JP5360013B2 - Method for producing rubber composition for solid golf ball - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a rubber composition for a homogeneous solid golf ball in which a cocrosslinking agent such as a metal unsaturated carboxylate is satisfactorily minutely dispersed and which can be manufactured with satisfactory operability. <P>SOLUTION: The method for producing the rubber composition for the solid golf ball containing (A) a base material rubber, (B) a filler, (C) an organic peroxide and (D) a cocrosslinking agent coated with a coating rubber includes: a step for coating the cocrosslinking agent with the coating rubber including a step (I) for preparing a liquid wherein the cocrosslinking agent is suspended and the coating rubber is dissolved in a solvent and a solvent removing step (II) for removing the solvent from the liquid prepared by the step (I); and a step for mixing the component (D) with each of the components (A) to (C) after the step for coating the cocrosslinking agent with the coating rubber. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a homogeneous solid golf ball rubber composition.

  Conventionally, when manufacturing a core ball or a one-piece golf ball in a solid golf ball having a multi-layer structure covered directly with a cover material or through an intermediate layer, a rubber component such as butadiene rubber, a metal of unsaturated carboxylic acid A method of producing a rubber composition containing a co-crosslinking agent such as a salt, a weight adjusting agent such as zinc oxide, a free radical initiator such as dicumyl peroxide and the like by heating and pressing is generally employed. Here, as the metal salt of unsaturated carboxylic acid as the above-mentioned co-crosslinking agent, zinc methacrylate, zinc acrylate, etc. are used from the viewpoint of appropriately adjusting the hardness and repulsion of the golf ball finally obtained. It is preferably used.

  These zinc methacrylate, zinc acrylate and the like are usually in a considerably large amount of 15 to 60 parts with respect to 100 parts of base rubber component such as polybutadiene (the same applies hereinafter) for the purpose of realizing suitable golf ball properties. Although these zinc methacrylates and zinc acrylates are fine powders, they are often scattered when kneading each component to obtain a rubber composition, or they adhere violently to a kneading machine such as a roll. In some cases, the kneading operation becomes difficult. Furthermore, since these zinc methacrylate and zinc acrylate are easy to form aggregates in the rubber composition, the ratio of zinc methacrylate and zinc acrylate that act substantially may be reduced. Since the degree of hardness of the golf ball is not constant, the hardness and repellency of the final golf ball may vary from lot to lot, or may vary depending on the hitting position, resulting in a problem that the quality of the golf ball is not constant. It was.

  As a technique for preventing such adhesion of zinc methacrylate and zinc acrylate to a kneader and a technique for realizing a good dispersion state in the rubber composition, there are the following.

  That is, in Patent Document 1: Japanese Patent No. 2720541, a master batch is prepared by blending a metal salt of an unsaturated carboxylic acid and a liquid rubber, and then the master batch is blended with the rubber, thereby unsaturated carboxylic acid. A technique for satisfactorily dispersing the metal salt in a rubber composition is described. However, since liquid rubber having a low molecular weight is used in the method, there is still room for improvement from the viewpoint of the resilience of the resulting core.

  In Patent Document 2: JP-A-4-314465 and Patent Document 3: JP-A-4-227733, a metal salt of an unsaturated carboxylic acid and a rubber are mixed in a solution state, the solvent is removed, and the core is left as it is. Techniques for molding are described. However, in this method, the amount of rubber must be relatively large, and application may be difficult when a large amount of a metal salt of an unsaturated carboxylic acid is blended. Further, in these methods, the solutions are mixed with each other and the solvent is removed to directly disperse the metal salt of the unsaturated carboxylic acid in the rubber. Therefore, a process for removing a large amount of solvent and a large amount of rubber composition There is a case where workability is inferior due to the need for a drying process of the product. This is especially true when a large amount of a metal salt of an unsaturated carboxylic acid is blended.

  In Patent Document 4: Japanese Patent Laid-Open No. 59-141961 and Patent Document 5: Japanese Patent Laid-Open No. 60-92781, the surface of a metal salt of an unsaturated carboxylic acid is coated with a higher fatty acid or a salt thereof, and then the rubber is coated. Techniques for blending are described. However, in this method, the effect cannot be expected unless the kneading temperature is set to a high temperature of 100 ° C. or higher, which is not preferable from the viewpoint of production cost, and may cause problems such as a scorch problem and a large scattering loss. .

  Patent Document 6: Japanese Patent Application Laid-Open No. 2002-85591, Patent Document 7: Japanese Patent Application Laid-Open No. 2002-159595, and Patent Document 8: Japanese Patent Application Laid-Open No. 2002-200195 disclose a metal salt of an unsaturated carboxylic acid with a thermoplastic resin. A technique for coating the surface of the rubber and then blending it with rubber is described. However, in this method, the kneading temperature needs to be set to a high temperature of 100 ° C. or higher, which may not be preferable as a production process. Further, the thermoplastic resin used for the coating may reduce the resilience of the golf ball finally obtained.

  Patent Document 9: Japanese Patent Application Laid-Open No. 2001-187167 describes a technique in which the surface of an unsaturated carboxylic acid is coated with a sulfur-containing compound and then blended with rubber. However, in this method, the effect of reducing the adhesion of the coating to the kneader may be insufficient.

  Even when a large amount of a metal salt of an unsaturated carboxylic acid is blended, the metal salt of the unsaturated carboxylic acid is finely dispersed in the rubber, there is no variation in characteristics among lots, and the production is performed with good workability. Thus, there has been a demand for a rubber composition that can be used, and a golf ball that ensures a stable quality and has a good flying performance.

Japanese Patent No. 2720541 JP-A-4-314465 JP-A-4-227733 JP 59-141961 A JP-A-60-92781 JP 2002-85591 A JP 2002-159595 A JP 2002-200195 A JP 2001-187167 A

  The present invention has been made in view of the above circumstances, and a homogeneous solid golf in which a co-crosslinking agent such as a metal salt of an unsaturated carboxylic acid is finely dispersed in rubber and can be manufactured with good workability. It aims at providing the manufacturing method of the rubber composition for balls.

  As a result of intensive studies to achieve the above object, the present inventors have been coated with (A) a base rubber, (B) a filler, (C) an organic peroxide, and (D) a coating rubber. And a step of coating the co-crosslinking agent with the coating rubber, wherein (I) the co-crosslinking agent is suspended in a solvent. And a step of preparing a solution in which the coating rubber is dissolved, and a step (II) of removing the solvent from the solution prepared by the above step, and after this rubber coating step, the component (D) and the above (A ) To (C) are mixed, and the manufacturing method of the rubber composition for a solid golf ball characterized by comprising the steps of: It came to an eggplant.

That is, the present invention provides the following method for producing a rubber composition for a solid golf ball.
Claim 1 :
Each component of the following (A)-(D),
(A) base rubber,
(B) a filler,
(C) an organic peroxide,
(D) a co-crosslinking agent coated with a coating rubber;
And a mass ratio of the co-crosslinking agent and the coating rubber in the component (D) is (co-crosslinking agent) / (coating rubber) = 100. / 1-100 / 9 (mass ratio), and the co-crosslinking agent is a mixture of a metal salt of an unsaturated carboxylic acid and a metal salt of a higher fatty acid, and the mixing ratio is (unsaturated carboxylic acid). (Acid metal salt) / (metal salt of higher fatty acid) = 90 / 10-80 / 20 (mass ratio), and the step of coating the co-crosslinking agent with the coating rubber,
(I) a step of preparing a liquid in which the co-crosslinking agent is suspended in the solvent and the coating rubber is dissolved;
(II) a solvent removal step of removing the solvent from the liquid prepared by the above step, and a step of mixing the component (D) and the components (A) to (C) after the rubber coating step. A method for producing a rubber composition for a solid golf ball.
Claim 2 :
Method for producing a non-metal salts of saturated carboxylic acids, rubber composition for a solid golf ball according to claim 1 wherein the zinc acrylate and / or zinc methacrylate.
Claim 3 :
Method for producing a metal salt of a higher fatty acid, according to claim 1 or 2 rubber composition for a solid golf ball wherein the zinc stearate and / or zinc palmitate.
Claim 4 :
The rubber composition for a solid golf ball according to any one of claims 1 to 3 , wherein the covering rubber is one or more selected from the group consisting of butadiene rubber, isoprene rubber, and natural rubber. Manufacturing method.
Claim 5 :
The rubber composition for a solid golf ball according to any one of claims 1 to 4 , wherein the component (A) is a butadiene rubber having a cis-1,4-bond ratio in a molecule of 40% or more. Manufacturing method.

  According to the method for producing a rubber composition for a solid golf ball of the present invention, since the co-crosslinking agent is finely dispersed well in the rubber, it has uniform hardness and resilience, and can be produced with good workability. Is possible. And, the golf ball using the rubber composition for a solid golf ball obtained by the manufacturing method of the present invention has little variation between lots or repulsion or hardness of the golf ball due to the golf ball hitting position, It is not only a golf ball with very stable quality, but also a golf ball with excellent resilience.

Hereinafter, the present invention will be described in more detail.
The rubber composition for golf balls obtained by the production method of the present invention includes the following components (A) to (D):
(A) base rubber,
(B) a filler,
(C) an organic peroxide,
(D) a co-crosslinking agent coated with a coating rubber;
A rubber composition for a solid golf ball comprising: (D) the mass ratio of the rubber and the co-crosslinking agent in the co-crosslinking agent coated with the coating rubber is (co-crosslinking agent) / (coating Rubber) = 100/1 to 100/9 (mass ratio).

  As the (A) base rubber, those used as a core ball material of a normal one-piece golf ball or a multi-layer structure solid golf ball can be used. % Or more, preferably 60% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more. If there are too few cis-1,4-bonds, the resilience may decrease.

When butadiene rubber is used as the component (A), its Mooney viscosity (ML _{1 + 4} (100 ° C.)) is usually 40 or more, preferably 50 or more, more preferably 52 or more, still more preferably 54 or more, The upper limit is usually 140 or less, preferably 120 or less, more preferably 100 or less, and still more preferably 80 or less. If the Mooney viscosity is too large, workability may be reduced, while if it is too small, resilience may be reduced.
The Mooney viscosity referred to in the present invention is an industrial viscosity index (JIS-K6300) measured with a Mooney viscometer, which is a kind of rotational plasticity meter, and ML _{1 + 4} as a unit symbol. (100 ° C.) is used. Further, M is Mooney viscosity, L is a large rotor (L type), 1 + 4 is a preheating time of 1 minute, and a rotor rotation time is 4 minutes, which is measured at 100 ° C.

When butadiene rubber is used as the component (A), the molecular weight distribution Mw / Mn (Mw: weight average molecular weight, Mn: number average molecular weight) is usually 2.0 or more, preferably 2.2 or more. More preferably 2.4 or more, still more preferably 2.6 or more, and the upper limit is usually 8.0 or less, preferably 7.5 or less, more preferably 4.0 or less, still more preferably 3.4 or less. When Mw / Mn is too small, workability may be reduced, and when Mw / Mn is too large, resilience may be reduced.
In addition, the molecular weight distribution value as used in the field of this invention is a value computed as a polystyrene conversion value by GPC method using THF as a solvent.

  As the component (A), in addition to the above-mentioned butadiene rubber, other diene rubbers such as styrene butadiene rubber, natural rubber, isoprene rubber, ethylene propylene diene rubber and the like are further blended as necessary. May be.

  As said (B) filler, inorganic fillers, such as a zinc oxide, barium sulfate, a calcium carbonate, can be mentioned, for example, As the compounding quantity, it is usually 1 mass part or more with respect to 100 mass parts of said (A) component. , Preferably 3 parts by mass or more, more preferably 5 parts by mass or more, more preferably 7 parts by mass or more, and the upper limit is usually 130 parts by mass or less, preferably 50 parts by mass or less, more preferably 45 parts by mass or less, still more preferably. It is 40 parts by mass or less.

  Commercially available products can be used as the (C) organic peroxide. For example, Park Mill D (manufactured by NOF Corporation), Perhexa 3M (manufactured by NOF Corporation), Perhexa C (manufactured by NOF Corporation), Perhexa HC ( (Nippon Yushi Co., Ltd.), Perhexa TMH (Nippon Yushi Co., Ltd.), Luperco 231XL (Atochem Co., Ltd.) and the like. If necessary, two or more different organic peroxides may be mixed and used.

  As a compounding quantity with respect to the said (A) component of such (C) component, it is 0.1 mass part or more normally with respect to 100 mass parts of said (A) component, Preferably it is 0.3 mass part or more, More preferably, it is 0. 0.5 parts by mass or more, more preferably 0.7 parts by mass or more, and usually 5 parts by mass or less, preferably 4 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less as the upper limit. If the blending amount of the component (C) with respect to the component (A) is too large or too small, it may not be possible to obtain suitable resilience, feel and durability.

In the co-crosslinking agent coated with the coating rubber (D), as the co-crosslinking agent, from the viewpoint of resilience, in the present invention, a metal salt of an unsaturated carboxylic acid or a metal of an unsaturated carboxylic acid A mixture of a salt and a metal salt of a higher fatty acid is preferably used.
Examples of such metal salts of unsaturated carboxylic acids include zinc salts and magnesium salts of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and fumaric acid. These may be used alone or in combination of two or more.
Examples of the higher fatty acid metal salts include stearic acid, palmitic acid, 12-hydroxystearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, lignoceric acid, lauric acid, myristic acid and the like. Examples include zinc salts and magnesium salts of higher fatty acids. These may be used alone or in combination of two or more.

のような完全中和形のものでも、

のような一部中和形のものでもよい。 As the metal salt of the unsaturated carboxylic acid, zinc acrylate and zinc methacrylate can be preferably used, but as the metal salt of the unsaturated carboxylic acid, for example,

Even a completely neutralized type like

A partially neutralized type such as

When a metal salt of an unsaturated carboxylic acid and a metal salt of a higher fatty acid are used in combination as the co-crosslinking agent in the component (D), the metal salt of the higher fatty acid is the metal salt of the unsaturated carboxylic acid and the above The proportion (mass%) in the total amount of the higher fatty acid and the metal salt is 10 mass% or more, and the upper limit is 20 mass% or less. When the proportion of the higher fatty acid metal salt in the total amount of the unsaturated carboxylic acid metal salt and the higher fatty acid metal salt exceeds 20 % by mass, the resilience may be lowered.

  As a compounding quantity with respect to the said (A) component of such (D) component, it is normally 10 mass parts or more with respect to 100 mass parts of said (A) component, Preferably it is 15 mass parts or more, More preferably, it is 20 mass parts or more, The upper limit is usually 60 parts by mass or less, preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and most preferably 40 parts by mass or less. If the blending amount of the component (D) with respect to the component (A) is too small, the resilience may be lowered. On the other hand, if the amount is too large, it may become too hard and unbearable.

Examples of the coating rubber used to coat the above-mentioned co-crosslinking agent in the co-crosslinking agent coated with the (D) coating rubber include, for example, butadiene rubber, isoprene rubber, butadiene-isoprene rubber, butadiene -Styrene rubber, butene rubber, ethylene-propylene rubber, etc. are mentioned. Among these, from the viewpoint of resilience, one or more selected from the group consisting of butadiene rubber, isoprene rubber, and natural rubber are preferable.
The Mooney viscosity ML _{1 + 4} (100 ° C.) of the coating rubber is usually 10 or more, preferably 20 or more, more preferably 30 or more, and the upper limit is usually 150 or less, preferably 100 or less, more preferably 80 or less. More preferably, it is 60 or less.

And the rubber in such (D) a co-crosslinking agent coated with coating rubber, the weight ratio of the co-crosslinking agent, as a weight ratio of the coating rubber for the co-crosslinking agent 100 parts by weight 1 part by weight or more, preferably 3 parts by mass or more, more preferably 5 parts by mass or more, or less 9 parts by mass as an upper limit. When the mass ratio of the coating rubber to 100 parts by mass of the co-crosslinking agent is less than 1 part, the effect of improving workability is reduced and the object of the present invention cannot be achieved. On the other hand, when it exceeds 9 parts, the solution viscosity at the time of the coating process increases, the work becomes difficult, and the object of the present invention cannot be achieved.

  In addition to the essential components (A) to (D) above, the rubber composition for a solid golf ball obtained by the production method of the present invention further includes a plasticizer, an anti-aging agent, other one-piece golf balls and multilayers as optional components. Components that can be normally used for the production of the core ball of the solid solid golf ball can be appropriately blended as necessary. Commercially available products can be used as the anti-aging agent, and examples thereof include NOCRACK NS-6, NS-30 (Ouchi Shinsei Chemical Co., Ltd.), Yoshinox 425 (Yoshitomi Pharmaceutical Co., Ltd.), and the like.

  Furthermore, an organic sulfur compound can be blended with the rubber composition for a solid golf ball from the viewpoint of adjusting hardness and resilience. Examples of such organic sulfur compounds include thiophenol, thionaphthol, halogenated thiophenol, or metal salts thereof. More specifically, pentachlorothiophenol, pentafluorothiophenol, pentabromothiophenol, para Examples thereof include zinc salts such as chlorothiophenol and pentachlorothiophenol, diphenyl polysulfide having 2 to 4 sulfur atoms, dibenzyl polysulfide, dibenzoyl polysulfide, dibenzothiazoyl polysulfide, dithiobenzoyl polysulfide and the like. Among them, pentachlorothiophenol zinc salt and diphenyl disulfide are preferably used.

As a compounding quantity of such an organic sulfur compound, it is 0.1 mass part or more normally with respect to 100 mass parts of said (A) component, Preferably it is 0.2 mass part or more, More preferably, it is 0.5 mass part or more, An upper limit Is usually 5 parts by mass or less, preferably 4 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably 2 parts by mass or less.
Furthermore, in order to improve the kneadability with the base rubber, the golf ball rubber composition preferably contains a metal salt of a higher fatty acid. The amount of the base is 100 parts by weight of the base rubber. Usually 0.5 parts by mass or more, preferably 1.0 part by mass or more, and the upper limit is usually 10 parts by mass or less, preferably 7 parts by mass or less. In particular, these may be used alone or in combination of two or more.

  As a method for producing the rubber composition for a solid golf ball, a rubber coating step of preparing the component (D) by coating a co-crosslinking agent with a coating rubber, and after this rubber coating step (D) It is a manufacturing method including the process of mixing a component and each component of said (A)-(C). Kneading at the time of kneading a rubber composition by including such a rubber coating step and a step of mixing the component (D) and each of the components (A) to (C) after the rubber coating step. Adhesion and scattering loss of the co-crosslinking agent to the machine can be reduced, so that not only good workability and productivity can be improved, but the co-crosslinking agent is always good in the rubber. Therefore, it is possible to improve the quality of the rubber composition and to suppress the quality variation between lots.

  From the viewpoint of equipment and workability, the rubber coating step includes (I) a step of preparing a solution in which a co-crosslinking agent is suspended in a solvent and a coating rubber is dissolved, and (II) a step prepared by this step. And a solvent removal step of removing the solvent from the solution.

Furthermore, the step (I) may be a step of suspending the co-crosslinking agent in a solvent, and then directly adding the coating rubber to the suspension and stirring and mixing. Steps (i) to (iii) of
(I) suspending the co-crosslinking agent in a solvent;
(Ii) dissolving the coating rubber in a solvent;
(Iii) mixing the suspended co-crosslinking agent with the dissolved coating rubber;
A process including

The solvent used in the step (I) is appropriately selected in view of the type of coating rubber or co-crosslinking agent to be used, and examples thereof include organic solvents such as toluene, xylene, benzene and cyclohexane. Aromatic organic solvents are preferred.
When the step (I) includes the steps (i) to (iii), the solvents used in the steps (i) and (ii) may be the same solvent or different solvents. However, it is preferable that at least the solvent used in the step (i) and the solvent used in the step (ii) are a combination of solvents that are mixed (compatible) with each other.

When the step (I) includes the steps (i) to (iii), the concentration of the co-crosslinking agent in the suspension prepared in the step (i) is usually 150 g / L or more, Preferably it is 200 g / L or more, and is 300 g / L or less normally as an upper limit, Preferably it is 250 g / L or less. If the co-crosslinking agent concentration in the suspension is less than 150 g / L, production efficiency may be poor. On the other hand, if it exceeds 300 g / L, the stirring efficiency may decrease and the uniformity may decrease.
Further, the concentration of the rubber for coating in the solution prepared in the step (ii) is usually 4 g / L or more, preferably 10 g / L or more, and the upper limit is usually 40 g / L or less, preferably 30 g / L or less. It is. When the concentration of the coating rubber in the solution is less than 4 g / L, the coating amount may decrease. On the other hand, when it exceeds 40 g / L, the dissolution time becomes long and the viscosity becomes high, which may make the operation difficult.

  In the step (I), when suspending the metal salt used as the co-crosslinking agent in the solvent, a compound in the form of the metal salt may be added to the solvent in advance. A method of reacting an unsaturated organic acid with a metal oxide or metal hydroxide to form a metal salt in a solvent is also preferably used.

The step (II) is a step for removing the solvent used in the step (I), but there is no particular limitation on the method for removing the solvent, and the solvent may be volatilized by heating or under reduced pressure conditions ( Removal may be promoted by using vacuum drying together.
The method for producing the rubber composition for a solid golf ball includes a rubber coating step of preparing the component (D) by coating a co-crosslinking agent with a coating rubber, and after this rubber coating step (D ) Component and the step of mixing the components (A) to (C), but there is no particular limitation on the mixing method of the component (D) and the components (A) to (C). And can be kneaded with an appropriate kneader such as a roll or a Banbury mixer.

The solid golf ball produced using the rubber composition for a solid golf ball is a one-piece golf ball obtained by heat-pressing the rubber composition for a solid golf ball using a mold. However, the core for a multi-layered solid golf ball is formed with the above rubber composition for a solid golf ball from the viewpoint of efficiently imparting resilience to the product golf ball, taking advantage of the characteristics of the thermoformed product. In addition, it is preferable that the golf ball has a multi-layered solid golf ball covered with one or more layers of a cover.
Here, as a condition at the time of heat and pressure molding using a mold, for example, a vulcanization temperature of 100 to 200 ° C. and a vulcanization time of 10 to 40 minutes can be employed.

  When the heat-molded product of the rubber composition for a solid golf ball is the solid core, the diameter of the solid core is 30.0 mm or more, preferably 32.0 mm or more, more preferably 35.0 mm or more, and still more preferably 37. The upper limit is usually 41.0 mm or less, preferably 40.5 mm or less, more preferably 40.0 mm or less, still more preferably 39.5 mm or less. In particular, the diameter of the solid core of the two-piece solid golf ball is 37.0 mm or more, preferably 37.5 mm or more, more preferably 38.0 mm or more, still more preferably 38.5 mm or more, and the upper limit is usually 41.0 mm or less, preferably It is 40.5 mm or less, more preferably 40.0 mm or less. The diameter of the solid core of the three-piece solid golf ball is 30.0 mm or more, preferably 32.0 mm or more, more preferably 34.0 mm or more, still more preferably 35.0 mm or more, and the upper limit is usually 40.0 mm or less, preferably Is 39.5 mm or less, more preferably 39.0 mm or less.

  The solid golf ball produced using the rubber composition for a solid golf ball can take various golf ball modes as described above, but a one-piece solid golf ball using the rubber composition for a solid golf ball, Alternatively, when a solid core is formed, the amount of deflection when a 980N (100 kg) load is applied is usually 2.0 mm or more, preferably 2.5 mm or more, more preferably 2.8 mm or more, and even more preferably 3.2 mm or more. The upper limit is 6.0 mm or less, preferably 5.5 mm or less, more preferably 5.0 mm or less, and most preferably 4.5 mm or less. If the amount of deformation is too small, the feeling of hitting will worsen, and in particular, the long shot that causes large deformation of the ball such as a driver may cause excessive spin and may not fly, and if the amount of deformation is too large, the feeling of hitting will become dull. At the same time, there is a case where the repulsion is not sufficient and does not fly, and the cracking durability due to repeated hitting is deteriorated.

  When the solid golf ball is a two-piece or multi-piece solid golf ball, it can be formed by injection molding or pressure molding a known cover material and intermediate layer material using the heat-molded product as a solid core.

  More specifically, these cover materials and intermediate layer material main materials may include thermoplastic or thermosetting polyurethane elastomers, polyester elastomers, ionomer resins, polyolefin elastomers, or mixtures thereof. These can be used individually by 1 type or in mixture of 2 or more types, Especially, a thermoplastic polyurethane-type elastomer and an ionomer resin can be mentioned suitably.

  Commercially available products can be used as the thermoplastic polyurethane-based elastomer. For example, diisocyanates such as Pandex T7298, T7295, T7890, TR3080, T8295, and T8290 (DIC Bayer Polymer) are aliphatic or Those that are aromatic may be mentioned. Examples of commercially available ionomer resins include Surlyn 6320, 8120 (manufactured by DuPont, USA), HiMilan 1706, 1605, 1855, 1601, 1557 (manufactured by Mitsui DuPont Polychemical).

  Furthermore, a polymer such as a thermoplastic elastomer other than the above can be blended as an optional component in the main material of the cover material or intermediate layer material. Specifically, as an optional polymer, a polyamide-based elastomer, a styrene-based block elastomer, a hydrogenated polybutadiene, an ethylene-vinyl acetate (EVA) copolymer, or the like can be blended.

  The solid golf ball can be manufactured by a known method and is not particularly limited. However, in the case of a two-piece or multi-piece solid golf ball, a predetermined injection molding is performed using the heat-molded product as a solid core. In the case of a two-piece solid golf ball, a known method of injecting the intermediate layer material and the cover material in order according to a predetermined method is arranged in a mold for use. It can be suitably employed. In some cases, the cover material can be manufactured by pressure molding.

  The thickness of the intermediate layer of the multi-piece solid golf ball is usually 0.5 mm or more, preferably 1.0 mm or more, and the upper limit is usually 3.0 mm or less, preferably 2.5 mm or less, more preferably 2.0 mm or less, Preferably it is 1.6 mm or less.

  In addition, the thickness of the cover is usually 0.7 mm or more, preferably 1.0 mm or more, and the upper limit is usually 3.0 mm or less, preferably two-piece solid golf balls or multi-piece solid golf balls. It is 5 mm or less, More preferably, it is 2.0 mm or less, More preferably, it is 1.6 mm or less.

  The solid golf ball may be in compliance with golf regulations for competition purposes, and may be formed with a diameter of 42.67 mm or more and a weight of 45.93 g or less. The upper limit of the diameter is usually 44.0 mm or less, preferably 43.5 mm or less, more preferably 43.0 mm or less. Moreover, as a minimum of a weight, it is 44.5g or more normally, Preferably it is 45.0g or more, More preferably, it is 45.1g or more, More preferably, it is 45.2g or more.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[ Example 1 and Example 2, Reference Examples I to IV, Comparative Example 1 ]
After preparing a toluene suspension of a co-crosslinking agent with the formulation (parts by mass) shown in Table 1, butadiene rubber was added and homogenized. Thereafter, toluene was removed by warm air and vacuum drying to obtain rubber-coated zinc acrylate (compositions A to D, F, G).
Next, BR (a butadiene rubber manufactured by JSR Co., Ltd., trade name BR01) as a base rubber with the composition shown in Table 2, any of the compositions A to D, F, G, or zinc acrylate, and a filler Zinc oxide and dicumyl peroxide (an organic peroxide manufactured by Nippon Oil & Fats Co., Ltd., trade name Park Mill D) are kneaded at 50 to 90 ° C. using a kneader (manufactured by Moriyama Seisakusho), and then Then, a core (outer diameter: 39.2 mm) for a two-piece golf ball was prepared by vulcanization in a mold at 160 ° C. for 15 minutes.
The degree of adhesion of zinc acrylate to the kneader at the time of kneading, the scattering state of the zinc acrylate powder, the deformation deformation of the obtained core under 100 kg (980 N) load, and the initial velocity of the core were evaluated according to the following criteria. The results are shown in Table 2.

ＢＲ／トルエン１Ｌ
トルエン１Ｌに対し、何ｇのブタジエンゴムが配合されているかを換算したもの。
作業性
ＢＲの溶解時間と均一化までの攪拌時間の観点から下記基準にて評価した。
良 ：溶解、攪拌が３時間未満。
可 ：溶解、攪拌が３時間以上６時間未満。
不可：溶解、攪拌が６時間以上及び／又は粘度が大きすぎて攪拌困難。

BR / Toluene 1L
Conversion of how many grams of butadiene rubber is blended with 1 liter of toluene.
From the viewpoint of dissolution time of workability BR and stirring time until homogenization, the following criteria were used for evaluation.
Good: Dissolution and stirring are less than 3 hours.
Possible: Dissolution and stirring are 3 hours or more and less than 6 hours.
Impossible: dissolution and stirring are 6 hours or more and / or viscosity is too large and stirring is difficult

ニーダー付着
混練終了時にローター及び内壁を観察し、それらへの付着量を目視にて観察した。
粉体飛散
混練時におけるニーダーのラムの上下時に、粉体の吹上を観察した。
コア硬度（ｍｍ）
１００ｋｇ荷重負荷時のコアのたわみ変形量。数値が大きいほど柔らかいことを示す。
コア硬度のσ
Ｎ＝１２でコア硬度を測定した場合の、測定値のσ（標準偏差）。
コア初速（ｍ／ｓ）
Ｒ＆Ａの承認する装置であるＵＳＧＡのドラム回転式の初速計と同方式の初速測定機を用いて測定した。ボールは２３±１℃条件下で３時間以上温調され、室温として２３±１℃条件下でテストされた。２５０ポンド（１１３．４ｋｇ）のストライキングマスを使って打撃速度１４３．８ｆｔ／ｓ（４３．８３ｍ／ｓ）にてボールを打撃した。１ダースのボールを各々４回打撃して６．２８ｆｔ（１．９１ｍ）の間を通過する時間を計測し、初速を計算した。約１５分間でこのサイクルを行なった。
コア初速のσ
Ｎ＝１２でコア初速を測定した場合の、測定値のσ（標準偏差）。

At the end of kneader adhesion kneading, the rotor and inner wall were observed, and the amount of adhesion to them was visually observed.
The powder was observed to be blown up and down the kneader ram during the powder scattering kneading.
Core hardness (mm)
Deflection amount of the core when 100kg load is applied. A larger value indicates softer.
Σ of core hardness
Σ (standard deviation) of the measured value when the core hardness is measured at N = 12.
Core initial speed (m / s)
The measurement was performed using an initial speed measuring machine of the same type as the USGA drum rotation type initial speed meter approved by R & A. The balls were tempered for more than 3 hours under 23 ± 1 ° C. conditions and tested at 23 ± 1 ° C. as room temperature. The ball was hit at a hitting speed of 143.8 ft / s (43.83 m / s) using a 250 pound (113.4 kg) striking mass. One dozen balls were hit four times, and the time required to pass between 6.28 ft (1.91 m) was measured, and the initial speed was calculated. This cycle was performed in about 15 minutes.
Core initial speed σ
Σ (standard deviation) of the measured value when the initial core speed is measured at N = 12.

In Example 1 and Example 2 , the loss of zinc acrylate was less than that of Comparative Example 1, and the hardness and initial speed of the obtained core were also better than those of Comparative Example 1. Further, the cores of Example 1 and Example 2 have uniform characteristics (hardness and initial speed. N = 12, σ (standard deviation) of core hardness = 0.04 to 0.06, σ (standard deviation) of core initial speed = 0.08 to 0.11), but the core of Comparative Example 1 has variations (hardness and initial speed. N = 12, σ of core hardness (standard deviation) = 0.10, σ of core initial speed (standard deviation) ) = 0.18).
When the rubber composition after kneading was visually observed, in the case of the rubber composition of Comparative Example 1, a poorly dispersed lump was observed. On the other hand, in the case of the rubber compositions of Example 1 and Example 2, the rubber composition after kneading was uniform and no poorly dispersed lump was observed.

Claims (5)

Each component of the following (A)-(D),
(A) base rubber,
(B) a filler,
(C) an organic peroxide,
(D) a co-crosslinking agent coated with a coating rubber;
And a mass ratio of the co-crosslinking agent and the coating rubber in the component (D) is (co-crosslinking agent) / (coating rubber) = 100. / 1-100 / 9 (mass ratio), and the co-crosslinking agent is a mixture of a metal salt of an unsaturated carboxylic acid and a metal salt of a higher fatty acid, and the mixing ratio is (unsaturated carboxylic acid). (Acid metal salt) / (metal salt of higher fatty acid) = 90 / 10-80 / 20 (mass ratio), and the step of coating the co-crosslinking agent with the coating rubber,
(I) a step of preparing a liquid in which the co-crosslinking agent is suspended in the solvent and the coating rubber is dissolved;
(II) a solvent removal step of removing the solvent from the liquid prepared by the above step, and a step of mixing the component (D) and the components (A) to (C) after the rubber coating step. A method for producing a rubber composition for a solid golf ball. Method for producing a non-metal salts of saturated carboxylic acids, rubber composition for a solid golf ball according to claim 1 wherein the zinc acrylate and / or zinc methacrylate. Method for producing a metal salt of a higher fatty acid, according to claim 1 or 2 rubber composition for a solid golf ball wherein the zinc stearate and / or zinc palmitate. The rubber composition for a solid golf ball according to any one of claims 1 to 3 , wherein the covering rubber is one or more selected from the group consisting of butadiene rubber, isoprene rubber, and natural rubber. Manufacturing method. The rubber composition for a solid golf ball according to any one of claims 1 to 4 , wherein the component (A) is a butadiene rubber having a cis-1,4-bond ratio in a molecule of 40% or more. Manufacturing method.