JP2005111256A - Golf ball and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To offer a golf ball which is excellent in balance of restitution, durability, and a feeling of hitting a ball and a manufacturing method thereof. <P>SOLUTION: In the golf ball equipped with a core and a cover of one or more layers which coats the core, at least one layer constituting the cover is formed of a cover material composition in which fullerene and/or a carbon nanotube (B) are uniformly dispersed in a thermoplastic resin (A). In the manufacturing method of the golf ball equipped with the core and the cover of one or more layers which coats the core, the process of forming at least one layer constituting the cover of the cover material composition with forming at least one layer constituting the cover of the cover composition including the constituent (A) and the constituent (B) includes a uniform dispersion process for uniformly dispersing the constituent (B) in the constituent (A). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a golf ball excellent in resilience, durability, and feel at impact, and a method for manufacturing the same.

  Conventionally, for the purpose of imparting excellent resilience to golf balls, various improvements have been made in the composition of golf ball materials, but the characteristics required of golf balls are not limited to excellent resilience. The important point is how to satisfy these multiple characteristics at a high level in various ways, such as soft feel and excellent durability.

For example, Patent Document 1: Japanese Patent Application Laid-Open No. 2002-253703 discloses a rubber material that forms a golf ball core (cis) for the purpose of obtaining a golf ball having excellent resilience performance and good shot feel. A technique of blending fullerene or a derivative thereof into a polybutadiene rubber having a 1,4-bond of 40% or more) is disclosed.
However, since fullerene or a derivative thereof has a special molecular shape, it is often difficult to uniformly and finely disperse it in a medium as compared with commonly used additives.
If the additive is not finely dispersed uniformly in the golf ball material, the golf ball's continuous impact durability may be reduced. There has been a demand for means for finely dispersing the fullerene or a derivative thereof in a golf ball material.

JP 2002-253703 A

  The present invention has been made in view of the above circumstances, and by fully dispersing fullerenes and / or carbon nanotubes in a golf ball material, the balance of excellent resilience, excellent durability, and good feel at impact is achieved. An object is to provide an excellent golf ball and a method for producing the same.

  As a result of intensive studies to achieve the above object, the present inventor can uniformly disperse fullerenes and / or carbon nanotubes in a thermoplastic resin as a golf ball material by adopting a specific blending method. I found it possible. In addition, by using a golf ball material composition in which fullerenes and / or carbon nanotubes are uniformly dispersed in a golf ball cover, a golf ball having an excellent balance of excellent resilience, excellent durability, and a good shot feeling can be obtained. It was found that it was obtained, and the present invention was made.

That is, the present invention provides the following golf balls and methods for producing the same.
Claim 1:
In a golf ball having a core and a cover of one or more layers covering the core, at least one layer constituting the cover is (A) a thermoplastic resin and (B) fullerene and / or carbon nanotubes are uniform A golf ball comprising a cover material composition dispersed in a golf ball.
Claim 2:
In a golf ball manufacturing method including a core and a cover of one or more layers covering the core, at least one layer constituting the cover is (A) a thermoplastic resin and (B) fullerene and / or carbon nanotube. And the step of forming at least one layer constituting the cover with the cover material composition uniformly includes the component (B) in the component (A). A method for producing a golf ball comprising a uniform dispersion step of dispersing.
Claim 3:
The golf ball manufacturing method according to claim 2, wherein the uniform dispersion step includes a step of dissolving or suspending the component (B) in an organic solvent and mixing the component with the component (A), and then volatilizing the solvent. Method.
Claim 4:
The golf ball according to claim 3, wherein the step of dissolving or suspending the component (B) in an organic solvent and mixing the component with the component (A) is performed in a state where the component (A) is melted. Production method.
Claim 5:
The uniform dispersion step includes a step of mixing the component (B) and a polar polymer having an aromatic functional group to produce a masterbatch, and then a step of mixing the masterbatch with the component (A). A method for manufacturing a golf ball according to claim 2.
Claim 6:
The method for producing a golf ball according to claim 5, wherein the step of mixing the master batch with the component (A) is a step performed in a state where the component (A) is melted.
Claim 7:
A step of forming at least one layer constituting the cover with a cover material composition in which (B) fullerene and / or carbon nanotubes are uniformly dispersed in the thermoplastic resin (A) is obtained through the uniform dispersion step. The method for manufacturing a golf ball according to claim 2, comprising a step of injection molding the cover material composition.

  The golf ball of the present invention is a golf ball excellent in balance of excellent resilience, excellent durability, and good shot feeling, and the golf ball manufacturing method of the present invention is preferably used for manufacturing the golf ball. It is done.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail.
The golf ball of the present invention is a golf ball comprising a core and a cover of one or more layers covering the core. At least one layer constituting the cover is composed of (A) a thermoplastic resin and (B) fullerene. And / or a golf ball comprising a cover material composition in which carbon nanotubes are uniformly dispersed. Here, in the present invention, “uniform” means that when the component (B) is blended with the component (A), the component (B) is 0.7 mm or less, preferably 0.45 mm or less. It means that it is dispersed in the component (A) by diameter, more preferably, the component (B) is dissolved in the component (A). When a press cake having a diameter of about 180 mm is produced by pressure molding with respect to the mixture of the component A) and the component (B), if the component (B) having a particle size larger than 0.7 mm is not visually confirmed, “uniform” Is determined.

  The (A) thermoplastic resin in the present invention includes (a) ionomer resin, (b) thermoplastic polyurethane, (c) thermoplastic polyester elastomer, and (d) thermoplastic block from the viewpoint of resilience and durability. Any resin or combination of copolymers is preferably used.

  Examples of the (a) ionomer resin include (a-1) an olefin-unsaturated carboxylic acid random copolymer, (a-2) a metal ion neutralized product of an olefin-unsaturated carboxylic acid random copolymer, (a- 3) an olefin-unsaturated carboxylic acid-unsaturated carboxylic acid ester random copolymer, and (a-4) a metal ion neutralized product of an olefin-unsaturated carboxylic acid-unsaturated carboxylic acid ester random copolymer. 1 type (s) or 2 or more types selected from the group are used. Here, the (a) ionomer resin in the present invention always contains at least either the component (a-2) or the component (a-4).

  As the olefin contained in each of the components (a-1) to (a-4), an α-olefin is preferably used. As the α-olefin, those having usually 2 or more carbon atoms and an upper limit of 8 or less, particularly 6 or less are preferable, and more specifically, ethylene, propylene, butene, pentene, hexene, heptene, octene and the like can be mentioned. In particular, ethylene is preferable. These olefins can also be used in combination.

  As the unsaturated carboxylic acid contained in each of the components (a-1) to (a-4), an α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms is preferably used. More specifically, acrylic acid, methacrylic acid, maleic acid, fumaric acid and the like can be mentioned, and acrylic acid and methacrylic acid are particularly preferable. These unsaturated carboxylic acids can also be used in combination.

It is recommended that the components (a-1) to (a-4) have an adjusted content (acid content) of unsaturated carboxylic acid.
The content of the unsaturated carboxylic acid contained in the component (a-1) or the component (a-2) is usually 4% by mass or more, preferably 6% by mass or more, more preferably 8% by mass or more, and further preferably 10%. The upper limit is usually 30% by mass or less, preferably 20% by mass or less, more preferably 18% by mass or less, and still more preferably 15% by mass or less. If the unsaturated carboxylic acid content is too small, the rigidity and resilience may be reduced, and the flying performance of the golf ball may be reduced. On the other hand, when there is too much unsaturated carboxylic acid content, a softness | flexibility may become inadequate.
Moreover, as content of unsaturated carboxylic acid contained in (a-3) component or (a-4) component, it is 4 mass% or more normally, Preferably it is 6 mass% or more, More preferably, it is 8 mass% or more, As an upper limit Usually, it is 15 mass% or less, Preferably it is 12 mass% or less, More preferably, it is 10 mass% or less. If the unsaturated carboxylic acid content is too low, the resilience may be reduced, and if the unsaturated carboxylic acid content is too high, the processability may be reduced.

  Furthermore, as the unsaturated carboxylic acid ester contained in each component of (a-3) and (a-4), the above-mentioned lower alkyl ester of unsaturated carboxylic acid is suitable. For example, the unsaturated carboxylic acid is methanol. , Ethanol, propanol, n-butanol, isobutanol, and other lower alcohols. Particularly preferred are acrylic acid esters and methacrylic acid esters. More specifically, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and the like can be mentioned. Particularly, butyl acrylate (n -Butyl acrylate, i-butyl acrylate) is preferable. These unsaturated carboxylic acid esters can be used in combination.

  The component (a-1) and the component (a-3) (hereinafter, the component (a-1) and the component (a-3) may be simply abbreviated as “random copolymer”). Can be obtained by blending the above-mentioned materials as desired and random copolymerizing them by a known method.

Moreover, said (a-2) component and (a-4) component (henceforth (a-2) component and (a-4) component are named generically, and only "the metal ion neutralized product of a random copolymer"). Can be abbreviated to be obtained by neutralizing an acid group in the random copolymer with a metal ion.
Here, examples of metal ions that neutralize acid groups include Na ⁺ , K ⁺ , Li ⁺ , Zn ⁺⁺ , Cu ⁺⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Co ⁺⁺ , Ni ⁺⁺ , and Pb. ^{++ and the} like can be mentioned, among which Li ⁺ , Na ⁺ , Mg ⁺⁺ , Ca ⁺⁺ , and Zn ⁺⁺ can be preferably used. In the neutralization, for example, compounds such as formate, acetate, nitrate, carbonate, bicarbonate, oxide, hydroxide and alkoxide of the above metal ions can be used.

  In the metal ion neutralized product of the random copolymer, the neutralization amount of the carboxylic acid is from the viewpoint of facilitating molding at the time of resin mixing and from the viewpoint of not impairing the resilience of the cover. The amount of the carboxylic acid group contained in the coalescence is usually 10 mol% or more, preferably 20 mol% or more, particularly 30 mol% or more, and the upper limit is usually 80 mol% or less, preferably 70 mol% or less.

The thermoplastic polyurethane (b) in the present invention is preferably composed of a polymer polyol compound constituting a soft segment, a monomolecular chain extender constituting a hard segment, and a diisocyanate.
The polymer polyol compound is not particularly limited, and examples thereof include polyester polyols, polyol polyols, polyether polyols, copolyester polyols, and polycarbonate polyols.

Examples of the polyester polyol include polycaprolactone glycol, poly (ethylene-1,4-adipate) glycol, and poly (butylene-1,4-adipate) glycol. Examples of the copolyester polyol include poly (diethylene glycol adipate) glycol. Examples of the polycarbonate polyol include poly (hexanediol-1,6-carbonate) glycol, and examples of the polyether polyol include polyoxytetramethylene glycol, but are not limited thereto. is not.
Moreover, as a number average molecular weight of these high molecular polyol compounds, it is 600-5000 normally, Preferably it is 1000-3000.

  As the diisocyanate, an aliphatic or aromatic diisocyanate usually used when polyurethane is used as a golf ball cover material is preferably used. Specifically, hexamethylene diisocyanate (HDI), 2,2,4 (2,4,4) -trimethylhexamethylene diisocyanate (TMDI), lysine diisocyanate (LDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) In particular, aromatic diisocyanate is preferably used from the viewpoint of compatibility with the component (B), and diphenylmethane diisocyanate (MDI) is preferably used from the viewpoint of compatibility when blended with other resins. Preferably used.

  The monomolecular chain extender is not particularly limited, and usual polyhydric alcohols and amines can be used. Specifically, 1,4-butylene glycol, 1,2-ethylene glycol can be used. 1,3-propylene glycol, 1,6-hexyl glycol, 1,3-butylene glycol, dicyclohexylmethylmethanediamine (hydrogenated MDI), isophoronediamine (IPDA), and the like.

The hardness of the (b) thermoplastic polyurethane is usually 70 to 100, preferably 80 to 98, more preferably 90 to 99, and still more preferably 95 to 98, as JIS-A hardness measured according to JIS K 6301. It is. If the JIS-A hardness is less than 70, the spin amount may increase excessively when hit by a driver, and the flight distance may decrease.
Moreover, as specific gravity of the said (b) thermoplastic polyurethane, it is 1.0-1.3 (g / cm < ³ >) normally, More preferably, it is 1.1-1.25 (g / cm < ³ >).

  As such a (b) thermoplastic polyurethane, a commercial item can be used, for example, Pandex T-R8175, T8190, T8160D (made by DIC Bayer Polymer Co., Ltd.) etc. can be used conveniently.

  The thermoplastic polyester elastomer (c) in the present invention is not particularly limited as long as it is a polyester-based thermoplastic elastomer, but a high-melting-point crystalline polymer segment (hard segment) comprising a crystalline aromatic polyester unit. ) And a low-melting polymer segment (soft segment) composed of an aliphatic polyether unit and / or an aliphatic polyester unit, a polyester-based block copolymer is preferably used.

  Here, as the high melting crystalline polymer segment composed of crystalline aromatic polyester units, preferably polybutylene terephthalate derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol is used. In addition, for example, orthophthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5 A dicarboxylic acid component such as sulfoisophthalic acid or an ester-forming derivative thereof and a diol having a molecular weight of 300 or less, such as ethylene glycol, trimethylene glycol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, neopentyl Aliphatic diols such as recall and decamethylene glycol, aliphatic cyclic diols such as 1,4-cyclohexanedimethanol and tricyclodecane dimethylol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) ) Propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] Examples include, but are not limited to, polyesters derived from aromatic diols such as cyclohexane, 4,4′-dihydroxy-p-terphenyl, and 4,4′-dihydroxy-p-quarterphenyl. Moreover, the copolyester which used 2 or more types of these dicarboxylic acid components and diol components together may be sufficient. Furthermore, a tri- or higher functional polycarboxylic acid component, a polyfunctional oxy component, a polyfunctional hydroxy component, and the like can be copolymerized within a range of 5 mol% or less.

In the low melting point polymer segment component comprising an aliphatic polyether unit and / or an aliphatic polyester unit, examples of the aliphatic polyether include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, and poly (tetramethylene). Oxide) glycol, poly (hexamethylene oxide) glycol, a copolymer of ethylene oxide and propylene oxide, an ethylene oxide addition polymer of poly (propylene oxide) glycol, a copolymer of ethylene oxide and tetrahydrofuran, and the like. Examples of the aliphatic polyester include poly (ε-caprolactone), polyenantlactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate. Among these, from the viewpoint of the elastic properties of the resulting polyester block copolymer, poly (tetramethylene oxide) glycol, poly (propylene oxide) glycol ethylene oxide addition polymer, poly (ε-caprolactone), polybutylene adipate, polyethylene adipate, etc. In particular, poly (tetramethylene oxide) glycol is preferred.
The number average molecular weight of such a low melting point polymer segment component is preferably about 300 to 6000 in the copolymerized state. In the present invention, the number average molecular weight means a number average molecular weight calculated in terms of polystyrene by the GPC method.

As the thermoplastic polyester elastomer (c), a thermoplastic polyester elastomer mainly composed of a high-melting crystalline polymer segment and a low-melting polymer segment comprising an aliphatic polyether unit and / or an aliphatic polyester unit is used. When used, the composition ratio of the high-melting crystalline polymer segment and the low-melting polymer segment [(high-melting crystalline polymer segment) / (low-melting polymer segment)] is usually 85/15 to 10/90 ( (Mass ratio), preferably 85/15 to 50/50 (mass ratio). If the proportion of the low melting point polymer segment component is too large, sufficient melting characteristics suitable for injection molding cannot be obtained, and it may be difficult to mix uniformly during melt blending. If the amount is too small, sufficient flexibility and resilience may not be obtained.
Further, the ratio of the total amount of the high-melting crystalline polymer segment and the low-melting polymer segment in the thermoplastic polyester elastomer is usually 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more.

The method for obtaining the thermoplastic polyester elastomer (c) is not particularly limited and can be produced by a known method. For example, the following methods (i) to (v) can be exemplified, and any method can be used. Can also be suitably employed.
(I) A method of subjecting a lower alcohol diester of a dicarboxylic acid, an excess amount of a low molecular weight glycol, and a low melting point polymer segment component to a transesterification reaction in the presence of a catalyst and polycondensing the resulting reaction product.
(Ii) A method of subjecting a dicarboxylic acid, an excessive amount of glycol and a low melting point polymer segment component to an esterification reaction in the presence of a catalyst, and polycondensing the resulting reaction product.
(Iii) A method in which a high-melting-point crystalline segment is prepared in advance and a low-melting-point segment component is added thereto and randomized by a transesterification reaction.
(Iv) A method of connecting a high melting crystalline segment and a low melting polymer segment with a chain linking agent.
(V) When poly (ε-caprolactone) is used in the low-melting polymer segment, a method in which an ε-caprolactone monomer is added to the high-melting crystalline segment.

  The hardness of the (c) thermoplastic polyester elastomer is not particularly limited, but from the viewpoint of improving the golf ball hit feeling, the hardness (Shore D hardness) measured according to ASTM D-2240 is usually 10 or more, Preferably, it is 20 or more, and the upper limit is usually 50 or less, preferably 40 or less. (C) The hardness of the thermoplastic polyester elastomer is preferably lower (soft) than the hardness of the (A) ionomer resin from the viewpoint of improving the golf ball hit feeling.

  The rebound resilience value measured according to BS standard 903 of the thermoplastic polyester elastomer (c) is not particularly limited, but is usually 40% or more, preferably 50% or more, and the upper limit is usually 90% or less. It is. (C) If the resilience modulus of the thermoplastic polyester elastomer is too small, resilience may be impaired, and the flying performance of the golf ball of the present invention may be reduced.

  Furthermore, the bending stiffness value measured according to JIS standard K-7106 of the thermoplastic polyester elastomer (c) is not particularly limited, but is usually 5 MPa or more, preferably 10 MPa or more, more preferably 15 MPa or more, The upper limit is usually as low as 250 MPa or less, preferably 200 MPa or less, more preferably 150 MPa or less. If the bending rigidity is too high, the feel and durability of the golf ball of the present invention may be deteriorated.

  The thermoplastic block copolymer (d) in the present invention includes a polyethylene crystal block (C) and / or a polystyrene crystal block (S) as a hard segment, and a block (B) composed of polybutadiene as a soft segment. From the group consisting of block (I) composed of isoprene, block (EB) composed of a relatively random copolymer structure of ethylene and butylene, and block (EP) composed of a relatively random copolymer structure of ethylene and propylene. What contains the 1 type (s) or 2 or more types selected is suitable. EB and / or EP are preferably used as the soft segment, and EB is preferably used among them.

  More specifically, the configuration of the thermoplastic block copolymer (d) is S-EB-S, S-B-S, S-I-S, S-EB, S-EB-S-EB, S -EP-S, S-EB-C, S-B-C, S-I-C, S-EP-C, C-EB-C, C-B-C, C-I-C, C-EB , C-EB-C-EB, C-EP-C and the like, but are not limited thereto. Among these, from the viewpoint of resilience, it is preferable to include a polyethylene crystal block (C) as a hard segment, and S-EP-C or C-EB-C is preferable as the above configuration.

When a C-EB-C type or S-EB-C type thermoplastic block copolymer is used as the thermoplastic block copolymer (d), the method for obtaining these copolymers is, for example, butadiene, or A method of hydrogenating a styrene-butadiene copolymer can be employed.
The polybutadiene or styrene-butadiene copolymer used as a target for such hydrogenation has a 1,4-polymer portion particularly having a 1,4-bond of 95% by mass or more as a bonding mode in the butadiene structure. In particular, polybutadiene having a 1,4-bond in the total amount of the butadiene structure of 50% by mass or more, more preferably 80% by mass or more is preferably used.
In this case, the amount of hydrogenation in the hydrogenated product (conversion rate of double bonds to saturated bonds in polybutadiene or styrene-butadiene copolymer) is preferably 60 to 100%, more preferably 90 to 100%. %. If the amount of hydrogen added is too small, deterioration such as gelation may occur in the blending process with an ionomer resin or the like, and problems may occur in the weather resistance and impact resistance of the cover when a golf ball is formed. .

  The content of the hard segment in the (d) thermoplastic block copolymer is preferably 10 to 50% by mass. If the amount of the hard segment is too large, the object of the present invention may not be effectively achieved due to lack of flexibility, and if the amount of the hard segment is too small, a problem may occur in the formability of the blend.

  The number average molecular weight of the thermoplastic block copolymer (d) is preferably 30,000 to 800,000. Furthermore, (d) The melt index value at 230 ° C. of the thermoplastic block copolymer (measured in accordance with JIS K 6760 with a test load of 21.2 N (2.16 kgf)) is usually 0.5 to 15 g / 10 min. More preferably, it is 1-7 g / 10min. If it is out of the above range, problems such as weld, sink, and short circuit may occur during injection molding.

  In addition, as said (d) thermoplastic block copolymer, it is preferable that it does not have a functional group which can react with ionomer resin from a viewpoint of implement | achieving moderate melt viscosity of a mixture.

In the above-mentioned (B) fullerene and / or carbon nanotube used in the present invention, as fullerene, for example, fullerene such as C ₆₀ , C ₇₀ , C ₇₄ , C ₇₆ , C ₇₈ , C ₈₀ , C _84, or halogen is introduced. And fullerene derivatives such as C ₆₀ F ₄₈ , C ₆₀ Cl ₂₄ , C ₆₀ Br ₂₄ , C ₆₀ (OH) ₂₄ having a hydroxyl group introduced, and hydrogenated C ₆₀ H ₂₄ . These may be used alone or in combination of two or more.
As such fullerenes, commercially available products can be used. For example, C60 manufactured by Frontier Carbon, mixed fullerene, hydroxylated fullerene, hydrogenated fullerene, porous fullerene, frontier black, and fullerene C ₆₀ manufactured by Tokyo Chemical Industry Co., Ltd. , C ₇₀ , fullerene C ₈₄ manufactured by Strem Chemicals, Inc., fullerene powder, hydrogenated, C ₆₀ (OH) _n (n20−28) manufactured by Johnson Matthey Company. Etc.
Moreover, a commercial item can also be used as said (B) carbon nanotube, and a single-walled carbon nanotube, a multi-walled carbon nanotube, etc. by Aldrich are mentioned.

The method for producing a golf ball of the present invention is the method for producing a golf ball comprising a core and a cover of one or more layers covering the core, wherein at least one layer constituting the cover is (A) a thermoplastic resin. And (B) a process of forming at least one layer constituting the cover with the cover material composition, the process comprising forming the cover material composition comprising fullerene and / or carbon nanotubes, A method for producing a golf ball comprising the step of uniformly dispersing in the component (A). From the viewpoint of improving dispersibility, the uniform dispersion step includes a step of dissolving or suspending the component (B) in an organic solvent and mixing the component with the component (A), and then a step of volatilizing the solvent. Is preferred.
Here, in the present invention, “dissolved or suspended in an organic solvent” means that the component (B) is dissolved in the organic solvent to form a uniform solution, or fine particles of the component (B) are dissolved in the organic solvent. This means a state where a suspension in which particles are dispersed is prepared, and as a determination method thereof, the above-mentioned organic solvent is mixed with the component (B), and after 30 minutes, the presence or absence of particle sedimentation is visually confirmed. If no sedimentation of particles occurs, it is determined that the particles are “dissolved or suspended in an organic solvent”.

Examples of the organic solvent used in the step of dissolving or suspending the component (B) in the organic solvent and mixing the component with the component (A) include, for example, methylnaphthalene, dimethylnaphthalene, phenylnaphthalene, chloronaphthalene, bromomethylnaphthalene, and the like. Naphthalene-based organic solvents: benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, xylene, trimethylbenzene, tetramethylbenzene, tetralin, dibromobenzene, anisole, chlorobenzene, dichlorobenzene, trichlorobenzene, and other benzene-based organic solvents; decalin, etc. Alkane-based organic solvents, haloalkane-based solvents such as tetrachloroethane; polar solvents such as carbon disulfide, methylthiophene, and methylpyrrolidone, and aromatic organic solvents are particularly preferable. Among them, toluene, xylene is preferably used.
Here, the concentration of the component (B) in the organic solvent is usually 0.1 mg / ml or more, preferably 1 mg / ml or more, more preferably 2 mg / ml or more, and the upper limit is usually 100 mg / ml or less, preferably 80 mg. / Ml or less, more preferably 50 mg / ml or less. When the concentration of the component (B) in the organic solvent is less than 0.1 mg / ml, workability may be reduced, whereas when it exceeds 100 mg / ml, dispersibility may be reduced.

The step of dissolving or suspending the component (B) in an organic solvent and mixing with the component (A) is a step performed in a state where the component (A) is melted from the viewpoint of improving dispersibility. Is preferred.
In the mixing step performed in such a state that the component (A) is melted, a mixer such as a twin screw extruder, a single screw extruder, a kneader, a Banbury mixer, etc., among which a twin screw extruder is preferably used. The above solution can be mixed with the component (A) in the molten state.
Setting temperature of the mixer when mixing the component (A) and the component (B) using a mixer such as a kneader or Banbury mixer, or using a twin screw extruder or a single screw extruder ( In the case of mixing the component (A) and the component (B), a twin-screw extruder or a single-screw extruder for adding the component (B) in the solution or suspension to the molten component (A) The set temperature is usually 150 ° C. or lower, preferably 120 ° C. or lower. A person skilled in the art thinks that mixing the component (B) at a high temperature with the component (B) dissolved or suspended in an organic solvent at a high temperature is not usually dangerous. By setting the temperature appropriately, both can be mixed relatively safely.

Here, the blending amount of the component (B) with respect to 100 parts by weight of the component (A) (net blending amount of the component (B)) is usually 0.01 parts by weight or more, preferably 0.05 parts by weight or more. The upper limit is usually 5 parts by mass or less, preferably 1 part by mass or less. If the net blending amount of the component (B) with respect to 100 parts by mass of the component (A) is less than 0.01 parts by mass, the effect of improving the physical properties may not appear, whereas if it exceeds 5 parts by mass, Dispersibility may decrease, and durability may decrease instead.
As a method of volatilizing the solvent after dissolving or suspending the component (B) in an organic solvent and mixing with the component (A), the solvent may be volatilized by heating at normal pressure. A vent port may be installed in a mixer such as a shaft extruder to perform vacuum degassing.

As the uniform dispersion step, from the viewpoint of compatibility with the component (B), a step of mixing the component (B) and a polar polymer having an aromatic functional group to prepare a master batch, and then the master And a step of mixing the batch with the component (A).
Examples of the polar polymer used in the step of preparing a masterbatch by mixing the component (B) and a polar polymer having an aromatic functional group include styrene polymers such as polystyrene and styrene elastomer or elastomers thereof; Aromatic polyesters such as polyester elastomers or their elastomers; Aromatic polyurethanes such as aromatic polyurethane elastomers or their elastomers; Aromatic polyamide elastomers such as polyetheresteramides, among others, styrenic elastomers, aromatic polyester elastomers, aromatics A group polyurethane elastomer is preferably used, more preferably a styrenic elastomer, and still more preferably a good compatibility with the component (A), and the terminal is modified by a modifying group such as an amino group. Styrenic elastomers are preferred.
Here, the blending ratio of the component (B) to the polar polymer is usually 1/99 to 99/1 as the value of ((B) component) / (polar polymer) (mass ratio), preferably 5 / 95-15 / 85.

After mixing the said (B) component and the polar polymer which has an aromatic functional group, producing a masterbatch, as a process mixed with the said (A) component, from a viewpoint of a dispersibility improvement, said (A) component It is preferable that the step is performed in a molten state.
In the mixing step performed in a state where the component (A) is melted, a mixer such as a twin screw extruder, a kneader, or a Banbury mixer, in particular, a twin screw extruder or a single screw extruder is used. Can be preferably used.
In addition, when using a twin-screw extruder or a single-screw extruder in this invention, in order to remove the said (B) component with a large particle size, the by-product, the impurity, etc. which were generated at the time of the said (B) component manufacture In addition, it is preferable to install a screen mesh in the extruder. As such a screen mesh, it is suitable to use a screen mesh of 90 mesh or more, preferably 120 mesh or more.

  Here, the blending amount of the component (B) with respect to 100 parts by weight of the component (A) (net blending amount of the component (B)) is usually 0.01 parts by weight or more, preferably 0.05 parts by weight or more. The upper limit is usually 5 parts by mass or less, preferably 1 part by mass or less. When the blending amount of the component (B) with respect to 100 parts by weight of the component (A) (net blending amount of the component (B)) is less than 0.01 parts by weight, the effect of improving physical properties may not appear. On the other hand, if it exceeds 5 parts by mass, the dispersibility may be lowered and the durability may be lowered instead.

The cover material composition according to the present invention may further include various additives such as pigments, dispersants, antioxidants, ultraviolet absorbers, light stabilizers, and the like as long as the object of the present invention is not impaired. An inorganic filler or the like can also be added.
The compounding amount of these additives is not particularly limited, but is usually 0.1 to 50 parts by mass, preferably 0. 0 to 100 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It is 5-30 mass parts, More preferably, it is 1-6 mass parts. If the compounding amount of the additive is too large, the uniform dispersion state of the component (B) may not be realized and the durability may be lowered. If the compounding amount of the additive is too small, the effect of the additive is obtained. There may not be.

In the golf ball manufacturing method of the present invention, the step of forming at least one layer constituting the cover with the cover material composition containing the (A) thermoplastic resin and (B) fullerene and / or carbon nanotubes, There is no particular limitation as long as it includes a uniform dispersion step in which the component (B) is uniformly dispersed in the component (A), and the cover material composition obtained through the uniform dispersion step as described above is used in advance. A method of molding a pair of hemispherical half cups and wrapping a core covered with a core or a cover with the half cups and press-molding may be adopted, or the component (A) and the component (B) May be simply dry blended to perform injection molding (in this case, the injection molding process includes a uniform dispersion process), but from the viewpoint of further improving dispersibility, the preferred uniform dispersion process described above. And more preferably includes the step of injection molding using a cover material composition obtained through.
In the case of performing such injection molding, the component (A) and the component (B) dissolved or suspended in an organic solvent or the component (B) mixed with a polar polymer are previously added to an injection molding machine. After mixing, it may be charged into an injection molding machine, or both may be charged simultaneously through separate inlets or the same inlet without being mixed in advance. By performing such injection molding, a reduction in manufacturing cost and a good dispersion state of the component (B) to the component (A) are achieved at the same time, which is preferable.

  The cover material composition according to the present invention preferably has a fluidity particularly suitable for injection molding and preferably has a melt index adjusted from the viewpoint of improving moldability. In this case, the test temperature 190 is in accordance with JIS K 6760. The melt index (MI) when measured at 0 ° C. and a test load of 21.2 N (2.16 kgf) is usually 0.5 dg / min or more, preferably 1 dg / min or more, more preferably 1.5 dg / min or more, More preferably, it is 2 dg / min or more, and the upper limit is usually 20 dg / min or less, preferably 10 dg / min or less, more preferably 5 dg / min or less, and further preferably 3 dg / min or less. . If the melt index is too large or too small, the workability may be significantly reduced.

  The core in the present invention may be either a wound core or a solid core, and can be produced according to a conventional method. When obtaining a solid core, for example, with respect to 100 parts by mass of cis-1,4-polybutadiene, α, β-monoethylenically unsaturated carboxylic acid such as acrylic acid or methacrylic acid or a metal ion neutralized product thereof, trimethylol Filling 10 parts by weight or more and 60 parts by weight or less of zinc oxide, barium sulfate, etc., alone or in combination of two or more selected from vulcanizing agents (crosslinking agents) such as functional monomers such as propane methacrylate 5 parts by mass or more and 30 parts by mass or less of an agent, 0.5 parts by mass or more and 5 parts by mass or less of a peroxide such as dicumyl peroxide, and 0.1 parts by mass or more and 1 part by mass of an anti-aging agent as necessary. After blending and press vulcanizing (crosslinking) the rubber composition, it can be formed into a spherical shape by heating and compressing at 140 to 170 ° C. for 10 to 40 minutes.

Such a core structure may be a single layer or a plurality of layers, but the core surface hardness in the present invention is usually 60 to 85, preferably JIS-C hardness measured according to JIS K 6301, preferably It is 65-83, More preferably, it is 67-80. If the core hardness is too high, the hit feeling may become too hard, or the spin may increase too much when W # 1 is hit. If each of the above hardnesses is too low, the hit feeling will be too soft or rebounded. In some cases, the distance becomes too low to obtain a sufficient flight distance, or the durability against cracking due to repeated impacts may deteriorate.
Further, the amount of deflection of the core under a load of 980 N (100 kg) is usually 2.0 mm or more, preferably 2.5 mm or more, more preferably 2.8 mm or more, still more preferably 3.2 mm or more, and the upper limit is usually It is 6.0 mm or less, preferably 5.5 mm or less, more preferably 5.0 mm or less, and still more preferably 4.5 mm or less. If the amount of deformation is too small, the feeling of hitting will worsen, and in particular, long shots that cause large deformation of the ball such as the driver may cause excessive spin and will not fly.If it is too soft, the feeling of hitting will become dull and rebound will occur. There is a case where it becomes insufficient and does not fly, and there is a case where durability against cracking due to repeated hitting is deteriorated.
The diameter of the core is usually 25 mm or more, preferably 36 mm or more, and the upper limit is usually 40 mm or less, preferably 39 mm or less, more preferably 38 mm or less.

The golf ball of the present invention is a golf ball obtained by covering at least one layer of cover formed of the cover material composition on the core as described above.
The cover layer formed of the cover material composition may be any part or all of the cover layer, and the golf ball of the present invention is a wound golf ball (a single layer or a multilayer having two or more layers). Any golf ball such as a two-piece solid golf ball, a three-piece solid golf ball, a multi-piece solid golf ball, and the like may be used.

The thickness of the cover layer formed from the cover material composition in the present invention is usually 0.5 mm or more, preferably 0.9 mm or more, more preferably 1.1 mm or more, and the upper limit is usually 3 mm or less, preferably 2 0.5 mm or less, more preferably 2.0 mm or less. If the cover thickness is too large, the resilience may decrease, and if the cover thickness is too small, the durability may decrease.
Further, in the golf ball of the present invention, a large number of dimples can be formed on the surface of the outermost layer cover, and various treatments such as ground treatment, stamping and painting can be performed on the cover.

The golf ball of the present invention may be in compliance with the golf regulations for competition purposes, and the diameter is usually 42.67 mm or more, preferably 43.00 mm or less, and the mass is usually 45.93 g or less, preferably 44.6 g. It can be formed as described above.
Further, the initial velocity of the golf ball of the present invention is usually 76.4 m / s or more, preferably 76.6 m / s or more, more preferably 76.8 m / s or more, and the upper limit is usually 77.7 m / s or less. Manufactured as follows. If the initial speed is too low, the flight distance may not be achieved. If the initial speed is too high, the golf ball is not within the standard of R & A (USGA).

[Examples and comparative examples]
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.

Create core
In the core formulation and vulcanization method shown in Table 1 below, 1 and no. 2 solid cores were created. Further, the deformation amount (mm) at 100 kg load was measured for the prepared solid core. Further, specific gravity, weight (g), and outer diameter (mm) were measured. The initial velocity (m / s) was measured according to the measurement method of USGA (R & A).

[Examples 1-3, 5]
Dynalon 4630P and fullerene were mixed at a weight ratio of 9: 1 and stirred using a lab plast mill at 120 ° C. for 5 minutes to prepare a fullerene master batch. For each example, a cover material mainly composed of an ionomer resin or a thermoplastic polyurethane elastomer weighed according to the composition shown in Table 2 below, a twin-screw extruder set at a maximum temperature of 200 ° C. (30 mmφ, L / D = 32) Was used and kneaded at a rate of 10 kg / h to obtain a cover material. Thereafter, the core No. in Table 1 arranged in the mold. 1 or core no. 2 was injection-molded with the above cover material to obtain a two-piece golf ball.
[Example 4]
For Example 4, a solution in which fullerene was dissolved in a toluene solvent at a concentration of 10 mg / ml was prepared. The cover material mainly composed of ionomer resin weighed according to the composition shown in Table 2 below is kneaded at a rate of 10 kg / h using a twin screw extruder (30 mmφ, L / D = 32) set at a maximum temperature of 200 ° C. To obtain a cover material.
In addition, said solution was added separately from the other raw material, and the preset temperature of the extruder of a solution addition site | part was set to 80 degreeC. Moreover, the solvent was evaporated and degassed under reduced pressure. Thereafter, the core No. in Table 1 arranged in the mold. 1 was injection molded to obtain a two-piece golf ball.

[Comparative Examples 1-6]
The cover material weighed according to the formulation shown in Table 2 below was kneaded at a rate of 10 kg / h using a twin screw extruder (30 mmφ, L / D = 32) set at a maximum temperature of 200 ° C. to obtain a cover material. . Thereafter, the core No. in Table 1 arranged in the mold. 1 or core no. The two-piece golf ball was obtained by injection molding the cover material into No. 2.

The performance of the obtained golf ball was examined as follows. The results are shown in Tables 2 and 3.
A uniform cover material is mixed and pressure-molded to produce a press cake with a diameter of 180 mm. If the (B) component and fullerene component larger than 0.7 mm are visually confirmed, it is determined that the material is not uniform and confirmed. If not, it was determined to be uniform.

Outer diameter and weight The outer diameter (mm) and weight (g) of the ball product were measured, respectively.
The amount of deformation (mm) at a load of 100 kg was measured for the hardness ball product. It shows that it is so soft that a numerical value is large.
Surface hardness The hardness was measured by ASTM D2240 or JIS K-7311 test method.
Initial velocity Initial velocity (m / s) was measured based on the measurement method of USGA (R & A).

Durability The ball was repeatedly fired toward the iron plate at an incident speed of 43 m / s, the number of hits until it was destroyed was examined, and the durability was evaluated according to the following criteria.
○ 100 times or more × less than 100 times

※フラーレン
Ｃ₆₀＝６０％，Ｃ₇₀＝２５％、その他の高次フラーレン
※ダイナロン４６３０Ｐ
スチレン系熱可塑性エラストマー
※ハイミラン１６０５
三井・デュポンポリケミカル社製、エチレン−メタクリル酸共重合体のナトリウムイオン中和物
※ハイミラン１７０６
三井・デュポンポリケミカル社製、エチレン−メタクリル酸共重合体の亜鉛イオン中和物

* Fullerene C ₆₀ = 60%, C ₇₀ = 25%, other higher-order fullerene * Dynalon 4630P
Styrenic thermoplastic elastomer * High Milan 1605
Made by Mitsui-DuPont Polychemical Co., Ltd., sodium ion neutralized product of ethylene-methacrylic acid copolymer * High Milan 1706
Neutralized zinc ion of ethylene-methacrylic acid copolymer manufactured by Mitsui DuPont Polychemical Co., Ltd.

※ＴＰＵ
ＭＤＩ−ＰＴＭＧタイプの熱可塑性ポリウレタンエラストマー

* TPU
MDI-PTMG type thermoplastic polyurethane elastomer

Claims (7)

  In a golf ball having a core and a cover of one or more layers covering the core, at least one layer constituting the cover is (A) a thermoplastic resin and (B) fullerene and / or carbon nanotubes are uniform A golf ball comprising a cover material composition dispersed in a golf ball.   In a golf ball manufacturing method including a core and a cover of one or more layers covering the core, at least one layer constituting the cover is (A) a thermoplastic resin and (B) fullerene and / or carbon nanotube. And the step of forming at least one layer constituting the cover with the cover material composition uniformly includes the component (B) in the component (A). A method for producing a golf ball comprising a uniform dispersion step of dispersing.   The golf ball manufacturing method according to claim 2, wherein the uniform dispersion step includes a step of dissolving or suspending the component (B) in an organic solvent and mixing the component with the component (A), and then volatilizing the solvent. Method.   The golf ball according to claim 3, wherein the step of dissolving or suspending the component (B) in an organic solvent and mixing the component with the component (A) is performed in a state where the component (A) is melted. Production method.   The uniform dispersion step includes a step of mixing the component (B) and a polar polymer having an aromatic functional group to produce a masterbatch, and then a step of mixing the masterbatch with the component (A). A method for manufacturing a golf ball according to claim 2.   The method for producing a golf ball according to claim 5, wherein the step of mixing the master batch with the component (A) is a step performed in a state where the component (A) is melted. A step of forming at least one layer constituting the cover with a cover material composition in which (B) fullerene and / or carbon nanotubes are uniformly dispersed in the thermoplastic resin (A) is obtained through the uniform dispersion step. The method for manufacturing a golf ball according to claim 2, comprising a step of injection molding the cover material composition.