to or less than 41.5 mm, more preferably equal to or less than 40.5 mm, and particularly preferably equal to or less than 39.0 mm. The weight of the inner sphere 10 is preferably 30 g or greater and 43 g or less. Crosslinking temperature of the inner sphere 10 is usually 130° C. or greater and 180° C. or less. The crosslinking time period of the inner sphere 10 is usually 10 minutes or longer and 50 minutes or less.
The first mid layer 12 is formed by a thermoplastic resin composition. Examples of the base polymer of this resin composition include ionomer resins, thermoplastic polyester elastomers, thermoplastic polyamide elastomers, thermoplastic polyurethane elastomers, thermoplastic polyolefin elastomers and styrene block-containing thermoplastic elastomers. In particular, ionomer resins are preferred. The ionomer resins are highly elastic. As described later, this golf ball 2 has a thin cover 8. Upon hitting of this golf ball 2, the first mid layer 12 is greatly deformed resulting from the cover 8 being thin. The mid layer 12 including the ionomer resin is responsible for the resilience performance.
Examples of preferred ionomer resin include binary copolymers formed with α-olefin and an α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms. Preferable binary copolymer comprises 80% by weight or more and 90% by weight or less α-olefin, and 10% by weight or more and 20% by weight or less α,β-unsaturated carboxylic acid. This binary copolymer provides excellent resilience performance. Examples of preferable other ionomer resin include ternary copolymers formed with α-olefin, an α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms and an α,β-unsaturated carboxylate ester having 2 to 22 carbon atoms. Preferable ternary copolymer comprises 70% by weight or more and 85% by weight or less α-olefin, 5% by weight or more and 30% by weight or less α,β-unsaturated carboxylic acid, and 1% by weight or more and 25% by weight or less α,β-unsaturated carboxylate ester. This ternary copolymer provides excellent resilience performance. In the binary copolymer and ternary copolymer, preferable α-olefin may be ethylene and propylene, while preferable α,β-unsaturated carboxylic acid may be acrylic acid and methacrylic acid. Particularly preferred ionomer resin is a copolymer formed with ethylene, and acrylic acid or 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.
Specific examples of the ionomer resin include trade names “Himilan 1555”, “Himilan 1557”, “Himilan 1605”, “Himilan 1706”, “Himilan 1707”, “Himilan 1856”, “Himilan 1855”, “Himilan AM7311”, “Himilan AM7315”, “Himilan AM7317”, “Himilan AM7318”, “Himilan AM7329” and “Himilan MK7320”, available from Du Pont-MITSUI POLYCHEMICALS Co., Ltd.; trade names “Surlyn® 6120”, “Surlyn® 6910”, “Surlyn® 7930”, “Surlyn® 7940”, “Surlyn® 8140”, “Surlyn® 8150”, “Surlyn® 8940”, “Surlyn® 8945”, “Surlyn® 9120”, “Surlyn® 9150”, “Surlyn® 9910”, “Surlyn® 9945” and “Surlyn® AD8546”, available from Dupont; and trade names “IOTEK 7010”, “IOTEK 7030”, “IOTEK 7510”, “IOTEK 7520”, “IOTEK 8000” and “IOTEK 8030”, available from EXXON Mobil Chemical 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.
The ionomer resin and other resin may be used in combination. When they are used in combination, the ionomer resin is included as the principal component of the base polymer, in light of the resilience performance. Proportion of the ionomer resin in the total base polymer accounts for preferably equal to or greater than 50% by weight, more preferably equal to or greater than 65% by weight, and particularly preferably equal to or greater than 75%.
In light of excellent compatibility with the ionomer resin, it is preferable that the styrene block-containing thermoplastic elastomer is used in combination. The styrene block-containing thermoplastic elastomer includes a polystyrene block as a hard segment and a soft segment. Typical soft segment is a diene block. 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 (SEBS). 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).
In light of 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 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.
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, SEBS, SEPS and SEEPS, and hydrogenated products thereof. Olefin component in the alloy is presumed to contribute to the improvement of compatibility with other base polymers. Use of this alloy may improve resilience performance of the golf ball 2. Preferably, an olefin having 2 to 10 carbon atoms may be used. Illustrative examples of suitable olefin include ethylene, propylene, butane and pentene. Ethylene and propylene are particularly preferable.
Specific examples of polymer alloys include “Rabalon® T3221C”, “Rabalon® T3339C”, “Rabalon® SJ4400N”, “Rabalon® SJ5400N”, “Rabalon® SJ6400N”, “Rabalon® SJ7400N”, “Rabalon® SJ8400N”, “Rabalon®SJ9400N” and “Rabalon®SR04”, trade names by Mitsubishi Chemical Corporation. Other specific examples of the styrene block-containing thermoplastic elastomer include “Epofriend® A1010”, a trade name by Daicel Chemical Industries; and “Septon HG-252”, a trade name by Kuraray Co., Ltd.
Into the resin composition of the first mid layer 12 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 the 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 first mid layer 12 can be accomplished. Into the first mid layer 12 may be also blended a coloring agent, crosslinked rubber powder or synthetic resin powder.
The first mid layer 12 has a hardness Hf of 45 or greater and 70 or less. By the first mid layer 12 having the hardness Hf of equal to or greater than 45, excellent resilience performance can be achieved. In these respects, the hardness Hf is more preferably equal to or greater than 48, and particularly preferably equal to or greater than 50. By the first mid layer 12 having the hardness Hf of equal to or less than 70, excellent feel at impact can be achieved. In this respect, the hardness Hf is more preferably equal to or less than 66, and particularly preferably equal to or less than 63.
In the present invention, the hardness Hf of the first mid layer 12, the hardness Hs of the second mid layer 14 and the hardness Hc of the cover 8 may be measured in accordance with a standard of “ASTM-D 2240-68”. For the measurement, an automated rubber hardness machine which is equipped with a Shore D type hardness scale (trade name “LA1”, available from Koubunshi Keiki Co., Ltd.) is used. For the measurement, a sheet which was formed by hot press, has a thickness of about 2 mm and consists of the same material as that of the first mid layer 12, the second mid layer 14 or the cover 8 is used. Prior to the measurement, the sheet is stored at a temperature of 23° C. for two weeks. When the measurement is carried out, three sheets are overlaid.
The first mid layer 12 has a thickness Tf of preferably 0.2 mm or greater and 2.0 mm or less. By the first mid layer 12 having the thickness Tf with thus range, both resilience performance and spin performance can be achieved. In this respect, the thickness Tf is more preferably equal to or greater than 0.5 mm, and particularly preferably equal to or greater than 0.8 mm. The thickness Tf is more preferably equal to or less than 1.6 mm, and particularly preferably equal to or less than 1.3 mm.
The sphere including the inner sphere 10 and the first mid layer 12 has a surface hardness SH1 of 40 or greater and 75 or less. By the sphere having the surface hardness SH1 of equal to or greater than 40, excellent resilience performance can be achieved. In this respect, the surface hardness SH1 is more preferably equal to or greater than 45, and particularly preferably equal to or greater than 50. The sphere having the surface hardness SH1 of equal to or less than 75 does not deteriorate feel at impact. In this respect, the surface hardness SH1 is more preferably equal to or less than 70, and particularly preferably equal to or less than 65.
The second mid layer 14 is formed by a thermoplastic resin composition. Examples of the base polymer of this resin composition include ionomer resins, thermoplastic polyester elastomers, thermoplastic polyamide elastomers, thermoplastic polyurethane elastomers, thermoplastic polyolefin elastomers and styrene block-containing thermoplastic elastomers. In particular, ionomer resins are preferred. The ionomer resins are highly elastic. As described later, this golf ball 2 has a thin cover 8. Upon hitting of this golf ball 2, the second mid layer 14 is greatly deformed resulting from the cover 8 being thin. The second mid layer 14 including the ionomer resin is responsible for the resilience performance. In the golf ball 2 with the first mid layer 12 which includes ionomer resin, and the second mid layer 14 which includes ionomer resin, the second mid layer 14 adheres firmly to the first mid layer 12. The firm adhesion is responsible for durability of the golf ball 2.
The ionomer resin and other resin may be used in combination. When they are used in combination, the ionomer resin is included as the principal component of the base polymer, in light of the resilience performance. Proportion of the ionomer resin in the total base polymer accounts for preferably equal to or greater than 50% by weight, more preferably equal to or greater than 70% by weight, and particularly preferably equal to or greater than 85%. In light of excellent compatibility with the ionomer resin, the styrene block-containing thermoplastic elastomer is preferably used in combination. The proportion of the ionomer resin in the second mid layer 14 is preferably greater than that in the first mid layer 12.
For the second mid layer 14, the same ionomer resin as that for the first mid layer 12 can be used. For the second mid layer 14, the same styrene block-containing thermoplastic elastomer as that for the first mid layer 12 can be used in combination. For the second mid layer 14, the same filler and additives as those for the first mid layer 12 can be blended.
The second mid layer 14 has a hardness Hs of preferably 50 or greater and 75 or less. By the second mid layer 14 having the hardness Hs of equal to or greater than 50, excellent resilience performance can be achieved. In addition, with the second mid layer 14 having the hardness Hs of equal to or greater than 50, the core 4 having a hard outside and a soft inside can be attained. This core 4 is responsible for suppression of the spin upon a shot with a driver. In these respects, the hardness Hs is more preferably equal to or greater than 55, and particularly preferably equal to or greater than 58. By the second mid layer 14 having the hardness Hs of equal to or less than 75, excellent feel at impact can be achieved. In this respect, the hardness Hs is more preferably equal to or less than 70, and particularly preferably equal to or less than 67.
The difference (Hs−Hf) between the hardness Hs of the second mid layer 14 and the hardness Hf of the first mid layer 12 is preferably equal to or greater than 3. By setting the difference (Hs−Hf) to be equal to or greater than 3, a core 4 having a hard outside and a soft inside can be attained. This core 4 is responsible for suppression of the spin upon a shot with a driver. Further, this core 4 is responsible for spin stability and feel at impact. In these respects, the difference (Hs−Hf) is more preferably equal to or greater than 5, and particularly preferably equal to or greater than 8. The difference (Hs−Hf) is preferably equal to or less than 20, and more preferably equal to or less than 15. In the golf ball 2 having two mid layers, various kinds of variation of the hardness distribution can be achieved.
The second mid layer 14 has a thickness Ts of preferably 0.2 mm or greater and 2.5 mm or less. By the second mid layer 14 having the thickness Ts of equal to or greater than 0.2 mm, excellent resilience performance can be achieved. In this respect, the thickness Ts is more preferably equal to or greater than 0.5 mm, and particularly preferably equal to or greater than 0.8 mm. The second mid layer 14 having the thickness Ts of equal to or less than 2.5 mm does not deteriorate feel at impact. In this respect, the thickness Ts is more preferably equal to or less than 2.2 mm, and particularly preferably equal to or less than 2.0 mm.
The core 4 formed by the inner sphere 10, the first mid layer 12 and the second mid layer 14 has a surface hardness SH2 of preferably 50 or greater and 80 or less. By the core 4 having the surface hardness SH2 of equal to or greater than 50, excellent resilience performance can be achieved. In this respect, the surface hardness SH2 is preferably equal to or greater than 55, and particularly preferably equal to or greater than 60. The core 4 having the surface hardness SH2 of equal to or less than 80 does not deteriorate feel at impact. In this respect, the surface hardness SH2 is more preferably equal to or less than 75, and particularly preferably equal to or less than 70.
The amount of compressive deformation D2 of the core 4 is preferably 1.8 mm or greater and 4.0 mm or less. By the core 4 having the amount of compressive deformation D2 of equal to or greater than 1.8 mm, excellent feel at impact can be achieved. In this respect, the amount of compressive deformation D2 is more preferably equal to or greater than 2.1 mm, particularly preferably equal to or greater than 2.3 mm. As described later, this golf ball 2 has a thin cover 8. Upon hitting of this golf ball 2, the core 4 is greatly deformed resulting from the cover 8 being thin. Owing to the core 4 having the amount of compressive deformation D2 of equal to or less than 4.0 mm, excellent resilience performance can be achieved. In this respect, the amount of compressive deformation D2 is more preferably equal to or less than 3.7 mm, and particularly preferably equal to or less than 3.4 mm.
In light of adhesion between the core 4 and the reinforcing layer 6 or the cover 8, the surface of the core 4 is preferably subjected to a treatment, whereby the roughness thereof is increased. Specific examples of the treatment include brushing, grinding and the like.
The reinforcing layer 6 lies between the second mid layer 14 and the cover 8, and improves adhesiveness therebetween. As described later, this golf ball 2 has an extremely thin cover 8. When such a thin cover 8 is hit with an edge of a clubface, a wrinkle is liable to be generated. The reinforcing layer 6 suppresses generation of such a wrinkle.
In the golf ball 2, as the principal component of the first mid layer 12 is an ionomer resin and the principal component of the second mid layer 14 is also an ionomer resin, the first mid layer 12 and the second mid layer 14 are adhered firmly. As described later, the principal component of the cover 8 is a thermoplastic polyurethane elastomer. Although the principal component of the cover 8 and that of the second mid layer 14 are different from each other, the second mid layer 14 and the cover 8 are adhered firmly by the reinforcing layer 6. In the golf ball 2, a separation of the first mid layer 12 and the second mid layer 14 is not liable to be caused, and a separation of the second mid layer 14 and the cover 8 is not liable to be caused, either. The golf ball 2 is excellent in durability.
For the base polymer of the reinforcing layer 6, a two-component cured thermosetting resin may be suitably 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 feature (e.g., strength at break) and durability of the reinforcing layer 6, two-component cured epoxy resins and two-component cured urethane resins are preferred.
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.
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 natural fatty acids containing a large amount of an unsaturated fatty acid such as linoleic acid, linolenic acid or 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 polyethylene diamine, polyoxyalkylene diamine and derivatives thereof.
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.
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 an 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.
It is preferred that urethane polyol is used as the polyol component of the base material. The urethane polyol has urethane bonds and at least two hydroxyl groups. Preferably, the urethane polyol has a hydroxyl group at its end. The urethane polyol may be obtained by allowing polyol and 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.
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-ε-caprolactone (PCL); polycarbonate polyols such as polyhexamethylene carbonate; and acrylic polyols. Two or more kinds of the polyol may be used in combination.
Polyisocyanate for use in production of 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′-diphenylmethanediisocyanate (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 (H12MDI), hydrogenated xylylene diisocyanate (H6XDI), 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, H6XDI, IPDI and H12MDI are preferred.
In the reaction of polyol and polyisocyanate for producing the urethane polyol, any known catalyst may be used. Typical catalyst may be dibutyltin dilaurate.
In light of strength of the reinforcing layer 6, ratio of the 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 6 to the cover 8, the ratio of the urethane bonds included in the urethane polyol is preferably equal to or less than 5 mmol/g. The ratio of the 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.
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 the adhesiveness of the reinforcing layer 6, 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.
In light of the adhesiveness of the reinforcing layer 6, 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.
The base material may contain, in addition to the urethane polyol, a polyol not having any urethane bond. The aforementioned polyol that is a raw material of the urethane polyol may be used in the base material. Polyols that are miscible 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.
The curing agent contains polyisocyanate or a derivative thereof. The aforementioned polyisocyanate that is a raw material of the urethane polyol may be used in the curing agent.
The reinforcing layer 6 may include additives such as a coloring agent (typically, titanium dioxide), a phosphate based stabilizer, an antioxidant, a light stabilizer, a fluorescent brightening agent, an ultraviolet absorbent, a blocking preventive agent and the like. The additive may be added either to the base material of the two-component cured thermosetting resin, or to the curing agent.
The reinforcing layer 6 is obtained by coating a liquid, which is prepared by dissolving or dispersing a base material and a curing agent in a solvent, on the surface of the second mid layer 14. In light of the workability, coating with a spray gun is preferred. The solvent is volatilized after the coating to permit a reaction of the base material with the curing agent thereby forming the reinforcing layer 6. 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.
In light of suppression of the wrinkle, the reinforcing layer 6 has a thickness Tr of preferably equal to or greater than 3 μm, and more preferably equal to or greater than 5 μm. In light of easy formation of the reinforcing layer 6, it is preferred that the thickness Tr is equal to or less than 300 μm, still more, equal to or less than 100 μm, yet more, equal to or less than 50 μm, and further, equal to or less than 20 μm. The thickness Tr is measured by observation of the cross section of the golf ball 2 with a micro scope. When the surface of the second mid layer 14 has roughness resulting from the surface roughening treatment, the thickness is measured immediately above the protruded portion.
In light of suppression of the wrinkle, the reinforcing layer 6 has a pencil hardness of preferably equal to or greater than 4B, and more preferably equal to or greater than B. In light of small loss of the force during transfer from the cover 8 to the second mid layer 14 upon hitting of the golf ball 2, the reinforcing layer 6 has a pencil hardness of preferably equal to or less than 3H. The pencil hardness is measured in accordance with a standard of “JIS K5400”.
When sufficient adhesion between the second mid layer 14 and the cover 8 is accomplished leading to less possibility to generate the wrinkle, the reinforcing layer 6 may not be provided.
The cover 8 is formed by a thermoplastic resin composition. Examples of base polymer of this resin composition include thermoplastic polyurethane elastomers, thermoplastic polyester elastomers, thermoplastic polyamide elastomers, thermoplastic polyolefin elastomers, styrene block-containing thermoplastic elastomers and ionomer resins. In particular, thermoplastic polyurethane elastomers are preferred. The thermoplastic polyurethane elastomers are soft. Great spin rate is achieved upon hitting the golf ball 2 having a cover 8 comprising a thermoplastic polyurethane elastomer, with a short iron. The cover 8 comprising a thermoplastic polyurethane elastomer is responsible for a control performance upon a shot with a short iron. The thermoplastic polyurethane elastomer is also responsible for the scuff resistance of the cover 8. Furthermore, by the thermoplastic polyurethane elastomer, excellent feel at impact can be achieved upon hitting with a putter or a short iron.
Other resin may be used in combination with the thermoplastic polyurethane elastomer. In light of the spin performance, the thermoplastic polyurethane elastomer is included in the base polymer as a principal component in the case of use in combination. Proportion of the thermoplastic polyurethane elastomer to total base polymer is preferably equal to or greater than 50% by weight, more preferably equal to or greater than 70% by weight, and particularly preferably equal to or greater than 85% by weight.
The thermoplastic polyurethane elastomer includes a polyurethane component as a hard segment, and a polyester component or a polyether component as a soft segment. Illustrative examples of the curing agent for the polyurethane component include alicyclic diisocyanate, aromatic diisocyanate and aliphatic diisocyanate. In particular, alicyclic diisocyanate is preferred. Because the alicyclic diisocyanate has no double bond in the main chain, yellowing of the cover 8 can be suppressed. Additionally, because the alicyclic diisocyanate is excellent in strength, the cover 8 can be prevented from being scuffed. Two or more kinds of the diisocyanate may be used in combination.
Illustrative examples of the alicyclic diisocyanate include 4,4′-dicyclohexylmethane diisocyanate (H12MDI), 1,3-bis(isocyanatomethyl)cyclohexane (H6XDI), isophorone diisocyanate (IPDI) and trans-1,4-cyclohexane diisocyanate (CHDI). In light of versatility and processability, H12MDI is preferred.
Illustrative examples of the aromatic diisocyanate include 4,4′-diphenylmethane diisocyanate (MDI) and toluene diisocyanate (TDI). Illustrative examples of the aliphatic diisocyanate include hexamethylene diisocyanate (HDI).
Thermoplastic polyurethane elastomers having a material hardness of equal to or less than 50, still more, equal to or less than 45, yet more, equal to or less than 38, and further, equal to or less than 34 are preferred. By such an elastomer, small hardness Hc of the cover 8 can be attained. In light of suppression of excessive spin, the material hardness is preferably equal to or greater than 20, and more preferably equal to or greater than 26. For the measurement of the material hardness, a sheet consisting of the polymer alone may be used. The measuring method is the same as the measuring method of the hardness Hf of the first mid layer 12.
Specific examples of the thermoplastic polyurethane elastomer include trade names “Elastollan XNY80A”, “Elastollan XNY85A”, “Elastollan XNY90A”, “Elastollan XNY97A”, “Elastollan XNY585” and “Elastollan XKP016N”, available from BASF Japan Ltd; and tradename “Rezamin P4585LS” and “Rezamin PS62490”, available from Dainichiseika Color & Chemicals Mfg. Co., Ltd. In light of possible achievement of small hardness Hc, “Elastollan XNY80A”, “Elastollan XNY85A” and “Elastollan XNY90A” are particularly preferred.
Into the cover 8 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. Also, the cover 8 may be blended with powder of a highly dense metal such as tungsten, molybdenum or the like for the purpose of adjusting the specific gravity.
The cover 8 has a hardness Hc of preferably 15 or greater and 50 or less. By the cover 8 having the hardness Hc of equal to or greater than 15, the spin upon a shot with a driver can be suppressed. This cover 8 can be responsible for the flight distance attained by the shot with a driver. In this respect, the hardness Hc is more preferably equal to or greater than 20, and particularly preferably equal to or greater than 25. By the cover 8 having the hardness Hc of equal to or less than 50, a great spin rate can be achieved upon a shot with a short iron. In this respect, the hardness Hc is more preferably equal to or less than 45, and particularly preferably equal to or less than 40.
The cover 8 has a thickness Tc of preferably equal to or less than 1.0 mm. As described above, the cover 8 is soft. The soft cover 8 is disadvantageous in terms of resilience coefficient of the golf ball 2. Upon a shot with a driver, the core 4 of the golf ball 2 is also deformed greatly. By setting the thickness Tc to be equal to or less than 1.0 mm, the cover 8 does not adversely affect the resilience coefficient to a large extent upon a shot with a driver, even though the cover 8 is soft. An excellent flight performance can be achieved upon a shot with a driver through using the ionomer resin in the first mid layer 12 and the second mid layer 14. Further, by the cover 8 having the thickness Tc of equal to or less than 1.0 mm, variance of the spin rate is suppressed.
In light of the flight performance and the spin stability, the thickness Tc is more preferably equal to or less than 0.8 mm, still more preferably equal to or less than 0.5 mm, and particularly preferably equal to or less than 0.4 mm. In light of spin performance, the thickness Tc is preferably equal to or greater than 0.1 mm, and more preferably equal to or greater than 0.2 mm.
The product (Tc·Hc) of the thickness Tc (mm) of the cover 8 and the hardness Hc of the cover 8 is preferably equal to or less than 25. The product (Tc·Hc) is an index which shows an influence of the cover 8 on a deformation behavior of the golf ball 2. The smaller the thickness Tc is, the smaller product (Tc·Hc) is obtained. The smaller the hardness Hc is, the smaller product (Tc·Hc) is obtained. The cover 8 having the product (Tc·Hc) of equal to or less than 25 is extremely thin and extremely soft. Upon hitting the golf ball 2 with a short iron, this cover 8 is sufficiently deformed irrespective of the thickness Tc being small. Due to this deformation, a long period of time of contact between the face of the short iron and the golf ball 2 can be achieved. The long period of time of contact results in a great spin rate. The long period of time of contact can also suppress variance of the spin rate. In addition, this cover 8 can also achieve an excellent scuff resistance performance. Moreover, by this cover 8, excellent feel at impact upon hitting with a putter or a short iron can be achieved. As the cover 8 is thin, the cover 8 does not deteriorate resilience performance when the golf ball 2 is hit with a driver irrespective of the hardness Hc being small. The golf ball 2 is excellent in spin performance, spin stability, scuff resistance performance, feel at impact and resilience performance.
The product (Tc·Hc) is more preferably equal to or less than 24, and particularly preferably equal to or less than 21. In light of suppression of excessive spin upon a shot with a driver, the product (Tc·Hc) is preferably equal to or greater than 4, and particularly preferably equal to or greater than 6.
The cover 8 has a hardness Hc being smaller than the central hardness Hi of the inner sphere 10. Upon hitting the golf ball 2 with a short iron, sufficient spin is attained. Upon hitting the golf ball 2 with a short iron, variance of the spin rate is small. The golf ball 2 having the hardness Hc being smaller than the central hardness Hi is excellent in control performance. Preferably, a smallest value in a hardness curve from the center point of the golf ball 2 to the surface of the cover 8 is attained in the cover 8.
In light of the spin performance, scuff resistance performance and feel at impact, the difference (Hi−Hc) between the central hardness Hi of the inner sphere 10 and the hardness Hc of the cover 8 is preferably equal to or greater than 1, more preferably equal to or greater than 2, and particularly preferably equal to or greater than 5. The difference (Hi−Hc) is preferably equal to or less than 30, and particularly preferably equal to or less than 25.
In the golf ball 2, the hardness Hs of the second mid layer 14 is greater than the hardness Hf of the first mid layer 12, and greater than the hardness Hc of the cover 8. The golf ball 2 has the core 4 with a hard outside and a soft inside and the soft cover 8. By the core 4, a small spin rate is achieved upon a shot with a driver. And by the cover 8, a great spin rate is achieved upon a shot with a short iron. Preferably, a peak in a hardness curve from a center point of the inner sphere 10 to a surface of the cover 8 is achieved in the second mid layer 14.
In light of resilience performance and spin performance, a ratio (Hs/Hc) of the hardness Hs of the second mid layer 14 to the hardness Hc of the cover 8 is preferably equal to or greater than 1.4, more preferably equal to or greater than 1.5, and particularly preferably equal to or greater than 1.6. The ratio (Hs/Hc) is preferably equal to or less than 3.7, more preferably equal to or less than 3.4, and particularly preferably equal to or less than 3.2.
The sum (Tf+Ts+Tc) of the thickness Tf of the first mid layer 12, the thickness Ts of the second mid layer 14 and the thickness Tc of the cover 8 is preferably 0.5 mm or greater and 3.7 mm or less. The golf ball 2 is excellent in resilience performance and spin performance. In this respect, the sum (Tf+Ts+Tc) is more preferably equal to or greater than 1.0 mm, and particularly preferably equal to or greater than 1.5 mm. The sum (Tf+Ts+Tc) is more preferably equal to or less than 3.4 mm, and particularly preferably equal to or less than 3.1 mm.
The amount of compressive deformation D3 of the golf ball 2 is preferably 2.0 mm or greater and 3.0 mm or less. The golf ball 2 having the amount of compressive deformation D3 of equal to or greater than 2.0 mm is excellent in feel at impact. In this respect, the amount of compressive deformation D3 is more preferably equal to or greater than 2.1 mm, and particularly preferably equal to or greater than 2.20 mm. The golf ball 2 having the amount of compressive deformation D3 of equal to or less than 3.0 mm is excellent in the resilience performance. In this respect, the amount of compressive deformation D3 is more preferably equal to or less than 2.9 mm, and particularly preferably equal to or less than 2.8 mm.
EXAMPLES
Example 1
A rubber composition was obtained by kneading 80 parts by weight of polybutadiene (trade name “BR-730”, available from JSR Corporation), 20 parts by weight of other polybutadiene (trade name “BR-51”, available from JSR Corporation), 27.0 parts by weight of zinc diacrylate (trade name “ZN-DA90S”, available from Nippon Shokubai Co., Ltd.), 5.0 parts by weight of zinc oxide (trade name “zinc oxide type II”, available from MITSUI MINING & SMELTING CO., LTD.), 0.8 part by weight of dicumyl peroxide (manufactured by NOF Corporation), 0.5 part by weight of diphenyldisulfide (manufactured by Sumitomo Seika Chemicals Co., Ltd.) and 17.4 parts by weight of barium sulfate. This rubber composition was placed into a mold having upper and lower mold half each having a hemispherical cavity, and heated under a temperature of 170° C. for 15 minutes to obtain an inner sphere having a diameter of 38.6 mm.
A resin composition was obtained by kneading 36 parts by weight of an ionomer resin (the aforementioned “Himilan 1605”), 36 parts by weight of other ionomer resin (the aforementioned “Himilan AM7329”), 28 parts by weight of styrene block-containing thermoplastic elastomer (the aforementioned “Rabalon SR04”), and 4 parts by weight of titanium dioxide in a biaxial extruder. This resin composition was rendered to cover around the inner sphere by injection molding to obtain a first mid layer. This first mid layer had a thickness Tf of 0.8 mm.
A resin composition was obtained by kneading 50 parts by weight of an ionomer resin (the aforementioned “Himilan 1605”), 40 parts by weight of other ionomer resin (the aforementioned “Himilan AM7329”), 10 parts by weight of styrene block-containing thermoplastic elastomer (the aforementioned “Rabalon SR04”), and 4 parts by weight of titanium dioxide in a biaxial extruder. This resin composition was rendered to cover around the first mid layer by injection molding to obtain a core formed by an inner sphere, the first mid layer, and a second mid layer. This second mid layer had a thickness Ts of 0.8 mm.
A coating composition containing a two-component cured epoxy resin as a base polymer (trade name “POLIN 750LE”, available from Shinto Paint Co., Ltd.) was prepared. The base material liquid of this coating composition consists of 30 parts by weight of a bisphenol A type solid epoxy resin and 70 parts by weight of a solvent. The curing agent liquid of this coating composition consists of 40 parts by weight of denatured polyamide amine, 55 parts by weight of a solvent and 5 parts by weight of titanium dioxide. Weight ratio of the base material liquid and the curing agent liquid is 1/1. This coating composition was coated on the surface of the second mid layer with a spray gun, and kept in an atmosphere of 40° C. for 24 hours to give a reinforcing layer. This reinforcing layer had a thickness Tr of 10 μm.
A resin composition was obtained by kneading 100 parts by weight of a thermoplastic polyurethane elastomer (the aforementioned “Elastollan XNY80A”), 4 parts by weight of titanium dioxide, and 0.1 part by weight of ultramarine blue in a biaxial extruder. Half shells were obtained from this resin composition with compression molding. The core was covered with two pieces of the half shells. The half shells and the core were placed into a final mold having upper and lower half each having a hemispherical cavity and numerous pimples on the inside face of the upper and lower mold to obtain a cover with compression molding. The cover had a thickness Tc of 0.5 mm. Numerous dimples having a shape inverted from the shape of the pimples were formed on the cover. 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, and a weight of 45.5 g.
Numerous dimples having a shape inverted from the shape of the pimple were formed on the cover. 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, and a weight of 45.5 g.
Examples 2 to 10 and Comparative Examples 1 to 3
In a similar manner to Example 1 except that the quality of the materials, the diameter of the inner sphere, the thickness Tf of the first mid layer, the thickness Ts of the second mid layer, and the thickness Tc of the cover were as listed in Tables 1 to 6 below, golf balls of Examples 2 to 10 and Comparative Examples 1 to 3 were obtained.
[Shot with Driver]
A driver with a metal head was attached to a swing machine available from Golf Laboratory Co. Then the golf balls were hit under a condition to give the head speed of 50 m/sec. The ball speed and spin rate immediately after the hitting, and travel distance (i.e., the distance from the launching point to the point where the ball stopped) were measured. Mean values of 10 times measurement are shown in Tables 4 to 6 below.
[Shot with Short Iron]
To the swing machine described above was attached an approach wedge. Then the machine condition was set to give the head speed of 21 m/sec, and the golf balls were hit therewith. Accordingly, spin rate immediately after the hitting was measured. Mean values of 10 times measurement were determined. Moreover, the difference between maximum value and minimum value among the ten measurements was calculated, and rating was performed based on the following criteria:
A: the difference being less than 100 rpm;
B: the difference being 100 rpm or greater and less than 200 rpm; and
C: the difference being 200 rpm or greater.
The results are shown in the following Tables 4 to 6.
[Evaluation of Feel at Impact]
Using a driver, the golf balls were hit by a high class golf player. Then, the golf player rated the feel at impact based on the following criteria:
A: satisfactory with a less impact shock;
B: average; and
C: unsatisfactory with a great impact shock.
The results are shown in the following Tables 4 to 6.
[Evaluation of Scuff Resistance Performance]
To the swing machine described above was attached a pitching wedge. Then the machine condition was set to give the head speed of 36 m/sec, and the golf balls were hit therewith. Accordingly, the surface of this golf ball was visually observed, and rating was performed based on the following criteria:
A: scuff mark hardly found;
B: scuff mark, and raising found; and
C: great scuff mark found, and raising being prominent.
The results are shown in the following Tables 4 to 6.







TABLE 1







Composition







(parts by weight)













Example 1
Example 2
Example 3
Example 4
Example 5

















Inner
BR-730
80
80
80
100
80


sphere
BR-51
20
20
20
—
20



Zinc diacrylate
27.0
26.0
24.0
29.5
23.0



Zinc oxide
5.0
5.0
5.0
5.0
5.0



Dicumyl peroxide
0.8
0.8
0.8
0.9
0.8



Diphenyl disulfide
0.5
0.5
0.5
0.3
0.5



Barium sulfate
17.4
17.8
18.5
16.3
18.9


First
Himilan 1605
36
—
—
—
50


mid
Himilan 8945
—
40
40
40
—


layer
Himilan AM7329
36
40
40
40
40



Rabalon SR04
28
20
20
20
10



Titanium dioxide
4
4
4
4
4


Second
Himilan 1605
50
50
50
50
50


mid
Himilan 8945
—
—
—
—
—


layer
Himilan AM7329
40
40
40
50
50



Rabalon SR04
10
10
10
—
—



Titanium dioxide
4
4
4
4
4


Cover
Elastollan XKP016N
—
—
—
—
—



Elastollan XNY97A
—
—
—
—
—



Elastollan XNY90A
100
100
100
—
—



Elastollan XNY80A
—
—
—
100
80



Rabalon SR04
—
—
—
—
20



Titanium dioxide
4
4
4
4
4
















TABLE 2







Composition







(parts by weight)

















Example



Example 6
Example 7
Example 8
Example 9
10

















Inner
BR-730
80
80
80
80
80


sphere
BR-51
20
20
20
20
20



Zinc diacrylate
24.0
27.0
27.5
26.0
26.0



Zinc oxide
5.0
5.0
5.0
5.0
5.0



Dicumyl peroxide
0.8
0.8
0.8
0.8
0.8



Diphenyl disulfide
0.5
0.5
0.5
0.5
0.5



Barium sulfate
18.5
17.4
17.2
17.8
17.8


First
Himilan 1605
—
36
50
—
—


mid
Himilan 8945
40
—
—
40
40


layer
Himilan AM7329
40
36
40
40
40



Rabalon SR04
20
28
10
20
20



Titanium dioxide
4
4
4
4
4


Second
Himilan 1605
50
50
50
50
50


mid
Himilan 8945
—
—
—
—
—


layer
Himilan AM7329
40
40
50
50
40



Rabalon SR04
10
10
—
—
10



Titanium dioxide
4
4
4
4
4


Cover
Elastollan XKP016N
—
—
—
—
—



Elastollan XNY97A
—
—
—
—
100



Elastollan XNY90A
—
—
100
—
—



Elastollan XNY80A
100
80
—
60
—



Rabalon SR04
—
20
—
40
—



Titanium dioxide
4
4
4
4
4
















TABLE 3







Composition







(parts by weight)











Comparative
Comparative
Comparative



Example 1
Example 2
Example 3















Inner
BR-730
80
80
100


sphere
BR-51
20
20
—



Zinc diacrylate
24.0
24.0
29.5



Zinc oxide
5.0
5.0
5.0



Dicumyl peroxide
0.8
0.8
0.9



Diphenyl disulfide
0.5
0.5
0.3



Barium sulfate
18.5
18.5
16.3


First
Himilan 1605
—
50
—


mid
Himilan 8945
40
—
40


layer
Himilan AM7329
40
40
40



Rabalon SR04
20
10
20



Titanium dioxide
4
4
4


Second
Himilan 1605
50
—
50


mid
Himilan 8945
—
40
—


layer
Himilan AM7329
40
40
50



Rabalon SR04
10
20
—



Titanium dioxide
4
4
4


Cover
Elastollan
—
—
50



XKP016N



Elastollan XNY97A
—
—
50



Elastollan XNY90A
100
100
—



Elastollan XNY80A
—
—
—



Rabalon SR04
—
—
—



Titanium dioxide
4
4
4
















TABLE 4







Results of Evaluation













Example 1
Example 2
Example 3
Example 4
Example 5

















Inner
Diameter (mm)
38.6
38.0
37.2
36.0
35.8


sphere
Central hardness Hi
40
39
42
38
39



Surface hardness SHi
57
56
60
55
55



Amount of compressive
3.60
3.70
3.25
4.00
4.10



deformation Di (mm)


First mid
Thickness Tf (mm)
0.8
1.0
1.0
1.3
1.6


layer
Hardness Hf
50
55
55
60
63


Sphere*
Surface hardness SH1
53
58
58
62
65



Amount of compressive
3.45
3.40
2.95
3.60
3.65



deformation D1 (mm)


Second mid
Thickness Ts (mm)
0.8
1.0
1.3
1.6
1.6


layer
Hardness Hs
60
60
63
63
67


Core
Surface hardness SH2
62
62
65
65
69



Amount of compressive
3.05
3.05
2.50
3.05
3.05



deformation D2 (mm)


Reinforcing
Thickness Tr (μm)
10
10
10
10
10


layer


Cover
Thickness Tc (mm)
0.5
0.4
0.5
0.5
0.3



Hardness Hc
38
38
38
26
21



Tc * Hc
19
15
19
13
6


Ball
Surface hardness SH3
64
64
64
63
62



Amount of compressive
2.77
2.80
2.22
2.83
2.86



deformation D3 (mm)



Defference Hs/Hc
1.6
1.6
1.7
2.4
3.2



Sum Tf + Ts + Tc (mm)
2.1
2.4
2.8
3.4
3.5


Driver
Ball speed (m/s)
75.3
75.5
76.6
75.5
75.5



Spin rate (rpm)
2280
2250
2400
2300
2380



Flight distance (m)
265.1
265.2
267.8
264.8
264.5


Short iron
Spin rate (rpm)
6570
6550
6700
6650
6530



Spin stability
A
A
A
A
A












Feel at impact
A
A
A
A
A


Scuff resistance performance
A
A
A
A
A





*Sphere formed by inner sphere and first mid layer













TABLE 5







Results of Evaluation

















Example



Example 6
Example 7
Example 8
Example 9
10

















Inner
Diameter (mm)
37.2
40.2
35.2
38.0
38.0


sphere
Central hardness Hi
42
41
42
39
39



Surface hardness SHi
60
59
60
56
56



Amount of compressive
3.25
3.50
3.50
3.70
3.70



deformation Di (mm)


First mid
Thickness Tf (mm)
1.0
0.5
1.3
1.0
1.0


layer
Hardness Hf
55
50
60
55
55


Sphere*
Surface hardness SH1
58
53
62
58
58



Amount of compressive
2.95
3.40
3.10
3.40
3.40



deformation D1 (mm)


Second mid
Thickness Ts (mm)
1.3
0.5
1.9
1.0
1.0


layer
Hardness Hs
63
60
63
67
60


Core
Surface hardness SH2
65
62
65
62
62



Amount of compressive
2.50
3.02
2.50
2.98
3.05



deformation D2 (mm)


Reinforcing
Thickness Tr (μm)
10
10
10
10
10


layer


Cover
Thickness Tc (mm)
0.8
0.3
0.6
0.4
0.4



Hardness Hc
26
21
38
18
47



Tc * Hc
21
6
23
7
19


Ball
Surface hardness SH3
63
62
64
61
65



Amount of compressive
2.39
2.84
2.19
2.72
2.71



deformation D3 (mm)



Difference Hs/Hc
2.4
2.9
1.7
3.7
1.3



Sum Tf + Ts + Tc (mm)
3.1
1.3
3.8
2.4
2.4


Driver
Ball speed (m/s)
76.3
75.7
76.2
75.6
75.7



Spin rate (rpm)
2370
2420
2460
2390
2110



Flight distance (m)
267.9
264.6
263.9
264.1
265.8


Short iron
Spin rate (rpm)
6730
6690
6880
6760
6300



Spin stability
B
A
A
A
B












Feel at impact
A
A
B
B
A


Scuff resistance performance
A
A
A
A
B





*Sphere formed by inner sphere and first mid layer













TABLE 6







Results of Evaluation











Compar-
Compar-
Compar-



ative
ative
ative



Example 1
Example 2
Example 3















Inner
Diameter (mm)
37.2
37.2
36.0


sphere
Central hardness Hi
42
42
38



Surface hardness SHi
60
60
55



Amount of compressive
3.25
3.25
4.00



deformation Di (mm)


First mid
Thickness Tf (mm)
1.0
1.0
1.3


layer
Hardness Hf
55
63
60


Sphere*
Surface hardness SH1
58
65
62



Amount of compressive
2.95
2.87
3.60



deformation D1 (mm)


Second
Thickness Ts (mm)
1.3
1.3
1.6


mid
Hardness Hs
63
55
63


layer


Core
Surface hardness SH2
65
58
65



Amount of compressive
2.50
2.53
3.05



deformation D2 (mm)


Re-
Thickness Tr (μm)
10
10
10


inforcing


layer


Cover
Thickness Tc (mm)
0.8
0.5
0.5



Hardness Hc
38
38
54



Tc * Hc
30
19
27


Ball
Surface hardness SH3
64
64
66



Amount of compressive
2.29
2.25
2.70



deformation D3 (mm)



Difference Hs/Hc
1.7
1.4
1.2



Sum Tf + Ts + Tc (mm)
3.1
2.8
3.4


Driver
Ball speed (m/s)
76.1
76.5
75.8



Spin rate (rpm)
2440
2480
2100



Flight distance (m)
262.9
263.3
265.7


Short iron
Spin rate (rpm)
6800
6600
6100



Spin stability
A
B
C










Feel at impact
B
B
C


Scuff resistance performance
A
A
C





*Sphere formed by inner sphere and first mid layer






As is clear from Tables 4 to 6, the golf balls of Examples are excellent in all terms of the flight performance, spin performance, spin stability, feel at impact and scuff resistance performance. Accordingly, advantages of the present invention are clearly indicated by these results of evaluation.
The description herein above is merely for illustrative examples, and various modifications can be made without departing from the principles of the present invention.

## Claims

1. A golf ball which comprises a spherical core and a cover positioned outside of the core and formed by a thermoplastic resin composition,
said core having an inner sphere, a first mid layer positioned outside of the inner sphere and formed by a thermoplastic resin composition, and a second mid layer positioned outside of the first mid layer and formed by a thermoplastic resin composition,
said second mid layer having a hardness Hs which is greater than a hardness Hf of the first mid layer and a hardness Hc of the cover,
said cover having the hardness Hc of equal to or less than 50, and a product (Tc·Hc) of a thickness Tc (mm) of the cover and a hardness Hc of the cover being equal to or less than 25, wherein a sum (Tf+Ts+Tc) of a thickness Tf of said first mid layer, a thickness Ts of said second mid layer and a thickness Tc of said cover is 0.5 mm or greater and 3.7 mm or less, and wherein the hardness Hc of said cover is smaller than a central hardness Hi of the inner sphere.

2. The golf ball according to claim 1, wherein a ratio (Hs/Hc) of a hardness Hs of the second mid layer to a hardness Hc of said cover is 1.4 or greater and 3.7 or less.

3. The golf ball according to claim 1, wherein a difference (Hs−Hf) of the hardness Hs of said second mid layer and the hardness Hf of the first mid layer is 3 or greater.

4. The golf ball according to claim 1, wherein a principal component of a base polymer of said first mid layer is an ionomer resin,
a principal component of a base polymer of said second mid layer is an ionomer resin, and
a principal component of a base polymer of said cover is a thermoplastic polyurethane elastomer.

5. The golf ball according to claim 1, which further has a reinforcing layer with a thickness of 3 μm or greater and 50 μm or less and positioned between said second mid layer and said cover.

6. The golf ball according to claim 1, wherein the thickness Tc of said cover is equal to or less than 1.0 mm.

7. A golf ball which comprises a spherical core and a cover positioned outside of the core and formed by a thermoplastic resin composition, said core having an inner sphere, a first mid layer positioned outside of the inner sphere and formed by a thermoplastic resin composition, and a second mid layer positioned outside of the first mid layer and formed by a thermoplastic resin composition,
said second mid layer having a hardness Hs which is greater than a hardness Hf of the first mid layer and a hardness Hc of the cover,
said cover having the hardness Hc of equal to or less than 50, and
a product (Tc·Hc) of a thickness Tc (mm) of the cover and a hardness Hc of the cover being equal to or less than 25, and wherein the hardness Hc of said cover is smaller than a central hardness Hi of the inner sphere.