# Patent

## Title
Golf ball

## Abstract

An object of the present invention is to provide a golf ball having an improved controllability and shot feeling while maintaining a flight distance on driver shots. The present invention provides a golf ball having a core, an intermediate layer disposed around the core, and a cover disposed around the intermediate layer, wherein the core has a center and an envelope layer disposed around the center, and has a specific hardness distribution, and the intermediate layer is formed from an intermediate layer composition comprising, as a resin component, (A) a modified polyester elastomer and (B) a binary ionomer resin, and having a flexural modulus ranging from 150 MPa to 450 MPa, a maximum loss factor (tan δ) between −20° C. and 0° C. of 0.08 or less, a repulsive modulus of 55% or more, and a slab hardness ranging from 60 to 90 in JIS-hardness.

## Background
FIELD OF THE INVENTION
The present invention relates to a golf ball, more particularly to a multi-piece golf ball including a center, an envelope layer, an intermediate layer and a cover.
DESCRIPTION OF THE RELATED ART
Golf balls comprising a center, a cover, and at least one intermediate layer disposed between the center and the cover are known. The intermediate layer is also referred to as “inner cover layer” or “outer core layer” based on the golf ball construction. In order to improve the golf ball performance, the golf ball construction and materials for the intermediate layer have been studied.
For example, Japanese Patent Publication No. H06-343718 A discloses a golf ball comprising (i) a spherical center, (ii) an inner cover layer molded on the spherical center, having a modulus of 15,000 to 70,000 psi, and containing a high acid content ionomer resin containing a copolymer with 17 to 25 weight % of α,β-unsaturated carboxylic acid, and (iii) an outer cover layer molded on the inner cover layer, having a modulus of 1,000 to 10,000 psi, and containing a polymer material selected from the group consisting of an ionomer resin and a nonionic thermoplastic elastomer.
Japanese Patent Publication No. H10-201880 A discloses a multi-layer golf ball having a greater moment of inertia comprising a core, an inner cover layer and an outer cover layer having a dimpled surface, wherein said core has a diameter from 1.28 to 1.57 inches and a weight of 18 to 38.7 grams, said inner cover layer has a thickness of from 0.01 to 0.200 inches and a weight, with core, of 32.2 to 44.5 grams and said outer cover layer has a thickness of from 0.01 to 0.110 inches and a weight, with core and inner cover layer, of 45.0 to 45.93 grams.
Japanese Patent Publication No. H07-24084 A discloses a three-piece golf ball comprising a center core having a diameter of 26 mm or more, a density of less than 1.4 and a JIS-C hardness of 80 or less, an intermediate layer having a thickness of 1 mm or more, specific gravity of less than 1.2 and a JIS-C hardness of less than 80, and a cover having a thickness of 1 to 3 mm, a JIS-C hardness of 85 or more, wherein the center core is formed from a rubber composition containing a polybutadiene as a base material, and the intermediate layer is formed from a thermoplastic polyester elastomer as a base material.
Japanese Patent Publication No. 2000-84117 A discloses a golf ball comprising a core, an intermediate layer around the core, and a cover around the intermediate layer, wherein said intermediate layer is formed mainly of a heated mixture of (A) a thermoplastic polyether ester elastomer having a Shore D hardness of 25 to 50, a tan δ value of 0.1 or less in the temperature range of −10° C. to 20° C. as determined by viscoelasticity measurement, and a glass transition temperature of not higher than −20° C. and (B) an olefin elastomer, modified olefin elastomer, styrene-conjugated diene block copolymer or hydrogenated styrene-conjugated diene block copolymer, having a JIS A hardness of 80 or less.
Japanese Patent Publication No. H06-142228 A discloses a multi-piece solid golf ball comprising a multi-layered solid core consisting of an inner core and one or at least two outer core layers covering the inner core, and a cover covering the multi-layered core, wherein the outer core layer is formed from a material mainly containing a mixture of 50% to 100% of a thermoplastic polyether ester elastomer having a Shore D hardness of 30 to 50, a glass transition temperature of −25° C. or less determined by differential thermal analysis (DSC) and 0% to 50% of an ionomer consisting of an ethylene-(meth)acrylic acid copolymer having a flexural modulus of 200 MPa to 400 MPa, and the cover is formed from an ionomer consisting of an ethylene-(meth)acrylic acid copolymer having a flexural modulus of 200 to 450 MPa, and a Shore D hardness of 55 to 68.
Japanese Patent Publication No. H10-80505 A discloses a golf ball comprising a core, an intermediate layer enclosing a surface of the core, and a cover enclosing a surface of the intermediate layer, wherein a resin component forming said intermediate layer contains a mixture of 10 to 60 parts by weight of a thermoplastic elastomer having a crystalline polyethylene block and 90 to 40 parts by weight of an ionomer resin having a melt index of at least 3 g/10 min. at 190° C. as a primary component.
Japanese Patent Publication No. 2000-176050 A discloses a multi-piece golf ball with at least three layers comprising a core, an intermediate layer, and a cover, wherein the intermediate layer is formed from a material blending a product obtained by heating and mixing 100 parts by mass of a thermoplastic polyester elastomer and 0.1 to 10 parts by mass of a metal compound containing magnesium oxide or magnesium hydroxide.
Japanese Patent Publication No. 2005-13487 A discloses a golf ball comprising a core and a cover of one or more layers enclosing the core, wherein at least one layer which constitutes said cover is formed primarily of a mixture comprising (A) an ionomer resin composition, (B) a thermoplastic elastomer selected from a thermoplastic polyester elastomer, thermoplastic block copolymer and thermoplastic polyurethane, and (C) a thermoplastic block copolymer terminated with a functional group capable of reacting with the ionomer resin, in such a proportion as to provide a A/(B+C) weight ratio between 50/50 and 98/2 and a B/C weight ratio between 9/1 and 1/1.
Japanese Patent Publication No. H10-328326 A discloses a multi-piece solid golf ball including a core and a cover covering the core, wherein the core comprises an inner core ball and an envelope layer covering the inner core ball, and a cover comprises an external layer and an internal layer, and wherein the external layer hardness of the cover ranges from 40 to 60 in Shore D, the internal layer hardness of the cover ranges from 55 to 70 in Shore D, the surface hardness of the envelope layer is higher than the surface hardness of the inner core ball, the hardness of the inner core ball is from 3.0 to 8.0 mm in a deformation amount under a load of 100 kg, and a ratio of the inner core ball hardness A to the ball hardness B is 1.1≦A/B≦3.5 in a deformation amount under a load of 100 kg.
Japanese Patent Publication No. 2001-17575 A discloses a solid golf ball formed of multi-layered structure having at least four layers comprising a core, an envelope layer covering the core, an intermediate layer covering the envelope layer and a cover covering the intermediate layer, wherein the core is comprised primarily of a thermoplastic resin or thermoplastic elastomer and has a diameter ranging from 3 to 18 mm and a Shore D hardness of 15 to 50, and wherein the envelope layer is comprised primarily of a thermoplastic resin or thermoplastic elastomer and the envelop layer and the intermediate layer have a substantially equal Shore D hardness at a boundary therebetween.
Japanese Patent Publication No. 2002-272880 A discloses a golf ball comprising a core and a cover disposed around the core, wherein the core comprises a center and at least one outer core layer adjacent the center and the cover comprises at least one inner cover layer and an outer cover layer, wherein (a) the center has an outer diameter from about 0.953 to about 3.56 cm (from about 0.375 to 1.4 in) and deflection of greater than about 4.5 mm under a load of 100 kg, (b) the outer core layer has an outer diameter from about 3.56 to 4.11 cm (from about 1.4 to 1.62 in), (c) the inner core layer has an outer diameter of greater than about 4.01 cm (about 1.58 in) and a material hardness of less than about 72 Shore D, and (d) the outer cover layer has a hardness of greater than about 50 Shore D.
Japanese Patent Publication No. 2003-205052 A discloses a multi-piece solid golf ball comprising a core (4) composed of a center (1) and an intermediate layer (2) formed on the center (1) and a cover (3) covering the core (4), wherein the center (1) has a diameter ranging from 10 to 20 mm and a central point hardness of 30 to 90 in JIS-A hardness, the intermediate layer (2) has a surface hardness of 50 to 70 in Shore D hardness, and the cover (3) comprises polyurethane-based thermoplastic elastomer as a main component, and has a Shore D hardness of 40 to 60 and a thickness of 0.3 to 1.5 mm.
Japanese Patent Publication No. 2004-130072 A discloses a multi-piece solid golf ball comprising a core (5) composed of a center (1), an intermediate layer (2) formed on the center (1) and an outer layer (3) formed on the intermediate layer (2) and a cover (4) covering the core (5), wherein the center (1) has a diameter ranging from 10 to 20 mm and a central point hardness of 30 to 85 in JIS-A hardness, the intermediate layer (2) has a surface hardness ranging from 30 to 55 in Shore D hardness, the outer layer (3) has a hardness of 65 to 85 in Shore D hardness and comprises a thermoplastic resin as a main component, and the cover (4) has a Shore D hardness of 35 to 55 and a thickness of 0.3 to 1.5 mm.
Japanese Patent Publication No. 2003-183484 A discloses a thermoplastic resin composition comprising a modified polyester elastomer obtained by a reaction between a polyester elastomer and an unsaturated carboxylic acid or a derivative thereof in the presence of a radical generator. As an application of the thermoplastic resin composition, a golf ball is exemplified.
SUMMARY OF THE INVENTION
Since 2010 a new groove regulation has entered in force in a professional golf world on clubs having a loft angle of 25° or more such as irons or wedges. This new regulation will be gradually applied to amateur golfers. Since this regulation reduces the spin rate on approach shots with irons or wedges, it becomes difficult to stop the golf ball on the green. Based on this background, golf balls that have a higher spin rate in order to stop easily on the green are required. As a method for increasing the spin rate on approach shots, employing a soft material for a cover material is known. However, with the method of employing a soft material for a cover material, there is a problem that the spin rate on driver shots increases and thus the flight distance on driver shots are reduced. Therefore, striking a balance between controllability on approach shots and the flight distance on driver shots is difficult.
As a method for striking a balance between the controllability on approach shots and flight distance on driver shots, there is a method of employing a soft material for the cover as well as using a core having an outer-hard/inner-soft structure. Use of the core having the outer-hard/inner-soft structure lowers the spin rate on driver shots and increases the flight distance on driver shots. However, when the golf ball comprising a core having the outer-hard/inner-soft structure and having an excessively large hardness distribution is hit with a driver, great energy loss occurs at this core. The energy loss results in deterioration of the resilience performance. The golf ball with low resilience results in the short flight distance on driver shots. When a core having the outer-hard/inner-soft structure and having an excessively small hardness distribution is hit with a short iron, the spin rate is low. The golf ball having the low spin rate results in deterioration of the control performance.
As another method for striking a balance between the controllability and flight distance on driver shots, a method of employing a soft material for cover as well as employing an intermediate layer having a high resilience has been studied. An intermediate layer composition having a higher resilience than the conventional intermediate layer composition using a blend of a polystyrene elastomer and an ionomer resin is required. Although the ionomer resin having a high neutralization degree provides a high resilience, the problem is that the moldability thereof is low. Materials having a high resilience tend to have a high hardness. If the intermediate layer has a high hardness, the problem is that a shot feeling becomes low. For providing a better shot feeling, lowering the hardness of the intermediate layer to some extent is required.
For striking a balance between the resilience and shot feeling, employing a polyester elastomer for the intermediate layer has been considered. However, it is difficult to provide a higher resilience in a range from 40 to 60 in Shore D hardness if the polyester elastomer is solely used for the intermediate layer composition. A blend of the ionomer resin for a higher resilience causes a problem that the durability becomes low.
The present invention has been achieved in view of the above circumstances. An object of the present invention is to provide a golf ball having an improved controllability and shot feeling while maintaining a flight distance on driver shots.
The present invention that has solved the above problems provides a golf ball having a core, an intermediate layer disposed around the core and a cover disposed around the intermediate layer, wherein the core has a center and an envelope layer disposed around the center, wherein a difference (He−Ho) between a JIS-C hardness He at the surface of the core and a JIS-C hardness Ho at the central point of the core is in a range from 15 to 30, and a JIS-C hardness Hc of the cover is less than the JIS-C hardness Ho at the central point of the core, wherein at all points P included in a zone at a distance of 1 mm to 15 mm from the central point of the core, a following mathematical expression is satisfied: −5.0≦H2−H1≦5.0, (in the above mathematical expression, H1 represents a JIS-C hardness at a point P1 that is located inside the point P along the radial direction and at a distance of 1 mm from the point P, and H2 represents a JIS-C hardness at a point P2 that is located outside the point P along the radial direction and at a distance of 1 mm from the point P), and wherein the intermediate layer is formed from an intermediate layer composition having a flexural modulus ranging from 150 MPa to 450 MPa, a maximum loss factor (tan δ) between −20° C. and 0° C. of 0.08 or less, a rebound resilience of 55% or more, and a slab hardness ranging from 60 to 90 in JIS-C hardness, and the intermediate layer composition comprises, as a resin component, 30 mass % to 70 mass % of (A) a modified polyester elastomer having a Shore A hardness of 95 or less; 70 mass % to 30 mass % of (B) a binary ionomer resin having a Shore D hardness of 65 or more, a flexural modulus of 300 MPa or more, and a melt flow rate (190° C., 2.16 kg) of 1.0 g/10 min or more; and 0 mass % to 50 mass % of (C) a thermoplastic resin other than (A) component and (B) component (provided that a total content of (A) component, (B) component, and (C) component is 100 mass %).
In the golf ball according to the present invention, the core has an appropriate hardness distribution. This core loses less energy upon hitting with a driver. The golf ball of the present invention provides a great flight distance upon hitting with a driver. The golf ball with the core having an appropriate hardness distribution produces a high spin rate when hitting with a short iron. The golf ball of the present invention is excellent in controllability upon hitting with a short iron.
The intermediate layer of the golf ball of the present invention is formed from the intermediate layer composition comprising (A) the modified polyester elastomer and (B) the binary ionomer resin. (A) The modified polyester elastomer has high compatibility with (B) the binary ionomer resin and has an action of softening the obtained intermediate layer. The obtained intermediate layer has a high resilience and can strike a balance between a soft shot feeling and resilience.
According to the present invention, the golf ball having an improved controllability and shot feeling while maintaining a flight distance on driver shots is obtained.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic cross sectional view illustrating an embodiment of the golf ball of the present invention;
FIG. 2 is a graph showing the hardness distribution of the core;
FIG. 3 is a graph showing the hardness distribution of the core;
FIG. 4 is a graph showing the hardness distribution of the core; and
FIG. 5 is a graph showing the hardness distribution of the core.



DESCRIPTION OF THE PREFERRED EMBODIMENT
The golf ball of the present invention has a core, an intermediate layer disposed around the core and a cover disposed around the intermediate layer, wherein the core has a center and an envelope layer disposed around the center, wherein a difference (He−Ho) between a JIS-C hardness He at the surface of the core and a JIS-C hardness Ho at the central point of the core is in a range from 15 to 30, and a JIS-C hardness Hc of the cover is less than the JIS-C hardness Ho at the central point of the core, wherein at all points P included in a zone at a distance of 1 mm to 15 mm from the central point of the core, a following mathematical expression is satisfied: −5.0≦H2−H1≦5.0, (in the above mathematical expression, H1 represents a JIS-C hardness at a point P1 that is located inside the point P along the radial direction and at a distance of 1 mm from the point P, and H2 represents a JIS-C hardness at a point P2 that is located outside the point P along the radial direction and at a distance of 1 mm from the point P), and wherein the intermediate layer is formed from an intermediate layer composition having a flexural modulus ranging from 150 MPa to 450 MPa, a maximum loss factor (tan δ) between −20° C. and 0° C. of 0.08 or less, a rebound resilience of 55% or more, and a slab hardness ranging from 60 to 90 in JIS-C hardness, and the intermediate layer composition comprises, as a resin component, 30 mass % to 70 mass % of (A) a modified polyester elastomer having a Shore A hardness of 95 or less; 70 mass % to 30 mass % of (B) a binary ionomer resin having a Shore D hardness of 65 or more, a flexural modulus of 300 MPa or more, and a melt flow rate (190° C., 2.16 kg) of 1.0 g/10 min or more; and 0 mass % to 50 mass % of (C) a thermoplastic resin other than (A) component and (B) component (provided that a total content of (A) component, (B) component, and (C) component is 100 mass %).
(1) Golf Ball Construction
The gold ball of the present invention has a core, an intermediate layer disposed around the core, and a cover disposed around the intermediate layer, wherein the core has a center and an envelope layer disposed around the center, wherein a difference (He−Ho) between a JIS-C hardness He at the surface of the core and a JIS-C hardness Ho at the central point of the core is in a range from 15 to 30, and a JIS-C hardness Hc of the cover is less than the JIS-C hardness Ho at the central point of the core, wherein at all points P included in a zone at a distance of 1 mm to 15 mm from the central point of the core, a following mathematical expression is satisfied: −5.0≦H2−H1≦5.0, (in the above mathematical expression, H1 represents a JIS-C hardness at a point P1 that is located inside the point P along the radial direction and at a distance of 1 mm from the point P, and H2 represents a JIS-C hardness at a point P2 that is located outside the point P along the radial direction and at a distance of 1 mm from the point P).
In the followings, the preferable embodiments of the present invention will be described, referring to the drawings.
FIG. 1 is a partially cutaway view of a golf ball 2 according to an embodiment of the present invention. The golf ball 2 includes a core 7, an intermediate layer 8 disposed around the core 7 and a cover 12 disposed around the intermediate layer 8. The core 7 has a center 4 and an envelope layer 6 disposed around the center 4. In order to improve the adhesion between the intermediate layer 8 and the cover 12, an adhesive layer 10 may be disposed between the intermediate layer 8 and the cover 12. On the surface of the cover 12, a large number of dimples 14 are formed. Of the surface of the golf ball 2, a part other than the dimples 14 is a land 16. The golf ball 2 includes a paint layer and a mark layer on the external side of the cover 12 although these layers are not shown in the drawings.
The central hardness Ho of the center (or the core) is preferably 40 or more, more preferably 45 or more, even more preferably 50 or more in JIS-C hardness. If the central hardness Ho is 40 or more in JIS-C hardness, the resilience improves. In light of suppression of the spin upon driver shots, the central hardness Ho is preferably 80 or less, more preferably 75 or less, and even more preferably 70 or less. The central hardness Ho is measured by pressing a JIS-C type hardness scale at a central point of a cut plane of the hemisphere obtained by cutting the center. For the measurement, a type P1 auto loading durometer manufactured by Kobunshi Keiki Co., Ltd., provided with a JIS-C type spring hardness tester is used.
The hardness of the center gradually increases from the central point toward the surface. The surface hardness of the center is more than the central hardness Ho.
The center preferably has a diameter of 10 mm or more, more preferably 12 mm or more, even more preferably 13 mm or more. Use of the center having a diameter of 10 mm or more provides a better shot feeling. In light of forming the envelope layer having a sufficient thickness, the center preferably has a diameter of 20 mm or less, more preferably 18 mm or less, even more preferably 17 mm or less.
The hardness of the envelope layer of the golf ball of the present invention preferably gradually increases from the innermost point toward the surface. The hardness He of the surface of the envelope layer (that is the surface of the core) is preferably 70 or more, and more preferably 75 or more in JIS-C hardness. If the hardness He of the surface of the core is 70 or more, the resilience improves. In light of the shot feeling, the surface hardness He of the envelope layer is preferably 90 or less, more preferably 88 or less, and even more preferably 87 or less in JIS-C hardness. The hardness He is measured by pressing the JIS-C type hardness scale on the surface of the core. For the measurement, a type P1 auto loading durometer manufactured by Kobunshi Keiki Co., Ltd., provided with a JIS-C type spring hardness tester is used.
In light of suppression of the spin, the difference (He−Hi) between the surface hardness He of the envelope layer and the hardness Hi of the innermost point of the envelope layer is preferably 10 or more, more preferably 12 or more, and even more preferably 15 or more. In light of easy manufacturing and durability, the hardness difference (He−Hi) is preferably 25 or less.
The hardness Hi is measured on a hemisphere obtained by cutting the core. By pushing a JIS-C type hardness scale on a cut plane of the hemisphere, the hardness Hi is measured. The hardness scale is pushed on a region sandwiched between a first circle and a second circle. The first circle corresponds to a boundary between the center and the envelope layer. The second circle is concentric with the first circle and has a radius greater than the first circle by 1 mm. For the measurement, a type P1 auto loading durometer manufactured by Kobunshi Keiki Co., Ltd., provided with a JIS-C type spring hardness tester is used.
The envelope layer preferably has a thickness of 8 mm or more, more preferably 9 mm or more, even more preferably 10 mm or more. If the thickness of the envelope payer is 8 mm or more, suppression of the spin becomes more effective. The envelope layer preferably has a thickness of 18 mm or less, more preferably 16 mm or less, even more preferably 15 mm or less. If the thickness of the envelope layer is 18 mm or less, the center having a large diameter is formed. Use of the center having a large diameter enhances an effect of suppression of the spin.
The hardness difference (He−Ho) between the surface hardness He of the core and the central hardness Ho of the core (center) is preferably 15 or more, and more preferably 18 or more. If the hardness difference (He−Ho) is 15 or more, suppression of the spin becomes more effective. In light of easy manufacturing and the resilience of the core, the hardness difference (He−Ho) is preferably 30 or less, and more preferably 25 or less. The hardness He is measured by pressing the JIS-C type hardness scale on the surface of the core. For the measurement, a type P1 auto loading durometer manufactured by Kobunshi Keiki Co., Ltd., provided with a JIS-C type spring hardness tester is used.
In the golf ball of the present invention, at all points P included in a zone at a distance of 1 mm to 15 mm from the central point of the core, a following mathematical expression is satisfied: −5.0≦H2−H1≦5.0.
In the above mathematical expression, H1 represents a JIS-C hardness at a point P1. The point P1 is located inside the point P along the radial direction. The distance of the point P1 from the point P is 1 mm. H2 represents a JIS-C hardness at a point P2. The point P2 is located outside the point P along the radial direction. The distance of the point P2 from the point P is 1 mm.

By pushing a JIS-C type hardness scale on a cut plane of a hemisphere obtained by cutting the core, the hardness H1 and H2 are measured. For the measurement, a type P1 auto loading durometer manufactured by Kobunshi Keiki Co., Ltd., provided with a JIS-C type spring hardness tester is used. Preferably, at all points P included in a zone at a distance of 1 mm to 15 mm from the central point of the core, a following mathematical expression is satisfied: 0.0<H2−H1≦3.0.

In light of the resilience performance, the intermediate layer preferably has a JIS-C hardness Hm of 60 or more, more preferably 65 or more, and even more preferably 70 or more. In light of the shot feeling, the JIC-hardness Hm of the intermediate layer is preferably 90 or less, and more preferably 88 or less. The JIS-C hardness of the intermediate layer is measured by a type P1 auto loading durometer manufactured by Kobunshi Keiki Co., Ltd., provided with a JIS-C type spring hardness tester. Upon measurement, slabs with a thickness of about 2 mm molded by heat-pressing are used. The slabs stored at the temperature of 23° C. for two weeks are used for the measurement. At the time of measurement, three or more of these slabs are stacked. The slabs formed from the intermediate layer composition are used for the measurement.
The intermediate layer preferably has a thickness of 0.5 mm or more, more preferably 0.7 mm or more, and even more preferably 0.8 mm or more. If the thickness of the intermediate layer is 0.5 mm or more, the shot feeling becomes better. The thickness of the intermediate layer is preferably 2.0 mm or less, more preferably 1.5 mm or less, even more preferably 1.3 mm or less. If the thickness of the intermediate layer is 2.0 mm or less, the resilience becomes better.
The JIS-C hardness Hc of the cover of the golf ball of the present invention is preferably 65 or less. Use of the soft cover can provide excellent controllability upon a shot with a short iron. In light of the controllability, the JIS-C hardness Hc is preferably 60 or less, and more preferably 55 or less. If the JIS-C hardness Hc is too small, the flight performance on driver shots is insufficient. In this light, the hardness Hc is preferably 20 or more, more preferably 25 or more, and even more preferably 35 or more. The hardness Hc of the cover is measured by the same method as that for the hardness of the intermediate layer.
The JIS-C hardness Hc of the cover of the golf ball of the present invention is less than the JIS-C hardness Ho of the central point of the core. The golf ball of the present invention is excellent in controllability upon a shot with a short iron. In light of the controllability, the difference (Ho−Hc) between the JIS-C hardness Ho of the central point of the core and the JIS-C hardness Hc of the cover is preferably 10 or more, more preferably 11 or more, and even more preferably 12 or more. The hardness difference (Ho−Hc) is preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less.
The cover preferably has a thickness Tc of 0.8 mm or less, more preferably 0.6 mm or less, and even more preferably 0.5 mm or less. If the thickness Tc of the cover is 0.8 mm or less, the flight performance on driver shots becomes better. The cover preferably has the thickness Tc of 0.10 mm or more, and more preferably 0.15 mm or more. If the thickness Tc of the cover is 0.10 mm or more, the controllability on approach shots becomes better.
The golf ball of the present invention may have an adhesive layer between the intermediate layer and the cover. The adhesive layer makes the intermediate layer and the cover adhere firmly. The adhesive layer suppresses delamination of the cover from the intermediate layer. As described later, the golf ball of the present invention preferably comprises a thin cover. When the golf ball with a thin cover is hit with an edge of a clubface, a wrinkle easily generates. The adhesive layer suppresses the generation of the wrinkle.
The adhesive layer preferably has a thickness of 0.001 mm or greater, and more preferably 0.002 mm or greater. If the thickness of the adhesive layer is 0.001 mm or more, the durability of the golf ball improves. The adhesive layer preferably has a thickness of 0.1 mm or less, and more preferably 0.05 mm or less. The thickness of the adhesive layer is measured by observing a cross section of the golf ball with a microscope. When the intermediate layer has concavities and convexities on its surface by surface roughening, the thickness of the adhesive layer is measured at the top of the convex part. The measurement underneath dimples should be avoided.
The adhesion strength between the intermediate layer and the cover is preferably 20 N or more. The golf ball having the adhesive strength of 20 N or more is excellent in durability. In this respect, the adhesion strength is preferably 22.0 N or more, and more preferably 22.3 N or more.
Upon measurement of the adhesion strength, test pieces comprising a first layer, an adhesive layer and a second layer are cut out from a golf ball. The size of the test pieces is “10 mm×50 mm”. The second layer is delaminated from the first layer near the end of the test pieces. The first layer is attached to a first chuck and the second layer is attached to a second chuck. The second chuck is moved relative to the first chuck, and the second layer is attached to the second chuck. The second chuck is moved relative to the first chuck, and the first layer is delaminated from the second layer. The force of the delamination is measured. The measurement was performed with “Autograph AG-IS” available from SHIMADZU CORPORATION and the crosshead speed was 50 mm/min.
The golf ball of the present invention has a diameter ranging from 40 mm to 45 mm. In light of satisfying a regulation of US Golf Association (USGA), the diameter is preferably 42.67 mm or more. In light of prevention of the air resistance, the diameter is preferably 44 mm or less, and more preferably 42.80 mm or less.
When the golf ball has a diameter ranging from 40 mm to 45 mm, the compression deformation amount of the golf ball of the present invention is preferably 2.3 mm or greater, more preferably 2.4 mm or greater, even more preferably 2.5 mm or greater. If the compression deformation amount is 2.3 or more, the golf ball with a good shot feeling can be obtained. The compression deformation amount is preferably 3.5 mm or less, more preferably 3.2 mm or less, and even more preferably 3.0 mm or less. If the compression deformation amount is 3.5 mm or less, the resilience improves.
Upon measurement of the compression deformation amount, the spherical body (center, core or golf ball) is placed on a hard plate made of metal. 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 an initial load of 98 N is applied to the spherical body up to the state in which a final load of 1275 N is applied thereto is the compression deformation amount.
The total number of the dimples formed on the surface of the golf ball of the present invention is preferably 200 or more and 500 or less. If the total number of the dimples is less than 200, the dimple effect is hardly obtained. On the other hand, if the total number of the dimples exceeds 500, the dimple effect is hardly obtained because the size of the respective dimples is small. The shape (shape in a plan view) of dimples includes, for example, without limitation, a circle, polygonal shapes such as roughly triangular shape, roughly quadrangular shape, roughly pentagonal shape, and roughly hexagonal shape, another irregular shape. The shape of the dimples is employed solely or in combination at least two of them.
(2) Intermediate Layer Composition
The intermediate layer of the golf ball of the present invention is formed from an intermediate layer composition containing (A) a modified polyester elastomer having a Shore A hardness of 95 or less; (B) a binary ionomer resin having a Shore D hardness of 65 or more, a flexural modulus of 300 MPa or more, and a melt flow rate (190° C., 2.16 kg) of 1.0 g/10 min or more; and, if desired, (C) a thermoplastic resin other than (A) component and (B) component.
First, (A) the modified polyester elastomer having a Shore A hardness of 95 or less will be explained. (A) The modified polyester elastomer used in the present invention is preferably obtained by carrying out a reaction between (a-3) an unsaturated carboxylic acid or a derivative thereof and (a-2) a polyester elastomer in a presence of (a-1) a radical generator. In the modification reaction, it is considered that the graft reaction of (a-3) the unsaturated carboxylic acid or a derivative thereof to (a-2) the polyester elastomer mainly occurs with some other reactions such as a reaction where the unsaturated carboxylic acid or a derivative is added to the terminal of the polyester elastomer, an ester exchange reaction, and decomposition. (A) The modified polyester elastomer preferably has (a-3) the unsaturated carboxylic acid or a derivative thereof which are grafted in a content ranging from 0.03 mass % to 20 mass %. The grafting content more preferably ranges from 0.06 mass % to 4 mass %, even more preferably 0.08 mass % to 1.5 mass %. If the grafting content falls within the above range, the dispersibility into (B) the binary ionomer resin improves and the durability of the obtained golf ball becomes better.
Although many polyester elastomers are known, as (a-2) the polyester elastomer, preferred is a polyester elastomer composed of an aromatic polyester component as a hard segment and a polyalkylene glycol or aliphatic polyester component as a soft segment. In the present invention, particularly preferred is a polyester polyether block copolymer having an aromatic polyester component as the hard segment and a polyalkylene glycol component as the soft segment. The content of the polyalkylene glycol component is preferably in a range from 5 mass % to 90 mass %, more preferably 30 mass % to 80 mass %, and even more preferably 55 mass % to 80 mass % in the block copolymer produced. In general, it tends to be difficult to produce the polymer having a high content of the polyalkylene glycol component by a condensation polymerization. Further, it is also difficult that the thermoplastic resin consisting of the polymer having a high content of the polyalkylene glycol as a material and the ionomer resin exhibits an appropriate hardness and a high rebound resilience. On the contrary, if the content of the polyalkylene glycol component is low, the elastic property becomes low. Thus, it is difficult that the intermediate layer composition consisting of the polymer having a low content of the polyalkylene glycol as a material and the ionomer resin exhibits an appropriate softness and a high rebound resilience. Further, the dispersibility into (B) the binary ionomer resin becomes low.
The polyester polyether block copolymer can be produced by preparing an oligomer by esterification or an ester exchange reaction in a conventional method, using an aliphatic diol or alicyclic diol each having 2 to 12 carbon atoms, and an aromatic dicarboxylic acid, aliphatic dicarboxylic acid or an alkyl ester thereof as a component forming the hard segment; and a polyalkylene glycol having a weight average molecular weight from 400 to 6,000 as a component forming the soft segment; and condensation polymerizing the obtained oligomer. Examples of the aliphatic diol or alicyclic diol each having 2 to 12 carbon atoms include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butane diol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol. Among them, preferred is 1,4-butane diol or ethylene glycol, particularly preferred is 1,4-butane diol. These diols may be used in combination of two or more, if desired.
As the aromatic dicarboxylic acid, those which are generally used as a raw material for polyester elastomers can be used. Examples thereof include terephthalic acid, isophthalic acid, phthalic acid, and 2,6-naphthalene dicarboxylic acid. The aromatic dicarboxylic acid preferably includes terephthalic acid or 2,6-naphthalene dicarboxylic acid, more preferably terephthalic acid. These aromatic dicarboxylic acids may be used in combination of two or more. Examples of the alkyl esters of the aromatic dicarboxylic acids include dimethyl esters and diethyl esters of the aromatic dicarboxylic acids. Preferred is dimethyl terephthalate or dimethyl 2,6-naphthalate. The alicyclic dicarboxylic acid preferably includes cyclohexane dicarboxylic acid. The alkyl ester thereof preferably includes a dimethyl ester or a diethyl ester. In addition to the above components, a small amount of a tri-functional alcohol, tricarboxylic acid, or esters thereof may be copolymerized, if desired. Also, an aliphatic dicarboxylic acid such as adipic acid or its dialkyl ester may be used as a comonomer.
The polyalkylene glycol having a weight-average molecular weight ranging from 400 to 6,000 is preferably used. The weight-average molecular weight is more preferably 500 to 4,000, even more preferably 600 to 3,000. In general, if the polyalkylene glycol having a low weight-average molecular weight is used, it becomes difficult that the resultant polyester elastomer exhibit the elastic property. On the contrary, the polyalkylene glycol having an excessively high weight-average molecular weight tends to cause the phase separation of the reaction system, and the properties of the resultant polyester elastomer tends to be lowered. Examples of the polyalkylene glycol include polyethylene glycol, poly(1,2- and 1,3-propylene ether) glycol, polytetramethylene glycol, and polyhexamethylene glycol. The commercial products of polyester elastomers include “Primalloy” (Mitsubishi Chemical Corporation), “Pelprene” (Toyobo Co., Ltd.), and “Hytrel” (Du Pont-Toray Co., Ltd.), etc.
(a-2) The polyester elastomer used in the present invention preferably has polybutylene terephthalate as the hard segment and polytetramethylene glycol as the soft segment.
Examples of (a-3) the unsaturated carboxylic acid used for the modification of the polyester elastomer include unsaturated carboxylic acids such as acrylic acid, maleic acid, fumaric acid, tetrahydrophtalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid, which may have an alkyl group, a halogen atom or the like as a substituent. Examples of the derivative thereof include an ester and an anhydride thereof. The anhydride having an unsaturated bond in the side chain can be also used. Examples include unsaturated carboxylic anhydrides such as (2-octene-1-yl)succinic anhydride, (2-dodecene-1-yl)succinic anhydride, (2-octadecene-1-yl)succinic anhydride, maleic anhydride, 2,3-dimethylmaleic anhydride, bromomaleic anhydride, dichloromaleic anhydride, citraconic anhydride, itaconic anhydride, 1-butene-3,4-dicarboxylic acid anhydride, 1-cyclopentene-1,2-dicarboxylic acid anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, endo-bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, and bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic anhydride; and unsaturated carboxylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, dimethyl maleate, 2-ethylhexyl maleate, 2-hydroxyethyl methacrylate. Among them, preferred is an anhydride of the unsaturated carboxylic acid, particularly preferred is an anhydride of maleic acid. These compounds having unsaturated bonds are suitably selected according to the type of the polyester elastomer to be modified and the modification conditions and may be used in combination of two or more.
As (a-1) the radical generator, various compounds can be used. Examples of the radical generator include organic or inorganic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane 2,5-dihyroperoxide, 2,5-dimethyl-2,5-bis(t-butyloxy)hexane, 3,5,5-trimethylhexanoyl peroxide, t-butyl peroxybenzoate, benzoyl peroxide, dicumyl peroxide, 1,3-bis(t-butylperoxyisopropyl)benzene, dibutyl peroxide, methyl ethyl ketone peroxide, potassium peroxide, and hydrogen peroxide; azo compounds such as 2,2′-azobisisobutyronitrile, 2,2′-azobis(isobutylamide)dihalide, 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], and azodi-t-butane; and carbon radical generators such as dicumyl. The radical generators are suitably selected according to the type of the polyester elastomer to be modified, the type of the unsaturated carboxylic acid or derivative thereof and the modification conditions, and may be used in combination of two or more.
In the modification reaction, the blending ratio of (a-3) component preferably ranges from 0.01 mass % to 30 mass %, more preferably 0.05 mass % to 5 mass %, even more preferably 0.1 mass % to 2 mass %, most preferably 0.1 mass % to 1 mass % with respect to 100 mass % of (a-2) component. The blending ratio of (a-1) component preferably ranges from 0.001 mass % to 3 mass %, more preferably 0.005 mass % to 0.5 mass %, even more preferably 0.01 mass % to 0.2 mass %, most preferably 0.01 mass % to 0.1 mass % with respect to 100 mass % of (a-2) component. In most preferable modification, the blending ratio of (a-3) component ranges from 0.1 mass % to 1 mass % and the blending ratio of (a-1) component ranges from 0.01 mass % to 0.1 mass %, with respect to 100 mass % of (a-2) component.
In general, if the blending amount of (a-3) component is low, the modification degree becomes small, and thus the intermediate layer composition obtained by blending the resultant polyester elastomer and the ionomer resin does not tend to exhibit a sufficient abrasion resistance. On the other hand, if the blending amount is excessive, the resultant polyester elastomer has a low viscosity when melt, and thus it is difficult to mold the intermediate layer composition obtained by blending the resultant polyester elastomer with the ionomer resin. Further, if the blending amount of (a-1) component is too low, the modification does not occur sufficiently, and thus the sufficient wear resistance is hardly exhibited. On the contrary, if the blending amount is too much, the resultant polyester elastomer has a low viscosity when melt, and thus the moldability becomes worse.
The modification for producing the modified polyester elastomer using (a-1) component, (a-2) component, and (a-3) component is conducted by a known method such as a melt kneading method, solution method and suspended dispersion method. Conventionally, the melt kneading method is preferable. In case of the melt kneading method, (a-2) component, (a-3) component, and (a-1) component may be uniformly mixed in a predetermined blending ratio using a Henschel mixer, a ribbon blender, a V-shape blender or the like and then the resultant mixture may be melt-kneaded using a Banbury mixer, a kneader, a roll, or a single- or multi- (e.g. twin-) screw kneading extruder. If necessary, (a-3) component and (a-2) component may be solved in a solvent for the modification reaction. The melt kneading is preferably performed at the temperature ranging from 100° C. to 300° C., more preferably 120° C. to 280° C., even more preferably 150° C. to 250° C., so as to avoid the thermal degradation of the resins.
(A) The modified polyester elastomer used in the present invention preferably has a slab hardness of 95 or less, more preferably 93 or less, even more preferably 91 or less in Shore A hardness, and preferably has a slab hardness of 70 or more, more preferably 75 or more, even more preferably 80 or more in Shore A hardness. If the slab hardness of the modified polyester elastomer falls within the above range, the intermediate layer composition tends to have a hardness in a desired range, and shows a good balance with the resilience. The slab hardness of the modified polyester elastomer means a hardness obtained by measuring the modified polyester elastomer formed in a sheet form, and can be measured by a later-described method.
Next, (B) the binary ionomer resin will be explained. The binary ionomer resin is one prepared by neutralizing at least a part of carboxyl groups in a binary copolymer composed of an olefin and an α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms with a metal ion. The olefin preferably includes an olefin having 2 to 8 carbon atoms. Examples of the olefin include ethylene, propylene, butene, pentene, hexene, heptene, and octene. Among them, ethylene is more preferred. Examples of the α,β-unsaturated carboxylic acid are acrylic acid, methacrylic acid, fumaric acid, maleic acid and crotonic acid. Among these, acrylic acid and methacrylic acid are particularly preferred. Among them, as (B) the binary ionomer resin, preferred is a metal ion-neutralized product of the binary copolymer composed of ethylene-(meth)acrylic acid.
The content of α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms in (B) the binary ionomer resin is preferably 15 mass % or more, more preferably 16 mass % or more, even more preferably 17 mass % or more, and is preferably 30 mass % or less, more preferably 25 mass % or less. If the content of α,β-unsaturated carboxylic acid is 15 mass % or more, the resilience and hardness become better, while if the acid content is 30 mass % or less, the balance among the resilience, moldability and hardness becomes better.
Examples of a metal (ion) used for neutralizing the binary copolymer include: monovalent metals (ions) such as sodium, potassium, lithium, or the like; divalent metals (ions) such as magnesium, calcium, zinc, barium, cadmium, or the like; trivalent metals (ions) such as aluminum or the like; and other metals (ions) such as tin, zirconium, or the like. Among these metals (ions), sodium, zinc and magnesium (ions) are preferably used because they provide excellent resilience, durability, or the like.
The degree of neutralization of the carboxylic groups contained in the binary ionomer resin is preferably 20 mole % or more, more preferably 30 mole % or more, and is preferably 90 mole % or less, more preferably 85 mole % or less. If the degree of neutralization is 20 mole % or more, the intermediate layer has a better resilience and durability. If the degree of neutralization is 90 mole % or less, the fluidity of the intermediate layer composition becomes better (resulting in good moldability). It is noted that the degree of neutralization of the carboxylic groups in the ionomer resin can be calculated by the following expression.

Degree of neutralization (mol %)=(the number of moles of carboxylic groups neutralized in the ionomer resin/the number of moles of all carboxylic groups contained in the ionomer resin)×100

Specific examples of the binary ionomer resin include trade name “Himilan® (e.g. Himilan 1605 (Na), Himilan 1706 (Zn), Himilan 1707 (Na), Himilan AM7311 (Mg), Himilan AM7329 (Zn))” commercially available from Du Pont-Mitsui Polychemicals Co., Ltd.
Further, examples include “Surlyn® (e.g. Surlyn 8945 (Na), Surlyn 9945 (Zn), Surlyn 8140 (Na), Surlyn 8150 (Na), Surlyn 9120 (Zn), Surlyn 9150 (Zn), Surlyn 6120 (Mg), Surlyn 7930 (Li), Surlyn 7940 (Li), Surlyn AD8546 (Li))” commercially available from E.I. du Pont de Nemours and Company.
Further, examples include “Lotek® (e.g. lotek 8000 (Na), lotek 8030 (Na), lotek 7010 (Zn), lotek 7030 (Zn))” commercially available from ExxonMobil Chemical Corporation.
The binary ionomer resins may be used alone or as a mixture of at least two of them. It is noted that Na, Zn, Li, and Mg described in the parentheses after the trade names indicate metal types of neutralizing metal ions for the metal-neutralized copolymer.
The flexural modulus of (B) the binary ionomer resin is preferably 300 MPa or more, more preferably 310 MPa or more, and even more preferably 330 MPa or more, and is preferably 600 MPa or less, more preferably 550 MPa or less, and even more preferably 500 MPa or less. If the flexural modulus of (B) the binary ionomer resin is too low, the elastic modulus of the intermediate layer becomes low, and the effects of increasing the launch angle and reducing the spin rate become small. On the other hand, if the flexural modulus of (B) the binary ionomer resin is too high, the elastic modulus of the intermediate layer becomes excessively high, and the durability and the shot feeling of the golf ball tend to deteriorate.
The melt flow rate (190° C., 2.16 kg) of the binary ionomer resin is preferably 1.0 g/10 min or more, more preferably 1.5 g/10 min or more, and even more preferably 2.0 g/10 min or more, and is preferably 30 g/10 min or less, more preferably 25 g/10 min or less, and even more preferably 20 g/10 min or less. If the melt flow rate (190° C., 2.16 kg) of the binary ionomer resin is 1.0 g/10 min or more, the fluidity of the intermediate layer composition becomes good, and it is possible to make a thin-walled intermediate layer. Thus, the spin rate when hitting a driver shot is reduced to give a great flight distance. If the melt flow rate (190° C., 2.16 kg) of the binary ionomer resin is 30 g/10 min or less, the durability of the obtained golf ball becomes better.
The binary ionomer resin preferably has a slab hardness of 65 or more, more preferably 66 or more, even more preferably 67 or more, and preferably has a slab hardness of 80 or less, more preferably 75 or less, even more preferably 70 or less in Shore D hardness. If the slab hardness of the binary ionomer resin is 65 or more in Shore D hardness, the intermediate layer becomes harder and thus the effect of the high launch angle and low spin rate becomes larger. If the slab hardness of the binary ionomer resin is 80 or less in Shore D hardness, the intermediate layer does not become excessively hard and the durability of the golf ball becomes better.
(C) Other Thermoplastic Resins than (A) Component and (B) Component
The intermediate layer composition used in the present invention may further comprise (C) other thermoplastic resins than (A) component and (B) component, in addition to (A) component and (B) component. Examples of (C) component include polyurethane, polyolefin, polyester, polyamide, polystyrene, polycarbonate, polyacetal, modified poly(phenyleneether), polyimide, polysulfone, polyethersulfone, poly(phenylenesulfide), polyarylate, polyamideimide, polyetherimide, polyetheretherketone, polyetherketone, polytetrafluororoethylene, polyaminobismaleimide, polybisamidetriazole, an acrylonitrile-butadiene-styrene copolymer, an acrylonitrile-styrene copolymer, an acrylonitrile-EPDM-styrene copolymer.
Specific examples of (C) component are a thermoplastic polyamide elastomer having a trade name “Pebax® (e.g. “Pebax 2533”)” commercially available from Arkema Inc., a thermoplastic polyurethane elastomer having a trade name “Elastollan® (e.g. “Elastollan XNY85A”)” commercially available from BASF Japan Ltd., a thermoplastic polyester elastomer having a trade name “Hytrel® (e.g. “Hytrel 3548” and “Hytrel 4047”)” commercially available from Du Pont-Toray Co., Ltd., a thermoplastic polystyrene elastomer having a trade name “Rabalon® (e.g. “Rabalon T3221C”)” commercially available from Mitsubishi Chemical Corporation, or the like.
In the present invention, the intermediate layer composition contains, as a resin component, (A) the modified polyester elastomer in an amount of 30 mass % to 70 mass %, (B) the binary ionomer resin in an amount of 70 mass % to 30 mass %, and (C) component in an amount of 0 mass % to 50 mass %, provided that a total content of (A) component, (B) component, and (C) component is 100 mass %. The contents of (A) component and (B) component preferably range from 35 mass % to 65 mass %, more preferably from 40 mass % to 60 mass %, respectively. If the contents of (A) component and (B) component fall within the above range, the intermediate layer has an appropriate rigidity and the golf ball has the high launch angle and low spin rate. Therefore, the golf ball travels a great distance. In addition, the shot feeling is improved.
The content of (C) component in the intermediate layer composition is preferably 0.1 mass % or more, more preferably 0.15 mass % or more, even more preferably 0.2 mass % or more, and is preferably 50 mass % or less, more preferably 45 mass % or less, even more preferably 40 mass % or less. If the content of (C) component falls within the above range, the intermediate layer composition has a desired hardness without lowering the mechanical properties.
The intermediate layer composition may further contain pigment components such as a white pigment (for example, titanium oxide) and a blue pigment; a mass adjusting agent; a dispersant; an antioxidant; an ultraviolet absorber; a light stabilizer; a fluorescent material or a fluorescent brightener or the like, as long as the performance of the golf ball of the present invention does not deteriorate.
Examples of the mass adjusting agent are metals such as gold, tungsten, molybdenum, lead, copper, iron, cast iron, pig iron, zinc, titanium, aluminum, zirconium; metal oxides such as aluminum oxide, bismuth oxide, cerium oxide, copper oxide, tin oxide, titanium oxide, yttrium oxide, zinc oxide, silica; barium sulfate; calcium carbonate; talc; montmorillonite; and mica. The mass adjusting agent may be used alone or in combination of two or more of them.
The blending amount of the mass adjusting agent is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, and is preferably 50 parts by mass or less, more preferably 47 parts by mass or less, even more preferably 44 parts by mass or less. If the blending amount of the mass adjusting agent is 1 part by mass or more, the density of the intermediate layer can be more easily adjusted. If the blending amount is 50 parts by mass or less, the dispersibility of the mass adjusting agent into the resin component becomes better.
The intermediate layer composition can be obtained by dry blending (A) the modified polyester elastomer and (B) the binary ionomer resin, followed by extruding and pelletizing. The dry blending may be carried out using for example, a mixer capable of blending a raw material in the form of pellet, more preferably a tumbler type mixer. In addition to the dry blending, the materials may be supplied respectively by the respective feeding machines. Extruding can be carried out by publicly known extruders such as a single-screw kneading extruder, a twin-screw kneading extruder, and a twin-single kneading extruder. The extruding condition is not particularly limited. For example, in the case of extruding with a twin-screw kneading extruder, the preferable conditions are screw diameter=45 mm; screw revolutions=50 rpm to 400 rpm; screw L/D=35 or less, and die temperature; 140° C. to 250° C. If desired, the modification of the polyester elastomer and the blending of the binary ionomer resin with the resultant modified polyester elastomer can be conducted at the same time by adding the binary ionomer resin as well as the radical generator and the unsaturated carboxylic acid to the polyester elastomer when preparing (A) the modified polyester elastomer.
The melt flow rate (230° C., 2.16 kg) of the intermediate layer composition is preferably 3 g/10 min or more, more preferably 5 g/10 min or more, and even more preferably 7 g/10 min or more, and is preferably 30 g/10 min or less, more preferably 27 g/10 min or less, and even more preferably 25 g/10 min or less. If the melt flow rate is 3 g/10 min or more, since the moldability of the intermediate layer is enhanced, it is easier to make a thin-walled intermediate layer.
The intermediate layer composition preferably has a flexural modulus of 150 MPa or more, more preferably 155 MPa or more, even more preferably 160 MPa or more, and preferably has a flexural modulus of 450 MPa or less, more preferably 430 MPa or less, even more preferably 400 MPa or less. If the flexural modulus of the intermediate layer composition is 150 MPa or more, it is possible to make the golf ball have an outer-hard and inner soft structure, resulting in a great flight distance. If the flexural modulus is 450 MPa or less, the obtained golf ball becomes appropriately soft and the shot feeling becomes better.
The intermediate layer composition preferably has a rebound resilience of 55% or more, more preferably 56% or more, even more preferably 57% or more. If the rebound resilience of the intermediate layer composition is 55% or more, the obtained golf ball travels a great distance. Herein, the flexural modulus and the rebound resilience is the flexural modulus and the rebound resilience of the intermediate layer composition molded into a sheet form and are measured by a method described later.
The intermediate layer composition preferably has a maximum loss factor (tan δ) of 0.08 or less, more preferably 0.07 or less, even more preferably 0.06 or less, and preferably has a maximum loss factor (tan δ) of 0.01 or more, more preferably 0.02 or more, even more preferably 0.03 or more, between −20° C. and 0° C. If the maximum value of the loss factor (tan δ) between −20° C. and 0° C. falls within the above range, the desirable resilience is obtained.
The intermediate layer composition preferably has a slab hardness of 60 or more, more preferably 65 or more, even more preferably 70 or more, and preferably has a slab hardness of 90 or less, more preferably 88 or less, even more preferably 86 or less in JIS-C hardness. If the intermediate layer composition has the slab hardness of 60 or more in JIS-C hardness, the intermediate layer has higher rigidity and the golf ball having more excellent resilience (distance) is obtained. On the other hand, if the intermediate layer composition has the slab hardness of 90 or less in JIS-C hardness, the obtained golf ball has higher durability. Herein, the slab hardness of the intermediate layer means the hardness of the intermediate layer composition molded into a sheet form and is measured by a later described method.
The melt flow rate, flexural modulus, rebound resilience, and slab hardness of the intermediate layer composition can be adjusted by appropriately selecting kinds, content or the like of (A) component, (B) component and (C) component.
(3) Center Composition and Envelope Layer Composition
For the center and the envelope layer of the golf ball of the present invention, a conventionally known rubber composition (hereinafter simply referred to as “center rubber composition” occasionally) may be employed, and it can be molded by, for example, heat-pressing a rubber composition containing a base rubber, a crosslinking initiator, a co-crosslinking agent, and a filler.
As the base rubber, a natural rubber and/or a synthetic rubber such as a polybutadiene rubber, a natural rubber, a polyisoprene rubber, a styrene polybutadiene rubber, and ethylene-propylene-diene terpolymer (EPDM) may be used. Among them, typically preferred is the high cis-polybutadiene having cis-1,4-bond in a proportion of 40% or more, more preferably 70% or more, even more preferably 90% or more in view of its superior repulsion property.
The center of the golf ball of the present invention is preferably formed by crosslinking a rubber composition including a polybutadiene rubber.
The crosslinking initiator is blended to crosslink the base rubber component. As the crosslinking initiator, an organic peroxide is preferably used. Examples of the organic peroxide for use in the present invention are 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. Among them, dicumyl peroxide is preferable. An amount of the crosslinking initiator to be blended in the rubber composition is preferably 0.3 part by mass or more, more preferably 0.4 part by mass or more, and is preferably 5 parts by mass or less, more preferably 3 parts by mass or less based on 100 parts by mass of the base rubber. If the amount is less than 0.3 part by mass, the center becomes too soft, and the resilience tends to be lowered, and if the amount is more than 5 parts by mass, the amount of the co-crosslinking agent must be increased in order to obtain the appropriate hardness, and thus the resilience is likely to be lowered.
The co-crosslinking agent is not particularly limited as long as it has the effect of crosslinking a rubber molecule by graft polymerization with a base rubber molecular chain; for example, α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms or a metal salt thereof, more preferably acrylic acid, methacrylic acid or a metal salt thereof may be used. As the metal constituting the metal salt, for example, zinc, magnesium, calcium, aluminum and sodium may be used, and among them, zinc is preferred because it provides high resilience.
The amount of the co-crosslinking agent to be used is preferably 10 parts or more, more preferably 15 parts or more, even more preferably 20 parts or more, and is preferably 55 parts or less, more preferably 50 parts or less, even more preferably 48 parts or less based on 100 parts of the base rubber by mass. If the amount of the co-crosslinking agent to be used is less than 10 parts by mass, the amount of the crosslinking initiator must be increased to obtain an appropriate hardness, which tends to lower the resilience. On the other hand, if the amount of the co-crosslinking agent to be used is more than 55 parts by mass, the center becomes too hard, so that the shot feeling may be lowered.
The filler contained in the center rubber composition or the envelope layer composition is mainly blended as a specific gravity adjusting agent in order to adjust the specific gravity of the golf ball obtained as the final product in the range of 1.0 to 1.5, and may be blended as required. Examples of the filler include an inorganic filler such as zinc oxide, barium sulfate, calcium carbonate, magnesium oxide, tungsten powder, and molybdenum powder. The amount of the filler to be blended in the rubber composition is preferably 0.5 part or more, more preferably 1 part or more, and is preferably 30 parts or less, more preferably 20 parts or less based on 100 parts of the base rubber by mass. If the amount of the filler to be blended is less than 0.5 part by mass, it becomes difficult to adjust the weight, while if it is more than 30 parts by mass, the weight ratio of the rubber component becomes small and the resilience tends to be lowered.
As the center rubber composition or the envelope layer composition, an organic sulfur compound, an antioxidant or a peptizing agent may be blended appropriately in addition to the base rubber, the crosslinking initiator, the co-crosslinking agent and the filler.
As the organic sulfur compound, diphenyl disulfide or a derivative thereof may be preferably used. Examples of the diphenyl disulfide or the derivative thereof include diphenyl disulfide; a mono-substituted diphenyl disulfide such as 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; a di-substituted diphenyl disulfide 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; a tri-substituted diphenyl disulfide such as bis (2,4,6-trichlorophenyl)disulfide, and bis(2-cyano-4-chloro-6-bromophenyl) disulfide; a tetra-substituted diphenyl disulfide such as bis(2,3,5,6-tetra chlorophenyl)disulfide; a penta-substituted diphenyl disulfide such as bis (2,3,4,5,6-pentachlorophenyl)disulfide and bis(2,3,4,5,6-pentabromophenyl) disulfide. These diphenyl disulfides or the derivative thereof can enhance resilience by having some influence on the state of vulcanization of vulcanized rubber. Among them, diphenyl disulfide and bis(pentabromophenyl)disulfide are preferably used since a golf ball having particularly high resilience can be obtained. The amount of the diphenyl disulfide or the derivative thereof to be blended is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, and is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less relative to 100 parts by mass of the base rubber.
The amount of the antioxidant to be blended is preferably 0.1 part or more and is preferably 1 part or less based on 100 parts of the base rubber by mass. Further, the amount of the peptizing agent is preferably 0.1 part or more and is preferably 5 parts or less based on 100 parts of the base rubber by mass.
Preferably, the core of the golf ball of the present invention comprises a center and an envelope layer, wherein the center is formed from a rubber composition not containing an organic sulfur compound and the envelope layer is formed from a rubber composition containing an organic sulfur compound, because the obtained core has the appropriate hardness distribution.
(4) Adhesive Layer Composition
An adhesive layer is formed from an adhesive layer composition containing a resin component. As the resin component, a two-component curing type thermosetting resin is suitably used. Specific examples thereof include epoxy resins, urethane resins, acryl resins, polyester based resins and cellulose based resins. Among them, a two-component curing type epoxy resin is preferred as the resin component. Particularly, the adhesive layer is preferably formed from a two-component curing type adhesive layer composition containing a bisphenol A type epoxy resin as a base resin and a polyamine compound as a curing agent.
The adhesive layer composition, for example, is obtained by blending a base resin containing a bisphenol A type epoxy resin and a solvent and a curing agent containing a polyamine compound and a solvent. Examples of the solvent in the base resin and curing agent include organic solvents such as xylene and toluene as well as water.
The polyamine compound contains polyamideamine or modified products thereof. Polyamideamine has multiple amino groups and one or more amide groups. This amino group can react with an epoxy group. Polyamideamine is obtained by a condensation reaction between a polymerized fatty acid and a polyamine. Typical polymerized fatty acids are synthesized 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. 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 90 mass % or more and a trimer content of 10 mass % or less, and being hydrogenated are preferred. Illustrative examples of preferred polyamine include polyethylene diamine, polyoxyalkylene diamine and derivatives thereof.
The adhesive layer composition preferably has a gel fraction of 40 mass % or more. The adhesive layer formed from the adhesive layer composition having the gel fraction of 40 mass % or more contains little bubble since the volatile component hardly remains in the adhesive layer. The adhesive layer composition firmly adheres to the intermediate layer as well as to the cover. In this light, the gel fraction is preferably 45 mass % or more, more preferably 50 mass % or more.
The gel fraction of the adhesive layer composition is preferably 80 mass % or less. The adhesive layer having the gel fraction of 80 mass % or less fully reacts with a base polymer of the intermediate layer as well as with a base polymer of the cover. This adhesive layer composition firmly adheres to the intermediate layer as well as to the cover. In this respect, the gel fraction is preferably 76 mass % or less, more preferably 70 mass % or less.
The adhesive layer formed from the adhesive layer composition having the gel fraction of 40 mass % or more and 80 mass % or less particularly exerts its effect in the golf ball with a thin cover. The adhesive layer formed from the adhesive layer composition having the gel fraction of 40 mass % or more and 80 mass % or less particularly exerts its effect in the golf ball with a soft cover.
Upon measurement of the gel fraction, the adhesive layer composition is coated on a PB-137T zinc phosphate-treated steel plate immediately after the base resin and curing agent is blended. The size of the steel plate is “150 mm×70 mm”. The steel plate has a thickness of 0.8 mm. This steel plate is kept under an environment of 40° C. for 24 hours to form a paint film composed of the adhesive layer composition. Test pieces are obtained from the steel plate and the paint film. The mass of the test pieces is measured, and the mass M1 of the paint film is calculated by reducing the mass of the steel plate from the mass of the test pieces. The test pieces are dipped into acetone and left for 24 hours. This test pieces are kept under an environment of 105° C. for 1 hour and then cooled to 23° C. The mass of the test pieces is measured, and the mass M2 of the paint film is calculated by reducing the mass of the steel plate from the measured mass of the test pieces. The gel fraction G is calculated based on the following expression.

G=(M2/M1)×100

In this adhesive layer composition, a ratio of epoxy equivalent of the bisphenol A type epoxy resin and amine active hydrogen equivalent of the curing agent is preferably 2.0/1.0 or more and 13.0/1.0 or less. If the adhesive layer composition having the ratio of 2.0/1.0 or more, the gel fraction does not become too small. Accordingly, the adhesive layer firmly adheres to the intermediate layer and the cover. In this light, the ratio is preferably 2.6/1.0 or more, more preferably 4.0/1.0 or more. If the adhesive layer composition has the ratio of 13.0/1.0 or less, the gel fraction does not become too large so that the adhesive layer firmly adheres to the intermediate layer and the cover. In this respect, the ratio is preferably 12.2/1.0 or less, more preferably 10.0/1.0 or less.
The amine active hydrogen equivalent of the curing agent is preferably 100 g/eq or more and 800 g/eq or less. If the adhesive layer composition has the curing agent with the amine active hydrogen equivalent of 100 g/eq or more, the gel fraction does not become too large so that the adhesive layer firmly adheres to the intermediate layer and the cover. In this respect, the equivalent is preferably 200 g/eq or more, and more preferably 300 g/eq or more. If the adhesive layer composition has the curing agent with the amine active hydrogen equivalent of 800 g/eq or less, the gel fraction does not become too small. Accordingly, the adhesive layer firmly adheres to the intermediate layer and the cover. In this light, the equivalent is preferably 600 g/eq or less, and more preferably 500 g/eq or less.
The adhesive layer composition contains water as volatile content. The term of volatile content means both water and an organic solvent. The proportion Pw of the water weight relative to the total weight of the volatile content is preferably 90 mass % or more. The adhesive layer composition having the proportion Pw of 90 mass % or more facilitates the control of the gel fraction. In this light, the proportion Pw is preferably 95 mass % or more, more preferably 99 mass % or more. The proportion Pw may be 100%. In light of environment, the proportion Po of the weight of the organic solvent relative to the total volume of the volatile content is preferably 10 mass % or less, more preferably 5 mass % or less, even more preferably 1 mass % or less.
The adhesive layer composition may contain additives such as a coloring agent (typically, titanium dioxide), an antioxidant, a light stabilizer, a fluorescent brightening agent, an ultraviolet absorbent, an anti-blocking agent or the like. The additives may be added either to the base resin or to the curing agent.
(5) Cover Composition
The cover of the golf ball of the present invention is formed from a cover composition containing a resin component. Examples of the resin components include an ionomer resin, a thermoplastic polyamide elastomer having a trade name “Pebax® (e.g. “Pebax 2533”)” commercially available from Arkema Inc., a thermoplastic polyester elastomer having a trade name “Hytrel® (e.g. “Hytrel 3548” and “Hytrel 4047”)” commercially available from Du Pont-Toray Co., Ltd., a thermoplastic polyurethane elastomer having a trade name “Elastollan® (e.g. “Elastollan XNY97A”)” commercially available from BASF Japan Ltd., a thermoplastic polystyrene elastomer having a trade name “Rabalon®” commercially available from Mitsubishi Chemical Corporation, and the like. These resin components may be used alone or in combination of two or more thereof.
The cover composition constituting the cover of the golf ball of the present invention preferably contains the thermoplastic polyurethane as a resin component. The content of the thermoplastic polyurethane in the resin component of the cover composition is preferably 50 mass % or more, more preferably 60 mass % or more, even more preferably 70 mass % or more.
The cover composition may contain a pigment component such as a white pigment (for example, titanium oxide), a blue pigment, a red pigment, or the like, a specific gravity adjusting agent such as zinc oxide, calcium carbonate, barium sulfate, or the like, a dispersant, an antioxidant, an ultraviolet absorber, a light stabilizer, a fluorescent material or a fluorescent brightener, or the like as long as they do not impair the performance of the cover.
The amount of the white pigment (for example, titanium oxide), with respect to 100 parts by mass of the resin component for forming the cover, is preferably 0.5 part by mass or more and more preferably 1 part by mass or more, and is preferably 10 parts by mass or less and more preferably 8 parts by mass or less. If the amount of the white pigment is 0.5 part by mass or more, it is possible to provide opacity to the cover. If the amount of the white pigment is more than 10 parts by mass, the durability of the resultant cover may deteriorate.
(6) Process for Producing Golf Ball
The center can be obtained by mixing, kneading the above mentioned rubber composition and molding the rubber composition in the mold. The conditions for press-molding the center rubber composition should be determined depending on the rubber composition. Specifically, the press-molding is preferably carried out for 10 to 60 minutes at the temperature of 130° C. to 200° C. under the pressure from 2.9 MPa to 11.8 MPa. Alternatively, the press-molding is preferably carried out in a two-step heating, for example, for 20 to 40 minutes at the temperature of 130° C. to 150° C., and continuously for 5 to 15 minutes at the temperature of 160° C. to 180° C.
For forming the envelope layer and intermediate layer, publicly known methods such as injection molding, compression molding and the like can be employed. In light of productivity, injection molding is preferred.
In case of forming the intermediate layer by injection molding, it is preferred to use upper and lower molds for forming the intermediate layer having a spherical cavity and pimples, wherein a part of the pimple also serves as a retractable hold pin. When forming the intermediate layer by injection molding, the hold pin is protruded to hold the center, and the resin composition which has been heated and melted is charged and then cooled to obtain the intermediate layer. For example, the resin composition heated and melted at the temperature of 150° C. to 230° C. is charged into a mold held under the pressure of 980 KPa to 1,500 KPa for 0.1 to 1 second. After cooling for 15 to 60 seconds, the mold is opened.
The molding temperature means the highest temperature where the temperature at the surface of the concave portion of the lower mold reaches from closing through opening the molds. Further, the flow beginning temperature of the intermediate layer composition can be measured in a pellet form with the following conditions by using a flow characteristics evaluation apparatus (Flow Tester CFT-500, manufactured by Shimadzu Corporation).
Measuring conditions: Area size of a plunger: 1 cm2, Die length: 1 mm, Die diameter: 1 mm, Load: 588.399 N, Start temperature: 30° C., and Temperature increase rate: 3° C./min.
The adhesive layer is obtained by applying, to the surface of the intermediate layer, liquids where the base material and the curing agent are dissolved or dispersed in a solvent. In light of workability, application with a spray gun is preferred. After the application, the solvent is volatilized to permit a reaction of the base material with the curing agent, thereby forming the adhesive layer.
An embodiment for molding a cover is not particularly limited, and includes an embodiment which comprises injection molding the cover composition directly onto the core, or an embodiment which comprises molding the cover composition into a hollow-shell, covering the core with a plurality of the hollow-shells and subjecting the core with a plurality of the hollow shells to the compression-molding (preferably an embodiment which comprises molding the cover composition into a half hollow-shell, covering the core with the two half hollow-shells, and subjecting the core with the two half hollow-shells to the compression-molding).
When molding the cover in a compression molding method, molding of the half shell can be performed by either compression molding method or injection molding method, and the compression molding method is preferred. The compression-molding of the cover composition into a half shell can be carried out, for example, under a pressure of 1 MPa or more and 20 MPa or less at a temperature of −20° C. or more and 70° C. or less relative to the flow beginning temperature of the cover composition. By performing the molding under the above conditions, a half shell having a uniform thickness can be formed. Examples of a method for molding the cover using half shells include compression molding by covering the core with two half shells. The compression molding of half shells into the cover can be carried out, for example, under a pressure of 0.5 MPa or more and 25 MPa or less at a temperature of −20° C. or more and 70° C. or less relative to the flow beginning temperature of the cover composition. By performing the molding under the above conditions, a golf ball cover having a uniform thickness can be formed.
In the case of directly injection molding the cover composition onto the core, it is preferred to use upper and lower molds for forming a cover having a spherical cavity and pimples, wherein a part of the pimple also serves as a retractable hold pin. When forming the cover by injection molding, the hold pin is protruded to hold the core, and the cover composition which has been heated and melted is charged and then cooled to obtain a cover. For example, the cover composition heated and melted at the temperature of 200° C. to 250° C. is charged into a mold held under the pressure of 9 MPa to 15 MPa for 0.5 to 5 second. After cooling for 10 to 60 seconds, the mold is opened and the golf ball with the cover molded is taken out from the mold. When molding a cover, the concave portions called “dimple” are usually formed on the surface.
After the cover is molded, the mold is opened and the golf ball body is taken out from the mold, and as necessary, the golf ball body is preferably subjected to surface treatments such as deburring, cleaning, and sandblast. If desired, a paint film or a mark may be formed. The paint film preferably has a thickness of, but not limited to, 5 μm or larger, and more preferably 7 μm or larger, and preferably has a thickness of 50 μm or smaller, more preferably 40 μm or smaller, and even more preferably 30 μm or smaller. If the thickness is smaller than 5 μm, the paint film is easy to wear off due to continued use of the golf ball, and if the thickness is larger than 50 μm, the effect of the dimples is reduced, resulting in deteriorating flying performance of the golf ball.
EXAMPLES
Hereinafter, the present invention will be described in detail by way of example. The present invention is not limited to examples described below. Various changes and modifications can be made without departing from the spirit and scope of the present invention.
[Evaluation Methods]
(1) Hardness of Core (JIS-C Hardness)
A type P1 auto loading durometer manufactured by Kobunshi Keiki Co., Ltd., provided with a JIS-C type spring hardness tester was used to measure the surface hardness He of the core. JIS-C hardness measured at the surfaces of the core was employed as the surface hardness He of the core. The core was cut into two hemispheres to obtain a cut plane, and a JIS-C hardness measured at the central point of the cut plane was employed as the central hardness Ho of the core. JIS-C hardness of points at predetermined distances from the core central point of the cut plane was measured.
(2) Slab Hardness (Shore D Hardness, Shore A Hardness)
Sheets with a thickness of about 2 mm were produced by injection molding the envelope layer composition, the intermediate layer composition or the cover composition and stored at 23° C. for two weeks. Three or more of these sheets were stacked on one another so as not to be affected by the measuring base plate on which the sheets were placed, and the stack was measured with a type LA1 auto loading durometer manufactured by Kobunshi Keiki Co., Ltd., provided with a Shore D or Shore A type spring hardness tester.
(3) Compression Deformation Amount (mm)
A compression deformation amount of the center, core or golf ball (a shrinking amount of the center, core or golf ball in the compression direction thereof), when applying an initial load of 98 N to a final load of 1275 N, was measured.
(4) Melt Flow Rate (MFR) (g/10 min)
The MFR was measured using a flow tester (Shimadzu flow tester CFT-100C manufactured by Shimadzu Corporation) in accordance with JIS K7210. The measurement was conducted under the conditions of the measurement temperature 190° C. or 230° C. and the load of 2.16 kg.
(5) Flexural Modulus (MPa) (3 Points Bending Test, MPa)
Sheets having a thickness about 2 mm were produced by heat-pressing the ionomer resin or the intermediate layer composition, and stored at 23° C. for two weeks. The flexural modulus was measured according to JIS K7171. The measurement was conducted at a temperature of 23° C. and a humidity of 50% RH.
(6) Rebound Resilience (%)
A sheet with a thickness of about 2 mm was produced by a heat press molding from the intermediate layer composition. A circle-shaped test piece having a diameter of 28 mm was cut out of this sheet, and 6 pieces of the test piece were stacked to prepare a cylindrical test piece having a thickness of about 12 mm and a diameter of 28 mm. The cylindrical test piece was subjected to the Lupke type rebound resilience test (testing temperature 23° C., humidity 50 RH %). Preparation of the test piece and the testing method are based on JIS K6255.
(7) Measurement of Loss Factor (tan δ)
Sheets with a thickness of 0.5 mm were produced from the intermediate layer composition. Test pieces having a length of 30 mm, a width of 4 mm, and a thickness of 0.5 mm in a plate-like form were cut out from these sheets. The both ends of test pieces were clamed with chucks so that the length of displacement becomes 20 mm. The Loss factor was measured under the following conditions using Viscoelasticity spectrometer Rheogel-E4000 available from UBM CO., Ltd to determine the Maximum Loss Factor (tan δ) between −20° C. to 0° C.
Initial load: Auto static load 200%
Amplitude: 0.025%
Frequency: 10 Hz
Initial temperature: −100° C.
End temperature: 100° C.
Temperature increasing rate: 4° C./min
Measuring mode: tensile mode
(8) Spin Rate on Approach Shots
An approach wedge (SRIXON I-302, Shaft S available from SRI Sports Limited) was installed on a swing robot available from Golf Laboratories, Inc. Golf balls were hit at a head speed of 21 m/sec., and a sequence of photographs of the hit golf ball were taken for measuring the spin rate (rpm). The measurement was performed ten times for each golf ball, and the average value is regarded as the spin rate (rpm).
(9) Spin Rate on Driver Shots
A driver (XXIO, shaft S, Loft angle: 11° available from SRI Sports Limited) was installed on a swing robot available from Golf Laboratories, Inc. Golf balls were hit at a head speed of 50 m/sec., and a sequence of photographs of the hit golf ball were taken for measuring the spin rate (rpm). The measurement was performed ten times for each golf ball, and the average value is regarded as the spin rate (rpm).
(10) Shot Feeling
Ten golfers hit golf balls with a driver, and were asked about the shot feeling. The evaluation was categorized as follows based on the number of golfers who answered, “the impact was small and the shot feeling was excellent”.
A: 8 or more
B: 6 to 7
C: 4 to 5
D: 3 or less
[Preparation of Modified Polyester Elastomer]
(1) Modified Polyester Elastomer 1
100 parts by mass of a polyester elastomer containing 65 mass % of polytetramethylene glycol and 35 mass % of polybutylene terephthalate and 0.5 parts by mass of maleic anhydride (pulverized product), and 0.13 parts by mass of benzoyl peroxide (50% water-containing product, NYPER BWK) were mixed with a mixer, and extruded with a twin screw extruder (TEX54α manufactured by The Japan Steel Works, Ltd.) at the conditions of 200° C., 250 revolutions, and 250 kg/hr for a graft reaction of maleic anhydride to produce a modified polyester elastomer 1. The obtained modified polyester elastomer 1 contained maleic acid component in a content of 0.4 mass %, with Shore A hardness of 84, and a melt flow rate (230° C., 21N) of 24 g/10 min.
(2) Modified Polyester Elastomer 2
The modified polyester elastomer 2 was produced in the same manner as in Modified Polyester Elastomer 1 except for using a polyester elastomer containing 77 mass % of polytetramethylene glycol and 23 mass % of polybutylene terephthalate. The obtained modified polyester elastomer contained maleic acid component in a content of 0.5 mass %, with Shore A hardness of 80, and a melt flow rate (230° C., 21N) of 30 g/10 min.
[Production of Golf Balls]
(1) Production of Core
Blending materials shown in Table 1 were kneaded to prepare rubber compositions No. 1 to No. 5. From the rubber compositions, cores as shown in tables 2 to 4 having spherical centers and envelope layers were prepared. The spherical centers were obtained by heating the rubber compositions in upper and lower molds, each having a hemispherical cavity, at 170° C. for 15 minutes. The rubber compositions were molded into hollow-shells, covering the spherical centers obtained above with the two half hollow-shells. The centers and half hollow-shells were heated in upper and lower molds, each having a hemispherical cavity, at 150° C. for 20 minutes, to prepare spherical cores. The amount of barium sulfate was appropriately adjusted to make the centers and envelope layers have the same density and the resultant golf ball have a mass of 45.3 g.












TABLE 1





Rubber composition No.
1
2
3
4
5





















Formulation
BR-730
100
100
100
100
100



Zinc acrylate
23
30
32
35
35



Zinc oxide
5
5
5
5
5



Diphenyl disulfide
0.5
—
—
—
—



Bis(pentabromo-
—
0.3
0.3
—
0.3



phenyl)disulfide



Dicumyl peroxide
0.7
0.9
0.9
0.9
0.9



Barium Sulfate
*1)
*1)
*1)
*1)
*1)





Formulation: parts by mass


*1): Appropriate amount


BR-730: “BR-730 (high-cis polybutadiene)” manufactured by JSR Corporation


Zinc acrylate: “ZNDA-90S” manufactured by Nihon Jyoryu Kogyo Co., Ltd.


Zinc oxide: “Ginrei R” manufactured by Toho Zinc Co., Ltd.


Barium sulfate: “Barium Sulfate BD” manufactured by Sakai Chemical Industry Co., Ltd.


Dicumyl peroxide: “Percumyl (registered trademark) D” manufactured by NOF Corporation


Diphenyl disulfide: manufactured by Sumitomo Seika Chemicals Company Limited






(2) Preparation of Intermediate Layer Composition and Cover Composition

Blending materials shown in Tables 2 to 4, 5 were mixed with a twin-screw kneading extruder to prepare, intermediate layer compositions and cover compositions in the pellet form, respectively. The extruding conditions were a screw diameter of 45 mm, a screw rotational speed of 200 rpm, and screw L/D=35, and the mixtures were heated to 160 to 230° C. at the die position of the extruder.












TABLE 2





Golf ball No.
1
2
3
4
5





















Center
Rubber composition No.
1
1
1
1
1



Crosslinking temperature (° C.)
170
170
170
170
170



Crosslinking time (min)
15
15
15
15
15



Diameter (mm)
15
15
15
15
15


Envelope
Rubber composition No.
2
2
3
2
2


layer
Crosslinking temperature (° C.)
150
150
150
150
150



Crosslinking time (min)
20
20
20
20
20


Core
Diameter (mm)
39.7
40.1
38.5
39.7
40.1



Volume rate (%)
80.4
82.8
73.3
80.4
82.8



Central hardness Ho (JIS-C)
65
65
63
65
65



Surface hardness He (JIS-C)
86
86
83
86
86



Hardness difference (He − Ho)
21
21
20
21
21



Hardness distribution
FIG. 2
FIG. 3
FIG. 4
FIG. 2
FIG. 3



H2 − H1 (minimum value)
0.8
0.8
0.8
0.8
0.8



H2 − H1 (maximum value)
4.8
4.0
3.0
4.8
4.0
















Intermediate
Formulation
Resin
(A)
Modified Polyester Elastomer 1
40
40
40
—
—


layer

Component

Modified Polyester Elastomer 2
—
—
—
40
40


composition



Slab hardness (Shore A)
84
84
84
80
80





(B)
Surlyn 8150
36
36
36
36
36






Surlyn 8945
—
—
—
—
—






Surlyn 9150
24
24
24
24
24






Himilan AM7329
—
—
—
—
—






Slab hardness (JIS-C)
97
97
97
97
97






Flexural modulus (MPa)
450
450
450
450
450






MFR(190° C. × 2.16 kg, g/10 min)
5
5
5
5
5





(C)
TPEE
—
—
—
—
—














Titanium oxide
4
4
4
4
4















Properties
Thickness (mm)
1.0
0.8
1.6
1.0
0.8




Slab hardness Hm (JIS-C/Shore D)
84/56
84/56
84/56
80/53
80/53




Flexural modulus (MPa)
273
273
273
231
231




Max Loss Factor (tan δ, −20° C. to 0° C.)
0.05
0.05
0.05
0.05
0.05




Rebound resilience (%)
59
59
59
57
57













Cover
Thickness (mm)
0.5
0.5
0.5
0.5
0.5



Hardness Hc (JIS-C/Shore D)
53/32
53/32
53/32
53/32
53/32


Golf Ball
Compression deformation amount (mm)
2.62
2.60
2.60
2.64
2.64



Spin rate on driver shots (rpm)
2430
2400
2435
2440
2440



Flight distance (m)
277
278
277
277
278



Spin rate on approach shots (rpm)
6850
6800
6950
7000
6820



Shot feeling
A
A
A
A
A





Formulation: parts by mass


MFR: Melt Flow Rate


















TABLE 3





Golf ball No.
6
7
8
9
10





















Center
Rubber composition No.
1
1
1
1
1



Crosslinking temperature (° C.)
170
170
170
170
170



Crosslinking time (min)
15
15
15
15
15



Diameter (mm)
15
15
15
15
15


Envelope
Rubber composition No.
3
2
2
2
2


layer
Crosslinking temperature (° C.)
150
150
150
150
150



Crosslinking time (min)
20
20
20
20
20


Core
Diameter (mm)
38.5
39.7
39.7
39.7
39.7



Volume rate (%)
73.3
80.4
80.4
80.4
80.4



Central hardness Ho (JIS-C)
63
65
65
65
65



Surface hardness He (JIS-C)
83
86
86
86
86



Hardness difference (He − Ho)
20
21
21
21
21



Hardness distribution
FIG. 4
FIG. 2
FIG. 2
FIG. 2
FIG. 2














H2 − H1 (minimum value)
0.8
0.8
0.8
0.8
0.8



H2 − H1 (maximum value)
3.0
4.8
4.8
4.8
4.8
















Intermediate
Formulation
Resin
(A)
Modified Polyester Elastomer 1
—
—
40
30
30


layer

Component

Modified Polyester Elastomer 2
40
45
—
—
—


composition



Slab hardness (Shore A)
80
80
84
84
84





(B)
Surlyn 8150
36
33
—
36
—






Surlyn 8945
—
—
36
—
42






Surlyn 9150
24
22
—
24
—






Himilan AM7329
—
—
24
—
28






Slab hardness (JIS-C)
97
97
94
97
94






Flexural modulus (MPa)
450
450
330
450
330






MFR(190° C. × 2.16 kg, g/10 min)
5
5
5
5
5





(C)
TPEE
—
—
—
10
—














Titanium oxide
4
4
4
4
4















Properties
Thickness (mm)
1.6
1.0
1.0
1.0
1.0




Slab hardness Hm (JIS-C/Shore D)
80/53
78/51
80/53
83/55
84/56




Flexural modulus (MPa)
231
222
215
220
202




Max Loss Factor (tan δ, −20° C. to 0° C.)
0.05
0.05
0.05
0.05
0.05




Rebound resilience (%)
57
57
57
59
56













Cover
Thickness (mm)
0.5
0.5
0.5
0.5
0.5



Hardness Hc (JIS-C/Shore D)
53/32
53/32
53/32
53/32
53/32


Golf Ball
Compression deformation amount (mm)
2.60
2.65
2.65
2.65
2.67



Spin rate on driver shots (rpm)
2480
2480
2550
2450
2500



Flight distance (m)
277
277
276
277
276



Spin rate on approach shots (rpm)
7050
7010
7050
7010
7070



Shot feeling
A
A
A
A
A





Formulation: parts by mass


MFR: Melt Flow Rate



















TABLE 4





Golf ball No.
11
12
13
14
15
16






















Center
Rubber composition No.
1
1
1
1
4
1



Crosslinking temperature (° C.)
170
170
170
170
170
170



Crosslinking time (min)
15
15
15
15
15
15



Diameter (mm)
15
15
15
15
15
15


Envelope
Rubber composition No.
2
2
2
2
2
5


layer
Crosslinking temperature (° C.)
150
150
150
150
150
150



Crosslinking time (min)
20
20
20
20
20
20


Core
Diameter (mm)
39.7
39.7
39.7
39.7
39.7
39.1



Volume rate (%)
80.4
80.4
80.4
80.4
80.4
76.8



Central hardness Ho (JIS-C)
65
65
65
65
65
64



Surface hardness He (JIS-C)
86
86
86
86
86
87



Hardness difference (He − Ho)
21
21
21
21
21
23



Hardness distribution
FIG. 2
FIG. 2
FIG. 2
FIG. 2
FIG. 2
FIG. 5



H2 − H1 (minimum value)
0.8
0.8
0.8
0.8
0.8
0.6



H2 − H1 (maximum value)
4.8
4.8
4.8
4.8
4.8
5.9

















Intermediate
Formulation
Resin
(A)
Modified Polyester Elastomer 1
50
60
20
80
40
40


layer

Component

Modified Polyester Elastomer 2
—
—
—
—
—
—


composition



Slab hardness (Shore A)
84
84
84
84
84
84





(B)
Surlyn 8150
30
24
35
10
36
36






Surlyn 8945
—
—
—
—
—
—






Surlyn 9150
20
16
35
10
24
24






Himilan AM7329
—
—
—
—
—
—






Slab hardness (JIS-C)
97
97
97
97
97
97






Flexural modulus (MPa)
450
450
450
450
450
450






MFR(190° C. × 2.16 kg, g/10 min)
5
5
5
5
5
5





(C)
TPEE
—
—
10
—
—
—















Titanium oxide
4
4
4
4
4
4
















Properties
Thickness (mm)
1.0
1.0
1.0
1.0
1.0
1.0




Slab hardness Hm (JIS-C/Shore D)
79/52
79/52
89/60
61/38
84/56
84/56




Flexural modulus (MPa)
200
180
285
60
273
273




Max Loss Factor (tan δ, −20° C. to 0° C.)
0.05
0.05
0.03
0.09
0.05
0.05




Rebound resilience (%)
60
62
54
64
59
59














Cover
Thickness (mm)
0.5
0.5
0.5
0.5
0.5
0.5



Hardness Hc (JIS-C/Shore D)
53/32
53/32
53/32
53/32
53/32
53/32


Golf Ball
Compression deformation amount (mm)
2.66
2.66
2.50
2.75
2.64
2.65



Spin rate on driver shots (rpm)
2530
2550
2350
2700
2450
2400



Flight distance (m)
276
276
279
273
277
276



Spin rate on approach shots (rpm)
7080
7100
6730
7200
6900
6780



Shot feeling
A
A
A
A
A
A





Formulation: parts by mass


MFR: Melt Flow Rate






Raw materials used in Tables 2 to 4 are as follows.
Surlyn 8150: Sodium ion neutralized ethylene-methacrylic acid copolymer (acid content: 17 mass % or more, flexural modulus: 364 MPa, Melt Flow Rate (190° C., 2.16 kg): 4.5, Shore D hardness: 68) available from E.I. du Pont de Nemours and Company.
Surlyn 8945: Zinc ion neutralized ethylene-methacrylic acid copolymer ionomer resin (acid content: 15 mass % or less, flexural modulus: 254 MPa, Melt Flow Rate (190° C., 2.16 kg): 5, Shore D hardness: 61) available from E.I. du Pont de Nemours and Company.
Surlyn 9150: Zinc ion neutralized ethylene-methacrylic acid copolymer ionomer resin (acid content: 17 mass % or more, flexural modulus: 252 MPa, Melt Flow Rate (190° C., 2.16 kg): 4.5, Shore D hardness: 64) available from E.I. du Pont de Nemours and Company.

HIMILAN AM7329: Zinc ion neutralized ethylene-methacrylic acid copolymer ionomer resin (Acid content: 15 mass % or less, flexural modulus: 240 MPa, Melt Flow Rate (190° C., 2.16 kg): 5, Shore D hardness: 59) available from Du Pont-Mitsui Polychemicals Co., Ltd.

TPEE: Thermoplastic polyester elastomer (65 mass % of polytetramethylene glycol and 35 mass % of polybutylene terephthalate)











TABLE 5







Cover composition
A




















Formulation
Elastollan XNY85A
100




Titanium oxide
 4










Slab hardness Hc (JIS-C/Shore D)
53/32







Formulation: parts by mass






Elastollan XNY85A: H12MDI-polyether thermoplastic polyurethane elastomer available from BASF Japan
(3) Production of Intermediate Layer
The intermediate layer compositions obtained above were injection-molded onto the cores to mold intermediate layers covering the centers. Upper and lower molds for the intermediate layer have a spherical cavity with pimples, a part of pimples serves a hold pin which is retractable.
When molding the intermediate layer, the hold pins were protruded to hold the core, the intermediate layer compositions heated at 260° C. was charged into the mold under a pressure of 80 tons within 0.3 seconds, and cooled for 30 seconds. Then, the mold was opened, and the intermediate layer was molded.
The adhesive layer was formed by coating a two-component thermosetting resin on the intermediate layer. A base resin of the two-component thermosetting resin is a water-based epoxy composition available from Shinto Paint Co., Ltd. The base resin includes 36 parts by mass of a bisphenol A epoxy resin and 64 parts by mass of water. Epoxy equivalent of the base resin is 1405 g/eq. A curing agent is a water-based amine composition available from Shinto Paint Co., Ltd. The curing agent includes 44 parts by mass of modified polyamideamine, 50 parts by mass of water, 1 part by mass of propylene glycol and 5 parts by mass of titanium dioxide. Active hydrogen equivalent of the curing agent is 348 g/eq. The adhesive layer was obtained by coating the adhesive layer composition on the surface of the intermediate layer with a spray gun and being kept under the temperature of 23° C. for 12 hours. The adhesive layer had a thickness of 0.003 mm. The gel fraction of the two-component thermosetting resin was 64 mass %.
(4) Molding of Half Shells
Compression molding of half shells were performed by, charging one pellet of the cover composition obtained as described above into each of depressed parts of lower molds for molding half shells, and applying pressure to mold half shells. Compression molding was performed at a temperature of 170° C. for 5 minutes under a molding pressure of 2.94 MPa.
(5) Molding of the Cover
The core obtained in (3) was covered with the two half shells obtained in (4) in a concentric manner, and the cover was molded by compression molding. Compression molding was performed at a temperature of 145° C. for 2 minutes under a molding pressure of 9.8 MPa.
Surface of the obtained golf ball body was subjected to a sandblast treatment, and marking, and then clear paint was applied thereto and dried in an oven at a temperature of 40° C. to obtain a golf ball having a diameter of 42.7 mm and a mass of 45.3 g. The performance of the obtained golf ball was evaluated, and results thereof are also shown in Tables 2 to 4. Additionally, the hardness distribution of the core of the obtained golf ball is shown in Table 6 and FIGS. 2 to 5.









TABLE 6









Hardness distribution of core of gold ball
























1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16




























Distance
0.0
65.0
65.0
65.0
65.0
65.0
65.0
65.0
65.0
65.0
65.0
65.0
65.0
65.0
65.0
65.0
65.0


from
5.0
67.0
67.0
67.0
67.0
67.0
67.0
67.0
67.0
67.0
67.0
67.0
67.0
67.0
67.0
67.0
66.5


center
6.5
68.0
68.0
68.0
68.0
68.0
68.0
68.0
68.0
68.0
68.0
68.0
68.0
68.0
68.0
68.0
—


(mm)
7.5
68.5
68.5
68.5
68.5
68.5
68.5
68.5
68.5
68.5
68.5
68.5
68.5
68.5
68.5
68.5
—



7.5
70.5
70.5
67.5
70.5
70.5
67.5
70.5
70.5
70.5
70.5
70.5
70.5
70.5
70.5
70.5
—



8.5
72.0
72.0
69.0
72.0
72.0
69.0
72.0
72.0
72.0
72.0
72.0
72.0
72.0
72.0
72.0
—



10.0
74.0
74.0
71.0
74.0
74.0
71.0
74.0
74.0
74.0
74.0
74.0
74.0
74.0
74.0
74.0
69.5



12.5
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
71.5



12.5
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
75.0



15.0
81.5
81.5
78.5
81.5
81.5
78.5
81.5
81.5
81.5
81.5
81.5
81.5
81.5
81.5
81.5
79.0



19.3
—
—
83.0
—
—
83.0
—
—
—
—
—
—
—
—
—
—



19.6
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
87.0



19.9
86.0
—
—
86.0
—
—
86.0
86.0
86.0
86.0
86.0
86.0
86.0
86.0
86.0
—



20.1
—
86.0
—
—
86.0
—
—
—
—
—
—
—
—
—
—
—





Hardness: JIS-C hardness






FIG. 2 indicates that a maximum value of H2−H1 is 4.8 and a minimum value thereof is 0.8. FIG. 3 indicates that a maximum value of H2−H1 is 4.0 and a minimum value thereof is 0.8. FIG. 4 indicates that a maximum value of H2−H1 is 3.0 and a minimum value thereof is 0.8. FIG. 5 indicates that a maximum value of H2−H1 is 5.9 and a minimum value thereof is 0.8. From the results shown in Tables 2 to 4, the golf ball of the present invention has an improved controllability and shot feeling while maintaining a flight distance on driver shots.
The present invention is directed to a golf ball and provides a golf ball having an improved controllability and shot feeling while maintaining a flight distance on driver shots. This application is based on Japanese Patent application No. 2011-070626 filed on Mar. 28, 2011, the contents of which are hereby incorporated by reference.

## Claims

1. A golf ball having a core, an intermediate layer disposed around the core and a cover disposed around the intermediate layer,
wherein the core has a center and an envelope layer disposed around the center,
wherein a difference (He−Ho) between a JIS-C hardness He at the surface of the core and a JIS-C hardness Ho at the central point of the core is in a range from 15 to 30, and a JIS-C hardness Hc of the cover is less than the JIS-C hardness Ho at the central point of the core,
wherein at all points P included in a zone at a distance of 1 mm to 15 mm from the central point of the core, a following mathematical expression is satisfied:


−5.0≦H2−H1≦5.0,


(in the above mathematical expression, H1 represents a JIS-C hardness at a point P1 that is located inside the point P along the radial direction and at a distance of 1 mm from the point P, and H2 represents a JIS-C hardness at a point P2 that is located outside the point P along the radial direction and at a distance of 1 mm from the point P), and
wherein the intermediate layer is formed from an intermediate layer composition having a flexural modulus ranging from 150 MPa to 450 MPa, a maximum loss factor (tan δ) between −20° C. and 0° C. of 0.08 or less, a rebound resilience of 55% or more, and a slab hardness ranging from 60 to 90 in JIS-C hardness, and the intermediate layer composition comprises, as a resin component,
30 mass % to 70 mass % of (A) a modified polyester elastomer having a Shore A hardness of 95 or less;
70 mass % to 30 mass % of (B) a binary ionomer resin having a Shore D hardness of 65 or more, a flexural modulus of 300 MPa or more, and a melt flow rate (190° C., 2.16 kg) of 1.0 g/10 min or more; and
0 mass % to 50 mass % of (C) a thermoplastic resin other than (A) component and (B) component (provided that a total content of (A) component, (B) component, and (C) component is 100 mass %).

2. The golf ball according to claim 1, wherein (A) the modified polyester elastomer is obtained by a reaction between 0.01 mass % to 30 mass % of (a-3) an unsaturated carboxylic acid or a derivative thereof and 100 mass % of (a-2) a polyester elastomer containing a polyalkylene glycol component in a content ranging from 5 mass % to 90 mass % in a presence of (a-1) a radical generator.

3. The golf ball according to claim 1, wherein a content of an acid component in (B) the binary ionomer resin is 15 mass % or more.

4. The golf ball according to claim 1, wherein (C) component is at least one member selected from the group consisting of polyurethane, polyolefin, polyester, polyamide, polystyrene, polycarbonate, polyacetal, modified poly(phenyleneether), polyimide, polysulfone, polyethersulfone, poly(phenylenesulfide), polyarylate, polyamideimide, polyetherimide, polyetheretherketone, polyetherketone, polytetrafluororoethylene, polyaminobismaleimide, polybisamidetriazole, an acrylonitrile-butadiene-styrene copolymer, an acrylonitrile-styrene copolymer, and an acrylonitrile-EPDM-styrene copolymer.

5. The golf ball according to claim 1, wherein the cover has the JIS-C hardness Hc of 65 or less.

6. The golf ball according to claim 1, wherein the cover has a thickness Tc of 0.8 mm or less.

7. The golf ball according to claim 1, wherein the intermediate layer has a thickness of 2.0 mm or less.

8. The golf ball according to claim 1, wherein the cover contains a thermoplastic polyurethane as a resin component.

9. The golf ball according to claim 1, wherein
the center has a diameter in a range from 10 mm to 20 mm,
the envelope layer has a thickness in a range from 8 mm to 18 mm,
the intermediate layer has a thickness of 2.0 mm or less, and
the cover has a thickness of 0.5 mm or less.

10. The golf ball according to claim 1, wherein a hardness difference between the JIS-C hardness Hc of the cover and the JIS-C hardness Ho at the central point of the core is in a range from 10 to 40.

11. The golf ball according to claim 1, wherein the center is formed from a rubber composition not containing an organic sulfur compound, and the envelope layer is formed from a rubber composition containing an organic sulfur compound.

12. The golf ball according to claim 1, further comprising an adhesive layer disposed between the intermediate layer and the cover, wherein the adhesive layer is obtained by curing an adhesive layer composition containing a bisphenol A type epoxy resin as a base material and a polyamine compound as a curing agent, and the adhesive layer composition has a gel fraction from 40 mass % to 80 mass % in an acetone.

13. The golf ball according to claim 1, where a difference (He−Hi) between the surface hardness He of the envelope layer and a hardness Hi of the innermost point of the envelope layer ranges from 10 to 25 in JIS-C hardness.

14. The golf ball according to claim 1, wherein at all points P included in the zone at the distance of 1 mm to 15 mm from the central point of the core, a following mathematical expression is satisfied: 0.0≦H2−H1≦3.0.

15. The golf ball according to claim 2, wherein a blending ratio of (a-1) component ranges from 0.001 mass % to 3 mass % with respect to 100 mass % of (a-2) component.

16. The golf ball according to claim 1, wherein the intermediate layer composition has a melt flow rate (230° C., 2.16 kg) in a range from 3 g/10 min to 30 g/10 min.