JP5499087B2 - Golf ball - Google Patents

Description

  The present invention relates to a golf ball. More specifically, the present invention relates to a golf ball including a core having a two-layer structure, an intermediate layer, an inner cover, and an outer cover.

  A golfer's greatest demand for a golf ball is flight performance. Golfers place particular importance on flight performance on shots with drivers. The flight performance correlates with the resilience performance of the golf ball. When a golf ball excellent in resilience performance is hit, it flies at a high speed and a large flight distance is achieved. Golf balls having a core with excellent resilience performance are described in Japanese Patent Application Laid-Open Nos. 61-37178, 2008-212681, 2008-523852, and 2009-119256.

  The core described in JP-A-61-37178 is obtained from a rubber composition containing a co-crosslinking agent and a crosslinking aid. This publication describes palmitic acid, stearic acid and myristic acid as crosslinking aids.

  The core described in JP2008-212681 is obtained from a rubber composition containing an organic peroxide, an α, β-unsaturated carboxylic acid metal salt and a fatty acid copper salt.

  The core described in JP-T-2008-523952 is obtained from a rubber composition containing a metal salt of an unsaturated monocarboxylic acid, a free radical initiator, and a non-conjugated diene monomer.

  The core described in JP-A-2009-119256 has a vinyl content of 2% or less, a cis 1,4-bond content of 80% or more, an active end, and the active end is an alkoxysilane compound. It is obtained from a rubber composition containing a modified polybutadiene.

  In order to achieve a large flight distance, an appropriate ballistic height is required. The ballistic height depends on the spin speed and launch angle. A golf ball that achieves a high trajectory with a high spin rate has insufficient flight distance. A golf ball that achieves a high trajectory with a large launch angle can provide a large flight distance. By adopting the outer-hard / inner-soft structure in the golf ball, a small spin speed and a large launch angle can be achieved. Devices relating to the hardness distribution of the core are described in JP-A-6-154357, JP-A-2008-194471, and JP-A-2008-194473.

  In the core described in JP-A-6-154357, the JIS-C hardness H1 at the center is 58 to 73, and the JIS-C hardness H2 in the region where the distance from the center is 5 mm to 10 mm is 65 to 75. The JIS-C hardness H3 at a point where the distance from the center is 15 mm is 74 or more and 82 or less, and the JIS-C hardness H4 of the surface is 76 or more and 84 or less. The hardness H2 is greater than the hardness H1, the hardness H3 is greater than the hardness H2, and the hardness H4 is equal to or greater than the hardness H3.

  In the core described in Japanese Patent Application Laid-Open No. 2008-194471, the Shore D hardness degree at the center is 30 or more and 48 or less, and the Shore D hardness at a point where the distance from the center is 4 mm is 34 or more and 52 or less. The Shore D hardness at a point where the distance is 8 mm is 40 to 58, the Shore D hardness at a point where the distance from the center is 12 mm is 43 to 61, and the distance from the surface is 2 mm to 3 mm. The Shore D hardness of a certain region is 36 or more and 54 or less, and the Shore D hardness of the surface is 41 or more and 59 or less.

  In the core described in Japanese Patent Application Laid-Open No. 2008-194473, the Shore D hardness at the center is 25 or more and 45 or less, and the Shore D hardness in the region where the distance from the center is 5 mm or more and 10 mm or less is 39 or more and 58 or less The Shore D hardness at a point where the distance from the center is 15 mm is 36 or more and 55 or less, and the Shore D hardness of the surface is 55 or more and 75 or less.

  Japanese Patent Application Laid-Open No. 2010-253268 describes a golf ball including a core, an envelope layer, an intermediate layer, and a cover. In this core, the hardness gradually increases from the center toward the surface. The difference between the surface JIS-C hardness and the center JIS-C hardness is 15 or more. The cover has a hardness greater than that of the intermediate layer, and the intermediate layer has a hardness greater than that of the envelope layer.

  Golfers also place importance on the spin performance of golf balls. If the backspin rate is high, the run is small. For golfers, a golf ball that is subject to backspin is likely to be stationary at a target point. When the side spin rate is high, the golf ball tends to bend. For golfers, golf balls that are susceptible to side spin tend to bend intentionally. A golf ball that is easily spun has excellent control performance. Advanced golfers place particular importance on control performance in shots with short irons.

JP-A-61-37178 JP 2008-212681 A Japanese translation of PCT publication No. 2008-523952 JP 2009-119256 A JP-A-6-154357 JP 2008-194471 A JP 2008-194473 A JP 2010-253268 A

  As described above, when a golf ball having a large launch angle and a low spin speed is hit with a driver, a large flight distance can be obtained. However, a golf ball with a low spin rate is inferior in control performance. Golf players want to achieve both flight distance and control performance.

  An object of the present invention is to provide a golf ball having excellent flight performance on a driver shot and control performance on a short iron shot.

The golf ball according to the present invention includes a core, an intermediate layer located outside the core, an inner cover located outside the intermediate layer, and an outer cover located outside the inner cover. The core has a center and an envelope layer located outside the center. The envelope layer is formed by crosslinking the rubber composition. This rubber composition
(A) base rubber,
(B) a co-crosslinking agent,
(C) a crosslinking initiator,
And (d) an acid and / or salt. The co-crosslinking agent (b)
(B1) an α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms and / or (b2) a metal salt of an α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms. . The shore D hardness Hc1 of the inner cover is larger than the shore D hardness Hc2 of the outer cover. The thickness T1 of the inner cover is not less than 0.1 mm and not more than 0.8 mm.

  Preferably, the amount of the acid and / or salt (d) is 0.5 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the base rubber (a).

Preferably, the acid and / or salt (d) is
(D1) Carboxylic acid and / or a salt thereof.

  Preferably, the carboxylic acid component of the carboxylic acid and / or its salt (d1) has 1 to 30 carbon atoms. Preferred carboxylic acids and / or salts (d1) thereof are fatty acid salts.

  Preferably, the JIS-C hardness H (0) of the center point of the core is 40 or more and 70 or less, and the JIS-C hardness H (100) of the surface of the core is 78 or more and 96 or less.

  Preferably, the difference (H (100) −H (0)) between the hardness H (100) and the hardness H (0) is 15 or more.

  Preferably, the Shore D hardness Hm of the intermediate layer is greater than the hardness Hc1. Preferably, the difference (Hm−Hc1) between the Shore D hardness Hm and the hardness Hc1 of the intermediate layer is 15 or more.

  Preferably, the Shore D hardness Hm of the intermediate layer is greater than the hardness Hc2. Preferably, the difference (Hm−Hc2) between the Shore D hardness Hm and the hardness Hc2 of the intermediate layer is 20 or more.

  Preferably, the difference (Hc1-Hc2) between the hardness Hc1 and the hardness Hc2 is 5 or more.

  Preferably, the thickness Tm of the intermediate layer is not less than 0.5 mm and not more than 1.6 mm. Preferably, the thickness T2 of the outer cover is 0.1 mm or more and 0.8 mm or less.

  Preferably, the difference (T1-T2) between the thickness T1 and the thickness T2 of the outer cover is −0.4 mm or more and 0.4 mm or less. Preferably, the sum (T1 + T2) of the thickness T1 and the thickness T2 of the outer cover is 1.0 mm or less.

Preferably, the rubber composition is
(E) An organic sulfur compound is further included. Preferred organic sulfur compounds (e) are thiophenols, diphenyl disulfides, thionaphthols and thiuram disulfides and metal salts thereof. Preferably, the rubber composition contains 0.05 parts by weight or more and 5.0 parts by weight or less of the organic sulfur compound (e) with respect to 100 parts by weight of the base rubber (a).

Preferably, the rubber composition contains an α, β-unsaturated carboxylic acid (b1). This rubber composition
(F) It further contains a metal compound.

  Preferably, the intermediate layer may be made of a resin composition, and the inner cover may be made of a resin composition whose base resin is different from the base resin of the intermediate layer. Preferably, the golf ball further includes a reinforcing layer between the intermediate layer and the inner cover.

  Preferably, the center has a diameter of 10 mm or more and 20 mm or less.

  Preferably, the acid and / or salt (d) is a zinc salt of a carboxylic acid. Preferred zinc salts of carboxylic acids include zinc octoate, zinc laurate, zinc myristate and zinc stearate.

  In the golf ball according to the present invention, the hardness distribution is appropriate. In this golf ball, there is little energy loss when hit. When this golf ball is hit with a driver, the spin speed is small. A large flight distance is achieved with a low spin speed. When this golf ball is hit with a short iron, the spin rate is high. This golf ball is excellent in control performance.

FIG. 1 is a partially cutaway sectional view showing a golf ball according to an embodiment of the present invention. FIG. 2 is a line graph showing the hardness distribution of the core of the golf ball of FIG.

  Hereinafter, the present invention will be described in detail based on preferred embodiments with appropriate reference to the drawings.

  A golf ball 2 shown in FIG. 1 includes a spherical core 4, an intermediate layer 6 positioned outside the core 4, a reinforcing layer 8 positioned outside the intermediate layer 6, and an outside of the reinforcing layer 8. And an outer cover 12 positioned outside the inner cover 10. A large number of dimples 14 are formed on the surface of the outer cover 12. A portion of the surface of the golf ball 2 other than the dimples 14 is a land 16. The golf ball 2 includes a paint layer and a mark layer on the outside of the outer cover 12, but these layers are not shown.

  The golf ball 2 has a diameter of 40 mm to 45 mm. The diameter is preferably 42.67 mm or more from the viewpoint that the American Golf Association (USGA) standard is satisfied. In light of suppression of air resistance, the diameter is preferably equal to or less than 44 mm, and more preferably equal to or less than 42.80 mm. The golf ball 2 has a mass of 40 g or more and 50 g or less. From the viewpoint of obtaining a large inertia, the mass is preferably 44 g or more, and more preferably 45.00 g or more. From the viewpoint that the USGA standard is satisfied, the mass is preferably equal to or less than 45.93 g.

  In the golf ball 2, the core 4 has a spherical center 18 and an envelope layer 20. The envelope layer 20 is located outside the center 18.

  In this golf ball 2, the center 18 is softer than the envelope layer 20. This center 18 can suppress spin. The diameter of the center 18 is preferably 10 mm or more and 20 mm or less. In the golf ball 2 including the center 18 having a diameter of 10 mm or more, spin can be suppressed. From this viewpoint, the diameter is more preferably 12 mm or more, and particularly preferably 14 mm or more. The golf ball 2 including the center 18 having a diameter of 20 mm or less is excellent in resilience performance. In this respect, the diameter is more preferably 18 mm or less, and particularly preferably 16 mm or less.

  The envelope layer 20 is harder than the center 18. When the golf ball 2 is hit with a driver, there is little energy loss in the envelope layer 20. The envelope layer 20 can contribute to the resilience performance of the golf ball 2. When the golf ball 2 is hit with a driver, the flight distance is large. When the golf ball 2 is hit with a golf club, no stress concentration occurs. Therefore, this golf ball 2 is excellent in durability.

  In the golf ball 2, the ratio of the radius of the center 18 to the radius of the core 4 is preferably less than 40%. Thereby, the envelope layer 20 can effectively contribute to the resilience performance of the golf ball 2. In this respect, the ratio is more preferably equal to or less than 39%. This ratio is preferably 20% or more. Thereby, the center 18 can contribute effectively to suppression of a spin. In this respect, the ratio is more preferably equal to or greater than 25%. When the golf ball 2 is hit with a driver, the flight distance is large.

In the present invention, JIS-C hardness is measured at nine measurement points obtained by dividing the core 4 from the center point to the surface into eight. The ratio of the distance from the center point of the core 4 to the radius of the core 4 of these measurement points is as follows. In the golf ball 2, the first point to the third point are included in the center 18. The envelope layer 20 includes the fourth point to the ninth point.
First point 0.0% (center point)
Second point 12.5%
Third point 25.0%
Fourth point 40.0%
5th point 50.0%
6th point 62.5%
Seventh point 75.0%
8th 87.5%
Ninth point 100.0% (surface)
The hardness from the first point to the eighth point is measured by pressing a JIS-C type hardness meter against the cut surface of the hemisphere obtained by cutting the core 4. The hardness of the ninth point is measured by pressing a JIS-C type hardness meter against the surface of the spherical core 4. For the measurement, an automatic rubber hardness measuring machine (trade name “P1” by Kobunshi Keiki Co., Ltd.) equipped with this hardness meter is used.

  FIG. 2 is a line graph showing the hardness distribution of the envelope layer 20 of the golf ball 2 of FIG. The horizontal axis of this graph represents the ratio (%) of the distance from the center point of the core 4 to the radius of the core 4. The vertical axis of this graph is JIS-C hardness. In this graph, points included in the envelope layer 20 among the first point to the ninth point are plotted. In the present embodiment, six points from the fourth point to the ninth point are plotted in this graph.

  FIG. 2 also shows a linear approximation curve obtained by the method of least squares based on the ratio of 6 measurement points and the hardness. This linear approximation curve is indicated by a dotted line. In FIG. 2, the broken line does not deviate significantly from the linear approximation curve. In other words, the polygonal line has a shape close to a linear approximation curve. In the envelope layer 20, the hardness increases linearly from the inside toward the outside. When the golf ball 2 is hit with a driver, the energy loss in the envelope layer 20 is small. This golf ball 2 is excellent in resilience performance. When the golf ball 2 is hit with a driver, the flight distance is large. When the golf ball 2 is hit with a golf club, no stress concentration occurs. Therefore, this golf ball 2 is excellent in durability.

R ² of the linear approximation curve obtained by the least square method in the envelope layer 20 is preferably 0.95 or more. R ² is an index representing the linearity of the broken line. In the envelope layer 20 in which R ² is 0.95 or more, the shape of the broken line of the hardness distribution is almost a straight line. The golf ball 2 including the envelope layer 20 having R ² of 0.95 or more has excellent resilience performance. R ² is more preferably 0.96 or more, and particularly preferably 0.97 or more. R ² is calculated by squaring the correlation coefficient R. The correlation coefficient R is obtained by dividing the covariance between the distance (%) from the center and the hardness (JIS-C) by the standard deviation of the distance (%) from the center and the standard deviation of the hardness (JIS-C). Is calculated by

  In the present invention, the JIS-C hardness of the measurement point where the ratio of the distance from the center point of the core 4 to the radius of the core 4 is x% is represented by H (x). The hardness of the center point of the core 4 is represented as H (0), and the surface hardness of the core 4 is represented as H (100). The difference (H (100) −H (0)) between the surface hardness H (100) and the center hardness H (0) is preferably 15 or more. The core 4 having a difference (H (100) −H (0)) of 15 or more has an outer-hard / inner-soft structure. When the golf ball 2 is hit with a driver, the core 4 has a large recoil (twisting back), so that spin is suppressed. The core 4 contributes to the flight performance of the golf ball 2. From the viewpoint of flight performance, the difference (H (100) −H (0)) is more preferably 23 or more, and particularly preferably 24 or more. From the viewpoint that the core 4 can be easily molded, the difference (H (100) −H (0)) is preferably 50 or less. In the core 4, the hardness gradually increases from the center point toward the surface.

  The center 12 is formed by crosslinking a rubber composition. Examples of the base rubber of the rubber composition include polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-propylene-diene copolymer, and natural rubber. Two or more kinds of rubbers may be used in combination. From the viewpoint of resilience performance, polybutadiene is preferred, and high cis polybutadiene is particularly preferred.

  Preferably, the rubber composition of the center 12 includes a co-crosslinking agent. From the viewpoint of resilience performance, preferred co-crosslinking agents are zinc acrylate, magnesium acrylate, zinc methacrylate and magnesium methacrylate. Preferably, the rubber composition includes an organic peroxide together with a co-crosslinking agent. Preferred organic peroxides include dicumyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di (t-butyl). Peroxy) hexane and di-t-butyl peroxide. Preferably, the rubber composition includes a sulfur compound.

  In the rubber composition of the center 12, various additives such as a filler, sulfur, a vulcanization accelerator, an anti-aging agent, a colorant, a plasticizer, and a dispersant are blended in appropriate amounts as necessary. Synthetic resin powder or crosslinked rubber powder may be blended with the rubber composition.

The envelope layer 14 is formed by crosslinking a rubber composition. This rubber composition
(A) base rubber,
(B) a co-crosslinking agent,
(C) contains a crosslinking initiator and (d) an acid and / or salt.

  Examples of the base rubber (a) include polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-propylene-diene copolymer, and natural rubber. From the viewpoint of resilience performance, polybutadiene is preferred. When polybutadiene and other rubber are used in combination, it is preferable that polybutadiene is a main component. Specifically, the ratio of the amount of polybutadiene to the total amount of the base rubber is preferably 50% by mass or more, and more preferably 80% by mass or more. The ratio of cis-1,4 bonds in the polybutadiene is preferably 40% by mass or more, and more preferably 80% by mass or more.

  Polybutadiene having a 1,2-vinyl bond ratio of 2.0% by mass or less is preferred. This polybutadiene can contribute to the resilience performance of the golf ball 2. In this respect, the 1,2-vinyl bond ratio is preferably equal to or less than 1.7% by mass, and particularly preferably equal to or less than 1.5% by mass.

  From the viewpoint that a polybutadiene having a small ratio of 1,2-vinyl bonds and excellent polymerization activity can be obtained, a rare earth element-based catalyst is preferably used for the synthesis of polybutadiene. In particular, polybutadiene synthesized with a catalyst containing neodymium which is a lanthanum series rare earth element compound is preferable.

The Mooney viscosity (ML _{1 + 4} (100 ° C.)) of polybutadiene is preferably 30 or more, more preferably 32 or more, and particularly preferably 35 or more. The Mooney viscosity (ML _{1 + 4} (100 ° C.)) is preferably 140 or less, more preferably 120 or less, still more preferably 100, and particularly preferably 80 or less. Mooney viscosity (ML _{1 + 4} (100 ° C.)) is measured in accordance with the provisions of “JIS K6300”. The measurement conditions are as follows.
Rotor: L rotor Preheating time: 1 minute Rotor rotation time: 4 minutes Temperature: 100 ° C

  From the viewpoint of workability, the molecular weight distribution (Mw / Mn) of polybutadiene is preferably 2.0 or more, more preferably 2.2 or more, further preferably 2.4 or more, and particularly preferably 2.6 or more. In light of resilience performance, the molecular weight distribution (Mw / Mn) is preferably 6.0 or less, more preferably 5.0 or less, still more preferably 4.0 or less, and particularly preferably 3.4 or less. The molecular weight distribution (Mw / Mn) is calculated by dividing the weight average molecular weight Mw by the number average molecular weight Mn.

The molecular weight distribution is measured by gel permeation chromatography (“HLC-8120GPC” manufactured by Tosoh Corporation). The measurement conditions are as follows.
Detector: differential refractometer Column: GMHHXL (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Mobile phase: Tetrahydrofuran molecular weight distribution is calculated as a standard polystyrene equivalent value.

The co-crosslinking agent (b)
(B1) an α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms and (b2) a metal salt of an α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms.

  The rubber composition may contain only the α, β-unsaturated carboxylic acid (b1) or only the metal salt (b2) of the α, β-unsaturated carboxylic acid as the co-crosslinking agent (b). The rubber composition may contain both α, β-unsaturated carboxylic acid (b1) and α, β-unsaturated carboxylic acid metal salt (b2) as the co-crosslinking agent (b).

  The metal salt (b2) of α, β-unsaturated carboxylic acid crosslinks the rubber molecule by graft polymerization to the molecular chain of the base rubber. When the rubber composition contains an α, β-unsaturated carboxylic acid (b1), the rubber composition preferably further contains a metal compound (f). This metal compound (f) reacts with the α, β-unsaturated carboxylic acid (b1) in the rubber composition. The salt obtained by this reaction is graft-polymerized to the molecular chain of the base rubber.

  Examples of the metal compound (f) include metal hydroxides such as magnesium hydroxide, zinc hydroxide, calcium hydroxide, sodium hydroxide, lithium hydroxide, potassium hydroxide and copper hydroxide; magnesium oxide, calcium oxide, Metal oxides such as zinc oxide and copper oxide; and metal carbonates such as magnesium carbonate, zinc carbonate, calcium carbonate, sodium carbonate, lithium carbonate and potassium carbonate. A compound containing a divalent metal is preferred. A compound containing a divalent metal reacts with the co-crosslinking agent (b) to form a metal bridge. A particularly preferred metal compound (f) is a zinc compound. Two or more metal compounds may be used in combination.

  Examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, fumaric acid, maleic acid and crotonic acid. The metal component in the metal salt (b2) of α, β-unsaturated carboxylic acid includes sodium ion, potassium ion, lithium ion, magnesium ion, calcium ion, zinc ion, barium ion, cadmium ion, aluminum ion, tin ion and Zirconium ions are exemplified. The metal salt (b2) of α, β-unsaturated carboxylic acid may contain two or more kinds of ions. From the viewpoint that metal crosslinking between rubber molecules is likely to occur, divalent metal ions such as magnesium ion, calcium ion, zinc ion, barium ion and cadmium ion are preferable. A particularly preferred metal salt (b2) of α, β-unsaturated carboxylic acid is zinc acrylate.

  In light of the resilience performance of the golf ball 2, the amount of the co-crosslinking agent (b) is preferably 15 parts by mass or more and particularly preferably 20 parts by mass or more with respect to 100 parts by mass of the base rubber. In light of feel at impact, this amount is preferably equal to or less than 50 parts by weight, more preferably equal to or less than 45 parts by weight, and particularly preferably equal to or less than 40 parts by weight.

  A preferred crosslinking initiator (c) is an organic peroxide. The organic peroxide contributes to the resilience performance of the golf ball 2. Suitable organic peroxides include dicumyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di (t- Butyl peroxy) hexane and di-t-butyl peroxide. From the viewpoint of versatility, dicumyl peroxide is preferable.

  In light of the resilience performance of the golf ball 2, the amount of the crosslinking initiator (c) is preferably 0.2 parts by mass or more and particularly preferably 0.5 parts by mass or more with respect to 100 parts by mass of the base rubber. In light of feel at impact and durability of the golf ball 2, this amount is preferably equal to or less than 5.0 parts by weight, and particularly preferably equal to or less than 2.5 parts by weight.

  In the present invention, the concept of acid and / or salt (d) does not include the co-crosslinking agent (b). As will be described later, the acid and / or the salt (d) is presumed to cut the metal crosslink by the co-crosslinking agent (b) in the envelope layer 14 forming a part of the core 4 when the core 4 is heated and formed. Yes.

  Examples of the acid and / or salt (d) include oxo acids such as carboxylic acid, sulfonic acid, and phosphoric acid and salts thereof; and hydrogen acids such as hydrochloric acid and hydrofluoric acid and salts thereof. Oxo acids and their salts are preferred. Carboxylic acid and its salt (d1) are preferred. Carboxylate is particularly preferred.

  The carboxylic acid component in the carboxylic acid and / or its salt (d1) has a carboxyl group. This carboxylic acid component reacts with the co-crosslinking agent (b). This reaction is presumed to break the metal bridge.

  The carbon number of the carboxylic acid component in the carboxylic acid and / or its salt (d1) is preferably 1 or more, 30 or less, more preferably 3 or more and 30 or less, and even more preferably 5 or more and 28 or less. Examples of carboxylic acids include aliphatic carboxylic acids (fatty acids) and aromatic carboxylic acids. As carboxylic acid and / or its salt (d1), a fatty acid and / or its salt are preferable. As for carbon number of the fatty acid component in a fatty acid and / or its salt, 1-30 is preferable.

  The rubber composition may contain a saturated fatty acid and / or a salt thereof, and may contain an unsaturated fatty acid and / or a salt thereof. Saturated fatty acids and / or their salts are preferred.

  As fatty acids, butyric acid (C4), valeric acid (C5), caproic acid (C6), enanthic acid (C7), caprylic acid (octanoic acid) (C8), pelargonic acid (C9), capric acid (decanoic 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), Noserin acid (C24), nervonic acid (C24), cerotic acid (C26), montanic acid (C28) and melissic acid (C30) can be mentioned. Two or more fatty acids may be used in combination. Octanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and behenic acid are preferred.

  The aromatic carboxylic acid has an aromatic ring and a carboxyl group. As aromatic carboxylic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid (benzene-1,2,3-tricarboxylic acid), trimellitic acid (benzene-1,2,4-tricarboxylic acid), Trimesic acid (benzene-1,3,5-tricarboxylic acid), merophanic acid (benzene-1,2,3,4-tetracarboxylic acid), planitic acid (benzene-1,2,3,5-tetracarboxylic acid) , Pyromellitic acid (benzene-1,2,4,5-tetracarboxylic acid), meritic acid (benzenehexacarboxylic acid), diphenic acid (biphenyl-2,2'-dicarboxylic acid), toluic acid (methylbenzoic acid) , Xylic acid, prenylic acid (2,3,4-trimethylbenzoic acid), γ-isoduric acid (2,3,5-trimethylbenzoic acid), duric acid 2,4,5-trimethylbenzoic acid), β-isoduric acid (2,4,6-trimethylbenzoic acid), α-isoduric acid (3,4,5-trimethylbenzoic acid), cumic acid (4-isopropylbenzoic acid) Acid), ubitoic acid (5-methylisophthalic acid), α-toluic acid (phenylacetic acid), hydroatropic acid (2-phenylpropanoic acid) and hydrocinnamic acid (3-phenylpropanoic acid).

  The rubber composition may include an aromatic carboxylate substituted with a hydroxyl group, an alkoxy group, or an oxo group. Examples of the carboxylic acid include salicylic acid (2-hydroxybenzoic acid), anisic acid (methoxybenzoic acid), cresotic acid (hydroxy (methyl) benzoic acid), o-homosalicylic acid (2-hydroxy-3-methylbenzoic acid), m-homosalicylic acid (2-hydroxy-4-methylbenzoic acid), p-homosalicylic acid (2-hydroxy-5-methylbenzoic acid), o-pyrocatechuic acid (2,3-dihydroxybenzoic acid), β-resorcylic acid (2,4-dihydroxybenzoic acid), γ-resorcylic acid (2,6-dihydroxybenzoic acid), protocatechuic acid (3,4-dihydroxybenzoic acid), α-resorcylic acid (3,5-dihydroxybenzoic acid), Vanillic acid (4-hydroxy-3-methoxybenzoic acid), isovanillic acid (3-hydroxy-4-methoxybenzoic acid), Ratrumic acid (3,4-dimethoxybenzoic acid), o-veratormic acid (2,3-dimethoxybenzoic acid), orthoric acid (2,4-dihydroxy-6-methylbenzoic acid), m-hemipic acid (4,5 -Dimethoxyphthalic acid), gallic acid (3,4,5-trihydroxybenzoic acid), syringic acid (4-hydroxy-3,5-dimethoxybenzoic acid), asaronic acid (2,4,5-trimethoxybenzoic acid) , Mandelic acid (hydroxy (phenyl) acetic acid), vanylmandelic acid (hydroxy (4-hydroxy-3-methoxyphenyl) acetic acid), homoanisic acid ((4-methoxyphenyl) acetic acid), homogentisic acid ((2,5-dihydroxyphenyl) ) Acetic acid), homoprotocatechuic acid ((3,4-dihydroxyphenyl) acetic acid), homovanillic acid ((4-hydroxy- -Methoxyphenyl) acetic acid), homoisovanillic acid ((3-hydroxy-4-methoxyphenyl) acetic acid), homoveratrumic acid ((3,4-dimethoxyphenyl) acetic acid), o-homoveratric acid ((2,3-dimethoxy) Phenyl) acetic acid), homophthalic acid (2- (carboxymethyl) benzoic acid), homoisophthalic acid (3- (carboxymethyl) benzoic acid), homoterephthalic acid (4- (carboxymethyl) benzoic acid), phthalonic acid (2 -(Carboxycarbonyl) benzoic acid), isophthalonic acid (3- (carboxycarbonyl) benzoic acid), terephthalonic acid (4- (carboxycarbonyl) benzoic acid), benzylic acid (hydroxydiphenylacetic acid), atrolactic acid (2-hydroxy) -2-phenylpropanoic acid), tropic acid (3-hydroxy-2-phenyl) Phenylpropanoic acid), mellilotic acid (3- (2-hydroxyphenyl) propanoic acid), furoleto acid (3- (4-hydroxyphenyl) propanoic acid), hydrocaffeic acid (3- (3,4-dihydroxyphenyl) propane Acid), hydroferulic acid (3- (4-hydroxy-3-methoxyphenyl) propanoic acid), hydroisoferulic acid (3- (3-hydroxy-4-methoxyphenyl) propanoic acid), p-coumaric acid (3 -(4-hydroxyphenyl) acrylic acid), umbelic acid (3- (2,4-dihydroxyphenyl) acrylic acid), caffeic acid (3- (3,4-dihydroxyphenyl) acrylic acid), ferulic acid (3- (4-hydroxy-3-methoxyphenyl) acrylic acid), isoferulic acid (3- (3-hydroxy-4-methoxypheny) ) Acrylic acid) and sinapinic acid (3- (4-hydroxy-3,5-dimethoxyphenyl) acrylic acid) may be exemplified.

  The cation component of the carboxylate is a metal ion or an organic cation. As metal ions, sodium ion, potassium ion, lithium ion, silver ion, magnesium ion, calcium ion, zinc ion, barium ion, cadmium ion, copper ion, cobalt ion, nickel ion, manganese ion, aluminum ion, iron ion, tin Examples include ions, zirconium ions, and titanium ions. Two or more ions may be used in combination.

  An organic cation is a cation having a carbon chain. An organic ammonium ion is mentioned as an organic cation. As organic ammonium ions, primary ammonium ions such as stearyl ammonium ion, hexyl ammonium ion, octyl ammonium ion and 2-ethylhexyl ammonium ion; secondary ammonium ions such as dodecyl (lauryl) ammonium ion and octadecyl (stearyl) ammonium ion A tertiary ammonium ion such as trioctylammonium ion; and a quaternary ammonium ion such as dioctyldimethylammonium ion and distearyldimethylammonium ion. Two or more organic cations may be used in combination.

  Preferred examples of the carboxylate include octanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid or potassium salt of oleic acid, magnesium salt, aluminum salt, zinc salt, iron salt, copper salt, nickel salt or cobalt salt. The A zinc salt of a carboxylic acid is particularly preferred. Preferred zinc salts of carboxylic acids include zinc octoate, zinc laurate, zinc myristate and zinc stearate. A particularly preferred zinc salt of carboxylic acid is zinc octoate.

  From the viewpoint of the linearity of the hardness distribution of the envelope layer 14, the amount of the acid and / or salt (d) is preferably 0.5 parts by mass or more, and 1.0 part by mass or more with respect to 100 parts by mass of the base rubber. More preferred is 2.0 parts by mass or more. In light of resilience performance, this amount is preferably equal to or less than 45 parts by weight, more preferably equal to or less than 40 parts by weight, and particularly preferably equal to or less than 30 parts by weight.

  The mass ratio of the co-crosslinking agent (b) and the acid and / or salt (d) in the rubber composition is preferably 3/7 or more and 9/1 or less. With the rubber composition having a mass ratio within the above range, the envelope layer 14 whose hardness increases linearly from the inside toward the outside can be obtained.

  As the co-crosslinking agent (b), zinc acrylate is preferably used. For the purpose of improving dispersibility in rubber, there is zinc acrylate whose surface is coated with stearic acid or zinc stearate. In the present invention, when this rubber composition contains zinc acrylate, the acid and / or salt (d) does not contain a coating agent.

  Preferably, the rubber composition further includes an organic sulfur compound (e). The organic sulfur compound (e) increases the linearity of the hardness distribution of the envelope layer 14. The organic sulfur compound (e) further increases the degree of the outer-hard / inner-soft structure.

  Examples of the organic sulfur compound (e) include organic compounds having a thiol group or a polysulfide bond having 2 to 4 sulfur atoms. The metal salt of this organic compound is also included in the organic sulfur compound (e). As the organic sulfur compound (e), aliphatic compounds such as aliphatic thiols, aliphatic thiocarboxylic acids, aliphatic dithiocarboxylic acids and aliphatic polysulfides; heterocyclic compounds; alicyclic thiols, alicyclic thiocarboxylic acids, fats Illustrative are alicyclic compounds such as cyclic dithiocarboxylic acids and alicyclic polysulfides; and aromatic compounds. Specific examples of the organic sulfur compound (e) include thiophenols, thionaphthols, polysulfides, thiocarboxylic acids, dithiocarboxylic acids, sulfenamides, thiurams, dithiocarbamates and thiazoles. Preferred organic sulfur compounds (e) are thiophenols, diphenyl disulfides, thionaphthols and thiuram disulfides and metal salts thereof.

  Specific examples of the organic sulfur compound (e) are represented by the following chemical formulas (1) to (4).

  In the chemical formula (1), R1 to R5 each represent H or a substituent.

  In the chemical formula (2), R1 to R10 each represent H or a substituent.

  In the chemical formula (3), R1 to R5 each represent H or a substituent, and M1 represents a monovalent metal atom.

  In the chemical formula (4), R1 to R10 each represent H or a substituent, and M2 represents a divalent metal atom.

In the above formulas (1) to (4), the substituent is a halogen group (F, Cl, Br, I), an alkyl group, a carboxyl group (—COOH), an ester of a carboxyl group (—COOR), a formyl group (— CHO), acyl group (—COR), halogenated carbonyl group (—COX), sulfo group (—SO ₃ H), ester of sulfo group (—SO ₃ R), halogenated sulfonyl group (—SO ₂ X), Selected from the group consisting of a sulfino group (—SO ₂ H), an alkylsulfinyl group (—SOR), a carbamoyl group (—CONH ₂ ), a halogenated alkyl group, a cyano group (—CN) and an alkoxy group (—OR). At least one kind.

  Examples of the organic sulfur compound represented by the chemical formula (1) include thiophenol; 4-fluorothiophenol, 2,5-difluorothiophenol, 2,4,5-trifluorothiophenol, 2,4,5. , 6-tetrafluorothiophenol, pentafluorothiophenol, 2-chlorothiophenol, 4-chlorothiophenol, 2,4-dichlorothiophenol, 2,5-dichlorothiophenol, 2,6-dichlorothiophenol, 2 , 4,5-trichlorothiophenol, 2,4,5,6-tetrachlorothiophenol, pentachlorothiophenol, 4-bromothiophenol, 2,5-dibromothiophenol, 2,4,5-tribromothio Phenol, 2,4,5,6-tetrabromothiophenol, pentabromothiol Halogen groups such as diol, 4-iodothiophenol, 2,5-diiodothiophenol, 2,4,5-triiodothiophenol, 2,4,5,6-tetraiodothiophenol and pentaiodothiophenol 4-methylthiophenol, 2,4,5-trimethylthiophenol, pentamethylthiophenol, 4-t-butylthiophenol, 2,4,5-tri-t-butylthiophenol and penta Thiophenols substituted with alkyl groups such as t-butylthiophenol; Thio substituted with carboxyl groups such as 4-carboxythiophenol, 2,4,6-tricarboxythiophenol and pentacarboxythiophenol Phenols; 4-methoxycarbonylthiophenol Thiophenols substituted with alkoxycarbonyl groups such as 2,4,6-trimethoxycarbonylthiophenol and pentamethoxycarbonylthiophenol; 4-formylthiophenol, 2,4,6-triformylthiophenol and pentaformyl Thiophenols substituted with formyl groups such as thiophenol; Thiophenols substituted with acyl groups such as 4-acetylthiophenol, 2,4,6-triacetylthiophenol and pentaacetylthiophenol; 4 Thiophenols substituted with carbonyl halide groups such as chlorocarbonylthiophenol, 2,4,6-tri (chlorocarbonyl) thiophenol and penta (chlorocarbonyl) thiophenol; 4-sulfothiophenol, 2, 4,6 -Thiophenols substituted with sulfo groups such as trisulfothiophenol and pentasulfothiophenol; such as 4-methoxysulfonylthiophenol, 2,4,6-trimethoxysulfonylthiophenol and pentamethoxysulfonylthiophenol Thiophenols substituted with alkoxysulfonyl groups; substituted with halogenated sulfonyl groups such as 4-chlorosulfonylthiophenol, 2,4,6-tri (chlorosulfonyl) thiophenol and penta (chlorosulfonyl) thiophenol Thiophenols; thiophenols substituted with sulfino groups such as 4-sulfinothiophenol, 2,4,6-trisulfinothiophenol and pentasulfinothiophenol; 4-methylsulfinylthiopheno Thiophenols substituted with alkylsulfinyl groups such as 2,4,6-tri (methylsulfinyl) thiophenol and penta (methylsulfinyl) thiophenol; 4-carbamoylthiophenol, 2,4,6-tri Thiophenols substituted with carbamoyl groups such as carbamoylthiophenol and pentacarbamoylthiophenol; such as 4-trichloromethylthiophenol, 2,4,6-tri (trichloromethyl) thiophenol and penta (trichloromethyl) thiophenol Thiophenols substituted with various halogenated alkyl groups; thiophenols substituted with cyano groups such as 4-cyanothiophenol, 2,4,6-tricyanothiophenol and pentacyanothiophenol; and 4-meth Shi thiophenol, thiophenols substituted with an alkoxy group such as 2,4,6-methoxythiophenol and penta-methoxy thiophenol and the like. These thiophenols are substituted with one type of substituent.

As another example of the organic sulfur compound represented by the chemical formula (1), a compound substituted with at least one kind of the above substituent and another substituent can be given. Examples of other substituents include a nitro group (—NO ₂ ), an amino group (—NH ₂ ), a hydroxyl group (—OH), and a phenylthio group (—SPh). Specific examples of this compound include 4-chloro-2-nitrothiophenol, 4-chloro-2-aminothiophenol, 4-chloro-2-hydroxythiophenol, 4-chloro-2-phenylthiothiophenol, 4 -Methyl-2-nitrothiophenol, 4-methyl-2-aminothiophenol, 4-methyl-2-hydroxythiophenol, 4-methyl-2-phenylthiothiophenol, 4-carboxy-2-nitrothiophenol, 4-carboxy-2-aminothiophenol, 4-carboxy-2-hydroxythiophenol, 4-carboxy-2-phenylthiothiophenol, 4-methoxycarbonyl-2-nitrothiophenol, 4-methoxycarbonyl-2-amino Thiophenol, 4-methoxycarbonyl-2-hydroxy Thiophenol, 4-methoxycarbonyl-2-phenylthiothiophenol, 4-formyl-2-nitrothiophenol, 4-formyl-2-aminothiophenol, 4-formyl-2-hydroxythiophenol, 4-formyl-2 -Phenylthiothiophenol, 4-acetyl-2-nitrothiophenol, 4-acetyl-2-aminothiophenol, 4-acetyl-2-hydroxythiophenol, 4-acetyl-2-phenylthiothiophenol, 4-chloro Carbonyl-2-nitrothiophenol, 4-chlorocarbonyl-2-aminothiophenol, 4-chlorocarbonyl-2-hydroxythiophenol, 4-chlorocarbonyl-2-phenylthiothiophenol, 4-sulfo-2-nitrothio Phenol, 4-sulfo- -Aminothiophenol, 4-sulfo-2-hydroxythiophenol, 4-sulfo-2-phenylthiothiophenol, 4-methoxysulfonyl-2-nitrothiophenol, 4-methoxysulfonyl-2-aminothiophenol, 4- Methoxysulfonyl-2-hydroxythiophenol, 4-methoxysulfonyl-2-phenylthiothiophenol, 4-chlorosulfonyl-2-nitrothiophenol, 4-chlorosulfonyl-2-aminothiophenol, 4-chlorosulfonyl-2- Hydroxythiophenol, 4-chlorosulfonyl-2-phenylthiothiophenol, 4-sulfino-2-nitrothiophenol, 4-sulfino-2-aminothiophenol, 4-sulfino-2-hydroxythiophenol, 4-sulfino 2-phenylthiothiophenol, 4-methylsulfinyl-2-nitrothiophenol, 4-methyl-2-aminosulfinylthiophenol, 4-methylsulfinyl-2-hydroxythiophenol, 4-methylsulfinyl-2-phenylthio Thiophenol, 4-carbamoyl-2-nitrothiophenol, 4-carbamoyl-2-aminothiophenol, 4-carbamoyl-2-hydroxythiophenol, 4-carbamoyl-2-phenylthiothiophenol, 4-trichloromethyl-2 -Nitrothiophenol, 4-trichloromethyl-2-aminothiophenol, 4-trichloromethyl-2-hydroxythiophenol, 4-trichloromethyl-2-phenylthiothiophenol, 4-cyano-2-nitrothiopheno 4-cyano-2-aminothiophenol, 4-cyano-2-hydroxythiophenol, 4-cyano-2-phenylthiothiophenol, 4-methoxy-2-nitrothiophenol, 4-methoxy-2-aminothio Examples include phenol, 4-methoxy-2-hydroxythiophenol and 4-methoxy-2-phenylthiothiophenol.

  Still another example of the organic sulfur compound represented by the chemical formula (1) includes a compound substituted with two or more kinds of substituents. Specific examples of this compound include 4-acetyl-2-chlorothiophenol, 4-acetyl-2-methylthiophenol, 4-acetyl-2-carboxythiophenol, 4-acetyl-2-methoxycarbonylthiophenol, 4-acetyl 2-formylthiophenol, 4-acetyl-2-chlorocarbonylthiophenol, 4-acetyl-2-sulfothiophenol, 4-acetyl-2-methoxysulfonylthiophenol, 4-acetyl-2-chlorosulfonylthiophenol, 4-acetyl-2-sulfinothiophenol, 4-acetyl-2-methylsulfinylthiophenol, 4-acetyl-2-carbamoylthiophenol, 4-acetyl-2-trichloromethylthiophenol, 4-acetyl-2-cyanothio Phenol Beauty 4-acetyl-2-methoxy-thiophenol and the like.

  Examples of the organic sulfur compound represented by the chemical formula (2) include diphenyl disulfide; bis (4-fluorophenyl) disulfide, bis (2,5-difluorophenyl) disulfide, bis (2,4,5-trifluoro). Phenyl) disulfide, bis (2,4,5,6-tetrafluorophenyl) disulfide, bis (pentafluorophenyl) disulfide, bis (4-chlorophenyl) disulfide, bis (2,5-dichlorophenyl) disulfide, bis (2, 4,5-trichlorophenyl) disulfide, bis (2,4,5,6-tetrachlorophenyl) disulfide, bis (pentachlorophenyl) disulfide, bis (4-bromophenyl) disulfide, bis (2,5-dibromophenyl) disulfide , Screws (2, 4, -Tribromophenyl) disulfide, bis (2,4,5,6-tetrabromophenyl) disulfide, bis (pentabromophenyl) disulfide, bis (4-iodophenyl) disulfide, bis (2,5-diiodophenyl) Diphenyl disulfides substituted with halogen groups such as disulfide, bis (2,4,5-triiodophenyl) disulfide, bis (2,4,5,6-tetraiodophenyl) disulfide and bis (pentaiodophenyl) disulfide Bis (4-methylphenyl) disulfide, bis (2,4,5-trimethylphenyl) disulfide, bis (pentamethylphenyl) disulfide, bis (4-t-butylphenyl) disulfide, bis (2,4,5) -Tri-t-butylphenyl) disulfide Diphenyl disulfides substituted with alkyl groups such as bis (penta-t-butylphenyl) disulfide; bis (4-carboxyphenyl) disulfide, bis (2,4,6-tricarboxyphenyl) disulfide and bis (penta Diphenyl disulfides substituted with carboxyl groups such as carboxyphenyl) disulfide; bis (4-methoxycarbonylphenyl) disulfide, bis (2,4,6-trimethoxycarbonylphenyl) disulfide and bis (pentamethoxycarbonylphenyl) disulfide Diphenyl disulfides substituted with alkoxycarbonyl groups such as: bis (4-formylphenyl) disulfide, bis (2,4,6-triformylphenyl) disulfide and bis (pentaformyl) Diphenyl disulfides substituted with formyl groups such as phenyl) disulfide; acyls such as bis (4-acetylphenyl) disulfide, bis (2,4,6-triacetylphenyl) disulfide and bis (pentaacetylphenyl) disulfide Group substituted diphenyl disulfides; halogens such as bis (4-chlorocarbonylphenyl) disulfide, bis (2,4,6-tri (chlorocarbonyl) phenyl) disulfide and bis (penta (chlorocarbonyl) phenyl) disulfide Diphenyl disulfides substituted with a carbonyl group; substituted with sulfo groups such as bis (4-sulfophenyl) disulfide, bis (2,4,6-trisulfophenyl) disulfide and bis (pentasulfophenyl) disulfide Diphenyl disulfides; diphenyls substituted with alkoxysulfonyl groups such as bis (4-methoxysulfonylphenyl) disulfide, bis (2,4,6-trimethoxysulfonylphenyl) disulfide and bis (pentamethoxysulfonylphenyl) disulfide Disulfides; substituted with sulfonyl halides such as bis (4-chlorosulfonylphenyl) disulfide, bis (2,4,6-tri (chlorosulfonyl) phenyl) disulfide and bis (penta (chlorosulfonyl) phenyl) disulfide Diphenyl disulfides; such as bis (4-sulfinophenyl) disulfide, bis (2,4,6-trisulfinophenyl) disulfide and bis (pentasulfinophenyl) disulfide Diphenyl disulfides substituted with a rufino group; such as bis (4-methylsulfinylphenyl) disulfide, bis (2,4,6-tri (methylsulfinyl) phenyl) disulfide and bis (penta (methylsulfinyl) phenyl) disulfide Diphenyl disulfides substituted with alkylsulfinyl groups; substituted with carbamoyl groups such as bis (4-carbamoylphenyl) disulfide, bis (2,4,6-tricarbamoylphenyl) disulfide and bis (pentacarbamoylphenyl) disulfide Diphenyl disulfides; bis (4-trichloromethylphenyl) disulfide, bis (2,4,6-tri (trichloromethyl) phenyl) disulfide and bis (penta (trichloromethyl) phenyl) Diphenyl disulfides substituted with halogenated alkyl groups such as disulfides; cyano such as bis (4-cyanophenyl) disulfide, bis (2,4,6-tricyanophenyl) disulfide and bis (pentacyanophenyl) disulfide Substituted diphenyl disulfides; and diphenyl substituted with alkoxy groups such as bis (4-methoxyphenyl) disulfide, bis (2,4,6-trimethoxyphenyl) disulfide and bis (pentamethoxyphenyl) disulfide Disulfides are exemplified. These diphenyl disulfides are substituted with one type of substituent.

As another example of the organic sulfur compound represented by the chemical formula (2), a compound substituted with at least one kind of the substituent and another substituent can be given. Examples of other substituents include a nitro group (—NO ₂ ), an amino group (—NH ₂ ), a hydroxyl group (—OH), and a phenylthio group (—SPh). Specific examples of this compound include bis (4-chloro-2-nitrophenyl) disulfide, bis (4-chloro-2-aminophenyl) disulfide, bis (4-chloro-2-hydroxyphenyl) disulfide, bis (4 -Chloro-2-phenylthiophenyl) disulfide, bis (4-methyl-2-nitrophenyl) disulfide, bis (4-methyl-2-aminophenyl) disulfide, bis (4-methyl-2-hydroxyphenyl) disulfide, Bis (4-methyl-2-phenylthiophenyl) disulfide, bis (4-carboxy-2-nitrophenyl) disulfide, bis (4-carboxy-2-aminophenyl) disulfide, bis (4-carboxy-2-hydroxyphenyl) ) Disulfide, bis (4-carboxy-2-fe) Ruthiophenyl) disulfide, bis (4-methoxycarbonyl-2-nitrophenyl) disulfide, bis (4-methoxycarbonyl-2-aminophenyl) disulfide, bis (4-methoxycarbonyl-2-hydroxyphenyl) disulfide, bis (4 -Methoxycarbonyl-2-phenylthiophenyl) disulfide, bis (4-formyl-2-nitrophenyl) disulfide, bis (4-formyl-2-aminophenyl) disulfide, bis (4-formyl-2-hydroxyphenyl) disulfide Bis (4-formyl-2-phenylthiophenyl) disulfide, bis (4-acetyl-2-nitrophenyl) disulfide, bis (4-acetyl-2-aminophenyl) disulfide, bis (4-acetyl-2-hydroxy) Enyl) disulfide, bis (4-acetyl-2-phenylthiophenyl) disulfide, bis (4-chlorocarbonyl-2-nitrophenyl) disulfide, bis (4-chlorocarbonyl-2-aminophenyl) disulfide, bis (4- Chlorocarbonyl-2-hydroxyphenyl) disulfide, bis (4-chlorocarbonyl-2-phenylthiophenyl) disulfide, bis (4-sulfo-2-nitrophenyl) disulfide, bis (4-sulfo-2-aminophenyl) disulfide Bis (4-sulfo-2-hydroxyphenyl) disulfide, bis (4-sulfo-2-phenylthiophenyl) disulfide, bis (4-methoxysulfonyl-2-nitrophenyl) disulfide, bis (4-methoxysulfonyl-2) -Aminofe Nyl) disulfide, bis (4-methoxysulfonyl-2-hydroxyphenyl) disulfide, bis (4-methoxysulfonyl-2-phenylthiophenyl) disulfide, bis (4-chlorosulfonyl-2-nitrophenyl) disulfide, bis (4 -Chlorosulfonyl-2-aminophenyl) disulfide, bis (4-chlorosulfonyl-2-hydroxyphenyl) disulfide, bis (4-chlorosulfonyl-2-phenylthiophenyl) disulfide, bis (4-sulfino-2-nitrophenyl) ) Disulfide, bis (4-sulfino-2-aminophenyl) disulfide, bis (4-sulfino-2-hydroxyphenyl) disulfide, bis (4-sulfino-2-phenylthiophenyl) disulfide, bis (4-methyl) Rufinyl-2-nitrophenyl) disulfide, bis (4-methylsulfinyl-2-aminophenyl) disulfide, bis (4-methylsulfinyl-2-hydroxyphenyl) disulfide, bis (4-methylsulfinyl-2-phenylthiophenyl) Disulfide, bis (4-carbamoyl-2-nitrophenyl) disulfide, bis (4-carbamoyl-2-aminophenyl) disulfide, bis (4-carbamoyl-2-hydroxyphenyl) disulfide, bis (4-carbamoyl-2-phenyl) Thiophenyl) disulfide, bis (4-trichloromethyl-2-nitrophenyl) disulfide, bis (4-trichloromethyl-2-aminophenyl) disulfide, bis (4-trichloromethyl-2-hydroxyphenyl) Disulfide, bis (4-trichloromethyl-2-phenylthiophenyl) disulfide, bis (4-cyano-2-nitrophenyl) disulfide, bis (4-cyano-2-aminophenyl) disulfide, bis (4-cyano-2) -Hydroxyphenyl) disulfide, bis (4-cyano-2-phenylthiophenyl) disulfide, bis (4-methoxy-2-nitrophenyl) disulfide, bis (4-methoxy-2-aminophenyl) disulfide, bis (4- Methoxy-2-hydroxyphenyl) disulfide and bis (4-methoxy-2-phenylthiophenyl) disulfide.

  Still another example of the organic sulfur compound represented by the chemical formula (2) includes a compound substituted with two or more kinds of substituents. Specific examples of this compound include bis (4-acetyl-2-chlorophenyl) disulfide, bis (4-acetyl-2-methylphenyl) disulfide, bis (4-acetyl-2-carboxyphenyl) disulfide, and bis (4-acetyl). -2-methoxycarbonylphenyl) disulfide, bis (4-acetyl-2-formylphenyl) disulfide, bis (4-acetyl-2-chlorocarbonylphenyl) disulfide, bis (4-acetyl-2-sulfophenyl) disulfide, bis (4-acetyl-2-methoxysulfonylphenyl) disulfide, bis (4-acetyl-2-chlorosulfonylphenyl) disulfide, bis (4-acetyl-2-sulfinophenyl) disulfide, bis (4-acetyl-2-methyl) Sulfinylfe Di) disulfide, bis (4-acetyl-2-carbamoylphenyl) disulfide, bis (4-acetyl-2-trichloromethylphenyl) disulfide, bis (4-acetyl-2-cyanophenyl) disulfide and bis (4-acetyl-) 2-methoxyphenyl) disulfide.

  Examples of the organic sulfur compound represented by the chemical formula (3) include thiophenol sodium salt; 4-fluorothiophenol sodium salt, 2,5-difluorothiophenol sodium salt, 2,4,5-trifluorothiophenol. Sodium salt, 2,4,5,6-tetrafluorothiophenol sodium salt, pentafluorothiophenol sodium salt, 4-chlorothiophenol sodium salt, 2,5-dichlorothiophenol sodium salt, 2,4,5-trichloro Thiophenol sodium salt, 2,4,5,6-tetrachlorothiophenol sodium salt, pentachlorothiophenol sodium salt, 4-bromothiophenol sodium salt, 2,5-dibromothiophenol sodium salt, 2,4,5 -Tribromothiophene Sodium salt, 2,4,5,6-tetrabromothiophenol sodium salt, pentabromothiophenol sodium salt, 4-iodothiophenol sodium salt, 2,5-diiodothiophenol sodium salt, 2,4,5- Thiophenol sodium salts substituted with halogen groups such as triiodothiophenol sodium salt, 2,4,5,6-tetraiodothiophenol sodium salt and pentaiodothiophenol sodium salt; 4-methylthiophenol sodium salt, 2 , 4,5-trimethylthiophenol sodium salt, pentamethylthiophenol sodium salt, 4-t-butylthiophenol sodium salt, 2,4,5-tri-t-butylthiophenol sodium salt and penta (t-butyl) thio Phenol nato Thiophenol sodium salts substituted with alkyl groups such as um salt; substituted with carboxyl groups such as 4-carboxythiophenol sodium salt, 2,4,6-tricarboxythiophenol sodium salt and pentacarboxythiophenol sodium salt Thiophenol sodium salts; sodium thiophenol substituted with alkoxycarbonyl groups such as 4-methoxycarbonylthiophenol sodium salt, 2,4,6-trimethoxycarbonylthiophenol sodium salt and pentamethoxycarbonylthiophenol sodium salt Salts; substituted with formyl groups such as 4-formylthiophenol sodium salt, 2,4,6-triformylthiophenol sodium salt and pentaformylthiophenol sodium salt Thiophenol sodium salts; thiophenol sodium salts substituted with acyl groups such as 4-acetylthiophenol sodium salt, 2,4,6-triacetylthiophenol sodium salt and pentaacetylthiophenol sodium salt; Thiophenol sodium salts substituted with halogenated carbonyl groups such as chlorocarbonylthiophenol sodium salt, 2,4,6-tri (chlorocarbonyl) thiophenol sodium salt and penta (chlorocarbonyl) thiophenol sodium salt; Thiophenol sodium salts substituted with a sulfo group such as sulfothiophenol sodium salt, 2,4,6-trisulfothiophenol sodium salt and pentasulfothiophenol sodium salt; Thiophenol sodium salts substituted with alkoxysulfonyl groups such as sodium nylthiophenol, sodium salt of 2,4,6-trimethoxysulfonylthiophenol and sodium salt of pentamethoxysulfonylthiophenol; sodium salt of 4-chlorosulfonylthiophenol 1,4,6-tri (chlorosulfonyl) thiophenol sodium salt and thiophenol sodium salts substituted with a sulfonyl halide group such as penta (chlorosulfonyl) thiophenol sodium salt; 4-sulfinothiophenol sodium salt Thiophenol sodium salts substituted with sulfino groups such as 2,4,6-trisulfinothiophenol sodium salt and pentasulfinothiophenol sodium salt; Thiophenol sodium salts substituted with alkylsulfinyl groups such as sulfinylthiophenol sodium salt, 2,4,6-tri (methylsulfinyl) thiophenol sodium salt and penta (methylsulfinyl) thiophenol sodium salt; 4-carbamoyl Thiophenol sodium salts substituted with carbamoyl groups such as thiophenol sodium salt, 2,4,6-tricarbamoylthiophenol sodium salt and pentacarbamoyl thiophenol sodium salt; 4-trichloromethylthiophenol sodium salt, 2,4,4 Thiophenols substituted with alkyl halide groups such as 6-tri (trichloromethyl) thiophenol sodium salt and penta (trichloromethyl) thiophenol sodium salt Sodium salts; thiophenol sodium salts substituted with cyano groups such as 4-cyanothiophenol sodium salt, 2,4,6-tricyanothiophenol sodium salt and pentacyanothiophenol sodium salt; and 4-methoxythiophenol sodium Illustrative are thiophenol sodium salts substituted with alkoxy groups such as salts, 2,4,6-trimethoxythiophenol sodium salt and pentamethoxythiophenol sodium salt. These thiophenol sodium salts are substituted with one kind of substituent.

As another example of the organic sulfur compound represented by the chemical formula (3), a compound substituted with at least one kind of the above substituent and another substituent can be given. Examples of other substituents include a nitro group (—NO ₂ ), an amino group (—NH ₂ ), a hydroxyl group (—OH), and a phenylthio group (—SPh). Specific examples of this compound include 4-chloro-2-nitrothiophenol sodium salt, 4-chloro-2-aminothiophenol sodium salt, 4-chloro-2-hydroxythiophenol sodium salt, 4-chloro-2- Phenylthiothiophenol sodium salt, 4-methyl-2-nitrothiophenol sodium salt, 4-methyl-2-aminothiophenol sodium salt, 4-methyl-2-hydroxythiophenol sodium salt, 4-methyl-2-phenyl Thiothiophenol sodium salt, 4-carboxy-2-nitrothiophenol sodium salt, 4-carboxy-2-aminothiophenol sodium salt, 4-carboxy-2-hydroxythiophenol sodium salt, 4-carboxy-2-phenylthio Thiophenol natri Salt, 4-methoxycarbonyl-2-nitrothiophenol sodium salt, 4-methoxycarbonyl-2-aminothiophenol sodium salt, 4-methoxycarbonyl-2-hydroxythiophenol sodium salt, 4-methoxycarbonyl-2-phenyl Thiothiophenol sodium salt, 4-formyl-2-nitrothiophenol sodium salt, 4-formyl-2-aminothiophenol sodium salt, 4-formyl-2-hydroxythiophenol sodium salt, 4-formyl-2-phenylthio Thiophenol sodium salt, 4-acetyl-2-nitrothiophenol sodium salt, 4-acetyl-2-aminothiophenol sodium salt, 4-acetyl-2-hydroxythiophenol sodium salt, 4-acetyl-2-phenol Ruthiothiophenol sodium salt, 4-chlorocarbonyl-2-nitrothiophenol sodium salt, 4-chlorocarbonyl-2-aminothiophenol sodium salt, 4-chlorocarbonyl-2-hydroxythiophenol sodium salt, 4-chlorocarbonyl- 2-phenylthiothiophenol sodium salt, 4-sulfo-2-nitrothiophenol sodium salt, 4-sulfo-2-aminothiophenol sodium salt, 4-sulfo-2-hydroxythiophenol sodium salt, 4-sulfo-2 -Phenylthiothiophenol sodium salt, 4-methoxysulfonyl-2-nitrothiophenol sodium salt, 4-methoxysulfonyl-2-aminothiophenol sodium salt, 4-methoxysulfonyl-2-hydroxythiopheno Sodium salt, 4-methoxysulfonyl-2-phenylthiothiophenol sodium salt, 4-chlorosulfonyl-2-nitrothiophenol sodium salt, 4-chlorosulfonyl-2-aminothiophenol sodium salt, 4-chlorosulfonyl-2- Hydroxythiophenol sodium salt, 4-chlorosulfonyl-2-phenylthiothiophenol sodium salt, 4-sulfino-2-nitrothiophenol sodium salt, 4-sulfino-2-aminothiophenol sodium salt, 4-sulfino-2- Hydroxythiophenol sodium salt, 4-sulfino-2-phenylthiothiophenol sodium salt, 4-methylsulfinyl-2-nitrothiophenol sodium salt, 4-methylsulfinyl-2-aminothiophene Sodium salt, 4-methylsulfinyl-2-hydroxythiophenol sodium salt, 4-methylsulfinyl-2-phenylthiothiophenol sodium salt, 4-carbamoyl-2-nitrothiophenol sodium salt, 4-carbamoyl-2-aminothio Phenol sodium salt, 4-carbamoyl-2-hydroxythiophenol sodium salt, 4-carbamoyl-2-phenylthiothiophenol sodium salt, 4-trichloromethyl-2-nitrothiophenol sodium salt, 4-trichloromethyl-2-amino Thiophenol sodium salt, 4-trichloromethyl-2-hydroxythiophenol sodium salt, 4-trichloromethyl-2-phenylthiothiophenol sodium salt, 4-cyano-2-nitrothiooff Nord sodium salt, 4-cyano-2-aminothiophenol sodium salt, 4-cyano-2-hydroxythiophenol sodium salt, 4-cyano-2-phenylthiothiophenol sodium salt, 4-methoxy-2-nitrothiophenol Examples include sodium salt, 4-methoxy-2-aminothiophenol sodium salt, 4-methoxy-2-hydroxythiophenol sodium salt and 4-methoxy-2-phenylthiothiophenol sodium salt.

  Still another example of the organic sulfur compound represented by the chemical formula (3) includes a compound substituted with two or more substituents. Specific examples of this compound include 4-acetyl-2-chlorothiophenol sodium salt, 4-acetyl-2-methylthiophenol sodium salt, 4-acetyl-2-carboxythiophenol sodium salt, 4-acetyl-2-methoxycarbonyl Thiophenol sodium salt, 4-acetyl-2-formylthiophenol sodium salt, 4-acetyl-2-chlorocarbonylthiophenol sodium salt, 4-acetyl-2-sulfothiophenol sodium salt, 4-acetyl-2-methoxysulfonyl Thiophenol sodium salt, 4-acetyl-2-chlorosulfonylthiophenol sodium salt, 4-acetyl-2-sulfinothiophenol sodium salt, 4-acetyl-2-methylsulfinylthiophenol sodium salt, 4 Acetyl-2-carbamoylthiophenol phenol sodium salt, 4-acetyl-2-trichloromethyl-thiophenol sodium salt, 4-acetyl-2-cyano thiophenol sodium salt and 4-acetyl-2-methoxy thiophenol sodium salt. In the chemical formula (3), examples of the monovalent metal represented by M1 include sodium, lithium, potassium, copper (I), and silver (I).

  As the organic sulfur compound represented by the chemical formula (4), thiophenol zinc salt; 4-fluorothiophenol zinc salt, 2,5-difluorothiophenol zinc salt, 2,4,5-trifluorothiophenol zinc salt, 2,4,5,6-tetrafluorothiophenol zinc salt, pentafluorothiophenol zinc salt, 4-chlorothiophenol zinc salt, 2,5-dichlorothiophenol zinc salt, 2,4,5-trichlorothiophenol zinc Salt, 2,4,5,6-tetrachlorothiophenol zinc salt, pentachlorothiophenol zinc salt, 4-bromothiophenol zinc salt, 2,5-dibromothiophenol zinc salt, 2,4,5-tribromo Thiophenol zinc salt, 2,4,5,6-tetrabromothiophenol zinc salt, pentabromothiophenol Lead salt, 4-iodothiophenol zinc salt, 2,5-diiodothiophenol zinc salt, 2,4,5-triiodothiophenol zinc salt, 2,4,5,6-tetraiodothiophenol zinc salt and Thiophenol zinc salts substituted with halogen groups such as pentaiodothiophenol zinc salt; 4-methylthiophenol zinc salt, 2,4,5-trimethylthiophenol zinc salt, pentamethylthiophenol zinc salt, 4-t-butyl Thiophenol zinc salts substituted with alkyl groups such as thiophenol zinc salt, 2,4,5-tri-t-butylthiophenol zinc salt and penta-t-butylthiophenol zinc salt; 4-carboxythiophenol zinc Salt, 2,4,6-tricarboxythiophenol zinc salt and pentacarboxythiophenol Thiophenol zinc salts substituted with carboxyl groups such as lead salts; alkoxy such as 4-methoxycarbonylthiophenol zinc salts, 2,4,6-trimethoxycarbonylthiophenol zinc salts and pentamethoxycarbonylthiophenol zinc salts Thiophenol zinc salts substituted with a carbonyl group; thiophenol zinc substituted with a formyl group such as 4-formylthiophenol zinc salt, 2,4,6-triformylthiophenol zinc salt and pentaformylthiophenol zinc salt Salts; 4-acetylthiophenol zinc salts, thiophenol zinc salts substituted with acyl groups such as 2,4,6-triacetylthiophenol zinc salts and pentaacetylthiophenol zinc salts; 4-chlorocarbonylthiophenol zinc Salt, 2,4,6- Thiophenol zinc salts substituted with a carbonyl halide group such as tri (chlorocarbonyl) thiophenol zinc salt and penta (chlorocarbonyl) thiophenol zinc salt; 4-sulfothiophenol zinc salt, 2,4,6-tri Thiophenol zinc salts substituted with sulfo groups such as sulfothiophenol zinc salt and pentasulfothiophenol zinc salt; 4-methoxysulfonylthiophenol zinc salt, 2,4,6-trimethoxysulfonylthiophenol zinc salt and penta Thiophenol zinc salts substituted with alkoxysulfonyl groups such as methoxysulfonylthiophenol zinc salt; 4-chlorosulfonylthiophenol zinc salt, 2,4,6-tri (chlorosulfonyl) thiophenol zinc salt and penta (chlorosulfonyl) Thio Thiophenol zinc salts substituted with a sulfonyl halide group such as enol zinc salt; such as 4-sulfinothiophenol zinc salt, 2,4,6-trisulfinothiophenol zinc salt and pentasulfinothiophenol zinc salt Thiophenol zinc salts substituted with sulfino groups; alkylsulfinyls such as 4-methylsulfinylthiophenol zinc salt, 2,4,6-tri (methylsulfinyl) thiophenol zinc salt and penta (methylsulfinyl) thiophenol zinc salt Group substituted thiophenol zinc salts; 4-carbamoylthiophenol zinc salts, thiophenol zinc salts substituted with carbamoyl groups such as 2,4,6-tricarbamoylthiophenol zinc salts and pentacarbamoylthiophenol zinc salts ; -Thiophenol zinc salts substituted with halogenated alkyl groups such as trichloromethylthiophenol zinc salt, 2,4,6-tri (trichloromethyl) thiophenol zinc salt and penta (trichloromethyl) thiophenol zinc salt; Thiophenol zinc salts substituted with a cyano group such as cyanothiophenol zinc salt, 2,4,6-tricyanothiophenol zinc salt and pentacyanothiophenol zinc salt; and 4-methoxythiophenol zinc salt, 2,4 Examples thereof include thiophenol zinc salts substituted with an alkoxy group such as 1,6-trimethoxythiophenol zinc salt and pentamethoxythiophenol zinc salt. These thiophenol zinc salts are substituted with one type of substituent.

As another example of the organic sulfur compound represented by the chemical formula (4), a compound substituted with at least one kind of the above substituent and another substituent can be given. Examples of other substituents include a nitro group (—NO ₂ ), an amino group (—NH ₂ ), a hydroxyl group (—OH), and a phenylthio group (—SPh). Specific examples of this compound include 4-chloro-2-nitrothiophenol zinc salt, 4-chloro-2-aminothiophenol zinc salt, 4-chloro-2-hydroxythiophenol zinc salt, 4-chloro-2- Phenylthiothiophenol zinc salt, 4-methyl-2-nitrothiophenol zinc salt, 4-methyl-2-aminothiophenol zinc salt, 4-methyl-2-hydroxythiophenol zinc salt, 4-methyl-2-phenyl Thiothiophenol zinc salt, 4-carboxy-2-nitrothiophenol zinc salt, 4-carboxy-2-aminothiophenol zinc salt, 4-carboxy-2-hydroxythiophenol zinc salt, 4-carboxy-2-phenylthio Thiophenol zinc salt, 4-methoxycarbonyl-2-nitrothiophenol zinc salt, 4-meth Sicarbonyl-2-aminothiophenol zinc salt, 4-methoxycarbonyl-2-hydroxythiophenol zinc salt, 4-methoxycarbonyl-2-phenylthiothiophenol zinc salt, 4-formyl-2-nitrothiophenol zinc salt, 4-formyl-2-aminothiophenol zinc salt, 4-formyl-2-hydroxythiophenol zinc salt, 4-formyl-2-phenylthiothiophenol zinc salt, 4-acetyl-2-nitrothiophenol zinc salt, 4 -Acetyl-2-aminothiophenol zinc salt, 4-acetyl-2-hydroxythiophenol zinc salt, 4-acetyl-2-phenylthiothiophenol zinc salt, 4-chlorocarbonyl-2-nitrothiophenol zinc salt, 4 -Chlorocarbonyl-2-aminothiophenol zinc salt, -Chlorocarbonyl-2-hydroxythiophenol zinc salt, 4-chlorocarbonyl-2-phenylthiothiophenol zinc salt, 4-sulfo-2-nitrothiophenol zinc salt, 4-sulfo-2-aminothiophenol zinc salt, 4-sulfo-2-hydroxythiophenol zinc salt, 4-sulfo-2-phenylthiothiophenol zinc salt, 4-methoxysulfonyl-2-nitrothiophenol zinc salt, 4-methoxysulfonyl-2-aminothiophenol zinc salt 4-methoxysulfonyl-2-hydroxythiophenol zinc salt, 4-methoxysulfonyl-2-phenylthiothiophenol zinc salt, 4-chlorosulfonyl-2-nitrothiophenol zinc salt, 4-chlorosulfonyl-2-aminothio Phenol zinc salt, 4-chlorosulfonyl- 2-hydroxythiophenol zinc salt, 4-chlorosulfonyl-2-phenylthiothiophenol zinc salt, 4-sulfino-2-nitrothiophenol zinc salt, 4-sulfino-2-aminothiophenol zinc salt, 4-sulfino- 2-hydroxythiophenol zinc salt, 4-sulfino-2-phenylthiothiophenol zinc salt, 4-methylsulfinyl-2-nitrothiophenol zinc salt, 4-methylsulfinyl-2-aminothiophenol zinc salt, 4-methyl Sulfinyl-2-hydroxythiophenol zinc salt, 4-methylsulfinyl-2-phenylthiothiophenol zinc salt, 4-carbamoyl-2-nitrothiophenol zinc salt, 4-carbamoyl-2-aminothiophenol zinc salt, 4- Carbamoyl-2-hydroxythi Phenol zinc salt, 4-carbamoyl-2-phenylthiothiophenol zinc salt, 4-trichloromethyl-2-nitrothiophenol zinc salt, 4-trichloromethyl-2-aminothiophenol zinc salt, 4-trichloromethyl-2- Hydroxythiophenol zinc salt, 4-trichloromethyl-2-phenylthiothiophenol zinc salt, 4-cyano-2-nitrothiophenol zinc salt, 4-cyano-2-aminothiophenol zinc salt, 4-cyano-2- Hydroxythiophenol zinc salt, 4-cyano-2-phenylthiothiophenol zinc salt, 4-methoxy-2-nitrothiophenol zinc salt, 4-methoxy-2-aminothiophenol zinc salt, 4-methoxy-2-hydroxy Thiophenol zinc salt and 4-methoxy-2-phenylthiothio Phenol zinc salts.

  Still another example of the organic sulfur compound represented by the chemical formula (4) includes a compound substituted with two or more kinds of substituents. Specific examples of this compound include 4-acetyl-2-chlorothiophenol zinc salt, 4-acetyl-2-methylthiophenol zinc salt, 4-acetyl-2-carboxythiophenol zinc salt, 4-acetyl-2-methoxycarbonyl Thiophenol zinc salt, 4-acetyl-2-formylthiophenol zinc salt, 4-acetyl-2-chlorocarbonylthiophenol zinc salt, 4-acetyl-2-sulfothiophenol zinc salt, 4-acetyl-2-methoxysulfonyl Thiophenol zinc salt, 4-acetyl-2-chlorosulfonylthiophenol zinc salt, 4-acetyl-2-sulfinothiophenol zinc salt, 4-acetyl-2-methylsulfinylthiophenol zinc salt, 4-acetyl-2- Carbamoylthiophenol zinc salt, 4-acetyl-2 Trichloromethylthiophenol zinc salt, 4-acetyl-2-cyano thiophenol zinc salt and 4-acetyl-2-methoxy thiophenol zinc salt. Examples of the divalent metal represented by M2 in the chemical formula (4) include zinc, magnesium, calcium, strontium, barium, titanium (II), manganese (II), iron (II), cobalt (II), nickel ( Illustrative are II), zirconium (II) and tin (II).

  As thionaphthols, 2-thionaphthol, 1-thionaphthol, 2-chloro-1-thionaphthol, 2-bromo-1-thionaphthol, 2-fluoro-1-thionaphthol, 2-cyano-1-thionaphthol 2-acetyl-1-thionaphthol, 1-chloro-2-thionaphthol, 1-bromo-2-thionaphthol, 1-fluoro-2-thionaphthol, 1-cyano-2-thionaphthol and 1-acetyl- Examples include 2-thionaphthol and metal salts thereof. 1-thionaphthol and 2-thionaphthol and their zinc salts are preferred.

  Examples of the sulfenamide-based organic sulfur compound include N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, and Nt-butyl-2-benzothiazole sulfenamide. Illustrated. Examples of the thiuram-based organic sulfur compound include tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, and dipentamethylenethiuram tetrasulfide. Dithiocarbamates include zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc ethylphenyldithiocarbamate, sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, copper (II) dimethyldithiocarbamate, iron dimethyldithiocarbamate (III ), Selenium diethyldithiocarbamate and tellurium diethyldithiocarbamate. Examples of thiazole-based organic sulfur compounds include 2-mercaptobenzothiazole (MBT); dibenzothiazyl disulfide (MBTS); sodium salt, zinc salt, copper salt or cyclohexylamine salt of 2-mercaptobenzothiazole; 2- (2,4- Illustrative are dinitrophenyl) mercaptobenzothiazole; and 2- (2,6-diethyl-4-morpholinothio) benzothiazole.

  Particularly preferred organic sulfur compounds (e) are 2-thionaphthol, bis (pentabromophenyl) disulfide, and 2,6-dichlorothiophenol from the viewpoint that an outer-hard / inner-soft structure is easily obtained.

  From the viewpoint of easily obtaining an outer-hard / inner-soft structure, the content of the organic sulfur compound (e) is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more with respect to 100 parts by weight of the base rubber. Preferably, 0.2 mass part or more is especially preferable. In light of resilience performance, this amount is preferably equal to or less than 5.0 parts by weight, more preferably equal to or less than 3.0 parts by weight, and particularly preferably equal to or less than 1.0 part by weight.

  A filler may be added to the envelope layer 14 for the purpose of adjusting specific gravity and the like. Suitable fillers include zinc oxide, barium sulfate, calcium carbonate and magnesium carbonate. The amount of the filler is appropriately determined so that the intended specific gravity of the core is achieved. A particularly preferred filler is zinc oxide. Zinc oxide functions not only as a specific gravity adjusting role but also as a crosslinking aid.

  An anti-aging agent, a colorant, a plasticizer, a dispersant, sulfur, a vulcanization accelerator, and the like are added to the rubber composition of the envelope layer 14 as necessary. Crosslinked rubber powder or synthetic resin powder may be dispersed in the rubber composition.

  When the core 4 is heated and molded, the base rubber (a) is crosslinked by the co-crosslinking agent (b). The reaction heat of this cross-linking reaction accumulates near the center of the core 4. Therefore, when the core 4 is heated and molded, the temperature at the center is high. The temperature gradually decreases from the center toward the surface. In the rubber composition, the acid reacts with the metal salt of the co-crosslinking agent (b) and binds to the cation. In the rubber composition, the salt reacts with the metal salt of the co-crosslinking agent (b) to exchange cations. This bond and exchange breaks the metal bridge. This coupling and exchange are likely to occur in the vicinity of the innermost part of the envelope layer 14 having a high temperature, and are unlikely to occur in the vicinity of the surface of the envelope layer 14. In other words, the cutting of the metal bridge is likely to occur in the vicinity of the innermost portion of the envelope layer 14 and hardly occurs in the vicinity of the surface. As a result, the crosslink density of the envelope layer 14 increases from the inside toward the outside. In the envelope layer 14, the hardness increases linearly from the inside toward the outside. Furthermore, when the rubber composition contains the organic sulfur compound (e) together with the acid and / or salt (d), the gradient of the hardness distribution can be controlled, and the degree of the outer-hard / inner-soft structure of the core 4 is increased. Can do. The spin speed when the golf ball 2 including the core 4 is hit with a driver is small. With this golf ball 2, excellent flight performance is achieved in shots with a driver.

  The hardness H (0) of the center point of the core 4 is preferably 40 or greater and 70 or less. The golf ball 2 having a hardness H (0) of 40 or more is excellent in resilience performance. In this respect, the hardness H (0) is more preferably equal to or greater than 45, and particularly preferably equal to or greater than 47. In the core 4 having a hardness H (0) of 70 or less, an outer-hard / inner-soft structure can be achieved. In the golf ball 2 having the core 4, spin can be suppressed. In this respect, the hardness H (0) is more preferably 68 or less, and particularly preferably 65 or less.

  The hardness H (100) of the surface of the core 4 is preferably 78 or more and 96 or less. In the core 4 having a hardness H (100) of 78 or more, an outer-hard / inner-soft structure can be achieved. In the golf ball 2 having the core 4, spin can be suppressed. In this respect, the hardness H (100) is more preferably equal to or greater than 80, and particularly preferably equal to or greater than 82. The golf ball 2 having a hardness H (100) of 96 or less is excellent in durability. In this respect, the hardness H (100) is more preferably equal to or less than 94, and particularly preferably equal to or less than 92.

  The diameter of the core 4 is preferably 38.0 mm or greater and 42.0 mm or less. The excellent resilience performance of the golf ball 2 can be achieved by the core 4 having a diameter of 38.0 mm or more. In this respect, the diameter is more preferably 39.0 mm or greater, and particularly preferably 39.5 mm or greater. In the golf ball 2 having the core 4 having a diameter of 42.0 mm or less, the mid layer 6, the inner cover 10, and the outer cover 12 can have a sufficient thickness. The golf ball 2 having a large thickness of the mid layer 6, the inner cover 10, and the outer cover 12 is excellent in durability. In this respect, the diameter is more preferably 41 mm or less, and particularly preferably 40 mm or less.

  A resin composition is suitably used for the mid layer 6. Examples of the base polymer of this resin composition include ionomer resin, polystyrene, polyester, polyamide and polyolefin.

  A particularly preferred base polymer is an ionomer resin. The golf ball 2 having the mid layer 6 containing an ionomer resin is excellent in resilience performance. The intermediate layer 6 may be used in combination with an ionomer resin and another resin. When used in combination, the main component of the base polymer is preferably an ionomer resin. Specifically, the ratio of the ionomer resin to the total amount of the base polymer is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

  A preferable ionomer resin includes a binary copolymer of an α-olefin and an α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms. A preferable binary copolymer contains 80% by mass or more and 90% by mass or less α-olefin and 10% by mass or more and 20% by mass or less α, β-unsaturated carboxylic acid. This binary copolymer is excellent in resilience performance. Other preferable ionomer resins include ternary α-olefin, α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms and α, β-unsaturated carboxylic acid ester having 2 to 22 carbon atoms. A copolymer is mentioned. Preferred terpolymers are 70% to 85% by weight α-olefin, 5% to 30% by weight α, β-unsaturated carboxylic acid, and 1% to 25% by weight. α, β-unsaturated carboxylic acid ester. This ternary copolymer is excellent in resilience performance. In the binary copolymer and ternary copolymer, preferred α-olefins are ethylene and propylene, and preferred α, β-unsaturated carboxylic acids are acrylic acid and methacrylic acid. A particularly preferred ionomer resin is a copolymer of ethylene and acrylic acid or methacrylic acid.

  In the binary copolymer and ternary copolymer, some of the carboxyl groups are neutralized with metal ions. Examples of the metal ions for neutralization include sodium ions, potassium ions, lithium ions, zinc ions, calcium ions, magnesium ions, aluminum ions, and neodymium ions. Neutralization may be performed with two or more metal ions. Particularly suitable metal ions from the viewpoint of resilience performance and durability of the golf ball 2 are sodium ion, zinc ion, lithium ion and magnesium ion.

  Specific examples of the ionomer resin include Mitsui Dupont Polychemical's trade names “HIMILAN 1555”, “HIMILAN 1557”, “HIMILAN 1605”, “HIMILAN 1706”, “HIMILAN 1707”, “HIMILAN 1856” and “HIMILAN 1855”. "High Milan AM7311", "High Milan AM7315", "High Milan AM7317", "High Milan AM7318", "High Milan AM7329", "High Milan MK7320" and "High Milan MK7329"; DuPont's trade names "Surlin 6120" and "Surlin 6910" , “Surlin 7930”, “Surlin 7940”, “Surlin 8140”, “Surlin 8150”, “Surlin 8940”, “Surlin 8945”, “Surlin 9120”, “Surlin 915” ", Surlyn 9910", "Surlin 9945", "Surlin AD8546", "HPF1000" and "HPF2000"; and ExxonMobil Chemical's trade names "IOTEK7010", "IOTEK7030", "IOTEK7510", "IOTEK7520", " IOTEK8000 "and" IOTEK8030 ".

  Two or more ionomer resins may be used in combination with the mid layer 6. An ionomer resin neutralized with a monovalent metal ion and an ionomer resin neutralized with a divalent metal ion may be used in combination.

  A preferred resin that can be used in combination with an ionomer resin is a styrene block-containing thermoplastic elastomer. The styrene block-containing thermoplastic elastomer is excellent in compatibility with the ionomer resin. A resin composition containing a styrene block-containing thermoplastic elastomer is excellent in fluidity.

  The styrene block-containing thermoplastic elastomer includes a polystyrene block as a hard segment and a soft segment. A typical soft segment is a diene block. Examples of the diene block compound include butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene. Butadiene and isoprene are preferred. Two or more compounds may be used in combination.

  The styrene block-containing thermoplastic elastomer includes styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-isoprene-butadiene-styrene block copolymer (SIBS), SBS hydrogenated, SIS hydrogenated and SIBS hydrogenated are included. Examples of the hydrogenated product of SBS include styrene-ethylene-butylene-styrene block copolymer (SEBS). As a hydrogenated product of SIS, styrene-ethylene-propylene-styrene block copolymer (SEPS) can be mentioned. Examples of the hydrogenated product of SIBS include styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS).

  In light of the resilience performance of the golf ball 2, the content of the styrene component in the styrene block-containing thermoplastic elastomer is preferably 10% by mass or more, more preferably 12% by mass or more, and particularly preferably 15% by mass or more. In light of the feel at impact of the golf ball 2, the content is preferably equal to or less than 50% by mass, more preferably equal to or less than 47% by mass, and particularly preferably equal to or less than 45% by mass.

  In the present invention, the styrene block-containing thermoplastic elastomer includes an alloy of one or two or more selected from the group consisting of SBS, SIS, SIBS, SEBS, SEPS and SEEPS, and hydrogenated products thereof, and an olefin. included. The olefin component in the alloy is presumed to contribute to the improvement of compatibility with the ionomer resin. By using this alloy, the resilience performance of the golf ball 2 is improved. Preferably, an olefin having 2 to 10 carbon atoms is used. Suitable olefins include ethylene, propylene, butene and pentene. Ethylene and propylene are particularly preferred.

  Specific examples of polymer alloys include Mitsubishi Chemical's trade names “Lavalon T3221C”, “Lavalon T3339C”, “Lavalon SJ4400N”, “Lavalon SJ5400N”, “Lavalon SJ6400N”, “Lavalon SJ7400N”, “Lavalon SJ8400N”, “ And “Lavalon SJ9400N” and “Lavalon SR04”. Other specific examples of the styrene block-containing thermoplastic elastomer include Daicel Chemical Industries' trade name “Epofriend A1010” and Kuraray's trade name “Septon HG-252”.

  The mid layer 6 may include a highly elastic resin as a base polymer. This highly elastic resin contributes to the high rigidity of the mid layer 6. Specific examples of the highly elastic resin include polyamide.

  If necessary, the resin composition of the intermediate layer 6 may include a colorant such as titanium dioxide, a filler such as barium sulfate, a dispersant, an antioxidant, an ultraviolet absorber, a light stabilizer, a fluorescent agent, and a fluorescent enhancer. An appropriate amount of whitening agent is blended.

  From the viewpoint that an outer-hard / inner-soft structure can be achieved in a sphere composed of the core 4 and the intermediate layer 6, the hardness Hm of the intermediate layer 6 is preferably 45 or more, and particularly preferably 55 or more. In light of the feel at impact of the golf ball 2, the hardness Hm is preferably equal to or less than 72, and particularly preferably equal to or less than 70. The hardness Hm is measured by a Shore D type hardness meter attached to an automatic rubber hardness measuring device (trade name “P1” of Kobunshi Keiki Co., Ltd.) in accordance with the provisions of “ASTM-D 2240-68”. For the measurement, a slab having a thickness of about 2 mm formed by hot pressing is used. A slab stored for 2 weeks at a temperature of 23 ° C. is used for the measurement. At the time of measurement, three slabs are overlaid. A slab made of the same resin composition as that of the mid layer 6 is used.

  The thickness Tm of the mid layer 6 is preferably 0.5 mm or greater and 1.6 mm or less. In the sphere provided with the intermediate layer 6 having a thickness Tm of 0.5 mm or more, the spin suppression effect by the outer-hard / inner-soft structure is great. In this respect, the thickness Tm is particularly preferably equal to or greater than 0.7 mm. The golf ball 2 including the mid layer 6 having a thickness Tm of 1.6 mm or less can include a large core 4. The large core 4 can contribute to the resilience performance of the golf ball 2. In this respect, the thickness Tm is particularly preferably equal to or less than 1.2 mm. The intermediate layer 6 may be composed of two or more layers. In this case, the total thickness of all layers is set within the above range.

  For the formation of the intermediate layer 6, known methods such as injection molding and compression molding can be employed.

  A resin composition is suitably used for the inner cover 10. A preferred base polymer of this resin composition is polyurethane. Polyurethane is soft. When the golf ball 2 provided with the inner cover 10 made of a resin composition containing polyurethane is hit with a short iron, the spin rate is high. The inner cover 10 made of this resin composition contributes to control performance in a shot with a short iron. Furthermore, polyurethane can contribute to an excellent feel at impact when hit with a putter or a short iron.

  From the viewpoint of easy molding of the inner cover 10, a preferred base polymer is a thermoplastic polyurethane elastomer. The thermoplastic polyurethane elastomer includes a polyurethane component as a hard segment and a polyester component or a polyether component as a soft segment. Examples of the isocyanate for the polyurethane component include alicyclic diisocyanates, aromatic diisocyanates and aliphatic diisocyanates. Two or more diisocyanates may be used in combination.

Examples of alicyclic diisocyanates include 4,4′-dicyclohexylmethane diisocyanate (H ₁₂ MDI), 1,3-bis (isocyanatomethyl) cyclohexane (H ₆ XDI), isophorone diisocyanate (IPDI), and trans-1,4- Examples are cyclohexane diisocyanate (CHDI). From the viewpoint of versatility and workability, H ₁₂ MDI is preferable.

  Aromatic diisocyanates include 4,4'-diphenylmethane diisocyanate (MDI) and toluene diisocyanate (TDI). As the aliphatic diisocyanate, hexamethylene diisocyanate (HDI) is exemplified.

  Specific examples of the thermoplastic polyurethane elastomer include BASF Japan trade names “Elastolan NY80A”, “Elastolan NY82A”, “Elastolan NY84A”, “Elastolan NY85A”, “Elastolan NY88A”, “Elastolan NY90A”. ”,“ Elastolan NY97A ”,“ Elastolan NY585 ”and“ Elastolan XKP016N ”; and trade names“ Rezamin P4585LS ”and“ Rezamin PS62490 ”of Dainichi Seika Kogyo K.K.

  A thermoplastic polyurethane elastomer and another resin may be used in combination. Examples of the resin that can be used in combination include thermoplastic polyester elastomers, thermoplastic polyamide elastomers, thermoplastic polyolefin elastomers, styrene block-containing thermoplastic elastomers, and ionomer resins. When the thermoplastic polyurethane elastomer and another resin are used in combination, the thermoplastic polyurethane elastomer is the main component of the base polymer from the viewpoint of spin performance. The ratio of the thermoplastic polyurethane elastomer in the total base polymer is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 85% by mass or more.

  The inner cover 10 may be provided with a colorant such as titanium dioxide and fluorescent pigment, a filler such as barium sulfate, a dispersant, an antioxidant, an ultraviolet absorber, a light stabilizer, a fluorescent agent, and a fluorescent whitening as necessary. An appropriate amount of agent or the like is blended.

  The Shore D hardness Hc1 of the inner cover 10 is preferably 60 or less. The golf ball 2 having the inner cover 10 having a hardness Hc1 of 60 or less is excellent in control performance. In this respect, the hardness Hc1 is more preferably equal to or less than 55, and particularly preferably equal to or less than 50. The hardness Hc1 is preferably 40 or more from the viewpoint of a flight distance in a shot with a driver. The hardness Hc1 is measured by the same method as the method for measuring the hardness Hm.

  The thickness T1 of the inner cover 10 is not less than 0.1 mm and not more than 0.8 mm. The golf ball 2 having a thickness T1 of 0.1 mm or more is excellent in control performance. In this respect, the thickness T1 is more preferably equal to or greater than 0.2 mm, and particularly preferably equal to or greater than 0.3 mm. The golf ball 2 having a thickness T1 of 0.8 mm or less is excellent in resilience performance. In this respect, the thickness T1 is more preferably equal to or less than 0.6 mm, and particularly preferably equal to or less than 0.5 mm.

  For forming the inner cover 10, known methods such as an injection molding method and a compression molding method can be employed.

  A resin composition is preferably used for the outer cover 12. A preferred base polymer of this resin composition is polyurethane. Polyurethane is soft. When the golf ball 2 provided with the outer cover 12 made of a resin composition containing polyurethane is hit with a short iron, the spin rate is high. The outer cover 12 made of this resin composition contributes to control performance in a shot with a short iron. The polyurethane also contributes to the scratch resistance performance of the outer cover 12. Furthermore, polyurethane can contribute to an excellent feel at impact when hit with a putter or a short iron.

  From the viewpoint of easy molding of the outer cover 12, a preferred base polymer is a thermoplastic polyurethane elastomer. The thermoplastic polyurethane elastomer described above with respect to the inner cover 10 can be used for the outer cover 12. In particular, an elastomer containing a polyurethane component obtained by a reaction between a polyol and an alicyclic diisocyanate is preferable. Since the alicyclic diisocyanate does not have a double bond in the main chain, yellowing of the outer cover 12 is suppressed. Moreover, since the alicyclic diisocyanate is excellent in strength, the outer cover 12 is prevented from being damaged.

  Particularly preferable thermoplastic polyurethane elastomers from the viewpoint that a small hardness of the outer cover 12 can be achieved are “Elastolan NY80A”, “Elastolan NY82A”, “Elastolan NY84A”, “Elastolan NY85A” and “Elastolan”. NY90A ".

  A thermoplastic polyurethane elastomer and other resin may be used in combination. The outer cover 12 may include the resin described above with respect to the inner cover 10. When the thermoplastic polyurethane elastomer is used in combination with another resin, the thermoplastic polyurethane elastomer is the main component of the base polymer from the viewpoint of spin performance and scratch resistance. The ratio of the thermoplastic polyurethane elastomer in the total base polymer is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 85% by mass or more.

  The outer cover 12 may be provided with a colorant such as titanium dioxide and fluorescent pigment, a filler such as barium sulfate, a dispersant, an antioxidant, an ultraviolet absorber, a light stabilizer, a fluorescent agent, and a fluorescent whitening as necessary. An appropriate amount of agent or the like is blended.

  The outer cover 12 preferably has a Shore D hardness Hc2 of 48 or less. The golf ball 2 having the outer cover 12 having a hardness Hc2 of 48 or less is excellent in control performance. In this respect, the hardness Hc2 is more preferably equal to or less than 40, and particularly preferably equal to or less than 32. The hardness Hc2 is preferably 10 or more from the viewpoint of a flight distance in a shot with a driver. The hardness Hc2 is measured by the same method as the method for measuring the hardness Hm.

  The thickness T2 of the outer cover 12 is preferably 0.1 mm or greater and 0.8 mm or less. The golf ball 2 having a thickness T2 of 0.1 mm or more is excellent in control performance. In this respect, the thickness T2 is more preferably equal to or greater than 0.2 mm, and particularly preferably equal to or greater than 0.3 mm. The golf ball 2 having a thickness T2 of 0.8 mm or less is excellent in resilience performance. In this respect, the thickness T2 is more preferably equal to or less than 0.6 mm, and particularly preferably equal to or less than 0.5 mm.

  For forming the outer cover 12, a known method such as an injection molding method or a compression molding method may be employed. When the outer cover 12 is molded, the dimples 14 are formed by pimples formed on the cavity surface of the mold.

Preferably, the hardness Hm of the mid layer 6, the hardness Hc1 of the inner cover 10, and the hardness Hc2 of the outer cover 12 satisfy the following mathematical relationship.
Hm> Hc1
Hm> Hc2
When the golf ball 2 is hit with a driver, the sphere composed of the core 4 and the mid layer 6 is greatly distorted because the head speed is high. Since this sphere has an outer-hard / inner-soft structure, the spin rate is suppressed. Since the hardness of the core 4 changes linearly, the golf ball 2 is launched at a high speed by the deformation and restoration of the core 4. A great flight distance is achieved by suppressing the spin speed and the high launch speed. When the golf ball 2 is hit with a short iron, since the head speed is low, the distortion of the sphere is small. The behavior of the golf ball 2 when hit with a short iron mainly depends on the inner cover 10 and the outer cover 12. Since the inner cover 10 and the outer cover 12 are soft, slip between the golf ball 2 and the club face is suppressed. By suppressing the slip, a high spin speed can be obtained. Excellent control performance is achieved due to the high spin rate. In the golf ball 2, both flight performance in a shot with a driver and control performance in a shot with a short iron are compatible.

  When the golf ball 2 is hit, the inner cover 10 and the outer cover 12 absorb the impact. This absorption achieves a soft feel at impact. In particular, when hit with a short iron or a putter, an excellent shot feeling is achieved by the inner cover 10 and the outer cover 12.

  From the viewpoint of achieving both flight performance and control performance, the difference (Hm−Hc1) between the hardness Hm and the hardness Hc1 is preferably 15 or more, and more preferably 18 or more. The difference (Hm−Hc1) is preferably 40 or less.

  From the viewpoint of achieving both flight performance and control performance, the difference (Hm−Hc2) between the hardness Hm and the hardness Hc2 is preferably 20 or more, and more preferably 36 or more. The difference (Hm−Hc2) is preferably 60 or less.

In this golf ball 2, the hardness Hc1 and the hardness Hc2 satisfy the following mathematical relationship.
Hc1> Hc2
In the golf ball 2, the intermediate layer 6, the inner cover 10, and the outer cover 12 have a lower hardness in this order. This golf ball 2 is excellent in feel at impact.

  From the viewpoint of feel at impact, the difference (Hc1−Hc2) between the hardness Hc1 and the hardness Hc2 is preferably 5 or more, and particularly preferably 10 or more. The difference (Hc1-Hc2) is preferably 30 or less.

  The difference (T1−T2) between the thickness T1 of the inner cover 10 and the thickness T2 of the outer cover 12 is preferably −0.4 mm or more and 0.4 mm or less. In the golf ball 2 in which the difference (T1-T2) is within the above range, the inner cover 10 and the outer cover 12 can be easily molded. In this respect, the difference (T1−T2) is more preferably −0.3 mm to 0.3 mm, and particularly preferably −0.2 mm to 0.2 mm.

  From the viewpoint of flight performance, the sum (T1 + T2) of the thickness T1 of the inner cover 10 and the thickness T2 of the outer cover 12 is preferably 1.0 mm or less, and particularly preferably 0.8 mm or less. In light of control performance, the sum (T1 + T2) is preferably equal to or greater than 0.2 mm, and particularly preferably equal to or greater than 0.4 mm.

  The golf ball 2 may include three or more layers as a cover.

  The reinforcing layer 8 is located between the intermediate layer 6 and the inner cover 10. The reinforcing layer 8 is firmly attached to the intermediate layer 6 and is also firmly attached to the inner cover 10. The reinforcing layer 8 suppresses the peeling of the inner cover 10 from the intermediate layer 6. In the golf ball 2, when the intermediate layer 6 is made of a resin composition and the inner cover 10 is made of a resin composition whose base resin is different from the base resin of the intermediate layer 6, the reinforcing layer 8 makes the inner cover 10 peeling from the intermediate layer 6 is effectively suppressed.

  As the base polymer of the reinforcing layer 8, a two-component curable thermosetting resin is preferably used. Specific examples of the two-component curable thermosetting resin include an epoxy resin, a urethane resin, an acrylic resin, a polyester resin, and a cellulose resin. From the viewpoint of the strength and durability of the reinforcing layer 8, a two-component curable epoxy resin and a two-component curable urethane resin are preferable.

  The two-component curable epoxy resin is obtained by curing the epoxy resin with a polyamide curing agent. Examples of the epoxy resin used in the two-component curable epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol AD type epoxy resin. The bisphenol A type epoxy resin is obtained by a reaction between bisphenol A and an epoxy group-containing compound such as epichlorohydrin. The bisphenol F type epoxy resin is obtained by a reaction between bisphenol F and an epoxy group-containing compound. The bisphenol AD type epoxy resin is obtained by a reaction between bisphenol AD and an epoxy group-containing compound. From the viewpoint of the balance of flexibility, chemical resistance, heat resistance and toughness, bisphenol A type epoxy resin is preferable.

  The polyamide-based curing agent has a plurality of amino groups and one or more amide groups. This amino group can react with an epoxy group. Specific examples of the polyamide curing agent include a polyamide amine curing agent and a modified product thereof. The polyamidoamine curing agent is obtained by a condensation reaction between a polymerized fatty acid and a polyamine. Typical polymerized fatty acids can be obtained by synthesizing natural fatty acids containing a large amount of unsaturated fatty acids such as linoleic acid and linolenic acid by heating in the presence of a catalyst. Specific examples of unsaturated fatty acids include tall oil, soybean oil, linseed oil and fish oil. A polymerized fatty acid having a dimer content of 90% by mass or more, a trimer content of 10% by mass or less, and hydrogenated is preferable. Preferred polyamines include polyethylene diamine, polyoxyalkylene diamine and derivatives thereof.

  In mixing the epoxy resin and the polyamide curing agent, the ratio of the epoxy equivalent of the epoxy resin and the amine active hydrogen equivalent of the polyamide curing agent is preferably 1.0 / 1.4 or more and 1.0 / 1.0 or less. .

  The two-component curable urethane resin is obtained by a reaction between the main agent and the curing agent. A two-component curable urethane resin obtained by a reaction between a main component containing a polyol component and a curing agent containing a polyisocyanate or a derivative thereof, a main component containing an isocyanate group-terminated urethane prepolymer, and a curing agent having active hydrogen. A two-component curable urethane resin obtained by reaction may be used. In particular, a two-component curable urethane resin obtained by a reaction between a main component containing a polyol component and a curing agent containing polyisocyanate or a derivative thereof is preferable.

  It is preferable that urethane polyol is used as the polyol component of the main agent. The urethane polyol has a urethane bond and at least two or more hydroxyl groups. Preferably, the urethane polyol has a hydroxyl group at its terminal. The urethane polyol can be obtained by reacting the polyol and the polyisocyanate at a ratio such that the hydroxyl group of the polyol component is excessive in molar ratio with respect to the isocyanate group of the polyisocyanate.

  The polyol used for the production of the urethane polyol has a plurality of hydroxyl groups. A polyol having a weight average molecular weight of 50 or more and 2000 or less is preferable, and a polyol having a weight average molecular weight of 100 or more and 1000 or less is particularly preferable. Examples of the low molecular weight polyol include diol and triol. Specific examples of the diol include ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol and 1,6-hexanediol. Specific examples of the triol include trimethylolpropane and hexanetriol. High molecular weight polyols include polyether polyols such as polyoxyethylene glycol (PEG), polyoxypropylene glycol (PPG) and polyoxytetramethylene glycol (PTMG); polyethylene adipate (PEA), polybutylene adipate (PBA) ) And polyhexamethylene adipate (PHMA); lactone polyester polyols such as poly-ε-caprolactone (PCL); polycarbonate polyols such as polyhexamethylene carbonate; and acrylic polyols. Two or more polyols may be used in combination.

The polyisocyanate used for the production of the urethane polyol has a plurality of isocyanate groups. Specific examples of the polyisocyanate include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI). ), 1,5-naphthylene diisocyanate (NDI), 3,3′-vitrylene-4,4′-diisocyanate (TODI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI) and paraphenylene diisocyanate ( aromatic polyisocyanates such as PPDI); 4,4'-dicyclohexylmethane diisocyanate _(H 12 MDI), hydrogenated xylylene diisocyanate _(H 6 XDI) and isophorone diisocyanate ( Alicyclic polyisocyanates such as PDI); and aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI) and the like. Two or more polyisocyanates may be used in combination. From the viewpoint of weather resistance, TMXDI, XDI, HDI, H ₆ XDI, IPDI and H ₁₂ MDI are preferred.

  A known catalyst can be used in the reaction of the polyol and the polyisocyanate for producing the urethane polyol. A typical catalyst is dibutyltin dilaurate.

  From the viewpoint of the strength of the reinforcing layer 8, the ratio of the urethane bond contained in the urethane polyol is preferably 0.1 mmol / g or more. From the viewpoint of the followability of the reinforcing layer 8 to the inner cover 10, the ratio of the urethane bond contained in the urethane polyol is preferably 5 mmol / g or less. The ratio of the urethane bond can be adjusted by adjusting the molecular weight of the polyol as a raw material and adjusting the blending ratio of the polyol and the polyisocyanate.

  In light of the short time required for the reaction between the main agent and the curing agent, the weight average molecular weight of the urethane polyol is preferably 4000 or more, and particularly preferably 4500 or more. From the viewpoint of adhesion of the reinforcing layer 8, the weight average molecular weight of the urethane polyol is preferably 10,000 or less, particularly preferably 9000 or less.

  From the viewpoint of adhesion of the reinforcing layer 8, the hydroxyl value (mgKOH / g) of the urethane polyol is preferably 15 or more, and particularly preferably 73 or more. From the viewpoint that the time required for the reaction between the main agent and the curing agent is short, the hydroxyl value of the urethane polyol is preferably 130 or less, and particularly preferably 120 or less.

  The main agent may contain a polyol having no urethane bond together with the urethane polyol. The aforementioned polyol, which is a raw material for urethane polyol, can be used as the main agent. Polyols that are compatible with urethane polyols are preferred. From the viewpoint that the time required for the reaction between the main agent and the curing agent is short, the ratio of the urethane polyol in the main agent is preferably 50% by mass or more and particularly preferably 80% by mass or more in terms of solid content. Ideally this ratio is 100% by weight.

  The curing agent contains polyisocyanate or a derivative thereof. The aforementioned polyisocyanate, which is a raw material of urethane polyol, can be used as a curing agent.

  The reinforcing layer 8 may contain additives such as a colorant (typically titanium dioxide), a phosphoric acid stabilizer, an antioxidant, a light stabilizer, a fluorescent brightener, an ultraviolet absorber, and an antiblocking agent. . The additive may be added to the main component of the two-component curable thermosetting resin, or may be added to the curing agent.

  The reinforcing layer 8 is obtained by applying a liquid in which the main agent and the curing agent are dissolved or dispersed in a solvent to the surface of the intermediate layer 6. From the viewpoint of workability, application with a spray gun is preferred. After application, the solvent volatilizes and the main agent and the curing agent react to form the reinforcing layer 8. Preferred solvents include toluene, isopropyl alcohol, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylbenzene, propylene glycol monomethyl ether, isobutyl alcohol and ethyl acetate.

  In light of feel at impact, the golf ball 2 has an amount of compressive deformation (comp′n) of preferably 2.3 mm or greater, and more preferably 2.5 mm or greater. In light of resilience performance, the amount of compressive deformation is preferably equal to or less than 3.5 mm, more preferably equal to or less than 3.3 mm, and particularly preferably equal to or less than 3.1 mm.

  A YAMADA compression tester is used to measure the amount of compressive deformation. In this tester, the golf ball 2 is placed on a metal rigid plate. A metal cylinder gradually descends toward the golf ball 2. The golf ball 2 sandwiched between the bottom surface of the cylinder and the rigid plate is deformed. The moving distance of the cylinder from the state where the initial load of 98 N is applied to the golf ball 2 to the state where the final load of 1274 N is applied is measured.

  Hereinafter, the effects of the present invention will be clarified by examples. However, the present invention should not be construed in a limited manner based on the description of the examples.

[Example 1]
100 parts by weight of high-cis polybutadiene (trade name “BR-730” from JSR), 23 parts by weight of zinc acrylate (trade name “Sunseller SR” from Sanshin Chemical Industry Co., Ltd.), 5 parts by weight of zinc oxide, appropriate amount Of rubber, 0.3 parts by mass of bis (pentabromophenyl) disulfide and 0.8 parts by mass of dicumyl peroxide were kneaded to obtain a rubber composition. This rubber composition was put into a mold composed of an upper mold and a lower mold each having a hemispherical cavity and heated at a temperature of 170 ° C. for 25 minutes to obtain a center having a diameter of 15 mm.

  100 parts by mass of high-cis polybutadiene (previously referred to as “BR-730”), 35 parts by weight of zinc acrylate (previously referred to as “Sunceller SR”), 5 parts by weight of zinc oxide, appropriate amount of barium sulfate, 0.2 parts by weight 2-thionaphthol, 0.8 part by mass of dicumyl peroxide and 5.0 parts by mass of zinc octoate were kneaded to obtain a rubber composition. A half shell was molded from this rubber composition. The center was covered with two half shells. The center and the half shell were both put into a mold composed of an upper mold and a lower mold each having a hemispherical cavity and heated at a temperature of 150 ° C. for 20 minutes to obtain a core having a diameter of 39.5 mm. . An envelope layer was formed from the rubber composition. The amount of barium sulfate was adjusted so that the specific gravity of the envelope layer coincided with the specific gravity of the center and the ball mass was 45.4 g.

  55 parts by mass of ionomer resin (the above-mentioned “Surlin 8945”), 45 parts by mass of other ionomer resin (the above-mentioned “Himilan AM7329”) and 3 parts by mass of titanium dioxide were kneaded with a twin-screw kneading extruder to obtain a resin composition. I got a thing. The core was put into the mold. The resin composition was injected around the core by an injection molding method to form an intermediate layer. The thickness of this intermediate layer was 1.0 mm.

  A coating composition (trade name “Porin 750LE”, manufactured by Shinto Paint Co., Ltd.) using a two-component curable epoxy resin as a base polymer was prepared. The main component liquid of this coating composition was 30 parts by mass of a bisphenol A type solid epoxy resin. The curing agent liquid of this coating composition is composed of 40 parts by mass of modified polyamidoamine, 55 parts by mass of solvent, and 5 parts by mass of titanium dioxide. The mass ratio with respect to the curing agent solution was 1/1, and this coating composition was applied to the surface of the intermediate layer with a spray gun and held at 23 ° C. for 12 hours to obtain a reinforcing layer. The layer thickness was 10 μm.

  100 parts by mass of thermoplastic polyurethane elastomer (previously “Elastollan XNY97A”), 0.2 parts by mass of hindered amine light stabilizer (trade name “Cinuvin 770” from Ciba Japan), 4 parts by mass of titanium dioxide and 0 parts by mass .04 parts by mass of ultramarine blue was kneaded with a twin-screw kneading extruder to obtain a resin composition. A half shell was molded from this resin composition by compression molding. A sphere composed of a core, an intermediate layer and a reinforcing layer was covered with two half shells. The sphere and half shell were put into a mold composed of an upper mold and a lower mold both having a hemispherical cavity. From this half shell, an inner cover was obtained by compression molding. The inner cover had a thickness of 0.3 mm.

  100 parts by mass of a thermoplastic polyurethane elastomer (“Elastollan XNY82A” described above), 0.2 parts by mass of a hindered amine light stabilizer (trade name “Tinubin 770” from Ciba Japan), 4 parts by mass of titanium dioxide and 0 .04 parts by mass of ultramarine blue was kneaded with a twin-screw kneading extruder to obtain a resin composition. A half shell was molded from this resin composition by compression molding. A sphere composed of a core, an intermediate layer, a reinforcing layer, and an inner cover was covered with the two half shells. Both the sphere and the half shell were put into a final mold which was composed of an upper mold and a lower mold each provided with a hemispherical cavity, and had many pimples on the cavity surface. An outer cover was obtained from this half shell by compression molding. The thickness of this outer cover was 0.3 mm. A dimple having a shape obtained by inverting the shape of the pimple was formed on the outer cover. A clear paint based on a two-component curable polyurethane was applied around the outer cover to obtain a golf ball of Example 1 having a diameter of 42.7 mm.

[Example 2-23 and Comparative Example 1-5]
The golf balls of Example 2-23 and Comparative Example 1-5 were manufactured in the same manner as in Example 1 except that the specifications of the core, intermediate layer, inner cover and outer cover were as shown in Table 13-18 below. Obtained. Details of the composition of the core are shown in Tables 1-4 below. The hardness distribution of the core is shown in Tables 7-12 below. Details of the composition of the intermediate layer are shown in Table 5 below. Details of the composition of the inner cover and outer cover are shown in Table 6 below.

[Blow by driver (W # 1)]
A driver with a titanium head (trade name “XXIO” from Dunlop Sports, shaft hardness: S, loft angle: 10.0 °) equipped with a titanium head was mounted on a swing machine manufactured by Tsurtemper. A golf ball was hit under the condition that the head speed was 45 m / sec. The spin speed immediately after hitting was measured. In addition, the distance from the launch point to the stationary point was measured. Average values of data obtained by 10 measurements are shown in Tables 13-18 below.

[Blowing by sand wedge (SW)]
A sand wedge (SW) was attached to the swing machine. A golf ball was hit under the condition that the head speed was 21 m / sec. The backspin rate immediately after the impact was measured. Average values of data obtained by 10 measurements are shown in Tables 13-18 below.

[durability]
The golf ball was held in a 23 ° C. atmosphere for 12 hours. The driver was mounted on the swing machine. The golf ball was repeatedly hit under the condition that the head speed was 45 m / sec. The number of hits until the golf ball was damaged was counted. The average value of the number of hits obtained by twelve measurements is shown as an index in Tables 13-18 below.

Details of the compounds described in Tables 1 to 4 are as follows.
BR730: High cis polybutadiene (cis-1,4-bond content: 96 mass%, 1,2-vinyl bond content: 1.3 mass%, Mooney viscosity (ML _{1 + 4} (100 ° C.)) from JSR Corporation
): 55, molecular weight distribution (Mw / Mn): 3)
Sunseller SR: Sanshin Chemical Co., Ltd. zinc acrylate (10 wt% stearic acid coating product)
ZN-DA90S: Zinc acrylate (10% by mass zinc stearate coated product) manufactured by Nippon Distillation Co., Ltd.
Zinc oxide: Toho Zinc Co., Ltd. trade name “Ginbao R”
Barium sulfate: The trade name “Barium sulfate BD” by Sakai Chemical
2-Thionaphthol: Tokyo Chemical Industry Co., Ltd. Bispentabromophenyl disulfide: Kawaguchi Chemical Industry Co., Ltd. 2,6-dichlorothiophenol: Tokyo Chemical Industry Co., Ltd. Dicumyl peroxide: NOF Corporation's trade name "Park Mill D"
Zinc octoate: Mitsuwa Chemical Co., Ltd. Zinc stearate: Wako Pure Chemical Industries, Ltd.

  As shown in Tables 13-18, the golf balls according to the examples are excellent in various performances. From this evaluation result, the superiority of the present invention is clear.

  The golf ball according to the present invention can be used for golf play and practice in a driving range.

2 ... Golf ball 4 ... Core 6 ... Intermediate layer 8 ... Reinforcement layer 10 ... Inner cover 12 ... Outer cover 14 ... Dimple 16 ... Land 18 ... Center 20 ... Enveloping layer

Claims (22)

A core, an intermediate layer located outside the core, an inner cover located outside the intermediate layer, and an outer cover located outside the inner cover;
The core has a center and an envelope layer located outside the center;
The envelope layer is
(A) base rubber,
(B) (b1) an α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms and / or (b2) an α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms. A co-crosslinking agent comprising a metal salt,
(C) a crosslinking initiator,
And
(D) Carboxylic acid and / or salt thereof (excluding α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms and metal salt thereof)
Is obtained by crosslinking a rubber composition containing
Depending on the carboxylic acid and / or its salt (d), the ratio (%) of the distance from the center point of the core to the radius of the core is 40.0%, 50.0%, 62.5%, 75. When the distance (%) from the center point and the JIS-C hardness of the six points included in the envelope layer of 0%, 87.5%, and 100.0% are plotted on the graph, the least square method is used. The R ² value of the obtained linear approximation curve is formed to be 0.95 or more,
The core has gradually increased hardness from the center point to the surface,
The difference (H (100) -H (0)) between the JIS-C hardness H (100) of the surface of the core and the JIS-C hardness H (0) of the center point of the core is 15 or more,
The Shore D hardness Hc1 of the inner cover is greater than the Shore D hardness Hc2 of the outer cover,
A golf ball having a thickness T1 of the inner cover of 0.1 mm to 0.8 mm. 2. The golf ball according to claim 1, wherein an amount of the carboxylic acid and / or a salt thereof (d) is 0.5 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the base rubber (a). The carboxylic acid and / or golf ball according to claim 1 or 2 carbon atoms in the carboxylic acid component is 1 to 30 in a salt thereof (d). 4. The golf ball according to claim 1, wherein the carboxylic acid and / or a salt thereof ( d ) is a fatty acid and / or a salt thereof. The core of the center point of the JIS-C hardness H (0) is 40 or more 70 or less, any one of claims 1 to 4 JIS-C hardness H of the surface of the core (100) is 78 or more 96 or less The golf ball described in 1. The golf ball according to any one of 5 Shore D hardness Hm of the intermediate layer is from claim 1 greater than the hardness Hc1. The golf ball according to claim 6 , wherein a difference (Hm−Hc1) between the hardness Hm and the hardness Hc1 is 15 or more. The golf ball according to any one of the Shore D hardness Hm of the intermediate layer is from claim 1 greater than the hardness Hc2 7. The golf ball according to claim 8 , wherein a difference (Hm−Hc2) between the hardness Hm and the hardness Hc2 is 20 or more. The golf ball according to any one of claims 1 to 9 the difference between the hardness Hc1 and the hardness Hc2 (Hc1-Hc2) is 5 or more. The golf ball according to any one of claims 1 to 10 thickness Tm of the intermediate layer is 0.5mm or more 1.6mm or less. The golf ball according to claim 1 1 1 the thickness T2 of the outer cover is 0.1mm or more 0.8mm or less. The golf ball according to any one of claims 1 to 12 the difference between the thickness T1 and the outer cover of the thickness T2 (T1-T2) is 0.4mm or less than -0.4 mm. The golf ball according to any one of claims 1 to 13 , wherein a sum (T1 + T2) of the thickness T1 and the thickness T2 of the outer cover is 1.0 mm or less. The rubber composition is
(E) The golf ball according to any one of claims 1 to 14, further comprising an organic sulfur compound. The golf ball according to claim 15 , wherein the organic sulfur compound (e) is a thiophenol, diphenyl disulfide, thionaphthol, thiuram disulfide, or a metal salt thereof. The golf according to claim 15 or 16 , wherein the rubber composition contains 0.05 to 5.0 parts by mass of the organic sulfur compound (e) with respect to 100 parts by mass of the base rubber (a). ball. The rubber composition contains the α, β-unsaturated carboxylic acid (b1),
Furthermore, this rubber composition
(F) The golf ball according to any one of claims 1 to 17 , comprising a metal compound. The intermediate layer is made of a resin composition, the inner cover is made of a resin composition whose base resin is different from that of the intermediate layer, and further includes a reinforcing layer between the intermediate layer and the inner cover. the golf ball according to any one of claims 1 to 18 of the. The golf ball according to any one of 19 claims 1 diameter of the center is 10mm or more 20mm or less. The carboxylic acid and / or golf ball according to any one of claims 1 20 a salt thereof (d) is a zinc salt of a carboxylic acid. The golf ball according to claim 21 , wherein the zinc salt of carboxylic acid is one or more selected from the group consisting of zinc octoate, zinc laurate, zinc myristate, and zinc stearate.

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