JP2023021031A - Rubber composition for golf ball, and golf ball - Google Patents

Abstract

To provide a rubber composition for a golf ball which can improve flight performance by exerting low-spin characteristics in hitting the golf ball by setting a hardness difference large in the hardness distribution in the core while keeping desired core hardness, and a golf ball made of the composition.SOLUTION: A rubber composition for a golf ball contains each component (a)-(d) and (f): (a) a base rubber; (b) α,β-unsaturated carboxylic acid and/or a metal salt thereof as a co-cross-linking agent; (c) a cross-linking initiator; (d) an alcohol; and (f) sulfur. A blending amount of the component (d) is 0.1 to 10 parts by mass relative to 100 parts by mass of (a) the base rubber. A golf ball has a core and a cover of a single layer or a plurality of layers for covering the core, and the core is made of the rubber composition.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a golf ball rubber composition and a golf ball using the same, and more particularly to a golf ball rubber composition suitable for use as a core material of a golf ball comprising one or more core layers and one or more cover layers. It relates to a golf ball using this.

Recently, two-piece solid golf balls and three-piece solid golf balls have become mainstream golf balls. These golf balls generally have a structure in which a core made of a rubber composition is covered with a single-layer or multiple-layer cover made of various resin materials. The core occupies most of the volume of the golf ball, and greatly affects ball properties such as resilience, hitting feel, and durability. Recently, various techniques have been proposed to realize a unique core hardness gradient by appropriately adjusting the cross-sectional hardness of the core, and to improve the flight distance by optimizing the spin characteristics of the driver or iron on a full shot. It is known that increasing the difference in hardness between the surface and center of the core has the effect of reducing driver spin on full shots. I know it will connect. Therefore, in order to improve the flight distance of a golf ball, there is a demand for a technique for increasing the hardness difference inside the core. One of the ways to realize this technology is to propose a structure in which the core is made of two layers of rubber. However, since the number of man-hours required to produce the core is greater than that of the single-layer rubber core, there are still expectations for a technique for increasing the hardness difference within the single-layer core.

Further, methods for adjusting the cross-sectional hardness of the core include appropriately adjusting the compounding components of the rubber composition of the core and the vulcanization temperature and time. Further, with respect to the compounding components of the rubber composition of the core, selection of the types of co-crosslinking agents and organic peroxides and adjustment of compounding amounts thereof can be mentioned. As co-crosslinking agents, it is known to use methacrylic acid, acrylic acid and their metal salts in the field of golf balls. However, the adjustment of the blending of the co-crosslinking agent is mainly aimed at adjusting the hitting feel of the ball by adjusting the hardness of the core, and the spin characteristics cannot be satisfied.

Japanese Unexamined Patent Publication No. 11-169485 proposes a technique of blending a specific amount of polyethylene glycol in a core rubber composition. However, this technology aims at improving mold releasability of a rubber molded product (core) by blending polyethylene glycol as an internal mold release agent. It is not a proposal of a technique for further realizing the internal hardness of the rubber molding and the low spin rate of the ball by selecting the type.

JP-A-11-169485

The present invention has been devised in view of the above-mentioned circumstances, and aims to improve flight performance by setting a large hardness difference in the core internal hardness distribution while maintaining a desired core hardness to exhibit low spin characteristics when hitting a golf ball. An object of the present invention is to provide a golf ball rubber composition obtained and a golf ball using the same.

As a result of intensive studies in order to achieve the above object, the inventors of the present invention have found that (a) a base rubber and (b) α, β- The desired The inventors have found that by setting a large hardness difference in the core internal hardness distribution while maintaining the core hardness of , the low spin characteristics when hitting a golf ball can be sufficiently exhibited, and the present invention has been accomplished. Although the reason is not clear, it is presumed as follows.

That is, by blending the alcohol into the core material, decomposition of the organic peroxide in the core blending is accelerated and a unique crosslinked structure of the butadiene rubber can be obtained. It is known that the decomposition efficiency of the organic peroxide in the core rubber composition changes depending on the temperature, and the decomposition efficiency increases as the temperature rises above a certain temperature. If the temperature is too high, the amount of decomposed radicals will be too large, and the radicals will recombine or be inactivated. As a result, the number of radicals that effectively work for cross-linking is reduced. Here, when decomposition heat is generated by decomposition of the organic peroxide during core vulcanization, the temperature near the core surface is maintained at approximately the same temperature as that of the vulcanization mold, but the temperature near the core center is maintained on the outside. Since the decomposition heat of the organic peroxide decomposed from the mold is accumulated, the temperature becomes considerably higher than the mold temperature. It is speculated that when alcohol is blended in the core, the hydroxyl group of the alcohol promotes the decomposition of the organic peroxide, and the radical reaction described above can be changed between the core center and the core surface. That is, in the vicinity of the core center, the decomposition of the organic peroxide is further promoted, and the deactivation of radicals is further promoted, resulting in a further decrease in the amount of effective radicals. can be obtained.

Furthermore, inside the core, the internal temperature becomes higher than the mold surface temperature due to self-heating due to the decomposition of the organic peroxide. In the vicinity of the center of the core, active sulfur derived from sulfur increases, and as a result, cross-linking and grafting reactions are inhibited, forming a low hardness region. On the other hand, in the vicinity of the surface of the core, a high hardness region is formed because the cross-linking and grafting reactions are completed before sufficient sulfur-derived active sulfur is generated. Therefore, it is considered that the hardness gradient inside the core increases.

Accordingly, the present invention provides the following golf ball rubber composition and golf ball.
1. Each of the components (a) to (d) and (f) below,
(a) base rubber,
(b) an α,β-unsaturated carboxylic acid and/or a metal salt thereof as a co-crosslinking agent;
(c) a cross-linking initiator;
(d) Alcohol and (f) Sulfur, wherein the content of component (d) is 0.1 to 10 parts by mass per 100 parts by mass of (a) base rubber. A rubber composition for balls.
2. 2. The golf ball rubber composition according to claim 1, wherein component (f) is added in an amount of 0.01 to 5.0 parts by mass per 100 parts by mass of component (a).
3. 3. The golf ball rubber composition according to 2 above, wherein component (f) is added in an amount of 0.01 to 1.0 part by mass per 100 parts by mass of component (a).
4. 2. The golf ball rubber composition according to 1 above, wherein the component (d) is a lower alcohol having a molecular weight of less than 500.
5. 5. The golf ball rubber composition according to 4 above, wherein the component (d) is a lower alcohol having a molecular weight of less than 200.
6. 2. The golf ball rubber composition according to claim 1, wherein component (d) is added in an amount of 0.5 to 5.0 parts by mass per 100 parts by mass of component (a).
7. 2. The golf ball rubber composition according to 1 above, wherein the component (d) is a monohydric, dihydric or trihydric alcohol.
8. 8. The golf ball rubber composition according to 7 above, wherein the component (d) is butanol, glycerin, ethylene glycol or propylene glycol.
9. 2. The golf ball rubber composition according to 1 above, which further contains an organic sulfur compound as component (e).
10. 2. The rubber composition for golf balls according to claim 1, wherein the vulcanized product of the rubber composition is a golf ball core.
11. 11. The rubber composition for a golf ball according to 10 above, wherein the hardness difference between the surface and the center of the vulcanized rubber composition is 20 or more in JIS-C hardness.
12. 12. A golf ball comprising a core and a single-layer or multi-layer cover covering the core, wherein the core is made of the rubber composition described in any one of 1 to 11 above. .
13. 13. The golf ball according to 12 above, wherein in the core hardness distribution, the difference in hardness between the surface and the center of the core is 20 or more in JIS-C hardness.
14. 13. The golf ball according to 12 above, wherein the center hardness of the core is 50 to 65 in JIS-C hardness.
15. 13. The golf ball according to 12 above, wherein the core has a surface hardness of 72 to 95 in JIS-C hardness.
16. 13. The golf ball according to 12 above, wherein the core has a compressive hardness (deformation) of 2.0 to 5.0 mm when an initial load of 98 N (10 kgf) is applied and a final load of 1275 N (130 kgf) is applied.

According to the rubber composition for a golf ball of the present invention, when the rubber composition is used as each constituent member of a golf ball, particularly as a core, it exhibits a low spin characteristic when hitting a golf ball and improves flight performance. can be done.

The present invention will be described in more detail below.
The golf ball rubber composition of the present invention is characterized by containing the following components (a) to (d) and (f).
(a) base rubber,
(b) an α,β-unsaturated carboxylic acid and/or a metal salt thereof as a co-crosslinking agent;
(c) a cross-linking initiator;
(d) alcohol, and (f) sulfur

The base rubber of component (a) is not particularly limited, but it is particularly preferable to use polybutadiene.

The above polybutadiene preferably has 60% or more, preferably 80% or more, more preferably 90% or more, and most preferably 95% or more of cis-1,4-bonds in its polymer chain. If too few cis-1,4-bonds occupy the bonds in the polybutadiene molecule, the resilience may decrease.

The content of 1,2-vinyl bonds in the polybutadiene is usually 2% or less, preferably 1.7% or less, more preferably 1.5% or less in the polymer chain. If the 1,2-vinyl bond content is too high, the resilience may decrease.

(ML ₁₊₄ (100° C.)) of the polybutadiene is preferably 20 or more, more preferably 30 or more, and the upper limit is preferably 120 or less, more preferably 100 or less, and still more preferably 80 or less. be.

The Mooney viscosity referred to in the present invention is an industrial index of viscosity (JIS K 6300) measured by a Mooney viscometer, which is a type of rotational plasticity meter, and the unit symbol is ML ₁₊₄ (100 °C) is used. M is Mooney viscosity, L is large rotor (L-type), 1+4 is preheating time of 1 minute, and rotor rotation time is 4 minutes.

As the polybutadiene, one synthesized using a rare earth element-based catalyst or a Group VIII metal compound catalyst can be used.

The base rubber may contain a polybutadiene rubber synthesized with a catalyst different from the lanthanum series rare earth element compound. Moreover, styrene-butadiene rubber (SBR), natural rubber, polyisoprene rubber, ethylene propylene diene rubber (EPDM), etc. may be compounded, and these may be used alone or in combination of two or more.

The proportion of polybutadiene in the entire rubber is preferably 60% by mass or more, more preferably 70% by mass or more, and most preferably 90% by mass or more. Further, 100% by mass of the base rubber, that is, all of the base rubber may be the polybutadiene.

Next, component (b) is a co-crosslinking agent, which is an α,β-unsaturated carboxylic acid and/or a metal salt thereof. The unsaturated carboxylic acid preferably has 3 to 8 carbon atoms, and specific examples include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and fumaric acid. Specific examples of the metal of the unsaturated carboxylic acid include zinc, sodium, magnesium, calcium, and aluminum, with zinc being particularly preferred. Therefore, zinc acrylate is most preferable as the co-crosslinking agent.

The amount of component (b) compounded is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and still more preferably 20 parts by mass or more per 100 parts by mass of the base rubber of component (a). is preferably 65 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 55 parts by mass or less. If the amount is less than the above range, the ball becomes too soft and has poor resilience.

The co-crosslinking agent of component (b) preferably has an average particle size of 3 to 30 μm, more preferably 5 to 25 μm, still more preferably 8 to 15 μm. If the co-crosslinking agent has an average particle size of less than 3 μm, it tends to aggregate in the rubber composition, increasing the reactivity between acrylic acid and reducing the reactivity between the base rubbers. In some cases, sufficient resilience performance cannot be obtained. If the co-crosslinking agent has an average particle size of more than 30 μm, the co-crosslinking agent particles become too large, resulting in golf balls with large variations in properties.

Component (c) is a cross-linking initiator, and as the cross-linking initiator, it is preferable to use an organic peroxide. It is preferred to use Examples of such organic peroxides include dicumyl peroxide (manufactured by NOF Corporation, "Percumyl D"), 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (manufactured by NOF Corporation), "Perhexa 25B"), di(2-t-butylperoxyisopropyl)benzene ("Perbutyl P" manufactured by NOF Corporation), etc., and dicumyl peroxide can be preferably used. Other commercially available products include "Perhexa C-40", "Nyper BW", "Perroyl L" (all manufactured by NOF Corporation), and Luperco 231XL (manufactured by Atochem). These may be used singly or in combination of two or more.

The amount of component (c) compounded is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, relative to 100 parts by mass of the base rubber, and the upper limit is preferably 5 parts by mass. Below, more preferably 4 parts by mass or less, still more preferably 3 parts by mass or less.

Next, component (d) is an alcohol component, preferably a lower alcohol with a molecular weight of less than 500, more preferably a lower alcohol with a molecular weight of less than 200. The term "alcohol" as used herein means a substance having one or more alcoholic hydroxy groups, and includes polyhydric alcohols having two or more hydroxy groups which are polycondensed. A lower alcohol means an alcohol having a small number of carbon atoms, that is, a small molecular weight. By including this lower alcohol in the rubber composition, it is possible to obtain a cured rubber (core) having a desired core hardness distribution during vulcanization (curing) of the rubber composition, thereby reducing the spin rate of the ball when hit. It is possible to sufficiently realize the conversion and make the flight performance excellent.

As the lower alcohol, monohydric, dihydric, or trihydric alcohols (alcohols having one, two, or three alcoholic hydroxy groups) are particularly preferred. Specifically, methanol, Examples include, but are not limited to, ethanol, propanol, butanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerin, and the like. Also, their molecular weight is less than 500, preferably less than 200, more preferably less than 150, and most preferably less than 100. If the molecular weight is too large, that is, if the number of carbon atoms is too large, the desired core hardness distribution cannot be obtained, and the spin rate of the ball cannot be sufficiently reduced when hit.

The amount of component (d) compounded is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the base rubber, and the upper limit is preferably 10 parts by mass. Below, more preferably 6 parts by mass or less, still more preferably 3 parts by mass or less. If the amount of component (d) is too large, the hardness will soften and the desired feel, durability and resilience cannot be obtained. There is a risk that it will not be possible to achieve a sufficiently low spin rate of the ball.

In addition to the components (a) to (d) described above, various additives such as fillers, anti-aging agents and other organic sulfur compounds can be added as long as they do not interfere with the effects of the present invention. .

As the filler, for example, zinc oxide, barium sulfate, calcium carbonate, etc. can be preferably used. These may be used individually by 1 type, and may use 2 or more types together. The amount of the filler compounded is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more with respect to 100 parts by mass of the base rubber. Moreover, the upper limit of this compounding ratio is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 40 parts by mass or less, relative to 100 parts by mass of the base rubber. If the blending amount is too large or too small, it may not be possible to obtain proper mass and suitable resilience.

Anti-aging agents are not particularly limited, but examples include 2,2-methylenebis(4-methyl-6-tertbutylphenol), 4,4-butylidenebis(3-methyl-6-tertbutylphenol), 2,2- Phenolic anti-aging agents such as methylenebis(4-ethyl-6-tertbutylphenol) can be mentioned, and commercially available products include Nocrac NS-6, Nocrac NS-30 and Nocrac NS-5 (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.). ) etc. can be adopted. These may be used individually by 1 type, and may use 2 or more types together. The amount of the antioxidant compounded is not particularly limited, but is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and the upper limit is preferably 1.0 parts per 100 parts by mass of the base rubber. It is no more than 0.7 parts by mass, more preferably no more than 0.4 parts by mass. If the blending amount is too large or too small, it may not be possible to obtain an appropriate core hardness gradient, resulting in failure to obtain suitable resilience, durability, and a low spin effect on full shots.

Furthermore, an organic sulfur compound can be contained as the (e) component. The organic sulfur compound (e) is not particularly limited, but examples thereof include thiophenols, thionaphthols, diphenylpolysulfides, halogenated thiophenols, and metal salts thereof. Specifically, zinc salts such as pentachlorothiophenol, pentafluorothiophenol, pentabromothiophenol, and parachlorothiophenol, diphenylpolysulfides having 2 to 4 sulfur atoms, dibenzylpolysulfides, dibenzoylpolysulfides, and dibenzothiazolyl Polysulfides, dithiobenzoyl polysulfides and the like can be mentioned. These may be used singly or in combination of two or more. Among them, zinc salt of pentachlorothiophenol and/or diphenyl disulfide can be preferably used.

The amount of the organic sulfur compound compounded is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 0.2 parts by mass or more, relative to 100 parts by mass of the base rubber. , the upper limit is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, and still more preferably 1 part by mass or less. If the amount of the organic sulfur compound is too large, the hardness of the heat-molded rubber composition may become too soft.

The rubber composition of the present invention contains sulfur as component (f). Commercially available sulfur can be used, for example, "Sulfax 5" manufactured by Tsurumi Chemical Industry Co., Ltd., "Sanmix S-80N" and "Sanmix IS-60N" manufactured by Sanshin Chemical Industry Co., Ltd., and Akrochem "AKROFORM S-80/EPR/P" manufactured by the company can be adopted.

The amount of sulfur as component (f) is not particularly limited, but is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and most preferably It is 0.05 parts by mass or more. The upper limit is preferably 5.0 parts by mass or less, more preferably 2.0 parts by mass or less, and most preferably 1.0 parts by mass or less. If the amount of the component (f) is too large, the cross-linking reaction by the organic peroxide is inhibited by the influence of sulfur, and the overall hardness of the molded product tends to be greatly softened. On the other hand, if the blending amount of the component (f) is too small, it may not be possible to increase the difference in core internal hardness between the surface and the core.

Regarding sulfur as the component (f), it is desirable to use it in the form of a masterbatch in order to improve the dispersibility of a very small amount of sulfur. Examples of such a sulfur masterbatch include the trade names "Sanmix S-80N", "Sanmix IS-60N" and "AKROFORM S-80/EPR/P".

The core can be produced by vulcanizing and curing a rubber composition containing the above components. For example, it is kneaded using a kneader such as a Banbury mixer or a roll, compression molded or injection molded using a core mold, and the temperature is about 100 as a temperature sufficient for the organic peroxide or co-crosslinking agent to act. By appropriately heating the molded article under conditions of up to 200° C. for 10 to 40 minutes, the molded article can be cured and produced.

Here, with the above-described compounding, the golf ball molded rubber product after vulcanization and curing can have a hardness gradient with a large difference in hardness between the surface and the center. By employing the golf ball rubber molded product described above as a golf ball core, it is possible to improve the durability of the golf ball while maintaining good spin characteristics.

The center hardness of the core is not particularly limited, but is preferably 40 or more, more preferably 45 or more, and still more preferably 50 or more according to the JIS-C standard, and the upper limit is preferably 75 or less, more preferably. is 70 or less, more preferably 65 or less. If the central hardness of the core deviates from the above range, the feel on impact may be poor, or the durability may be lowered, and the low spin rate effect may not be obtained.

The surface hardness of the core is not particularly limited, but is preferably 65 or more, more preferably 70 or more, and still more preferably 72 or more according to the JIS-C standard, and the upper limit is preferably 95 or less, more preferably. is 90 or less, more preferably 88 or less. If the surface hardness of the core is lower than the above range, the resilience will be low and a sufficient flight distance may not be obtained. On the other hand, if the surface hardness of the core is higher than the above range, the feel on impact may become too hard, and the durability to cracking due to repeated impact may deteriorate.

Regarding the hardness distribution of the core, the difference in hardness between the surface and the center is sufficiently large. Specifically, it is preferable that the difference in hardness between the surface A and the center B of the core is 20 or more in JIS-C hardness. , more preferably 25 or more, still more preferably 30 or more, and the upper limit is preferably 50 or less, more preferably 45 or less, and still more preferably 40 or less. If the value of the hardness difference is too small, the effect of reducing the spin rate on W#1 hits may not be sufficient, and the flight distance may not be obtained. On the other hand, if the hardness difference is too large, the golf ball may have a low initial velocity when actually hit, resulting in a poor flight distance or poor durability to cracking upon repeated hitting. Here, the above center hardness means the hardness measured at the center of a cross section obtained by cutting the core in half (to pass through the center), and the surface hardness is measured at the surface (spherical surface) of the core. means hardness to be applied. JIS-C hardness means hardness measured with a spring type hardness tester (JIS-C type) specified in JIS K 6301-1975.

Moreover, it is preferable that the hardness gradient of the core used in the present invention is such that the hardness is the same or increases from the center of the core toward the surface, and does not decrease.

In addition, the compression hardness (deformation amount) of the core (heat-formed product) when an initial load of 98 N (10 kgf) is applied and a final load of 1275 N (130 kgf) is applied is not particularly limited, but is preferably 2. 0 mm or more, more preferably 2.3 mm or more, and still more preferably 2.5 mm or more, and the upper limit is preferably 6.0 mm or less, more preferably 5.5 mm or less, and still more preferably 5.0 mm or less. recommended. If the value is too large, the core becomes too soft, and a sufficient spin-lowering effect may not be obtained, resulting in a decrease in resilience. On the other hand, when the value is too smaller than the above value, the spin-lowering effect cannot be obtained, and the feel on impact may become hard.

The diameter of the core is not particularly limited and depends on the layered structure of the golf ball to be manufactured, but it is preferably 30 mm or more, more preferably 35 mm or more, and the upper limit is preferably 41 mm or less, more preferably 40 mm or less. . If the core diameter deviates from this range, the initial velocity of the ball may be low, or appropriate spin characteristics may not be obtained.

The rubber composition is suitable for use as a golf ball core, as described above. Also, the golf ball of the present invention preferably has a structure comprising a core and one or more layers of a cover.

Next, the one-layer or multiple-layer cover covering the core will be described.
The cover material is not particularly limited, but known materials such as various ionomer resins and urethane elastomers used in golf balls can be used.

Also, in order to further reduce the spin rate of the ball, it is particularly preferable to use a highly neutralized ionomer material for the layer adjacent to the core. Specifically, it is preferable to use a material containing the following components (i) to (iv).
(i-1) an olefin-unsaturated carboxylic acid binary random copolymer and/or a metal ion neutralized product of an olefin-unsaturated carboxylic acid binary random copolymer;
(ii-2) Metal ion-neutralized product of olefin-unsaturated carboxylic acid-unsaturated carboxylic acid ester ternary random copolymer and/or olefin-unsaturated carboxylic acid-unsaturated carboxylic acid ester ternary random copolymer (i) base resin and (ii) non-ionomer thermoplastic elastomer are blended at a mass ratio of 100:0 to 0:100, and are blended at a mass ratio of 100:0 to 50:50. For 100 parts by mass of the resin component,
(iii) 5 to 80 parts by mass of fatty acids and/or derivatives thereof having a molecular weight of 228 to 1500;
(ix) A mixed material containing 0.1 to 17 parts by mass of a basic inorganic metal compound capable of neutralizing unneutralized acid groups in components (i) and (iii). In particular, when a mixed material of the above components (i) to (ix) is used, it is preferable to employ one in which 70% or more of the acid groups are neutralized.

As the material of the outermost layer of the cover, it is preferable to use a urethane material, particularly a thermoplastic urethane elastomer, as the main material.

Furthermore, one or more layers of cover (intermediate layer) may be formed between the layer adjacent to the core and the outermost cover layer. In this case, it is preferable to use a thermoplastic resin such as an ionomer as the intermediate layer material.

To obtain the cover of the present invention, for example, a single layer or a multi-layered core having two or more layers prepared in advance according to the type of ball is placed in a mold, the above mixture is heated, mixed and melted, and injection molded. , a method of covering the periphery of the core with a desired cover, or the like. In this case, the manufacture of the cover can be operated with excellent thermal stability, flowability, and moldability, so that the final golf ball has a high resilience as well as a good hitting performance. Good feel and excellent scratch resistance. In addition to the above, the method of forming the cover may be, for example, by forming a pair of hemispherical half cups in advance from the cover material of the present invention, wrapping the core with the half cups, and heating at 120 to 170° C. for 1 to 5 minutes. , a method of pressure molding, or the like can also be employed.

When the cover is a single layer, its thickness can be 0.3 to 3 mm. When the cover has two layers, the thickness of the outer cover layer can be 0.3 to 2.0 mm, and the thickness of the inner cover layer can be 0.3 to 2.0 mm. The Shore D hardness of each layer (cover layer) constituting the cover is not particularly limited, but is preferably 40 or more, more preferably 45 or more, and the upper limit is preferably 70 or less. Preferably it is 65 or less.

A large number of dimples are formed on the surface of the outermost layer of the cover, and various treatments such as base treatment, stamping, and painting can be performed on the cover. In particular, when the cover formed of the cover material of the present invention is subjected to such a surface treatment, workability can be improved because the moldability of the surface of the cover is good.

The present invention relates to a golf ball in which at least one layer of the rubber composition is used as a core material, and the type of golf ball is particularly limited as long as it has a core and at least one or more cover layers. For example, solid golf balls such as two-piece or three-piece solid golf balls in which a solid core is covered with a cover, multi-piece golf balls having a structure of three or more layers, and a single layer or two or more layers on a wound core. It can also be used for the core of a thread-wound golf ball covered with a multi-layered cover.

EXAMPLES Hereinafter, the present invention will be specifically described by showing examples and comparative examples, but the present invention is not limited to the following examples.

[Examples 1 to 3, Comparative Examples 1 to 3]
Using a core material containing polybutadiene as a main component shown in Table 1 below, a core composition was prepared by compounding the rubbers of Examples 1 to 3 and Comparative Examples 1 to 3, and then vulcanized at 155° C. for 20 minutes. A core with a diameter of 38.6 mm was produced through a process of polishing the core surface.

Details about the above formulations are as follows.
・ Polybutadiene rubber: trade name “BR01” (manufactured by JSR)
・ Zinc oxide: Product name “Three kinds of zinc oxide” (manufactured by Sakai Chemical Co., Ltd.)
· Anti-aging agent (1): trade name "Nocrac NS-6" (phenol-based anti-aging agent: manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)
Anti-aging agent (2): trade name “Nocrac MB” (benzimidazole-based anti-aging agent: manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)
・Zinc acrylate: Product name “ZN-DA85S” (85% zinc acrylate/15% zinc stearate), manufactured by Nippon Shokubai Co., Ltd. ・Zinc methacrylate: Product name “M-CP” (100% zinc methacrylate) Asada・Pentachlorothiophenol zinc salt: manufactured by Wako Pure Chemical Industries, Ltd. ・Sulfur: trade name “Sulfax 5” (95% fine sulfur powder) manufactured by Tsurumi Chemical Industry ・Propylene glycol (lower dihydric alcohol): molecular weight 76.1 (manufactured by Hayashi Pure Chemical Industry Co., Ltd.)
・Water: pure water (manufactured by Seiki Pharmaceutical Co., Ltd.)
・Organic peroxide (dicumyl peroxide): trade name “Percumyl D” (manufactured by NOF Corporation)

Core Cross-Sectional Hardness For the cores having a diameter of 38.6 mm of each of the above examples and comparative examples, the cross-sectional hardness of each position including the surface and the center was measured by the following method.
(1) Core surface hardness
At a temperature of 23 ± 1 ° C., the needle of the hardness meter is set vertically on the surface of the spherical core, JIS-C hardness is measured at four points on the surface of the core at random, and the average value is calculated. Using one ball as the measured value, the average value of three measured cores was obtained. The measured values are listed in Table 3.
(2) Core cross-sectional hardness
Cut the core into a plane so that the cross section passes through the center of the core, set the needle of the hardness tester so that it is perpendicular to the flat cross section at a temperature of 23 ± 1 ° C., and use a JIS-C hardness tester to The hardness was measured at the center of the hemispherical core and at positions every 2 mm from the center toward the surface, and the hardness was taken as the measured value for one ball, and the average value for three measured cores was obtained. The measured values are listed in Table 3.

Compression hardness of core and ball The core and ball are compressed at a temperature of 23±1°C at a speed of 10 mm/s, and from the initial load of 98 N (10 kgf) to the final load of 1275 N (130 kgf). The compression hardness (deformation) (mm) of the core and ball was measured, and the average value of 10 measurements was obtained.

Formation of cover (intermediate layer and outermost layer) Next, using an injection mold, an intermediate layer material (ionomer resin material) shown in Table 2 is injection-molded around the above-mentioned core surface to obtain a thickness of An intermediate layer of 1.3 mm and 64 Shore D hardness was formed. Next, using another injection molding die, the outermost layer material (urethane resin material) shown in Table 2 was injection-molded around the intermediate layer-covered spheres to a thickness of 0.8 mm and a Shore D hardness of 40. formed the outermost layer of

The details of the ingredients in the above table are as follows.
- "Himilan 1706", "Himilan 1557" and "Himilan 1605": ionomer resins manufactured by Mitsui Dow Polychemicals - "TPU": trade name "Pandex" manufactured by DIC Covestro Polymer Co., Ltd., ether type thermoplastic Polyurethane "Shore D hardness 40"
・ “Polyethylene wax”: trade name “Sanwax 161P” (manufactured by Sanyo Kasei Co., Ltd.)
・ "Isocyanate compound": 4,4'-diphenylmethane diisocyanate

The resulting golf balls were evaluated for driver spin rate by the following method. Table 3 shows the results.

Driver Spin Rate A driver (W#1) was attached to the golf hitting robot, and the spin rate of the ball immediately after hitting at a head speed of 45 m/s was measured with an initial condition measuring device. The club used was Bridgestone Sports "TourB XD-3 Driver (2016 model)" (loft angle 9.5°).

As shown in Table 3, Examples 1 to 3, in which a rubber composition containing alcohol and sulfur was used as a core material, compared to Comparative Examples 1 to 3, the difference in hardness between the center and surface of the core was JIS A sufficient hardness difference of 20 or more is obtained for -C, and the spin rate of the golf ball when hit with a driver is about 100 to 500 rotations compared to the comparative example where the hardness difference is less than 20, which is not sufficient. was also low. From this, it can be seen that the flight performance is improved.

Claims (16)

Each of the components (a) to (d) and (f) below,
(a) base rubber,
(b) an α,β-unsaturated carboxylic acid and/or a metal salt thereof as a co-crosslinking agent;
(c) a cross-linking initiator;
(d) Alcohol and (f) Sulfur, wherein the content of component (d) is 0.1 to 10 parts by mass per 100 parts by mass of (a) base rubber. A rubber composition for balls. The rubber composition for a golf ball according to claim 1, wherein component (f) is added in an amount of 0.01 to 5.0 parts by mass per 100 parts by mass of component (a). 3. The rubber composition for a golf ball according to claim 2, wherein component (f) is added in an amount of 0.01 to 1.0 part by mass per 100 parts by mass of component (a). 2. The rubber composition for a golf ball according to claim 1, wherein component (d) is a lower alcohol having a molecular weight of less than 500. 5. The golf ball rubber composition according to claim 4, wherein component (d) is a lower alcohol having a molecular weight of less than 200. The rubber composition for a golf ball according to claim 1, wherein component (d) is added in an amount of 0.5 to 5.0 parts by mass per 100 parts by mass of component (a). 2. The rubber composition for a golf ball according to claim 1, wherein component (d) is a monohydric, dihydric or trihydric alcohol. 8. The golf ball rubber composition according to claim 7, wherein said component (d) is butanol, glycerin, ethylene glycol or propylene glycol. 2. The rubber composition for a golf ball according to claim 1, further comprising an organic sulfur compound as component (e). 2. The rubber composition for a golf ball according to claim 1, wherein the vulcanized product of said rubber composition is a golf ball core. 11. The rubber composition for a golf ball according to claim 10, wherein the hardness difference between the surface and the center of the vulcanized rubber composition is 20 or more in JIS-C hardness. A golf ball comprising a core and a single-layer or multi-layer cover covering the core, wherein the core is formed from the rubber composition according to any one of claims 1 to 11. Golf ball. 13. The golf ball according to claim 12, wherein in the core hardness distribution, the difference in hardness between the surface and the center of the core is 20 or more in JIS-C hardness. 13. The golf ball of claim 12, wherein the center hardness of the core is 50 to 65 in JIS-C hardness. 13. The golf ball of claim 12, wherein the core has a surface hardness of 72 to 95 in terms of JIS-C hardness. 13. The golf ball according to claim 12, wherein the core has a compression hardness (deformation) of 2.0 to 5.0 mm when an initial load of 98 N (10 kgf) is applied and a final load of 1275 N (130 kgf) is applied.