# Patent

## Title
Golf ball

## Abstract

A golf ball, showing a lower spin rate and a greater flight distance on driver shots by controlling a hardness distribution of the spherical core thereof, comprises a spherical core and at least one cover layer covering the spherical core. The spherical core is formed from a rubber composition containing (a) a base rubber, (b) an α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms and/or a metal salt thereof as a co-crosslinking agent, (c) a crosslinking initiator, (d1) a salt of a carboxylic acid having 1 to 4 carbon atoms, or an aromatic carboxylic acid and/or a salt thereof, and (d2) at least one compound selected from the group consisting of an aliphatic carboxylic acid having 5 or more carbon atoms, a salt of an aliphatic carboxylic acid having 5 or more carbon atoms, thiobenzoic acids, salts of thiobenzoic acids, a mercaptocarboxylic acid derivative and a dithiodicarboxylic acid derivative.

## Background
FIELD OF THE INVENTION
The present invention relates to a golf ball traveling a great flight distance on driver shots, in particular, an improvement of a core of a golf ball.
DESCRIPTION OF THE RELATED ART
As a method for improving a flight distance on driver shots, for example, there are methods of using a core having high resilience and using a core having a hardness distribution in which the hardness increases toward the surface of the core from the center thereof. The former method has an effect of enhancing an initial speed, and the latter method has an effect of a higher launch angle and a lower spin rate. A golf ball having a higher launch angle and a low spin rate travels a great distance.
For example, Japanese Patent Publications Nos. S61-37178 A, S61-113475 A, S61-253079 A, 2008-212681 A, 2008-523952 T and 2009-119256 A disclose a technique of enhancing resilience of the core. Japanese Patent Publications Nos. S61-37178 A and S61-113475 A disclose a solid golf ball having an inner core where zinc acrylate as a co-crosslinking agent, palmitic acid, stearic acid, or myristic acid as a co-crosslinking activator, zinc oxide as another co-crosslinking activator, and a reaction rate retarder are blended, with respect to 100 parts by weight of a rubber.
Japanese Patent Publication No. S61-253079 A discloses a solid golf ball formed from a rubber composition containing an α,β-unsaturated carboxylic acid in an amount of 15 parts to 35 parts by weight, a metal compound to react with the α,β-unsaturated carboxylic acid and form a salt thereof in an amount of 7 parts to 60 parts by weight, and a high fatty acid metal salt in an amount of 1 part to 10 parts by weight with respect to 100 parts by weight of a base rubber.
Japanese Patent Publication No. 2008-212681 A discloses a golf ball comprising, as a component, a molded and crosslinked product obtained from a rubber composition essentially comprising a base rubber, a filler, an organic peroxide, an α,β-unsaturated carboxylic acid and/or a metal salt thereof, a copper salt of a saturated or unsaturated fatty acid.
Japanese Patent Publication No. 2008-523952 T discloses a golf ball, or a component thereof, molded from a composition comprising a base elastomer selected from the group consisting of polybutadiene and mixtures of polybutadiene with other elastomers, at least one metallic salt of an unsaturated monocarboxylic acid, a free radical initiator, and a non-conjugated diene monomer.
Japanese Patent Publication No. 2009-119256 A discloses a method of manufacturing a golf ball, comprising preparing a masterbatch of an unsaturated carboxylic acid and/or a metal salt thereof by mixing the unsaturated carboxylic acid and/or the metal salt thereof with a rubber material ahead, using the masterbatch to prepare a rubber composition containing the rubber material, and employing a heated and molded product of the rubber composition as a golf ball component, wherein the masterbatch of the unsaturated carboxylic acid and/or the metal salt thereof comprises: (A) from 20 wt % to 100 wt % of a modified polybutadiene obtained by modifying a polybutadiene having a vinyl content of from 0 to 2%, a cis-1,4 bond content of at least 80% and active terminals, the active terminal being modified with at least one type of alkoxysilane compound, (B) from 80 wt % to 0 wt % of a diene rubber other than (A) the above rubber component [the figures are represented by wt % in the case that a total amount of (A) and (B) equals to 100 wt %], and (C) an unsaturated carboxylic acid and/or a metal salt thereof.
For example, Japanese Patent Publications Nos. H6-154357 A, 2008-194471 A, 2008-194473 A and 2010-253268 A disclose a core having a hardness distribution. Japanese Patent Publication No. H6-154357 A discloses a two-piece golf ball comprising a core formed of a rubber composition containing a base rubber, a co-crosslinking agent and an organic peroxide, and a cover covering said core, wherein the core has the following hardness distribution according to JIS-C type hardness meter readings: (1) hardness at center: 58-73, (2) hardness at 5 to 10 mm from center: 65-75, (3) hardness at 15 mm from center: 74-82, (4) surface hardness: 76-84, wherein hardness (2) is almost constant within the above range, and the relation (1)<(2)<(3)≦(4) is satisfied.
Japanese Patent Publication No. 2008-194471 A discloses a solid golf ball comprising a solid core and a cover layer that encases the core, wherein the solid core is formed of a rubber composition composed of 100 parts by weight of a base rubber that includes from 60 to 100 parts by weight of a polybutadiene rubber having a cis-1,4 bond content of at least 60% and synthesized using a rare-earth catalyst, from 0.1 to 5 parts by weight of an organic sulfur compound, an unsaturated carboxylic acid or a metal salt thereof, an inorganic filler, and an antioxidant; the solid core has a deformation from 2.0 mm to 4.0 mm, when being applied a load from an initial load of 10 kgf to a final load of 130 kgf, and has the hardness distribution shown in the following table.










TABLE 1







Hardness distribution in solid core
Shore D harness









Center
30 to 48



Region located 4 mm from center
34 to 52



Region located 8 mm from center
40 to 58



Region located 12 mm from center (Q)
43 to 61



Region located 2 to 3 mm inside of surface (R)
36 to 54



Surface (S)
41 to 59



Hardness difference [(Q)-(S)]
 1 to 10



Hardness difference [(S)-(R)]
 3 to 10










Japanese Patent Publication No. 2008-194473 A discloses a solid golf ball comprising a solid core and a cover layer that encases the core, wherein the solid core is formed of a rubber composition composed of 100 parts by weight of a base rubber that includes from 60 to 100 parts by weight of a polybutadiene rubber having a cis-1,4 bond content of at least 60% and synthesized using a rare-earth catalyst, from 0.1 to 5 parts by weight of an organic sulfur compound, an unsaturated carboxylic acid or a metal salt thereof, and an inorganic filler; the solid core has a deformation from 2.0 mm to 4.0 mm, when being applying a load from an initial load of 10 kgf to a final load of 130 kgf, and has the hardness distribution shown in the following table.










TABLE 2







Hardness distribution in solid core
Shore D harness









Center
25 to 45



Region located 5 to 10 mm from center
39 to 58



Region located 15 mm from center
36 to 55



Surface (S)
55 to 75



Hardness difference
20 to 50



between center and surface










Japanese Patent Publication No. 2010-253268 A discloses a multi-piece solid golf ball comprising a core, an envelope layer encasing the core, an intermediate layer encasing the envelope layer, and a cover which encases the intermediate layer and has formed on a surface thereof a plurality of dimples, wherein the core is formed primarily of a rubber material and has a hardness which gradually increases from a center to a surface thereof, the hardness difference in JIS-C hardness units between the core center and the core surface being at least 15 and, letting (I) be the average value for cross-sectional hardness at a position about 15 mm from the core center and at the core center and letting (II) be the cross-sectional hardness at a position about 7.5 mm from the core center, the hardness difference (I)-(II) in JIS-C hardness units being within ±2; and the envelope layer, intermediate layer and cover have hardness which satisfy the condition: cover hardness>intermediate layer hardness>envelope layer hardness.
SUMMARY OF THE INVENTION
Enhancing a degree of an outer-hard inner-soft structure of a spherical core provides a golf ball having a low spin rate on driver shots. The golf ball having a low spin rate on driver shots travels a great flight distance. The inventors of the present invention further made a study on the hardness distribution of the spherical core, and have found that a golf ball having a low hardness at 37.5% point from the core center, when a radius of the spherical core is divided into equal parts having a 12.5% interval, shows a much lowered spin rate on driver shots. However, if the degree of the outer-hard inner-soft structure of the spherical core is enhanced by increasing the surface hardness of the spherical core, the 37.5% point hardness also tends to become high. On the contrary, if the 37.5% point hardness is lowered, the surface hardness of the spherical core becomes low so that the degree of the outer-hard inner-soft structure of the spherical core is lowered. In other words, it is very difficult to strike a balance between enhancing the degree of the outer-hard inner-soft structure of the spherical core and lowering the 37.5% point hardness of the spherical core.
The present invention has been made in view of the above situations and an object of the present invention is to provide a golf ball showing a much lowered spin rate on driver shots and traveling a great flight distance by controlling a hardness distribution of the spherical core.
The present invention provides a golf ball comprising a spherical core and at least one cover layer covering the spherical core, wherein the spherical core is formed from a rubber composition containing (a) a base rubber, (b) an α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms and/or a metal salt thereof as a co-crosslinking agent, (c) a crosslinking initiator, (d1) a salt of a carboxylic acid having 1 to 4 carbon atoms, or an aromatic carboxylic acid and/or a salt thereof, and (d2) at least one compound selected from the group consisting of an aliphatic carboxylic acid having 5 or more carbon atoms, a salt of an aliphatic carboxylic acid having 5 or more carbon atoms, thiobenzoic acids, salts of thiobenzoic acids, a mercaptocarboxylic acid derivative and a dithiodicarboxylic acid derivative.
In the present invention, by blending (d1) the salt of the carboxylic acid having 1 to 4 carbon atoms, or the aromatic carboxylic acid and/or the salt thereof, and (d2) at least one compound selected from the group consisting of the aliphatic carboxylic acid having 5 or more carbon atoms, the salt of the aliphatic carboxylic acid having 5 or more carbon atoms, the thiobenzoic acids, the salts of the thiobenzoic acids, the mercaptocarboxylic acid derivative and the dithiodicarboxylic acid derivative into the rubber composition which is used to form the spherical core, the 37.5% point hardness can be lowered without lowering the surface hardness of the spherical core. As a result, the golf ball of the present invention enjoys both effects of an outer-hard inner-soft structure and a lowered 37.5% point hardness, and thus travels a greater flight distance on driver shots.
(d1) The salt of the carboxylic acid having 1 to 4 carbon atoms, or the aromatic carboxylic acid and/or the salt thereof, and (d2) at least one compound selected from the group consisting of the aliphatic carboxylic acid having 5 or more carbon atoms, the salt of the aliphatic carboxylic acid having 5 or more carbon atoms, the thiobenzoic acids, the salts of the thiobenzoic acids, the mercaptocarboxylic acid derivative and the dithiodicarboxylic acid derivative sometimes may be merely referred to as “(d) component” in the present invention.
The action of (d) the component in the rubber composition used for the golf ball of the present invention, for example, is considered as follows. The metal salt of (b) the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms blended in the rubber composition is considered to form an ion cluster in the core, thereby crosslinking the rubber molecular chain with metals. By blending (d) the component into this rubber composition, (d) the component exchanges a cation with the ion cluster formed from the metal salt of (b) the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms, thereby breaking the metal crosslinking formed by the metal salt of the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms. This cation exchange reaction easily occurs at the core central part where the temperature is high, but less occurs toward the core surface. When molding a core, the internal temperature of the core is high at the core central part and decreases toward the core surface, since reaction heat from a crosslinking reaction of the rubber composition accumulates at the core central part. In other words, the breaking of the metal crosslinking by (d) the component easily occurs at the core central part, but less occurs toward the surface. As a result, it is conceivable that since a crosslinking density in the core increases from the center of the core toward the surface thereof, the core hardness increases linearly or almost linearly from the center of the core toward the surface thereof. In addition, it is considered that, among (d) the component, (d1) the component has an action of enhancing the degree of the outer-hard inner-soft structure, and (d2) the component has an action of lowering 37.5% point hardness.
The present invention provides a golf ball traveling a great flight distance on driver shots.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a partially cutaway sectional view showing the golf ball according to the preferable embodiment of the present invention;
FIG. 2 is a graph showing the hardness distribution of the spherical core;
FIG. 3 is a graph showing the hardness distribution of the spherical core;
FIG. 4 is a graph showing the hardness distribution of the spherical core;
FIG. 5 is a graph showing the hardness distribution of the spherical core;
FIG. 6 is a graph showing the hardness distribution of the spherical core;
FIG. 7 is a graph showing the hardness distribution of the spherical core;
FIG. 8 is a graph showing the hardness distribution of the spherical core;
FIG. 9 is a graph showing the hardness distribution of the spherical core.



DESCRIPTION OF THE PREFERRED EMBODIMENT
The golf ball of the present invention comprises a spherical core and at least one cover layer covering the spherical core, wherein the spherical core is formed from a rubber composition containing (a) a base rubber, (b) an α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms and/or a metal salt thereof as a co-crosslinking agent, (c) a crosslinking initiator, (d1) a salt of a carboxylic acid having 1 to 4 carbon atoms, or an aromatic carboxylic acid and/or a salt thereof, and (d2) at least one compound selected from the group consisting of an aliphatic carboxylic acid having 5 or more carbon atoms, a salt of an aliphatic carboxylic acid having 5 or more carbon atoms, thiobenzoic acids, salts of thiobenzoic acids, a mercaptocarboxylic acid derivative and a dithiodicarboxylic acid derivative.
First, (a) the base rubber used in the present invention will be explained. As (a) the base rubber used in the present invention, natural rubber and/or synthetic rubber can be used. For example, polybutadiene rubber, natural rubber, polyisoprene rubber, styrene polybutadiene rubber, ethylene-propylene-diene rubber (EPDM), or the like can be used. These rubbers may be used solely or two or more of these rubbers may be used in combination. Among them, typically preferred is the high cis-polybutadiene having a cis-1,4 bond in a proportion of 40 mass % or more, more preferably 80 mass % or more, even more preferably 90 mass % or more in view of its superior resilience property.
The high-cis polybutadiene preferably has a 1,2-vinyl bond in a content of 2 mass % or less, more preferably 1.7 mass % or less, and even more preferably 1.5 mass % or less. If the content of 1,2-vinyl bond is excessively high, the resilience may be lowered.
The high-cis polybutadiene preferably includes one synthesized using a rare-earth element catalyst. When a neodymium catalyst, which employs a neodymium compound of a lanthanum series rare-earth element compound, is used, a polybutadiene rubber having a high content of a cis-1,4 bond and a low content of a 1,2-vinyl bond is obtained with excellent polymerization activity. Such a polybutadiene rubber is particularly preferred.
The high-cis polybutadiene preferably has a Mooney viscosity (ML1+4(100° C.)) of 30 or more, more preferably 32 or more, even more preferably 35 or more, and preferably has a Mooney viscosity (ML1+4(100° C.)) of 140 or less, more preferably 120 or less, even more preferably 100 or less, and most preferably 80 or less. It is noted that the Mooney viscosity (ML1+4(100° C.)) in the present invention is a value measured according to JIS K6300 using an L rotor under the conditions of: a preheating time of 1 minute; a rotor rotation time of 4 minutes; and a temperature of 100° C.
The high-cis polybutadiene preferably has a molecular weight distribution Mw/Mn (Mw: weight average molecular weight, Mn: number average molecular weight) of 2.0 or more, more preferably 2.2 or more, even more preferably 2.4 or more, and most preferably 2.6 or more, and preferably has a molecular weight distribution Mw/Mn of 6.0 or less, more preferably 5.0 or less, even more preferably 4.0 or less, and most preferably 3.4 or less. If the molecular weight distribution (Mw/Mn) of the high-cis polybutadiene is excessively low, the processability may deteriorate. If the molecular weight distribution (Mw/Mn) of the high-cis polybutadiene is excessively high, the resilience may be lowered. It is noted that the measurement of the molecular weight distribution is conducted by gel permeation chromatography (“HLC-8120GPC”, manufactured by Tosoh Corporation) using a differential refractometer as a detector under the conditions of column: GMHHXL (manufactured by Tosoh Corporation), column temperature: 40° C., and mobile phase: tetrahydrofuran, and calculated by converting based on polystyrene standard.
Next, (b) the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms and/or the metal salt thereof will be explained. (b) The α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms and/or the metal salt thereof is blended as a co-crosslinking agent in the rubber composition and has an action of crosslinking a rubber molecule by graft polymerization to a base rubber molecular chain. In the case that the rubber composition used in the present invention contains only the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms as the co-crosslinking agent, the rubber composition preferably further contains (e) a metal compound. Neutralizing the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms with the metal compound in the rubber composition provides substantially the same effect as using the metal salt of the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms. Further, in the case of using the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms and the metal salt thereof in combination, (e) the metal compound may be used as an optional component.
The α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms includes, for example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, and the like.
Examples of the metal constituting the metal salt of the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms include: a monovalent metal ion such as sodium, potassium, lithium or the like; a divalent metal ion such as magnesium, calcium, zinc, barium, cadmium or the like; a trivalent metal ion such as aluminum or the like; and other metal ion such as tin, zirconium or the like. The above metal ion can be used solely or as a mixture of at least two of them. Among these metal ions, the divalent metal ion such as magnesium, calcium, zinc, barium, cadmium or the like is preferable. Use of the divalent metal salt of the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms easily generates a metal crosslinking between the rubber molecules. Especially, as the divalent metal salt, zinc acrylate is preferable, because zinc acrylate enhances the resilience of the resultant golf ball. The α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms and/or the metal salt thereof may be used solely or in combination at least two of them.
The content of (b) the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms and/or the metal salt thereof is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, even more preferably 40 parts by mass or less, with respect to 100 parts by mass of (a) the base rubber. If the content of (b) the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms and/or the metal salt thereof is less than 15 parts by mass, the content of (c) the crosslinking initiator which will be explained below must be increased in order to obtain the appropriate hardness of the constituting member formed from the rubber composition, which tends to cause the lower resilience. On the other hand, if the content of (b) the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms and/or the metal salt thereof exceeds 50 parts by mass, the constituting member formed from the rubber composition becomes excessively hard, which tends to cause the lower shot feeling.
(c) The crosslinking initiator is blended in order to crosslink (a) the base rubber component. As (c) the crosslinking initiator, an organic peroxide is preferred. Specific examples of the organic peroxide include an organic peroxide such as dicumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-t-butyl peroxide or the like. The organic peroxide may be used solely or in combination at least two of them. Among them, dicumyl peroxide is preferably used.
The content of (c) the crosslinking initiator is preferably 0.2 part by mass or more, and more preferably 0.5 part by mass or more, and is preferably 5.0 parts by mass or less, and more preferably 2.5 parts by mass or less, with respect to 100 parts by mass of (a) the base rubber. If the content of (c) the crosslinking initiator is less than 0.2 part by mass, the constituting member formed from the rubber composition becomes so soft that the golf ball tends to have the lower resilience. If the content of (c) the crosslinking initiator exceeds 5.0 parts by mass, the amount of (b) the co-crosslinking agent must be decreased in order to obtain the appropriate hardness of the constituting member formed from the rubber composition, probably resulting in the insufficient resilience or lower durability of the golf ball.
Next, (d1) the salt of the carboxylic acid having 1 to 4 carbon atoms, or the aromatic carboxylic acid and/or the salt thereof will be explained below. (d1) The salt of the carboxylic acid having 1 to 4 carbon atoms, or the aromatic carboxylic acid and/or the salt thereof are considered to have an action of making the obtained spherical core have an outer-hard inner-soft structure. The salt of the carboxylic acid having 1 to 4 carbon atoms preferably includes an aliphatic carboxylic acid (sometimes may be merely referred to as “fatty acid salt” in the present invention). The fatty acid salt may be either a saturated fatty acid salt or an unsaturated fatty acid salt, but the saturated fatty acid salt is preferable. Specific examples of the fatty acid component (IUPAC name) of the saturated fatty acid salt are methanoic acid (C1), ethanoic acid (C2), propanoic acid (C3) and butanoic acid (C4). Specific examples of the fatty acid component (IUPAC name) of the unsaturated fatty acid salt are ethenoic acid (C2) and butenoic acid (C4). It is noted that the salt of the carboxylic acid having 1 to 4 carbon atoms does not include (b) the metal salt of the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms (for example, the metal salt of propenoic acid (acrylic acid)) used as the co-crosslinking agent.
The cation component of the salt of the carboxylic acid may be any one of an ammonium ion, a metal ion and an organic cation. The metal ion includes, for example, a monovalent metal ion such as sodium, potassium, lithium, silver or the like; a bivalent metal ion such as magnesium, calcium, zinc, barium, cadmium, copper, cobalt, nickel, manganese or the like; a trivalent metal ion such as aluminum or iron, and other metal ion such as tin, zirconium, titanium or the like. The metal ion preferably includes zinc ion or magnesium ion. The metal ion may be used alone or as a mixture of at least two of them.
The organic cation is a cation having a carbon chain. The organic cation includes, for example, without limitation, an organic ammonium ion. Examples of the organic ammonium ion are: a primary ammonium ion such as stearyl ammonium ion, hexyl ammonium ion, octyl ammonium ion, 2-ethylhexyl ammonium ion, or the like; a secondary ammonium ion such as dodecyl (lauryl) ammonium ion, octadecyl (stearyl) ammonium ion, or the like; a tertiary ammonium ion such as trioctyl ammonium ion, or the like; and a quaternary ammonium ion such as dioctyldimethyl ammonium ion, distearyldimethyl ammonium ion, or the like. The organic cation may be used alone or as a mixture of at least two of them.
In the present invention, zinc acetate (zinc ethanoate) is preferably used as (d1) the salt of the carboxylic acid having 1 to 4 carbon atoms.
The aromatic carboxylic acid includes an aromatic carboxylic acid having a benzene ring in the molecule thereof, and an aromatic carboxylic acid having a heteroaromatic ring in the molecule thereof. The aromatic carboxylic acid may be used solely or in combination of at least two of them.
Specific examples of the carboxylic acid having a benzene ring include, for example, an aromatic carboxylic acid having a carboxyl group directly bonding to the benzene ring, an aromatic-aliphatic carboxylic acid having an aliphatic carboxylic acid bonding to the benzene ring, a polynuclear aromatic carboxylic acid having a carboxyl group directly bonding to a fused benzene ring, and a polynuclear aromatic-aliphatic carboxylic acid having an aliphatic carboxylic acid bonding to a fused benzene ring. The fused benzene ring structure includes, for example, naphthalene, anthracene, phenalene, phenanthrene, tetracene and pyrene.
The number of carboxyl group in the carboxylic acid having a benzene ring may be one (monocarboxylic acid), two or more (polycarboxylic acid), but one is preferred. A substituent group other than the carboxyl group may directly bond to the benzene ring or fused benzene ring. Such a substituent group includes, for example, an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms), an aryl group (preferably phenyl group), an amino group, a hydroxyl group, an alkoxy group (preferably an alkoxy group having 1 to 4 carbon atoms), an oxo group, or a halogen group.
Specific examples of the aromatic carboxylic acid having a carboxyl group directly bonding to the benzene ring include, for example, benzoic acid (C7), phthalic acid (C8), isophthalic acid (C8), terephthalic acid (C8), benzene-1,2,3-tricarboxylic acid (C9), benzene-1,2,4-tricarboxylic acid (C9), benzene-1,3,5-tricarboxylic acid (C9), benzene-1,2,3,4-tetracarboxylic acid (C10), benzene-1,2,3,5-tetracarboxylic acid (C10), benzene-1,2,4,5-tetracarboxylic acid (C10), and benzene hexacarboxylic acid (C12). Specific examples of the aromatic-aliphatic carboxylic acid having an aliphatic carboxylic acid bonding to the benzene ring include, for example, phenylacetic acid (C8), 2-phenylpropanoic acid (C9), and 3-phenylpropanoic acid (C9).
Furthermore, examples of the carboxylic acid having a benzene ring substituted with an alkyl group, an aryl group, an amino group, a hydroxyl group, an alkoxy group or an oxo group include, for example, methylbenzoic acid (C8), dimethylbenzoic acid (C9), 2,3,4-trimethylbenzoic acid (C10), 2,3,5-trimethylbenzoic acid (C10), 2,4,5-trimethylbenzoic acid (C10), 2,4,6-trimethylbenzoic acid (C10), 3,4,5-trimethylbenzoic acid (C10), 4-isopropylbenzoic acid (C10), 4-tert-butylbenzoic acid (C11), 5-methylisophthalic acid (C9), biphenyl-4-carboxylic acid (C13), biphenyl-2,2′-dicarboxylic acid (C14), 4-dimethylaminobenzoic acid (C9), 2-hydroxybenzoic acid (C7), methoxybenzoic acid (C8), hydroxy (methyl)benzoic acid (C8), 2-hydroxy-3-methylbenzoic acid (C8), 2-hydroxy-4-methylbenzoic acid (C8), 2-hydroxy-5-methylbenzoic acid (C8), 2,3-dihydroxybenzoic acid (C7), 2,4-dihydroxybenzoic acid (C7), 2,6-dihydroxybenzoic acid (C7), 3,4-dihydroxybenzoic acid (C7), 3,5-dihydroxybenzoic acid (C7), 4-hydroxy-3-methoxybenzoic acid (C8), 3-hydroxy-4-methoxybenzoic acid (C8), 3,4-dimethoxybenzoic acid (C9), 2,3-dimethoxybenzoic acid (C9), 2,4-dimethoxybenzoic acid (C9), 2,4-dihydroxy-6-methylbenzoic acid (C8), 4,5-dimethoxyphthalic acid (C10), 3,4,5-trihydroxybenzoic acid (C7), 4-hydroxy-3,5-dimethoxybenzoic acid (C9), 2,4,5-trimethoxybenzoic acid (C10), hydroxy(phenyl) acetic acid (C8), hydroxy(4-hydroxy-3-methoxyphenyl)acetic acid (C9), (4-methoxyphenyl)acetic acid (C9), (2,5-dihydroxyphenyl)acetic acid (C8), (3,4-dihydroxyphenyl)acetic acid (C8), (4-hydroxy-3-methoxyphenyl)acetic acid (C9), (3-hydroxy-4-methoxyphenyl)acetic acid (C9), (3,4-dimethoxyphenyl)acetic acid (C10), (2,3-dimethoxyphenyl)acetic acid (C10), 2-(carboxymethyl)benzoic acid (C9), 3-(carboxymethyl)benzoic acid (C9), 4-(carboxymethyl)benzoic acid (C9), 2-(carboxycarbonyl)benzoic acid (C9), 3-(carboxycarbonyl)benzoic acid (C9), 4-(carboxycarbonyl)benzoic acid (C9), 2-hydroxy-2-phenylpropanoic acid (C9), 3-hydroxy-2-phenylpropanoic acid (C9), 3-(2-hydroxyphenyl)propanoic acid (C9), 3-(4-hydroxyphenyl)propanoic acid (C9), 3-(3,4-dihydroxyphenyl)propanoic acid (C9), 3-(4-hydroxy-3-methoxyphenyl)propanoic acid (C10), 3-(3-hydroxy-4-methoxyphenyl)propanoic acid (C10), 3-(4-hydroxyphenyl)acrylic acid (C9), 3-(2,4-dihydroxyphenyl)acrylic acid (C9), 3-(3,4-dihydroxyphenyl)acrylic acid (C9), 3-(4-hydroxy-3-methoxyphenyl)acrylic acid (C10), 3-(3-hydroxy-4-methoxyphenyl)acrylic acid (C10), and 3-(4-hydroxy-3,5-dimethoxyphenyl)acrylic acid (C11).
Examples of the carboxylic acid having a benzene ring substituted with a halogen atom include, a carboxylic acid where at least one hydrogen atom in benzoic acid is substituted with a fluoro group such as fluorobenzoic acid, difluorobenzoic acid, trifluorobenzoic acid, tetrafluorobenzoic acid, pentafluorobenzoic acid; a carboxylic acid where at least one hydrogen atom in benzoic acid is substituted with a chloro group such as chlorobenzoic acid, dichlorobenzoic acid, trichlorobenzoic acid, tetrachlorobenzoic acid, pentachlorobenzoic acid; a carboxylic acid where at least one hydrogen atom in benzoic acid is substituted with a bromo group such as bromobenzoic acid, dibromobenzoic acid, tribromobenzoic acid, tetrabromobenzoic acid, pentabromobenzoic acid; and a carboxylic acid where at least one hydrogen atom in benzoic acid is substituted with an iodo group such as iodobenzoic acid, diiodobenzoic acid, triiodobenzoic acid, tetraiodobenzoic acid, pentaiodobenzoic acid.
Specific examples of the polynuclear aromatic carboxylic acid having a carboxyl group directly bonding to the fused benzene ring include, for example, 1-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, 1-anthracenecarboxylic acid, 2-anthracenecarboxylic acid, 9-anthracenecarboxylic acid, phenanthrenecarboxylic acid and pyrenecarboxylic acid. Specific examples of the polynuclear aromatic-aliphatic carboxylic acid having an aliphatic carboxylic acid bonding to the fused benzene ring include, for example, naphthylacetic acid and naphthylpropionic acid.
Examples of the carboxylic acid having a fused benzene ring substituted with a halogen atom include fluoronaphthalenecarboxylic acid, chloronaphthalenecarboxylic acid, bromonaphthalenecarboxylic acid, fluoroanthracenecarboxylic acid, chloroanthracenecarboxylic acid and bromoanthracenecarboxylic acid.
Examples of the carboxylic acid having a heteroaromatic ring include, for example, a carboxylic acid having a carboxyl group directly bonding to the heteroaromatic ring. The hetero atom contained in the heteroaromatic ring can be one kind, or two or more kinds. The hetero atom includes a nitrogen atom, oxygen atom, sulfur atom or the like. Among them, the oxygen atom or sulfur atom is preferred. In addition, the number of the hetero atom in the heteroaromatic ring structure is not particularly limited, but preferably 2 or less, and more preferably 1. The heteroaromatic ring includes, for example, a pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, indole ring, quinoline ring, benzofuran ring, benzothiophene ring, or the like.
The carboxylic acid having a heteroaromatic ring may be a compound having only a carboxyl group as a substituent group to the heteroaromatic ring, or a compound having another substituent group directly bonding to the heteroaromatic ring in addition to the carboxyl group. Further, the substituent group may bond to a nitrogen atom constituting the heteroaromatic ring. The substituent group includes, for example, halogen, a hydroxyl group, a mercapto group, an alkyl group, an aryl group, an aralkyl group, an alkylaryl group, an alkoxyl group, an amino group which may be substituted, a cyano group, or a thiocarboxyl group.
Specific examples of the carboxylic acid having a heteroaromatic ring and/or the salt thereof include, for example, carboxylic acids having a five-membered heteroaromatic ring such as a pyrrolecarboxylic acid, furancarboxylic acid, thiophenecarboxylic acid, imidazolecarboxylic acid, pyrazolecarboxylic acid, oxazolecarboxylic acid, thiazolecarboxylic acid or the like; carboxylic acids having a six-membered heteroaromatic ring such as a pyridinecarboxylic acid, pyrazinecarboxylic acid or the like; a carboxylic acid having a fused heteroaromatic ring such as an indolecarboxylic acid, quinolinecarboxylic acid, benzofurancarboxylic acid, benzothiophenecarboxylic acid or the like; and the like.
In the present invention, benzoic acid is preferably used as the aromatic carboxylic acid and/or the salt thereof.
The cation component of the salt of the aromatic carboxylic acid includes those exemplified in the cation component of the fatty acid salt.
The content of the (d1) component is preferably 0.5 part by mass or more, more preferably 1.0 part by mass or more, even more preferably 1.5 parts by mass or more, and is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, even more preferably 30 parts by mass or less, most preferably 25 parts by mass or less, with respect to 100 parts by mass of (a) the base rubber. If the content is lower than 0.5 part by mass, the effect of adding the (d1) component tends to be insufficient because of the low amount, and if the content exceeds 40 parts by mass, the resilience of the core may be lowered, since the hardness of the resultant core may be lowered as a whole.
(d2) At least one compound selected from the group consisting of the aliphatic carboxylic acid having 5 or more carbon atoms, the salt of the aliphatic carboxylic acid having 5 or more carbon atoms, the thiobenzoic acids, the salts of the thiobenzoic acids, the mercaptocarboxylic acid derivative and the dithiodicarboxylic acid derivative used in the present invention will be explained below. (d2) At least one compound selected from the group consisting of the aliphatic carboxylic acid having 5 or more carbon atoms, the salt of the aliphatic carboxylic acid having 5 or more carbon atoms, the thiobenzoic acids, the salts of the thiobenzoic acids, the mercaptocarboxylic acid derivative and the dithiodicarboxylic acid derivative are considered to have an action of making the obtained spherical core have an outer-hard inner-soft structure as well as lowering 37.5% point hardness.
The aliphatic carboxylic acid having 5 or more carbon atoms may be either a saturated fatty acid or an unsaturated fatty acid. The aliphatic carboxylic acid having 5 or more carbon atoms may have a branched structure or a cyclic structure. The carbon atom number of the aliphatic carboxylic acid having 5 or more carbon atoms is preferably 5 to 30, more preferably 5 to 18, even more preferably 5 to 13. It is noted that the carboxylic acid having 5 or more carbon atoms and/or the salt thereof does not include (b) the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms and/or the metal salt thereof used as the co-crosslinking agent.
Specific examples of the saturated fatty acids having 5 or more carbon atoms (IUPAC name) are pentanoic acid (C5), hexanoic acid (C6), heptanoic acid (C7), octanoic acid (C8), nonanoic acid (C9), decanoic acid (C10), undecanoic acid (C11), dodecanoic acid (C12), tridecanoic acid (C13), tetradecanoic acid (C14), pentadecanoic acid (C15), hexadecanoic acid (C16), heptadecanoic acid (C17), octadecanoic acid (C18), nonadecanoic acid (C19), icosanoic acid (C20), henicosanoic acid (C21), docosanoic acid (C22), tricosanoic acid (C23), tetracosanoic acid (C24), pentacosanoic acid (C25), hexacosanoic acid (C26), heptacosanoic acid (C27), octacosanoic acid (C28), nonacosanoic acid (C29), and triacontanoic acid (C30).
Specific examples of the unsaturated fatty acid having 5 or more carbon atoms (IUPAC name) are pentenoic acid (C5), hexenoic acid (C6), heptenoic acid (C7), octenoic acid (C8), nonenoic acid (C9), decenoic acid (C10), undecenoic acid (C11), dodecenoic acid (C12), tridecenoic acid (C13), tetradecenoic acid (C14), pentadecenoic acid (C15), hexadecenoic acid (C16), heptadecenoic acid (C17), octadecenoic acid (C18), nonadecenoic acid (C19), icosenoic acid (C20), henicosenoic acid (C21), docosenoic acid (C22), tricosenoic acid (C23), tetracosenoic acid (C24), pentacosenoic acid (C25), hexacosenoic acid (C26), heptacosenoic acid (C27), octacosenoic acid (C28), nonacosenoic acid (C29), and triacontenoic acid (C30).
Specific examples of the fatty acid having 5 or more carbon atoms (common name) are, valeric acid (C5), caproic acid (C6), enanthic acid (C7), caprylic acid (C8), pelargonic acid (C9), capric acid (C10), lauric acid (C12), myristic acid (C14), myristoleic acid (C14), pentadecylic acid (C15), palmitic acid (C16), palmitoleic acid (C16), margaric acid (C17), stearic acid (C18), elaidic acid (C18), vaccenic acid (C18), oleic acid (C18), linoleic acid (C18), linolenic acid (C18), 12-hydroxystearic acid (C18), arachidic acid (C20), gadoleic acid (C20), arachidonic acid (C20), eicosenoic acid (C20), behenic acid (C22), erucic acid (C22), lignoceric acid (C24), nervonic acid (C24), cerotic acid (C26), montanic acid (C28), and melissic acid (C30).
The cation component of the salt of the aliphatic carboxylic acid having 5 or more carbon atoms includes those exemplified in the cation component of the fatty acid salt having 1 to 4 carbon atoms.
The thiobenzoic acids and/or the salts thereof used in the present invention will be explained below. The thiobenzoic acids preferably include a thiobenzoic acid and/or a derivative thereof, or a dithiobenzoic acid and/or a derivative thereof. The thiobenzoic acid and/or the derivative thereof include the compound represented by the following formula (1). The dithiobenzoic acid and/or the derivative thereof include the compound represented by the following formula (2).




(wherein, R1 to R5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, an alkyl group, an aryl group, an aralkyl group, an alkylaryl group, an alkoxyl group, an amino group which may be substituted, a cyano group, an oxo group, a carboxyl group, or a thio carboxyl group.)




(wherein, R6 to R10 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, an alkyl group, an aryl group, an aralkyl group, an alkylaryl group, an alkoxyl group, an amino group which may be substituted, a cyano group, an oxo group, a carboxyl group, or a thio carboxyl group.)
The halogen atom in formulae (1) and (2) includes fluorine, chlorine, bromine and iodine.
The alkyl group includes a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. Among them, preferred is an alkyl group having 1 to 6 carbon atoms, and more preferred is an alkyl group having 1 to 4 carbon atoms. The aryl group includes a phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group and fluorenyl group. Among them, preferred is a phenyl group. The aralkyl group includes a benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group and naphthylethyl group. The alkylaryl group includes a tolyl group, xylyl group, cumenyl group and mesityl group.
The alkoxyl group includes a methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, and decyloxy group. Among them, preferred is an alkoxyl group having 1 to 6 carbon atoms, and more preferred is an alkoxyl group having 1 to 4 carbon atoms.
The amino group which may be substituted preferably includes an amino group where one or more hydrogen atoms in the amino group are substituted with an alkyl group or aryl group. The amino group which may be substituted includes a methylamino group, dimethylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, tert-butylamino group, pentylamino group, hexylamino group, 2-ethylhexylamino group, phenylamino group, diphenylamino group, and naphthylamino group.
The salts of the thiobenzoic acids include a salt of the compound (the thiobenzoic acid and/or the derivative thereof) represented by the formula (1) and a salt of the compound (the dithiobenzoic acid and/or the derivative thereof) represented by the formula (2). The cation component of the salts may be any one of an ammonium ion, a metal ion and an organic cation. The cation component of the salts of the thiobenzoic acids includes those exemplified in the cation component of (d1) the carboxylic acid salt having 1 to 4 carbon atoms.
Specific examples of the thiobenzoic acids and/or the salts thereof include thiobenzoic acid, chlorothiobenzoic acid, bromothiobenzoic acid, methylthiobenzoic acid, ethylthiobenzoic acid, methoxythiobenzoic acid, ethoxythiobenzoic acid, hydroxythiobenzoic acid, cyanothiobenzoic acid, dimethylaminothiobenzoic acid, mercaptothiobenzoic acid, dithiobenzoic acid, chlorodithiobenzoic acid, bromodithiobenzoic acid, methyldithiobenzoic acid, ethyldithiobenzoic acid, methoxydithiobenzoic acid, ethoxydithiobenzoic acid, hydroxydithiobenzoic acid, cyanodithiobenzoic acid, dimethylaminodithiobenzoic acid, mercaptodithiobenzoic acid, and the salts thereof. Among them, thiobenzoic acid is preferred. Those thiobenzoic acids and/or the salts thereof may be used solely or in combination at least two of them.
The mercaptocarboxylic acid derivative and/or the dithiodicarboxylic acid derivative will be explained below. The mercaptocarboxylic acid has one thiol group (mercapto group) and one carboxyl group in the molecule thereof. The mercaptocarboxylic acid derivative includes, for example, a compound where a hydrogen atom in the carboxyl group of the mercaptocarboxylic acid is substituted with a substituent group and/or a salt of thereof. The dithiodicarboxylic acid has one disulfide bond and two carboxyl groups in the molecule thereof. The dithiodicarboxylic acid derivative includes, for example, a compound where a hydrogen atom in at least one of carboxyl groups of the dithiodicarboxylic acid is substituted with a substituent group. The mercaptocarboxylic acid derivative and/or the dithiodicarboxylic acid derivative may be used solely or in combination at least two of them.
The cation component of the salts includes those exemplified in the cation component of (d1) the carboxylic acid salt having 1 to 4 carbon atoms.
The mercaptocarboxylic acid derivative and/or the dithiodicarboxylic acid derivative preferably include compounds represented by the formulae (3) to (6):




(in the formula (3), R11 represents an alkyl group, an amino group or a metal atom, and m1 represents an integer number of 1 to 5.)




(in the formula (4), R12 represents an alkyl group, an amino group or a metal atom, M1 represents a monovalent metal ion, an ammonium ion or an organic cation, and m2 represents an integer number of 1 to 5.)




(in the formula (5), R13 and R14 each independently represent an alkyl group, an amino group or a metal atom, M2 represents a bivalent metal ion, and m3 and m4 each independently represent an integer number of 1 to 5.)




(in the formula (6), R15 and R16 each independently represent an alkyl group, an amino group or a metal atom, and n1 and n2 each independently represent an integer number of 1 to 5.).
The alkyl group represented by R11 to R16 includes: a straight-chain alkyl group such as a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, n-henicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, n-triacontyl, or the like; a branched-chain alkyl group such as an isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 2-ethylhexyl group, isooctyl group, or the like; and a cyclic alkyl group such as a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, or the like. Among them, preferred is an alkyl group having 1 to 30 carbon atoms, and more preferred is an alkyl group having 4 to 20 carbon atoms, and even more preferred is an alkyl group having 8 to 18 carbon atoms. The straight-chain alkyl group or the branched-chain alkyl group is preferred.
The alkyl group may be substituted. The substituted alkyl group preferably includes an alkyl group where one or more hydrogen atoms in the alkyl group are substituted with halogen, an alkoxyl group or the like.
The halogen includes, for example, fluorine, chlorine, bromine, and iodine. The alkoxyl group includes a methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, and decyloxy group. Among them, preferred is an alkoxyl group having 1 to 6 carbon atoms, and more preferred is an alkoxyl group having 1 to 4 carbon atoms.
The amino group represented by R11 to R16 may be substituted. The substituted amino group preferably includes an amino group where one or more hydrogen atoms in the amino group are substituted with an alkyl group or aryl group. The amino group which may be substituted includes a methylamino group, dimethylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, tert-butylamino group, pentylamino group, hexylamino group, 2-ethylhexylamino group, phenylamino group, diphenylamino group, and naphthylamino group.
The metal atom represented by R11 to R16 includes, for example, a monovalent metal ion such as sodium, potassium, lithium, silver, or the like; a bivalent metal ion such as magnesium, calcium, zinc, barium, cadmium, copper, cobalt, nickel, manganese, or the like; a trivalent metal ion such as aluminum or iron, and other metal ion such as tin, zirconium, titanium, or the like. The metal ion may be used alone or as a mixture of at least two of them.
The monovalent metal ion represented by M1 includes, for example, sodium, potassium, lithium, silver, and the like. The monovalent metal ion may be used alone or as a mixture of at least two of them.
The bivalent metal ion represented by M2 includes magnesium, calcium, zinc, barium, cadmium, copper, cobalt, nickel, manganese, or the like. The bivalent metal ion may be used alone or as a mixture of at least two of them. Preferably, m1, m2, m3 and m4 each independently are an integer number of 1 to 5, more preferably an integer number of 1 to 4, even more preferably an integer number of 1 to 3. Preferably, n1 and n2 each independently are an integer number of 1 to 5, more preferably an integer number of 1 to 4, and even more preferably an integer number of 1 to 3.
Specific examples of the mercaptocarboxylic acid include, for example, thioglycolic acid, 3-mercaptopropionic acid, 4-mercaptobutyric acid, 5-mercaptovaleric acid, 6-mercaptohexanoic acid, 7-mercaptoheptanoic acid, 8-mercaptooctanoic acid, 9-mercaptononanoic acid, 10-mercaptodecanoic acid, and the like. Specific examples of the dithiodicarboxylic acid include, for example, dithiodiglycolic acid, 3,3′-dithiodipropionic acid, 4,4′-dithiobisbutyric acid, 5,5′-dithiodivaleric acid, bis(5-carboxypentyl)persulfide, and the like. These mercaptocarboxylic acids and dithiodicarboxylic acids may be used solely or in combination at least two of them. Among them, the thioglycolic acid derivative and/or the dithiodiglycolic acid derivative are preferably used as the mercaptocarboxylic acid derivative and/or the dithiodicarboxylic acid derivative.
The thioglycolic acid derivative and/or the dithiodiglycolic acid derivative preferably include: a thioglycolic acid alkyl ester such as thioglycolic acid methyl, thioglycolic acid ethyl, thioglycolic acid propyl, thioglycolic acid butyl, thioglycolic acid pentyl, thioglycolic acid hexyl, thioglycolic acid heptyl, thioglycolic acid octyl, thioglycolic acid nonyl, thioglycolic acid decyl, thioglycolic acid undecyl, thioglycolic acid dodecyl, thioglycolic acid tridecyl, thioglycolic acid tetradecyl, thioglycolic acid pentadecyl, thioglycolic acid hexadecyl, thioglycolic acid heptadecyl, thioglycolic acid octadecyl, thioglycolic acid-2-ethylhexyl, or the like; a salt of the thioglycolic acid alkyl ester; and a dithiodiglycolic acid alkyl ester such as 2,2′-dithiobis(acetic acid methyl), 2,2′-dithiobis(acetic acid ethyl), 2,2′-dithiobis(acetic acid propyl), 2,2′-dithiobis(acetic acid butyl), 2,2′-dithiobis(acetic acid pentyl), 2,2′-dithiobis(acetic acid hexyl), 2,2′-dithiobis(acetic acid heptyl), 2,2′-dithiobis(acetic acid octyl), 2,2′-dithiobis(acetic acid nonyl), 2,2′-dithiobis(acetic acid decyl), 2,2′-dithiobis(acetic acid undecyl), 2,2′-dithiobis(acetic acid dodecyl), 2,2′-dithiobis(acetic acid tridecyl), 2,2′-dithiobis(acetic acid tetradecyl), 2,2′-dithiobis(acetic acid pentadecyl), 2,2′-dithiobis(acetic acid hexadecyl), 2,2′-dithiobis(acetic acid heptadecyl), 2,2′-dithiobis(acetic acid octadecyl), 2,2′-dithiobisacetic acid bis(2-ethylhexyl), 2,2′-dithiobis(acetic acid isooctyl), or the like. Among them, thioglycolic acid n-octyl, thioglycolic acid n-octadecyl and thioglycolic acid-2-ethylhexyl are more preferred.
The content of the (d2) component is preferably 0.5 part by mass or more, more preferably 1.0 part by mass or more, even more preferably 1.5 parts by mass or more, and is preferably 40 parts by mass or less, preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, with respect to 100 parts by mass of (a) the base rubber. If the content is less than 0.5 part by mass, the effect of adding the (d2) component tends to be insufficient because of the low amount, and if the content exceeds 40 parts by mass, the resilience of the core may be lowered, since the hardness of the resultant core may be lowered as a whole.
The total content of the (d1) component and the (d2) component is preferably 1.0 part by mass or more, more preferably 1.5 parts by mass or more, even more preferably 2.0 parts by mass or more, and is preferably 40 parts by mass or less, preferably 30 parts by mass or less, more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, with respect to 100 parts by mass of (a) the base rubber. If the total content is less than 1.0 part by mass, the effect of adding the (d1) component and the (d2) component tends to be insufficient because of the low amount, and if the total content exceeds 40 parts by mass, the resilience of the core may be lowered, since the hardness of the resultant core may be lowered as a whole.
The mass ratio ((d1)+(d2)/(b)) of the total content of the (d1) component and the (d2) component to the content of (b) the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms and/or the metal salt thereof is preferably 0.01 or more, more preferably 0.02 or more, even more preferably 0.03 or more, further preferably 0.04 or more, and is preferably 1.0 or less, more preferably 0.8 or less, even more preferably 0.5 or less. If the mass ratio ((d1)+(d2)/(b)) is 0.01 or more, the effect of improving the flight distance by the (d) component becomes large, and if the mass ratio ((d1)+(d2)/(b)) is 0.5 or less, lowering the hardness of the core is suppressed, and thus the rebound resilience becomes better.
In the present invention, an absolute value of a difference between a SP value of the (d1) component and a SP value of the (d2) component is preferably 2.0 or more, more preferably 2.3 or more, even preferably 2.5 or more, and is preferably 6.0 or less, more preferably 5.5 or less, even more preferably 5.0 or less. If the absolute value of the difference between the SP value of the (d1) component and the SP value of the (d2) component is within the above range, the 37.5% point hardness may be easily lowered without lowering the surface hardness of the spherical core.
The SP value is δt defined by the following formula.



  
    
      
        δ
        ⁢
        
          
        
        ⁢
        d
      
      =
      
        
          Σ
          ⁢
          
            
          
          ⁢
          
            F
            di
          
        
        V
      
    
    ,
    
      

    
    ⁢
    
      
        δ
        ⁢
        
          
        
        ⁢
        p
      
      =
      
        
          
            Σ
            ⁢
            
              
            
            ⁢
            
              F
              pi
              2
            
          
        
        V
      
    
    ,
    
      

    
    ⁢
    
      
        δ
        ⁢
        
          
        
        ⁢
        h
      
      =
      
        
          
            Σ
            ⁢
            
              
            
            ⁢
            
              E
              hi
            
          
          V
        
      
    
  




  
    
      δ
      t
      2
    
    =
    
      
        δ
        d
        2
      
      +
      
        δ
        p
        2
      
      +
      
        δ
        h
        2
      
    
  



In the formula, V is volume V (cm3/mol) by the Fedors method; Fdi, Fpi and Ehi are solubility parameter components by the Hoftyzer-Van Krevelen method. δd is London dispersion force, δp is dipole-dipole force, and δh is hydrogen bonding force. The detailed calculation method of the SP value is described in Chapter 7 of Properties of Polymers (D. W. VANKREVELEN, publisher: ELSEVIER, Third impression, 2003). Fdi, Fpi, Ehi and V of the main functional groups are shown in Table 3.











TABLE 3






Fdi
Fpi




Kind of atomic
J1/2 • cm3/2 •
J1/2 • cm3/2 •
Ehi
V


group
mol−1
mol−1
J/mol
cm3/mol



















—CH3
420
0
0
33.5


—CH2—
270
0
0
16.1


 






80
0
0
−1.0


 






−70
0
0
−19.2


 


═CH2
400
0
0
28.5


═CH—
200
0
0
13.5


═C<
70
0
0
−5.5


Phenyl
1430
110
0
71.4


Phenylene(o,m,p)
1270
110
0
52.4


—F
(220)
—
—
18.0


—Cl
450
550
400
24.0


—Br
(550)
—
—
30.0


—CN
430
1100
2500
24.0


—OH
210
500
20000
10.0


—O—
100
400
3000
3.8


—COH(aldehyde)
470
800
4500
22.3


—CO—
290
770
2000
10.8


—COOH
530
420
10000
28.5


—COO—
390
490
7000
18.0


HCOO-(formate)
530
—
—
32.5


—NH2
280
—
8400
19.2


—NH—
160
210
3100
4.5


—N<
20
800
5000
−9.0


—NO2
500
1070
1500
24.0






(aliphatic)


—S—
440
—
—
12


═PO4—
740
1890
13000
28.0









It is noted that, the SP value of the (d) components such as a salt, carboxylic acid, thiol or the like is calculated based on the anion structure thereof after metal ion dissociation or hydrogen dissociation, since the (d) components exchange a cation with the ion cluster formed from the metal salt of (b) the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms. As the SP values of the major (d) components, zinc acetate has 21.77, benzoic acid has 22.90, and thioglycolic acid 2-ethylhexyl has 18.68.
The rubber composition used in the present invention may further contain (e) the metal compound where necessary. (e) The metal compound is a filler which is added for improving properties of the rubber composition. (e) The metal compound can be used, for example, without limitation, as a neutralizing agent for neutralizing the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms in the case that the rubber composition contains only (b) the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms as the co-crosslinking agent, a weight adjusting agent for adjusting the weight of the spherical core, a hardness adjusting agent for adjusting the hardness of the spherical core, or an inorganic pigment. (e) The metal compound can be used for any purpose or multiple purposes.
(e) The metal compound used for neutralizing (b) the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms as the co-crosslinking agent includes, for example, a metal hydroxide such as magnesium hydroxide, zinc hydroxide, calcium hydroxide, sodium hydroxide, lithium hydroxide, potassium hydroxide, copper hydroxide, or the like; a metal oxide such as magnesium oxide, calcium oxide, zinc oxide, copper oxide, or the like; a metal carbonate such as magnesium carbonate, zinc carbonate, calcium carbonate, sodium carbonate, lithium carbonate, potassium carbonate, or the like. Among these, (e) the metal compound preferably includes a divalent metal compound, more preferably includes a zinc compound. The divalent metal compound reacts with (b) the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms, thereby forming a metal crosslinking. Use of the zinc compound provides a golf ball with excellent resilience. The content of (e) the metal compound used as the neutralizing agent may be appropriately determined in accordance with moles of the carboxyl group and the desired degree of neutralization of (b) the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms.
(e) The metal compound used as the filler for adjusting the mass or hardness of the spherical core includes, for example, zinc oxide, barium sulfate, calcium carbonate, magnesium oxide, tungsten powder, molybdenum powder, or the like. (e) The metal compound used as the filler for adjusting the mass or hardness of the spherical core preferably includes zinc oxide. It is considered that zinc oxide functions as a vulcanization activator and increases the hardness of the entire core. The content of (e) the metal compound used as the filler is preferably 0.5 part by mass or more, more preferably 1 part by mass or more, and is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, with respect to 100 parts by mass of the base rubber.
(e) The metal compound can be used solely or as a mixture of at least two of them.
The rubber composition used in the present invention may further contain (f) an organic sulfur compound. (f) The organic sulfur compound is a compound that is different from the thiobenzoic acids and/or the salts thereof, the mercaptocarboxylic acid derivative and/or the dithiodicarboxylic acid derivative included in the (d2) component.
(f) The organic sulfur compound includes, for example, thiols (thiophenols and thionaphthols), polysulfides, sulfenamides, thiurams, and thiazoles.
Examples of the thiols include, for example, thiophenols and thionaphthols. The thiophenols include, for example, thiophenol; thiophenols substituted with a fluoro group, such as 2-fluorothiophenol, 4-fluorothiophenol, 2,4-difluorothiophenol, 2,5-difluorothiophenol, 2,6-difluorothiophenol, 2,4,5-trifluorothiophenol, 2,4,5,6-tetrafluorothiophenol, pentafluorothiophenol and the like; thiophenols substituted with a chloro group, such as 2-chlorothiophenol, 4-chlorothiophenol, 2,4-dichlorothiophenol, 2,5-dichlorothiophenol, 2,6-dichlorothiophenol, 2,4,5-trichlorothiophenol, 2,4,5,6-tetrachlorothiophenol, pentachlorothiophenol and the like; thiophenols substituted with a bromo group, such as 2-bromothiophenol, 4-bromothiophenol, 2,4-dibromothiophenol, 2,5-dibromothiophenol, 2,6-dibromothiophenol, 2,4,5-tribromothiophenol, 2,4,5,6-tetrabromothiophenol, pentabromothiophenol and the like; thiophenols substituted with an iodo group, such as 2-iodothiophenol, 4-iodothiophenol, 2,4-diiodothiophenol, 2,5-diiodothiophenol, 2,6-diiodothiophenol, 2,4,5-triiodothiophenol, 2,4,5,6-tetraiodothiophenol, pentaiodothiophenol and the like; or a metal salt thereof. As the metal salt, zinc salt is preferred.
Examples of the thionaphthols (naphthalenethiols) are 2-thionaphthol, 1-thionaphthol, 1-chloro-2-thionaphthol, 2-chloro-1-thionaphthol, 1-bromo-2-thionaphthol, 2-bromo-1-thionaphthol, 1-fluoro-2-thionaphthol, 2-fluoro-1-thionaphthol, 1-cyano-2-thionaphthol, 2-cyano-1-thionaphthol, 1-acetyl-2-thionaphthol, 2-acetyl-1-thionaphthol, and a metal salt thereof. Preferable examples include 2-thionaphthol, 1-thionaphthol, or the metal salt thereof.
Examples of the metal salt are a monovalent metal salt such as sodium, lithium, potassium, copper (I), silver (I) or the like, and a divalent metal salt such as zinc, magnesium, calcium, strontium, barium, titanium (II), manganese (II), iron (II), cobalt (II), nickel (II), zirconium (II), and tin (II) or the like, and preferred is the divalent metal salt, more preferred is the zinc salt. Specific examples of the metal salt are, for example, the zinc salt of 1-thionaphthol and zinc salt of 2-thionaphthol.
The content of (f) the organic sulfur compound is preferably 0.05 part by mass or more, more preferably 0.1 part by mass or more, and is preferably 5.0 parts by mass or less, more preferably 2.0 parts by mass or less, with respect to 100 parts by mass of (a) the base rubber. If the content of (f) the organic sulfur compound is less than 0.05 part by mass, the effect of adding (f) the organic sulfur compound cannot be obtained and thus the resilience may not be enhanced. If the content of (f) the organic sulfur compound exceeds 5.0 parts by mass, the compression deformation amount of the obtained golf ball becomes large and thus the resilience may be lowered.
The rubber composition used in the present invention may include an additive such as an antioxidant, a peptizing agent, and a softener where necessary.
The blending amount of the antioxidant is preferably 0.1 part by mass or more and 1 part by mass or less, with respect to 100 parts by mass of (a) the base rubber. In addition, the blending amount of the peptizing agent is preferably 0.1 part by mass or more and 5 parts by mass or less, with respect to 100 parts by mass of (a) the base rubber.
The rubber composition used in the present invention is obtained by mixing and kneading (a) the base rubber, (b) the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms and/or the metal salt thereof, (c) the crosslinking initiator, (d) component, and other additives where necessary. The kneading can be conducted, without any limitation, with a well-known kneading machine such as a kneading roll, a banbury mixer, a kneader, or the like.
The spherical core of the golf ball of the present invention can be obtained by molding the rubber composition after kneaded. The temperature for molding the spherical core is preferably 120° C. or more, more preferably 150° C. or more, even more preferably 160° C. or more, and is preferably 170° C. or less. If the molding temperature exceeds 170° C., the surface hardness of the core tends to decrease. The molding pressure preferably ranges from 2.9 MPa to 11.8 MPa. The molding time preferably ranges from 10 minutes to 60 minutes.
The spherical core preferably has a hardness difference (Hs-Ho) between a surface hardness Hs and a center hardness Ho of 25 or more, more preferably 27 or more, even more preferably 30 or more, and preferably has a hardness difference of 80 or less, more preferably 70 or less, even more preferably 60 or less in JIS-C hardness. If the hardness difference between the surface hardness and the center hardness is large, the golf ball having a great flight distance due to the high launch angle and low spin rate is obtained.
The spherical core preferably has the center hardness Ho of 30 or more, more preferably 35 or more, even more preferably 40 or more in JIS-C hardness. If the center hardness Ho is less than 30 in JIS-C hardness, the core becomes so soft that the resilience thereof may be lowered. Further, the spherical core preferably has the center hardness Ho of 70 or less, more preferably 65 or less, even more preferably 60 or less in JIS-C hardness. If the center hardness Ho exceeds 70 in JIS-C hardness, the core becomes so hard that the shot feeling thereof tends to be lowered.
The spherical core preferably has the surface hardness Hs of 76 or more, more preferably 78 or more, and preferably has the surface hardness Hs of 100 or less, more preferably 95 or less in JIS-C hardness. If the surface hardness is 76 or more in JIS-C hardness, the spherical core does not become excessively soft, and thus the better resilience is obtained. Further, if the surface hardness of the spherical core is 100 or less in JIS-C hardness, the spherical core does not become excessively hard, and thus the better shot feeling is obtained.
In a preferable embodiment, the spherical core is such that R2 of the linear approximation curve obtained by a least square method is 0.85 or higher, when JIS-C hardness, which is measure at nine points obtained by dividing a radius of the spherical core into equal parts having a 12.5% interval therebetween, is plotted against the distance (%) from a core center. The hardness of the spherical core is JIS-C hardness measured at nine points obtained by dividing a radius of the spherical core into equal parts having a 12.5% interval. That is, JIS-C hardness is measured at nine points, namely at distances of 0% (core center), 12.5%, 25%, 37.5%, 50%, 62.5%, 75%, 87.5%, 100% (core surface) from the core center. Next, the measurement results are plotted to make a graph having JIS-C hardness as a vertical axis and distance (%) from the core center as a horizontal axis. In the present invention, R2 of a linear approximation curve obtained from this graph by the least square method is preferably 0.85 or higher. R2 of the linear approximation curve obtained by the least square method indicates the linearity of the obtained plot. In the present invention, R2 of 0.85 or higher means that, the spherical core has a hardness distribution where the hardness increases linearly or almost linearly. If the spherical core having the hardness distribution where the hardness increases linearly or almost linearly is used for the golf ball, the spin rate on driver shots decreases. As a result, the flight distance on driver shots increases. R2 of the linear approximation curve is preferably 0.90 or higher, and more preferably 0.95 or higher. The higher linearity provides a greater flight distance on driver shots.
The spherical core preferably has a hardness (H37.5) at 37.5% point from the core center of 30 or more, more preferably 35 or more, and preferably 80 or less, more preferably 70 or less, in JIS-C hardness. If the hardness at 37.5% point from the core center is in the above range, the spin rate on driver shot becomes lower.
The spherical core preferably has a diameter of 34.8 mm or more, more preferably 36.8 mm or more, and even more preferably 38.8 mm or more, and preferably has a diameter of 42.2 mm or less, more preferably 41.8 mm or less, and even more preferably 41.2 mm or less, and most preferably 40.8 mm or less. If the spherical core has the diameter of 34.8 mm or more, the thickness of the cover does not become too thick and thus the resilience becomes better. On the other hand, if the spherical core has the diameter of 42.2 mm or less, the thickness of the cover does not become too thin, and thus the cover functions better.
When the spherical core has the diameter of from 34.8 mm to 42.2 mm, a compression deformation amount (a shrinking amount of the spherical core along the compression direction) of the spherical core when applying a load from an initial load of 98 N to a final load of 1275 N is preferably 2.0 mm or more, more preferably 2.8 mm or more, and is preferably 6.0 mm or less, more preferably 5.0 mm or less. If the compression deformation amount is 2.0 mm or more, the shot feeling of the golf ball becomes better. If the compression deformation amount is 6.0 mm or less, the resilience of the golf ball becomes better.
The golf ball cover of the present invention is formed from a cover composition containing a resin component. Examples of the resin component include, for example, an ionomer resin; a thermoplastic polyurethane elastomer having a commercial name of “Elastollan (registered trademark)” commercially available from BASF Japan Ltd; a thermoplastic polyamide elastomer having a commercial name of “Pebax (registered trademark)” commercially available from Arkema K. K.; a thermoplastic polyester elastomer having a commercial name of “Hytrel (registered trademark)” commercially available from Du Pont-Toray Co., Ltd.; and a thermoplastic styrene elastomer having a commercial name of “Rabalon (registered trademark)” commercially available from Mitsubishi Chemical Corporation; and the like.
The ionomer resin includes a product 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, a product prepared by neutralizing at least a part of carboxyl groups in a ternary copolymer composed of an olefin, an α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms and an α,β-unsaturated carboxylic acid ester with a metal ion, or a mixture of those. The olefin preferably includes an olefin having 2 to 8 carbon atoms. Examples of the olefin are ethylene, propylene, butene, pentene, hexene, heptene, and octene. The olefin more preferably includes ethylene. Examples of the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms are acrylic acid, methacrylic acid, fumaric acid, maleic acid and crotonic acid. Among these, acrylic acid and methacrylic acid are particularly preferred. Examples of the β,β-unsaturated carboxylic acid ester include a methyl ester, ethyl ester, propyl ester, n-butyl ester, isobutyl ester of acrylic acid, methacrylic acid, fumaric acid, maleic acid or the like. In particular, acrylic acid ester and methacrylic acid ester are preferable. Among these, the ionomer resin preferably includes a metal ion-neutralized product of a binary copolymer composed of ethylene-(meth)acrylic acid and a metal ion-neutralized product of a ternary copolymer composed of ethylene-(meth)acrylic acid-(meth)acrylic acid ester.
Specific examples of the ionomer resin include trade name “Himilan (registered trademark) (e.g. the binary copolymerized ionomer such as Himilan 1555 (Na), Himilan 1557 (Zn), Himilan 1605 (Na), Himilan 1706 (Zn), Himilan 1707 (Na), Himilan AM3711 (Mg); and the ternary copolymerized ionomer such as Himilan 1856 (Na), Himilan 1855 (Zn))” commercially available from Du Pont-Mitsui Polychemicals Co., Ltd.
Further, examples of the ionomer resin also include “Surlyn (registered trademark) (e.g. the binary copolymerized ionomer such as Surlyn 8945 (Na), Surlyn 9945 (Zn), Surlyn 8140 (Na), Surlyn 8150 (Na), Surlyn 9120 (Zn), Surlyn 9150 (Zn), Surlyn 6910 (Mg), Surlyn 6120 (Mg), Surlyn 7930 (Li), Surlyn 7940 (Li), Surlyn AD8546 (Li); and the ternary copolymerized ionomer such as Surlyn 8120 (Na), Surlyn 8320 (Na), Surlyn 9320 (Zn), Surlyn 6320 (Mg), HPF 1000 (Mg), HPF 2000 (Mg))” commercially available from E.I. du Pont de Nemours and Company.
Further, examples of the ionomer resin also include “lotek (registered trademark) (e.g. the binary copolymerized ionomer such as lotek 8000 (Na), lotek 8030 (Na), lotek 7010 (Zn), lotek 7030 (Zn); and the ternary copolymerized ionomer such as lotek 7510 (Zn), lotek 7520 (Zn))” commercially available from ExxonMobil Chemical Corporation.
It is noted that Na, Zn, Li, and Mg described in the parentheses after the trade names indicate metal ion type for neutralizing the ionomer resin. The ionomer resin may be used solely or in combination at least two of them.
The cover composition constituting the cover of the golf ball of the present invention preferably includes, as a resin component, a thermoplastic polyurethane elastomer or an ionomer resin. In case of using the ionomer resin, it is preferred to use a thermoplastic styrene elastomer together. The content of the polyurethane or ionomer resin in the resin component of the cover composition is preferably 50 mass % or more, more preferably 60 mass % or more, and even more preferably 70 mass % or more.
In the present invention, the cover composition may further contain a pigment component such as a white pigment (for example, titanium oxide), a blue pigment, and a red pigment; a weight adjusting agent such as zinc oxide, calcium carbonate, and barium sulfate; a dispersant; an antioxidant; an ultraviolet absorber; a light stabilizer; a fluorescent material or a fluorescent brightener; and the like, as long as they do not impair the performance of the cover.
The content of the white pigment (for example, titanium oxide) is preferably 0.5 part by mass or more, more preferably 1 part by mass or more, and is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, with respect to 100 parts by mass of the resin component constituting the cover. If the content of the white pigment is 0.5 part by mass or more, it is possible to impart the opacity to the resultant cover. Further, if the content of the white pigment is more than 10 parts by mass, the durability of the resultant cover may deteriorate.
The slab hardness of the cover composition is preferably set in accordance with the desired performance of the golf ball. For example, in case of a so-called distance golf ball which focuses on a flight distance, the cover composition preferably has a slab hardness of 50 or more, more preferably 55 or more, and preferably has a slab hardness of 80 or less, more preferably 70 or less in shore D hardness. If the cover composition has the slab hardness of 50 or more, the obtained golf ball has a high launch angle and low spin rate on driver shots and iron shots, and thus the flight distance becomes large. If the cover composition has the slab hardness of 80 or less, the golf ball excellent in durability is obtained.
Further, in case of a so-called spin golf ball which focuses on controllability, the cover composition preferably has a slab hardness of less than 50, and preferably has a slab hardness of 20 or more, more preferably 25 or more in shore D hardness. If the cover composition has the slab hardness of less than 50, the flight distance on driver shots can be improved by the core of the present invention, as well as the obtained golf ball readily stops on the green due to the high spin rate on approach shots. If the cover composition has the slab hardness of 20 or more, the abrasion resistance improves. In case of a plurality of cover layers, the slab hardness of the cover composition constituting each layer can be identical or different, as long as the slab hardness of each layer is within the above range.
An embodiment for molding the 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, but the compression-molding method is preferred. The compression-molding of the cover composition into 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 a method of covering the core with two half shells and then subjecting the core with the two half shells to the compression-molding. 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 injection-molding the cover composition, the cover composition extruded in a pellet form beforehand may be used for injection-molding, or the materials such as the base resin components and the pigment may be dry blended, followed by directly injection-molding the blended material. It is preferred to use upper and lower molds having a spherical cavity and pimples for forming the cover, wherein a part of the pimples also serves as a retractable hold pin. When molding 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, it is preferred that the cover composition heated and melted at the temperature ranging from 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 seconds, and after cooling for 10 to 60 seconds, the mold is opened and the golf ball with the cover molded is ejected from the mold.
The concave portions called “dimple” are usually formed on the surface of the cover. The total number of the dimples is preferably 200 or more and 500 or less. If the total number is less than 200, the dimple effect is hardly obtained. On the other hand, if the total number 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, a polygonal shape such as a roughly triangular shape, a roughly quadrangular shape, a roughly pentagonal shape, a roughly hexagonal shape, and another irregular shape. The shape of the dimples is employed solely or at least two of them may be used in combination.
In the present invention, the thickness of the cover of the golf ball is preferably 4.0 mm or less, more preferably 3.0 mm or less, even more preferably 2.0 mm or less. If the thickness of the cover is 4.0 mm or less, the resilience and shot feeling of the obtained golf ball become better. The thickness of the cover is preferably 0.3 mm or more, more preferably 0.5 mm or more, and even more preferably 0.8 mm or more, and most preferably 1.0 mm or more. If the thickness of the cover is less than 0.3 mm, the durability and the wear resistance of the cover may deteriorate. If the cover has a plurality of layers, it is preferred that the total thickness of the cover layers falls within the above range.
After the cover is molded, the mold is opened and the golf ball body is ejected 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, and more preferably 40 μm or smaller, 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 lowering flying performance of the golf ball.
When the golf ball of the present invention has a diameter in a range from 40 mm to 45 mm, a compression deformation amount of the golf ball (a shrinking amount of the golf ball in the compression direction thereof) when applying a load from an initial load of 98 N to a final load of 1275 N to the golf ball is preferably 2.0 mm or more, more preferably 2.4 mm or more, even more preferably 2.5 mm or more, most preferably 2.8 mm or more, and is preferably 5.0 mm or less, more preferably 4.5 mm or less. If the compression deformation amount is 2.0 mm or more, the golf ball does not become excessively hard, and thus exhibits good shot feeling. On the other hand, if the compression deformation amount is 5.0 mm or less, the resilience is enhanced.
The golf ball construction of the present invention is not limited, as long as the golf ball comprises a spherical core and at least one cover layer covering the spherical core. FIG. 1 is a partially cutaway sectional view showing the golf ball 2 according to the preferable embodiment of the present invention. The golf ball 2 comprises a spherical core 4, and a cover 12 covering the spherical core 4. A plurality of dimples 14 are formed on the surface of the cover. Other portions than dimples 14 on the surface of the golf ball 2 are land 16. The golf ball 2 is provided with a paint layer and a mark layer outside the cover 12, but these layers are not depicted.
The spherical core preferably has a single layered structure. Unlike the multi-layered structure, the spherical core of the single layered structure does not have an energy loss at the interface of the multi-layered structure when being hit, and thus has an improved resilience. The cover has a structure of at least one layer, for example a single layered structure, or a multi-layered structure of at least two layers. The golf ball of the present invention includes, for example, a two-piece golf ball comprising a spherical core and a single layered cover disposed around the spherical core; a multi-piece golf ball comprising a spherical core and at least two cover layers disposed around the spherical core (including a three-piece golf ball); and a wound golf ball comprising a spherical core, a rubber thread layer which is formed around the spherical core, and a cover disposed over the rubber thread layer. The present invention can be suitably applied to any one of the above 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) Compression Deformation Amount (mm)
A compression deformation amount of the core or golf ball (a shrinking amount of the core or golf ball in the compression direction thereof), when applying a load from an initial load of 98 N to a final load of 1275 N to the core or golf ball, was measured.
(2) Slab Hardness (Shore D Hardness)
Sheets with a thickness of about 2 mm were produced by injection-molding 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 substrate on which the sheets were placed, and the hardness of the stack was measured with a type P1 auto loading durometer manufactured by Kobunshi Keiki Co., Ltd., provided with a Shore D type spring hardness tester prescribed in ASTM-D2240.
(3) Hardness Distribution of Spherical 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 hardness of the spherical core. The hardness measured at the surface of the spherical core was adopted as the surface hardness of the spherical core. The spherical core was cut into two hemispheres to obtain a cut plane, and the hardness was measured at the central point and at predetermined distances from the central point. The core hardness was measured at 4 points at predetermined distances from the central point of the cut plane of the core. The core hardness was calculated by averaging the hardness measured at the 4 points.
(4) Flight Distance (m) and Spin Rate (rpm) on Driver Shots
A metal-headed W#1 driver (XXIO, Shaft: S, loft: 11°, manufactured by Dunlop Sports Limited) was installed on a swing robot M/C manufactured by Golf Laboratories, Inc. A golf ball was hit at a head speed of 40 m/sec, and the flight distance (the distance from the launch point to the stop point) and the spin rate right after hitting the golf ball were measured. This measurement was conducted twelve times for each golf ball, and the average value thereof was adopted as the measurement value for the golf ball. A sequence of photographs of the hit golf ball were taken for measuring the spin rate (rpm) right after hitting the golf ball. The flight distance and spin rate on the driver shots of the golf ball are shown as a difference from those of the golf ball (core) No. 4.
[Production of Golf Ball]
(1) Production of Core
The rubber compositions having formulations shown in Table 4 were kneaded with a kneading roll and heat-pressed in upper and lower molds, each having a hemispherical cavity, at 170° C. for 20 minutes to prepare spherical cores having a diameter of 39.8 mm.















TABLE 4





Golf ball No.
1
2
3
4
5
6
7
8
























Rubber
(a) BR730
100
100
100
100
100
100
100
100


composition
(b) Sanceler SR
38
34
45
23
27
40
23
35


(part by mass)
(f) 2-Thionaphthol
0.1
0.1
0.2
—
0.1
—
0.1
0.2



(d1) Zinc acetate
12
6
—
—
—
—
12
—



(d1) Benzoic acid
—
—
5.2
—
—
—
—
5



(d2) Thioglycolic acid 2-ethylhexyl
4
4
4
—
—
4
—
—



(e) Zinc oxide
5
5
5
5
5
5
5
5



(c) Dicumyl peroxide
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8















Absolute value of SP values difference
3.1
3.1
4.2
—
—
—
—
—


(|(d1) − (d2)|)
















Core hardness
Center hardness
40.4
39.5
48.7
56.8
56.2
47.1
50.2
46.6


distribution
12.5% point hardness
45.4
46.8
53.3
60.7
62.7
51.8
59.3
51.7


(JIS-C)
25% point hardness
51.6
53.9
57.2
64.5
67.1
56.5
65.2
58.0



37.5% point hardness
54.6
56.4
58.6
66.5
68.3
57.8
67.1
61.8



50% point hardness
55.4
58.3
59.8
67.2
68.5
59.2
67.8
64.3



62.5% point hardness
56.9
62.5
65.7
67.6
68.2
66.7
67.3
64.4



75% point hardness
66.8
70.1
75.3
71.3
71.6
71.5
74.3
75.6



87.5% point hardness
75.6
72.2
78.1
72.1
75.4
70.5
79.1
83.2



Surface hardness
83.5
78.8
83.5
80.6
83.9
77.5
84.0
90.1



Surface hardness − center hardness
43.1
39.3
34.8
23.8
27.7
30.4
33.8
43.5



R2 of approximated curve
0.93
0.98
0.96
0.92
0.87
0.97
0.92
0.96



Slope of approximated curve
0.39
0.36
0.34
0.19
0.21
0.29
0.28
0.41















Compression deformation amount (mm)
4.22
4.13
4.13
4.09
4.06
4.08
3.96
4.00


Slab hardness (Shore D) of cover composition
65
65
65
65
65
65
65
65


Cover thickness (mm)
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
















Golf Ball
Driver spin rate (rpm)
−160
−150
−160
0
0
−100
−20
−120



Driver flying distance (m)
4.5
4.0
4.0
0.0
0.7
2.4
0.5
3.3



Compression deformation amount (mm)
3.52
3.43
3.43
3.39
3.36
3.38
3.26
3.30





BR730: a high-cis polybutadiene (cis-1,4 bond content = 96 mass %, 1,2-vinyl bond content = 1.3 mass %, Moony viscosity (ML1+4 (100° C.) = 55, molecular weight distribution (Mw/Mn) = 3) available from JSR Corporation


Sanceler SR: zinc acrylate (product of 10 mass % stearic acid coating) available from Sanshin Chemical Industry Co., Ltd.


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


Barium sulfate: “Barium sulfate BD” manufactured by Sakai Chemical Industry Co., Ltd., adjustment was made such that the finally obtained golf ball had a mass of 45.4 g.


2-Thionaphthol: available from Tokyo Chemical Industry Co., Ltd.


Zinc acetate: available from Wako Pure Chemical Industries, Ltd. (purity 98 mass % or more)


Thioglycolic acid 2-ethylhexyl: available from Tokyo Chemical Industry Co., Ltd. (purity 98 mass % or more)


Benzoic acid: available from Sigma-Aldrich Co., Ltd. (purity 99.5 mass % or more)


Dicumyl peroxide: “PERCUMYL ® D” available from NOF Corporation.






(2) Production of Cover

Cover materials shown in Table 5 were extruded with a twin-screw kneading extruder to prepare the cover composition in the pellet form. The extruding conditions of the cover composition 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 150 to 230° C. at the die position of the extruder. The obtained cover composition was injection-molded onto the spherical core obtained above to produce the golf ball having the spherical core and the cover covering the spherical core.







TABLE 5





Cover composition



















Formulation
Himilan 1605
50




Himilan 1706
50




Titanium oxide
4










Slab hardness (Shore D)
65







Formulation: parts by mass



Himilan 1605: Sodium ion neutralized ethylene-methacrylic acid copolymer ionomer resin available from Du Pont-Mitsui Polychemicals Co., Ltd



Himilan 1706: Zinc ion neutralized ethylene-methacrylic acid copolymer ionomer resin available from Du Pont-Mitsui Polychemicals Co., Ltd






Apparent from the results in Table 4, the golf balls comprising a spherical core and at least one cover layer covering the spherical core, wherein the spherical core is formed from a rubber composition containing (a) a base rubber, (b) an α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms and/or a metal salt thereof as a co-crosslinking agent, (c) a crosslinking initiator, (d1) a salt of a carboxylic acid having 1 to 4 carbon atoms, or an aromatic carboxylic acid and/or a salt thereof, and (d2) at least one compound selected from the group consisting of an aliphatic carboxylic acid having 5 or more carbon atoms, a salt of an aliphatic carboxylic acid having 5 or more carbon atoms, thiobenzoic acids, salts of thiobenzoic acids, a mercaptocarboxylic acid derivative and a dithiodicarboxylic acid derivative, have a low spin rate and travel great flight distance on driver shots, respectively.
The golf ball of the present invention has a great flight distance on the driver shots. This application is based on Japanese Patent application No. 2013-115474 filed on May 31, 2013, the content of which are hereby incorporated by reference.

## Claims

1. A golf ball comprising a spherical core and at least one cover layer covering the spherical core,
wherein the spherical core is formed from a rubber composition containing
(a) a base rubber,
(b) an α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms and/or a metal salt thereof as a co-crosslinking agent,
(c) a crosslinking initiator,
(d1) a salt of a carboxylic acid having 1 to 4 carbon atoms, or an aromatic carboxylic acid and/or a salt thereof, and
(d2) a mercaptocarboxylic acid derivative.

2. The golf ball according to claim 1, wherein the mercaptocarboxylic acid derivative includes at least one compound selected from the group consisting of compounds represented by the following formulae (3) to (5):



in the formula (3), R11 represents an alkyl group, an amino group or a metal atom, and m1 represents an integer number of 1 to 5;




in the formula (4), R12 represents an alkyl group, an amino group or a metal atom, M1 represents a monovalent metal ion, an ammonium ion or an organic cation, and m2 represents an integer number of 1 to 5;




in the formula (5), R13 and R14 each independently represent an alkyl group, an amino group or a metal atom, M2 represents a bivalent metal ion, and m3 and m4 each independently represent an integer number of 1 to 5.

3. The golf ball according to claim 1, wherein the mercaptocarboxylic acid derivative is a thioglycolic acid derivative.

4. The golf ball according to claim 1, wherein (d2) the mercaptocarboxylic acid derivative includes a thioglycolic acid alkyl ester and/or a salt of a thioglycolic acid alkyl ester.

5. The golf ball according to claim 1, wherein the rubber composition contains benzoic acid as the (d1) component.

6. The golf ball according to claim 1, wherein the rubber composition contains zinc acetate as the (d1) component.

7. The golf ball according to claim 1, wherein an absolute value of a difference between a SP value of the (d1) component and a SP value of the (d2) component is 2 or more.

8. The golf ball according to claim 1, wherein the rubber composition contains (d1) the salt of the carboxylic acid having 1 to 4 carbon atoms, or the aromatic carboxylic acid and/or the salt thereof in a content ranging from 0.5 part to 40 parts by mass with respect to 100 parts by mass of (a) the base rubber.

9. The golf ball according to claim 1, wherein the rubber composition contains (d2) the mercaptocarboxylic acid derivative in a content ranging from 0.5 part to 40 parts by mass with respect to 100 parts by mass of (a) the base rubber.

10. The golf ball according to claim 1, wherein a content of (b) the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms and/or the metal salt thereof is 15 parts to 50 parts by mass with respect to 100 parts by mass of (a) the base rubber.

11. The golf ball according to claim 1, wherein a total content of (d1) the salt of the carboxylic acid having 1 to 4 carbon atoms, or the aromatic carboxylic acid and/or the salt thereof and (d2) the mercaptocarboxylic acid derivative ranges from 1.0 part to 40 parts by mass with respect to 100 parts by mass of (a) the base rubber.

12. The golf ball according to claim 1, wherein a mass ratio [{(d1)+(d2)}/(b)] of a total content of (d1) the salt of the carboxylic acid having 1 to 4 carbon atoms, or the aromatic carboxylic acid and/or the salt thereof and (d2) the mercaptocarboxylic acid derivative to a content of (b) the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms and/or the metal salt thereof ranges from 0.01 to 1.0.

13. The golf ball according to claim 7, wherein the absolute value of the difference between the SP value of the (d1) component and the SP value of the (d2) component is 6.0 or less.

14. The golf ball according to claim 1, wherein the spherical core has a hardness difference (Hs-Ho) between a surface hardness Hs thereof and a center hardness Ho thereof of 25 or more in JIS-C hardness.

15. The golf ball according to claim 1, wherein the spherical core is such that R2 of a linear approximation curve obtained from a least square method is 0.85 or higher, when JIS-C hardness, which is measured at nine points obtained by dividing a radius of the spherical core into equal parts having a 12.5% interval therebetween, is plotted against the distance (%) from a core center.

16. The golf ball according to claim 1, wherein the spherical core has a 37.5% point hardness of 30 or more and 80 or less in JIS-C hardness.

17. The golf ball according to claim 1, wherein the rubber composition further contains (f) an organic sulfur compound.

18. The golf ball according to claim 17, wherein a content of (f) the organic sulfur compound is 0.05 part to 5 parts by mass with respect to 100 parts by mass of (a) the base rubber.