CN102526998B - Golf ball - Google Patents
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- CN102526998B CN102526998B CN201110463020.9A CN201110463020A CN102526998B CN 102526998 B CN102526998 B CN 102526998B CN 201110463020 A CN201110463020 A CN 201110463020A CN 102526998 B CN102526998 B CN 102526998B
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Abstract
The invention aims to provide a golf ball having the largest flying distance. The golf ball comprises a ball-shaped core and at least one housing coating the ball-shaped core. The ball-shaped core is made from rubber composition having (a) base material rubber, (b) Alpha, Beta-unsaturated carboxylic acid having 3-8 carbon atoms served as co-crosslink agent and/or metallic salt thereof, (c) cross-linking initiator, (d) carboxylic acid having 1-13 carbon atoms. When (b) is Alpha, Beta-unsaturated carboxylic acid having 3-8 carbon atoms served as co-crosslink agent, the rubber composition further contains (e) metallic compound.
Description
Technical field
The present invention relates to the golf that a kind of batting flying distance of kicking off is large, in more detail, relate to a kind of improvement of golf ball.
Background technology
When kicking off to bat (driver shot) as prolongation, the method for golf ball flight distance, such as, have, and uses the method for high least ball, uses the method for the ball with the hardness distribution that hardness increases progressively to surface from the center of ball.The former is improved the effect of golf initial velocity, and the latter is improved and hits angle, reduces the effect rotated.Hit the golf of the high and low rotation of angle, its flying distance can increase.
As improving the least technology of ball, such as, there is patent document 1 ~ 6.A kind of solid golf ball with kernel is disclosed in patent document 1,2, described kernel, relative to rubber 100 weight portion, is mixed with as the zinc acrylate resin of co-crosslinker, palmitic acid, stearic acid or myristic acid as co-crosslinking auxiliary agent, the zinc oxide as co-crosslinking auxiliary agent, reaction speed retarding agent.
Patent Document 3 discloses a kind of solid golf ball obtained by rubber composition, described rubber composition is relative to substrate rubber 100 weight portion, α containing 15 ~ 35 weight portions, beta-unsaturated carboxylic acid, 7 ~ 60 weight portions with this α, beta-unsaturated carboxylic acid reaction forms the metallic compound of salt and the higher fatty acid metal salt of 1 ~ 10 weight portion.
Patent document 4 discloses a kind of golf, it is characterized in that, in substrate rubber, with packing material, organic peroxide, α, beta-unsaturated carboxylic acid and/or its slaine are essential component, wherein to mix the cross moulding thing of the rubber composition of saturated or unrighted acid mantoquita as part.
Patent document 5 discloses a kind of golf and constituent thereof, wherein, be shaped from the composition of at least one slaine containing the foundation elasticity body selected from polybutadiene and the group that forms with other elastomeric mixed with polybutadiene thing, unsaturated monocarboxylic, radical initiator and non-conjugated diene monomers.
Patent document 6 discloses a kind of manufacture method of golf, it is characterized in that, unsaturated carboxylic acid and/or its slaine is mixed in elastomeric material, make the masterbatch of unsaturated carboxylic acid and/or its slaine in advance, this masterbatch is utilized to make rubber composition containing described elastomeric material, be the manufacture method of golf ball using the heating molding of this rubber composition as golf part, described unsaturated carboxylic acid and/or its slaine masterbatch contain following (A) ~ (C).
(A) modified polybutadiene 20 ~ 100 quality %, its ethylene contents be 0 ~ 2% and the content of cis Isosorbide-5-Nitrae-combination account for more than 80%, and have reactive terminal, its reactive terminal is formed by least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure modification
(B) diene rubber 80 ~ 0 quality % outside above-mentioned (A) rubber constituent
[quality % when above-mentioned numeral is 100 with total metering of (A) and (B).]
(C) unsaturated carboxylic acid and/or its slaine
Such as, patent document 7 ~ 10 discloses a kind of ball with hardness distribution.Patent document 7 discloses a kind of two-piece golf ball, wherein, by containing substrate rubber, the ball of the rubber composition formation of co-crosslinker and organic peroxide, in the two-piece golf ball formed with shell, this ball represents in JIS-C type hardness tester, having core rigidities 1 is 58 ~ 73, hardness 2 apart from center 5 ~ 10mm is 65 ~ 75, hardness 3 apart from center 15mm is 74 ~ 82, case hardness 4 is the hardness distribution of 76 ~ 84, hardness 2 is roughly certain in hardness range, and, other meets the relation of 1 < 2 < 3≤4.
Patent document 8 discloses a kind of golf, wherein, possess solid ball and coated it outer shell solid golf ball in, described solid ball is formed by rubber composition, in this rubber composition, relative to containing 60 ~ 100 quality % containing more than 60% cis-1, 4-combines, rubber substrate 100 mass parts of the polybutadiene rubber utilizing rare earth element series catalysts to synthesize, organosulfur compound also containing 0.1 ~ 5 mass parts, unsaturated carboxylic acid or its slaine, inorganic fillers and age resister, simultaneously, the deflection when load of solid ball is from initial stage load 10kgf to final load 130kgf is 2.0 ~ 4.0mm, and, solid ball has hardness distribution as shown in the table.
[table 1]
Solid ball hardness distribution | Shore D hardness |
Center | 30~48 |
Apart from the part of center 4mm | 34~52 |
Apart from the part of center 8mm | 40~58 |
Apart from the part (Q) of center 12mm | 43~61 |
Apart from the inboard portion (R) of surface 2 ~ 3mm | 36~54 |
Surface (S) | 41~59 |
Difference of hardness [(Q)-(S)] | 1~10 |
Difference of hardness [(S)-(R)] | 3~10 |
Patent document 9 discloses a kind of solid golf ball, possess solid ball and coated it outer shell solid golf ball in, described solid ball is formed by rubber composition, in this rubber composition, relative to containing 60 ~ 100 mass parts containing more than 60% cis-1, 4-combines, rubber substrate 100 mass parts of the polybutadiene rubber utilizing rare earth element series catalysts to synthesize, also containing 0.1 ~ 5 mass parts organosulfur compound, unsaturated carboxylic acid or its slaine, inorganic fillers, simultaneously, the deflection when load of solid ball is from initial stage load 10kgf to final load 130kgf is 2.0 ~ 4.0mm, and, solid ball has hardness distribution as shown in the table.
[table 2]
Solid ball hardness distribution | Shore D hardness |
Center | 25~45 |
Apart from the part of center 5 ~ 10mm | 39~58 |
Apart from the part of center 15mm | 36~55 |
Surface | 55~75 |
Center and surperficial difference of hardness | 20~50 |
Patent document 10 discloses a kind of multilayer solid golf ball, it is characterized in that, there is ball, be coated on the embracing layer of ball, be coated on the intermediate layer of embracing layer, what be coated on intermediate layer is formed in the multilayer solid golf ball of the shell of most indentures on surface, described ball is that main material is made with elastomeric material, increase gradually from the center of ball to ball case hardness, the difference of hardness on ball center and ball surface is shown in more than 15 with JIS-C scale of hardness, and the section hardness mean value of the position and ball center that are about 15mm apart from ball center is set to (I), when section hardness apart from the position of ball center 7.5mm is set to (II), two difference of hardness (I)-(II) with JIS-C scale of hardness be shown in ± 2 within, described embracing layer simultaneously, the hardness of intermediate layer and shell meets the condition of shell hardness > intermediate layer hardness > embracing layer hardness.
Prior art
Patent document
Patent document 1: Japanese Laid-Open Patent Publication 61-37178 publication
Patent document 2: Japanese Laid-Open Patent Publication 61-113475 publication
Patent document 3: Japanese Laid-Open Patent Publication 61-253079 publication
Patent document 4: Japanese Patent Laid-Open 2008-212681 publication
Patent document 5: Japan Patent spy table 2008-523952 publication
Patent document 6: Japanese Patent Laid-Open 2009-119256 publication
Patent document 7: Japanese Patent Laid-Open 6-154357 publication
Patent document 8: Japanese Patent Laid-Open 2008-194471 publication
Patent document 9: Japanese Patent Laid-Open 2008-194473 publication
Patent document 10: Japanese Patent Laid-Open 2010-253268 publication
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide the golf that a kind of flying distance of kicking off to bat is large.
The present inventor is for the purpose of the Novel golf providing flying quality excellence, propose about " a kind of golf; it is characterized in that; there is the shell of spherical ball and the coated described spherical ball at least more than one deck; described spherical ball is formed by rubber composition; be the α of 3 ~ 8 as the carbon number of co-crosslinker containing (a) substrate rubber, (b) in described rubber composition, beta-unsaturated carboxylic acid and/or its slaine, (c) cross-linked evocating agent, (d) carboxylate and (e) organosulfur compound; When (b) only contains as co-crosslinker the α that carbon number is 3 ~ 8, during beta-unsaturated carboxylic acid, described rubber composition is further containing (f) metallic compound; The content of described (d) carboxylate, relative to (a) substrate rubber 100 mass parts, is more than 10 mass parts, discontented 40 mass parts " application (No. 2010-294589, Japan Patent Patent).
No. 2010-294589 invention related to of Japan Patent Patent, its hardness distribution that will be intended to spherical ball roughly linearly increases from ball center to surface.Because the distribution of ball hardness roughly linearly increases from ball center to surface, and the amplitude crescendo of outer just interior soft structure, cause rotation amount to decline, improve the performance of flying distance.The reason of ball hardness distribution roughly straight line increase from ball center to surface, has following viewpoint.When being shaped by ball, for the temperature of ball inside, ball central part is higher, then reduces near ball surface.This is because the heat of reaction of cross-linking reaction is accumulated at ball central part.When ball is shaped, described (d) carboxylate and (b) carbon number are the α of 3 ~ 8, and the reacting metal salt of beta-unsaturated carboxylic acid produces the slaine of carboxylic acid.That is, (d) described carboxylate and carbon number are the slaine exchange cation of the α of 3 ~ 8, beta-unsaturated carboxylic acid, cut off the α that carbon number is 3 ~ 8, the metal corsslinking of the slaine generation of beta-unsaturated carboxylic acid.This cation exchange reaction easily occurs at the ball central part that the temperature of ball inside is higher, is then difficult to gradually occur near surface.In other words, the ball central part that is breaking at of metal corsslinking easily occurs, and then becomes difficulty gradually near surface.Its result, because the crosslink density of ball inside, increases from ball center to surface, so think ball hardness, from ball center to surface, roughly straight line increases.
And the present inventor after further study, finds by adopting (d) carbon number to be the carboxylate of 1 ~ 13, the outer just interior soft Amplitude Ratio of spherical ball is in the past stronger, reduces the rotation amount of kicking off to bat, thus completes the present invention.
Solve the means of problem
Golf of the present invention, it is characterized in that, there is the shell of ball and the coated described spherical ball at least more than one deck, described spherical ball is formed by rubber composition, described rubber composition contains (a) substrate rubber, (b) as the carbon number of co-crosslinker between the α of 3 ~ 8, and beta-unsaturated carboxylic acid and/or its slaine, (c) cross-linked evocating agent, (d) carbon number are the carboxylate of 1 ~ 13; When (b) as co-crosslinker only containing carbon number between the α of 3 ~ 8, during beta-unsaturated carboxylic acid, described rubber composition is further containing (e) metallic compound.The present invention passes through to form as above, and the amplitude grow of the outer just interior soft structure of spherical ball, the rotation amount of batting of kicking off reduces, flying distance increases.In addition, the spherical ball that the present invention the uses linearity that its ball hardness distributes sometimes can a part reduce, and in this case, outer just interior soft Amplitude Ratio is in the past more strong, and the rotation amount of kicking off to bat reduces.
By adopting (d) carbon number to be the carboxylic acid of 1 ~ 13, the outer just reason that interior soft Amplitude Ratio is in the past stronger of spherical ball has following consideration.As mentioned above, carboxylic acid and carbon number are the slaine exchange cation of the α of 3 ~ 8, beta-unsaturated carboxylic acid, and cutting off by carbon number is the α of 3 ~ 8, the metal corsslinking that the slaine of beta-unsaturated carboxylic acid produces.Think that the effect cutting off this metal corsslinking is subject to the impact that added carbon number is the carboxylate molal quantity of 1 ~ 13.Meanwhile, carbon number be 1 ~ 13 carboxylate also work as the plasticizer of spherical ball.If increase add the combined amount (quality) that carbon number is the carboxylate of 1 ~ 13, ball entirety can be softened.This plasticization effect is subject to the impact of the combined amount (quality) of added carboxylic acid.Consider that these act on, by using the carboxylic acid of carbon number few (molecular weight is little), compared with when using the carboxylic acid of carbon number many (molecular weight is large), when identical combined amount (quality), addible molal quantity increases.That is, while suppressing the spherical ball entirety caused because of plasticization effect to be softened, the action effect cutting off metal corsslinking can be improved again.
The effect of invention
According to the present invention, the golf that a kind of batting flying distance of kicking off is large can be provided.
Accompanying drawing explanation
Fig. 1: a part of sectional view be cut open of golf that one of display embodiment of the present invention is involved.
Fig. 2: the chart of display ball hardness distribution.
Fig. 3: the chart of display ball hardness distribution.
Fig. 4: the chart of display ball hardness distribution.
Fig. 5: the chart of display ball hardness distribution.
Fig. 6: the chart of display ball hardness distribution.
Fig. 7: the chart of display ball hardness distribution.
Fig. 8: the chart of display ball hardness distribution.
Fig. 9: the chart of display ball hardness distribution.
Figure 10: the chart of display ball hardness distribution.
Figure 11: the chart of display ball hardness distribution.
Figure 12: the chart of display ball hardness distribution.
Detailed description of the invention
Golf of the present invention, it is characterized in that, there is the shell of ball and at least more than one deck coated described spherical ball, described spherical ball is formed by rubber composition, described rubber composition contains (a) substrate rubber, (b) as the carbon number of co-crosslinker between the α of 3 ~ 8, and beta-unsaturated carboxylic acid and/or its slaine, (c) cross-linked evocating agent, (d) carbon number are the carboxylate of 1 ~ 13; When (b) as co-crosslinker only containing carbon number between the α of 3 ~ 8, during beta-unsaturated carboxylic acid, described rubber composition is further containing (e) metallic compound.
First, (a) substrate rubber used in the present invention is described.As (a) substrate rubber, natural rubber and/or synthetic rubber can be used, such as, polybutadiene rubber, natural rubber, polyisoprene rubber, styrene polybutadiene rubber, Ethylene-Propylene-Diene rubber (EPDM) etc. can be used.These may be used alone, two or more kinds can also be used.Wherein, containing more than 40 quality %, preferably more than 80 quality %, more preferably the high-cis polybutadiene of the cis-Isosorbide-5-Nitrae-combination favourable to bounce-back of 90 quality % is suitable especially.
Described high-cis polybutadiene, preferably the content that combines of 1,2-vinyl is at below 2 quality %, more preferably below 1.7 quality %, further preferred below 1.5 quality %.If the content that 1,2-vinyl combines is too much, sometimes leastly to reduce.
Described high-cis polybutadiene, be advisable with the material of rare earth element series catalysts synthesis, particularly, when using the Nd-based catalyst that have employed as the neodymium compound of group of the lanthanides row rare-earth element compound, 1 is obtained with the polymerization activity of excellence, 4-cis is high in conjunction with content, 1,2-ethene in conjunction with the low polybutadiene rubber of content, thus preferably.
Described high-cis polybutadiene, Mooney viscosity (ML
1+4(100 DEG C)) preferably more than 30, more preferably more than 32, further preferably more than 35, preferably less than 140, more preferably less than 120, further preferably less than 100, most preferably less than 80.In addition, said Mooney viscosity (ML in the present invention
1+4(100 DEG C)) refer to, with JIS K6300 for benchmark, use L rotor, the numerical value measured under the condition of 1 minute preheating time, rotor rotational time 4 minutes, 100 DEG C.
As described high-cis polybutadiene, its molecular weight distribution mw/mn (Mw: weight average molecular weight, Mn: number-average molecular weight) preferably more than 2.0, more preferably more than 2.2, further preferably more than 2.4, most preferably more than 2.6, preferably less than 6.0, more preferably less than 5.0, further preferably less than 4.0, most preferably less than 3.4.If the molecular weight distribution (Mw/Mn) of high-cis polybutadiene, too small, may reduce operability, may reduce least if excessive.In addition, molecular weight distribution, by gel permeation chromatography (East ソ-Inc., " HLC-8120GPC "), use differential refractometer as detector, chromatographic column: GMHHXL (East ソ-Inc.), chromatogram column temperature: 40 DEG C, mobile phase: measure under the condition of oxolane are the numerical value calculated using polystyrene standard as scaled value.
Secondly, just (b) carbon number is the α of 3 ~ 8, and beta-unsaturated carboxylic acid and/or its slaine are described.B () carbon number is the α of 3 ~ 8, beta-unsaturated carboxylic acid and/or its slaine, is be mixed in rubber composition as co-crosslinker, by the strand of glycerol polymerization in substrate rubber, plays the effect be cross-linked rubber molecule.In the rubber composition used in the present invention, be only the α of 3 ~ 8 containing carbon number as co-crosslinker, during beta-unsaturated carboxylic acid, rubber composition contains (e) metallic compound further as essential component.Because in rubber composition, by with in metallic compound and carbon number be the α of 3 ~ 8, beta-unsaturated carboxylic acid, can obtain in fact with the α that the carbon number used as co-crosslinker is 3 ~ 8, effect same during beta-unsaturated carboxylic acid slaine.In addition, as co-crosslinker, carbon number is the α of 3 ~ 8, beta-unsaturated carboxylic acid and slaine thereof used time, also can use (e) metallic compound as any composition.
As the α that carbon number is 3 ~ 8, beta-unsaturated carboxylic acid, can enumerate as acrylic acid, methacrylic acid, fumaric acid, maleic acid, butenoic acid etc.
As forming the α that carbon number is 3 ~ 8, the metal of the slaine of beta-unsaturated carboxylic acid, can enumerate: 1 valence metal ions such as sodium, potassium, lithium; The bivalent metal ions such as magnesium, calcium, zinc, barium, cadmium; Aluminium etc. 3 valence metal ion; Other ion such as tin, zirconium.Described metal ingredient can use separately or as two or more mixture.This wherein, as described metal ingredient, the divalent metals such as preferably magnesium, calcium, zinc, barium, cadmium.Because by the α that use carbon number is 3 ~ 8, the divalent metal salt of beta-unsaturated carboxylic acid, easily generates metal corsslinking between rubber molecule.Particularly, as divalent metal salt, consider from the least height of obtained golf, zinc acrylate resin is advisable.In addition, carbon number is the α of 3 ~ 8, beta-unsaturated carboxylic acid and/or its slaine, can separately or two or more combinationally use.
B () carbon number is the α of 3 ~ 8, the content of beta-unsaturated carboxylic acid and/or its slaine is relative to (a) substrate rubber 100 mass parts, preferably more than 15 mass parts, more preferably more than 20 mass parts, preferably below 50 mass parts, more preferably below 45 mass parts, further preferably below 35 mass parts.B () carbon number is the α of 3 ~ 8, when the content of beta-unsaturated carboxylic acid and/or its slaine is discontented with 15 mass parts, in order to make the parts formed by rubber composition, there is suitable hardness, the amount of aftermentioned (c) cross-linked evocating agent don't fail to be increased, will the least tendency reducing golf be had like this.On the other hand, carbon number is the α of 3 ~ 8, if the content of beta-unsaturated carboxylic acid and/or its slaine is more than 50 mass parts, then the parts formed by rubber composition are really up to the mark, likely cause the decline of the golf ball feel of the ball.
C () cross-linked evocating agent mixes in order to crosslinked (a) substrate rubber composition.As (c) cross-linked evocating agent, be advisable with organic peroxide.Described organic peroxide, specifically can enumerate: cumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethyl-cyclohexane, 2,5-dimethyl-2,5-bis-(t-butylperoxy) hexane, di-tert-butyl peroxides etc.These organic peroxides can a kind be used alone, also can two or more also use.Preferably cumyl peroxide is used in the middle of these.
The content of (c) cross-linked evocating agent relative to (a) substrate rubber 100 mass parts, preferably more than 0.2 mass parts, more preferably more than 0.5 mass parts, preferably below 5.0 mass parts, more preferably below 2.5 mass parts.During discontented 0.2 mass parts, the parts formed by rubber composition are too soft, the least of golf has the tendency that declines, if more than 5.0 mass parts, then in order to ensure that the parts formed by rubber composition have suitable hardness, be necessary the use amount reducing described (b) co-crosslinker, like this, golf not least, likely makes durability worsen.
Then, the carboxylate being 1 ~ 13 with regard to (d) carbon number is described.(d) carbon number used in the present invention is the carboxylate of 1 ~ 13, as long as have the salt of the compound of carboxyl, just be not particularly limited, but do not comprise the α that (b) carbon number used as co-crosslinker is 3 ~ 8, the salt of beta-unsaturated carboxylic acid.Think that (d) carbon number is the carboxylate of 1 ~ 13, at the central part of ball when ball is formed, have that to cut off by (b) carbon number be the α of 3 ~ 8, the effect of the metal corsslinking that the slaine of beta-unsaturated carboxylic acid produces.
As the carboxylate preferred aliphat carboxylate (being sometimes called for short " aliphatic acid " salt in the present invention) that described (d) carbon number is 1 ~ 13.Be the carboxylate of 1 ~ 13 as described carbon number, preferred carbon number is the carboxylate of 1 ~ 12.The carbon number of carboxylate reduces, and understands the problems such as toxic or foul smell.In addition, carbon number refers to the carbon number of carboxylic acid composition.
Described soap can be any one in Salt of saturated fatty acid, unsaturated fatty acid salt, preferred Salt of saturated fatty acid.As the fatty acid composition concrete example of described soap, can enumerate as butyric acid (C4), valeric acid (C5), caproic acid (C6), enanthic acid (C7), caprylic acid (sad) (C8), n-nonanoic acid (C9), capric acid (capric acid) (C10), laurate (C12) etc.Described fatty acid composition can use separately or as two or more mixture.As described fatty acid composition, preferred caprylic acid (sad) (C8), n-nonanoic acid (C9), capric acid (capric acid) (C10), laurate (C12), further preferred caprylic acid (sad) (C8), capric acid (capric acid) (C10) and laurate (C12).
As the cation constituent of above-mentioned carboxylate, can in metal ion and organic cation optional one.As metal ion, can enumerate as 1 valence metal ions such as sodium, potassium, lithium, silver; The divalent metal ions such as magnesium, calcium, zinc, barium, cadmium, copper, cobalt, nickel, manganese; 3 valence metal ion such as aluminium, iron; Other ions such as tin, zirconium, titanium.As the cation constituent of described carboxylate, preferred zinc ion.Described cation constituent can be used alone or uses as two or more mixture.
Above-mentioned organic cation is the cation with carbochain.As above-mentioned organic cation, be not particularly limited, can enumerate as organic amine ion.As above-mentioned organic amine ion, can enumerate as primary amine ions such as stearylamine ion, hexyl amine ion, octyl amine ion, 2-DEHA ions; The secondary amine ions such as dodecyl (lauryl) amine ion, 18 (alkane) base (tristearin) amine ion; The tertiary amine ion such as trioctylphosphine amine ion; The quaternary ammonium ions etc. such as dioctyl dimethyl ammonium ion, distearyl Dimethyl Ammonium ion.These organic cations may be used alone, two or more kinds can also be used.In addition, the carbon number carbon number that to be the carbon number of the carboxylate of 1 ~ 13 be in carboxylic acid composition, and do not comprise the carbon number in organic cation.
Be the carboxylate of 1 ~ 13 as described (d) carbon number, the slaine of preferred caprylic acid (sad) (C8), n-nonanoic acid (C9), capric acid (capric acid) (C10) or laurate (C12), the further zinc salt of preferably caprylic acid (sad) (C8), capric acid (capric acid) (C10) and laurate (C12).
Described (d) carbon number is that the content of the carboxylate of 1 ~ 13 is relative to (a) substrate rubber 100 mass parts, preferably more than 0.5 mass parts, more preferably more than 1.0 mass parts, further preferably more than 1.5 mass parts, preferably below 30 mass parts, more preferably below 25 mass parts, further preferably below 20 mass parts.If content is very few, then adding (d) carbon number is that the effect of the carboxylate of 1 ~ 13 is insufficient, spherical ball outer just in soft amplitude likely diminish.In addition, if content is too much, the ball hardness obtained likely can globality decline, and makes least reduction.Moreover, for improving the zinc acrylate resin that uses as co-crosslinker to the dispersiveness of rubber, use carbon number to be the surface of the carboxylate process zinc acrylate resin of 1 ~ 13 sometimes.Use like this is that the carboxylate of 1 ~ 13 is when carrying out surface treatment to zinc acrylate resin with carbon number, in the present invention, the carbon number as surface conditioning agent is that the amount of the carboxylate of 1 ~ 13 is included in the middle of the content that (d) carbon number is the carboxylate of 1 ~ 13.Such as, when to use carbon number to be the surface treatment amount of the carboxylate of 1 ~ 13 be zinc acrylate resin 25 mass parts of 10 quality %, carbon number is the amount of the carboxylate of 1 ~ 13 is 2.5 mass parts, the amount of zinc acrylate resin is 22.5 mass parts, as the content that (d) carbon number is the carboxylate of 1 ~ 13, then 2.5 mass parts to be calculated interior.
The rubber composition that the present invention uses is only the α of 3 ~ 8 containing carbon number as co-crosslinker, during beta-unsaturated carboxylic acid, as required composition further containing (e) metallic compound.As above-mentioned (e) metallic compound, as long as (b) carbon number in energy and in rubber composition is between the α of 3 ~ 8, beta-unsaturated carboxylic acid, is not particularly limited.As (e) above-mentioned metallic compound, can enumerate as metal hydroxides such as magnesium hydroxide, zinc hydroxide, calcium hydroxide, NaOH, lithium hydroxide, potassium hydroxide, Kocide SDs; The metal oxides such as magnesia, calcium oxide, zinc oxide, cupric oxide; The metal carbonate compounds such as magnesium carbonate, zinc carbonate, calcium carbonate, sodium carbonate, lithium carbonate, potash.As the preferred divalent metallic compound of (e) metallic compound, more preferably zinc compound.Because divalent metallic compound and carbon number are between the α of 3 ~ 8, beta-unsaturated carboxylic acid reacts, and forms metal corsslinking.In addition, by using zinc compound, least high golf can be obtained.Can independent a kind use these (e) metallic compound, also can two or more also use.
The ball that the present invention uses rubber composition preferably contains (f) organosulfur compound further.Described ball rubber composition is outside the carboxylate of 1 ~ 13 at (d) carbon number, by using in the lump with (f) organosulfur compound, the roughly linearity of sustainable maintenance ball hardness distribution, controls the amplitude of the outer just interior soft structure of ball.As (f) organosulfur compound, as long as the organic compound containing sulphur atom in molecule, be not particularly limited, can enumerate as: there is mercapto (-SH), or number of sulfur atoms is the organic compound of the polythiaether key (-S-S-,-S-S-S-or-S-S-S-S-) of 2 ~ 4, or their slaine (-SM ,-S-M-S-,-S-M-S-S-,-S-S-M-S-S-,-S-M-S-S-S-etc., M is metallic atom).In addition, f () described organosulfur compound, can in aliphatic compound (aliphatic mercaptan, analiphatic sulphur carboxylic acid, aliphatic dithiocarboxylic acid, aliphatic polysulfide etc.), hetero ring type compound, ester ring type compound (ester ring type mercaptan, ester ring type thionothiolic acid, ester ring type dithiocarboxylic acid, ester ring type polysulfide etc.) and aromatic compound optional one.As (f) organosulfur compound, can enumerate as benzenethiol class, thionaphthol class, multiple sulfides, thionothiolic acid class, dithiocarboxylic acid class, sulfenamide, thiuram (thiuram) class, dithiocar-bamate, thiazoles etc.Based on the viewpoint that the hardness distribution of spherical ball increases, as (f) organosulfur compound, preferably there is organosulfur compound or its slaine of mercapto (-SH), preferred benzenethiol class, thionaphthol class or their slaine.As slaine, can enumerate as sodium, lithium, potassium, copper (I), the silver 1 valency slaine such as (I); The divalent slaines such as zinc, magnesium, calcium, strontium, barium, titanium (II), manganese (II), iron (II), cobalt (II), nickel (II), zirconium (II), tin (II).
As benzenethiol class, can to enumerate as benzenethiol; The benzenethiol class that 4-fluoro thiophenol, 2,5-difluoro thiophenols, 2,4,5-trifluoro-benzene thiophenols, 2,4,5,6-phenyl tetrafluoride thiophenols, phenyl-pentafluoride thiophenol etc. replaced by fluorine; The benzenethiol class that 2-chlorothio-phenol, 4-chlorothio-phenol, 2,4-thiophenol dichlorobenzenes, 2,5-thiophenol dichlorobenzenes, 2,4,5-trichloro-benzenes thiophenols, 2,4,5,6-tetrachlorobenzene thiophenols, reptazin etc. are replaced by chlorine; The benzenethiol class that 4-bromo thiophenol, 2,5-dibromobenzene thiophenols, 2,4,5-tribromo-benzene thiophenols, 2,4,5,6-tetrabromo-benzene thiophenols, phenyl-pentabromide thiophenol etc. are replaced by bromine; The benzenethiol class that 4-iodobenzene thiophenol, 2,5-diiodo-benzene thiophenols, 2,4,5-triiodo-benzene thiophenols, 2,4,5,6-tetraiodo-benzene thiophenols, pentaiodobenzene thiophenol etc. are replaced by iodine or their slaine.As slaine, preferred zinc salt.
As naphthyl mercaptan class (thionaphthol class); can enumerate as 2-thionaphthol, 1-thionaphthol, 2-chloro-1-thionaphthol, 2-bromo-1-thionaphthol, 2-fluoro-1-thionaphthol, 2-cyano group-1-thionaphthol, 2-acetyl group-1-thionaphthol, 1-chloro-2-thionaphthol, 1-bromo-2-thionaphthol, the fluoro-2-thionaphthol of 1-, 1-cyano group-2-thionaphthol, 1-acetyl group-2-thionaphthol or their slaine, preferred 1-thionaphthol, 2-thionaphthol and their zinc salt.
As sulfenamide system organosulfur compound, can enumerate as n-cyclohexyl-2-[4-morpholinodithio sulfenamide, n-hydroxyl divinyl-2-[4-morpholinodithio sulfenamide, n-tert-butyl-2-[4-morpholinodithio sulfenamide.As thiuram system organic sulfur compound, can enumerate as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylene thiuram tetrasulfide etc.As dithiocarbamates, can enumerate as PZ, zinc diethyl dithiocarbamate, zinc dibutyl dithiocarbamate, zinc-ethylphenyl dithiocarbamate, SDD, sodium diethyldithiocarbamate, cupric dimethyldithio carbamate (II), ferric dimethyl dithiocarbamate (III), selenium diethyl dithiocarbamate, tellurium diethyl dithiocarbamate etc.As thiazole system organic sulfur compound, can enumerate as the sodium salt of 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), 2-mercaptobenzothiazole, zinc salt, mantoquita or cyclohexyl amine salt, 2-(2,4-dinitrophenyl) mercaptobenzothiazoler, 2-(2,6-diethyl-4-morpholino sulphur) benzothiazole etc.
(f) described organosulfur compound can more than separately or two kinds used in combination.
F the content of () organosulfur compound, relative to (a) substrate rubber 100 mass parts, preferably more than 0.05 mass parts, more preferably more than 0.1 mass parts, preferably below 5.0 mass parts, more preferably below 2.0 mass parts.If discontented 0.05 mass parts, then can not get the effect of adding (f) organosulfur compound, likely can not improve the least of golf.In addition, if more than 5.0 mass parts, the compress variation of the golf obtained increases, and likely reduces least.
The rubber composition that the present invention uses, as required, can also add pigment, for adjusting the additive such as filler, age resistor, peptizer, softening agent of weight etc.In addition, as mentioned above, the rubber composition used in the present invention is only the α of 3 ~ 8 containing carbon number as co-crosslinker, and during beta-unsaturated carboxylic acid, preferred rubber composition is further containing (e) metallic compound.
As the pigment mixed in rubber composition, can enumerate as Chinese white, blue pigment, violet pigment etc.As described Chinese white, preferably use titanium oxide.Although the kind of titanium oxide is not particularly limited, based on the reason that covering is good, preferably use rutile-type.In addition, the content of titanium oxide relative to (a) substrate rubber 100 mass parts, preferably more than 0.5 mass parts, more preferably more than 2 mass parts, preferably below 8 mass parts, more preferably below 5 mass parts.
Rubber composition contains Chinese white and blue pigment is also preferred configuration.Blue pigment mixes to make white seem more bright-coloured, can enumerate as ultramarine, cobalt blue, phthalocyanine blue etc.In addition, as described violet pigment, can enumerate as anthraquinone purple, dioxazine violet, crystal violet etc.
The content of described blue pigment relative to (a) substrate rubber 100 mass parts, preferably more than 0.001 mass parts, more preferably more than 0.05 mass parts, preferably below 0.2 mass parts, more preferably below 0.1 mass parts.If discontented 0.001 mass parts, then blue not obvious, seem some yellowing, if more than 0.2 mass parts, then excessivelys blue, the white appearance that loses distinctness.
As the filler used in rubber composition, mainly in order to adjust the weight of the golf obtained as final products, and the weight regulator of mixing, can mix as required.As described filler, the inorganic fillers such as zinc oxide, barium sulfate, calcium carbonate, magnesia, tungsten powder, molybdenum powder can be enumerated.The content of described filler relative to substrate rubber 100 mass parts, preferably more than 0.5 mass parts, more preferably more than 1 mass parts, preferably below 30 mass parts, more preferably below 25 mass parts, further preferably below 20 mass parts.If the content of filler is discontented with 0.5 mass parts, be then difficult to adjustment weight, if more than 30 mass parts, then the percentage by weight of rubber constituent diminishes, has and reduce least tendency.
The content of described age resistor relative to (a) substrate rubber 100 mass parts, preferably more than 0.1 mass parts, below 1 mass parts.In addition, the content of peptizer relative to (a) substrate rubber 100 mass parts, preferably more than 0.1 mass parts, below 5 mass parts.
The rubber composition that the present invention uses, to be mixing (a) substrate rubber, (b) carbon number the be α of 3 ~ 8, beta-unsaturated carboxylic acid and/or its slaine, (c) cross-linked evocating agent, (d) carbon number are carboxylate and other the additive as required of 1 ~ 13, obtain through mixing.Method of mixing is not particularly limited, such as, the known mullers such as mixing roller, Ben Baili banbury, kneader can be used to carry out mixing.
The globose nucleus that golf of the present invention has, by obtaining the rubber composition after mixing at metal die internal shaping.Be shaped the temperature preferably more than 120 DEG C of spherical ball, more preferably more than 150 DEG C, preferably more than 160 DEG C further, preferably less than 170 DEG C.If forming temperature is more than 170 DEG C, ball case hardness has to reduce to be inclined to.In addition, the preferred 2.9MPa ~ 11.8MPa of pressure during shaping.Curring time preferably 10 minutes ~ 60 minutes.
Above-mentioned spherical ball, by ball radius with 12.5% interval on average divide, measure the hardness of 9 points that this on average divides, when these hardness are mapped with the distance to ball center, obtained the R of linear curve of approximation by least square method
2preferably more than 0.95.R
2if more than 0.95, then the linearity of the hardness distribution of ball high, reduce rotation amount of kicking off to bat, improve the performance of flying distance.
For the hardness of spherical ball, by any radius of spherical ball with 12.5% interval on average divide, measure the JIS-C hardness of 9 points that this on average divides.That is, apart from the distance at ball center be 0% (ball center), 12.5%, 25%, 37.5%, 50%, 62.5%, 75%, 87.5%, 9 some places on 100% (ball surface) measure JIS-C hardness.Then, using the JIS-C hardness of pressing said determination as axis of ordinates, apart from the distance (%) at ball center as axis of abscissas, measurement result is made chart as curve.In the present invention, the linear curve of approximation R obtained by this curve negotiating least square method
2preferably more than 0.95.The R of the linear curve of approximation obtained by least square method
2be judge obtain the linear index of curve.In the present invention, R
2if more than 0.95, then mean that the hardness of this spherical ball distributes roughly linearly.Use the golf of the spherical ball of hardness distribution substantially linear, the rotation amount of kicking off to bat can be reduced.Its result, the flying distance of kicking off to bat increases.The R of described linear curve of approximation
2more preferably more than 0.96.By improving linearity, the flying distance of kicking off to bat can be larger.
The case hardness Hs of described spherical ball and the difference of hardness (Hs-Ho) of core rigidities Ho, represent with JIS-C hardness, preferably more than 27, more preferably more than 28, further preferably more than 30, particularly preferably more than 31, most preferably more than 32, preferably less than 80, more preferably less than 70, further preferably less than 60.If ball surface is large with the difference of hardness at ball center, can obtains and go out angle and lower rotation, golf that flying distance is large compared with high strike.
The core rigidities Ho of spherical ball, represents with JIS-C hardness, preferably more than 30, more preferably more than 40, further preferably more than 45.The core rigidities Ho of spherical ball with thumb down with JIS-C hardness 30 time, reduce least because crossing soft sometimes.In addition, the core rigidities Ho of spherical ball, represents with JIS-C hardness, preferably less than 70, more preferably less than 65, further preferably less than 60.If described core rigidities Ho represents more than 70 with JIS-C hardness, then really up to the mark, have and reduce the tendency of touch.
The case hardness Hs of spherical ball, represents with JIS-C hardness, preferably more than 76, more preferably more than 78, further preferably more than 80, preferably less than 100, more preferably less than 95.If represent with JIS-C hardness, the case hardness of described spherical ball is decided to be more than 76, then spherical ball can not become excessively soft, can obtain good least.In addition, if represent with JIS-C hardness, the case hardness of described spherical ball is decided to be less than 100, then spherical ball can not really up to the mark, good touch can be obtained.
The diameter of described spherical ball, preferred more than 34.8mm, more preferably more than 36.8mm, further preferred more than 38.8mm, preferred below 42.2mm, more preferably below 41.8mm, further preferred below 41.2mm, most preferably below 40.8mm.If the diameter of described spherical ball is at more than 34.8mm, then the thickness of shell can not be blocked up, and least meeting is better.On the other hand, if the diameter of spherical ball is at below 42.2mm, then shell can not be excessively thin, more can play the function of shell.
Described spherical ball, when diameter is 34.8mm ~ 42.2mm, compress variation (the central reduction amount towards compression direction) during load from the load condition of initial stage load 98N to final load 1275N, preferred more than 2.0mm, more preferably more than 2.8mm, preferred below 6.0mm, more preferably below 5.0mm.If described compress variation is at more than 2.0mm, then touch is better, if at below 6.0mm, then better least.
Golf ball of the present invention is formed by the shell composition containing resinous principle.As described resinous principle, can to enumerate as ionomer resin, the thermoplastic polyurethane elastomer that BASF Japan (joint-stock company) peddles with trade name " エ ラ ス ト ラ Application (registration mark) ", the thermoplastic polyamide elastomer that ア Le ケ マ (joint-stock company) peddles with trade name " ペ バ Star Network ス (registration mark) ", the thermoplastic polyester elastomer that East レ デ ュ Port Application (joint-stock company) peddles with trade name " Ha イ ト レ Le (registration mark) ", the thermoplastic styrene elastomer etc. that Mitsubishi Chemical (joint-stock company) peddles with trade name " ラ バ ロ Application (registration mark) ".
As described ionomer resin, can enumerate as: alkene and carbon number are the α of 3 ~ 8, carboxyl in the bipolymer of beta-unsaturated carboxylic acid at least partially the material that neutralizes by metal ion, alkene and carbon number are the α of 3 ~ 8, beta-unsaturated carboxylic acid and α, the carboxyl of the terpolymer of beta-unsaturated carboxylic acid ester is at least partially by the material that metal ion neutralizes, or their mixture.As described alkene, preferred carbon number is the alkene of 2 ~ 8, can enumerate as ethene, propylene, butylene, amylene, hexene, heptene, octene etc., particularly preferably ethene.As the α that carbon number is 3 ~ 8, beta-unsaturated carboxylic acid, can enumerate as acrylic acid, methacrylic acid, fumaric acid, maleic acid, butenoic acid etc., particularly preferably acrylic acid or methacrylic acid.In addition, as α, beta-unsaturated carboxylic acid ester, can use as the methyl esters of acrylic acid, methacrylic acid, fumaric acid, maleic acid etc., ethyl ester, propyl ester, positive butyl ester, isobutyl ester etc., particularly preferably acrylate and methacrylate.This wherein, as described ionomer resin, the metal ion corrective of optimal ethylene-(methyl) acrylic acid bipolymer, the metal ion corrective of ethene-(methyl) acrylic acid-(methyl) acrylate terpolymer.
If the concrete example of described ionomer resin is with trade name example, can enumerate that Mitsui デ ュ Port Application Port リ ケ ミ カ Le (joint-stock company) peddles " Ha イ ミ ラ Application (Himilan) (registration mark) (can enumerate as Ha イ ミ ラ Application 1555 (Na), Ha イ ミ ラ Application 1557 (Zn), Ha イ ミ ラ Application 1605 (Na), Ha イ ミ ラ Application 1706 (Zn), Ha イ ミ ラ Application 1707 (Na), Ha イ ミ ラ Application AM3711 (Mg) etc., Ha イ ミ ラ Application 1856 (Na) is had as terpolymer ionomers resin, Ha イ ミ ラ Application 1855 (Zn) etc. ".
Further, as the ionomer resin that デ ュ ポン company peddles, can enumerate that " サ-リ Application (Surlyn) (registration mark) (can be enumerated as サ-リ Application 8945 (Na), サ-リ Application 9945 (Zn), サ-リ Application 8140 (Na), サ-リ Application 8150 (Na), サ-リ Application 9120 (Zn), サ-リ Application 9150 (Zn), サ-リ Application 6910 (Mg), サ-リ Application 6120 (Mg), サ-リ Application 7930 (Li), サ-リ Application 7940 (Li), サ-リ Application AD8546 (Li) etc., サ-リ Application 8120 (Na) is had as terpolymer ionomers resin, サ-リ Application 8320 (Na), サ-リ Application 9320 (Zn), サ-リ Application 6320 (Mg), HPF1000 (Mg), HPF2000 (Mg) etc.) ".
In addition, as the ionomer resin that エ Network ソ Application モ-PVC Le chemistry (joint-stock company) is peddled, can enumerate: " ア イ オ テ Star Network (Iotek) (registration mark) (can enumerate as: ア イ オ テ Star Network 8000 (Na), ア イ オ テ Star Network 8030 (Na), ア イ オ テ Star Network 7010 (Zn), ア イ オ テ Star Network 7030 (Zn) etc., have ア イ オ テ Star Network 7510 (Zn), ア イ オ テ Star Network 7520 (Zn) etc. as terpolymer ionomers resin) ".
In addition, Na, Zn, Li, Mg etc. described in the bracket after the trade name of described ionomer resin, represent the metal species with metal ion in them.Described ionomer resin can be used alone, also can two or more is used in combination.
Form the shell composition of golf ball of the present invention, as resinous principle, preferably containing thermoplastic polyurethane elastomer or ionomer resin.When using ionomer resin, preferably to use with thermoplastic styrene elastomer.The shell containing ratio of the polyurethane in composition resin composition or ionomer resin, preferably more than 50 quality %, more preferably more than 60 quality %, further preferred more than 70 quality %.
Described shell composition, except above-mentioned resinous principle, the weight regulator such as pigment composition, zinc oxide, calcium carbonate and barium sulfate, dispersant, age resistor, ultra-violet absorber, light stabilizer, fluorescent material or the fluorescent whitening agents etc. such as Chinese white (such as titanium oxide), blue pigment, red pigment can also be contained in the scope of harmless shell performance.
The content of described Chinese white (such as titanium oxide) relative to resinous principle 100 mass parts forming shell, preferably more than 0.5 mass parts, more preferably more than 1 mass parts, preferably below 10 mass parts, more preferably below 8 mass parts.By making the content of Chinese white be more than 0.5 mass parts, shell covering can be given.In addition, if the content of Chinese white is more than 10 mass parts, the durability of the shell obtained is reduced sometimes.
Slab (slab) hardness of described shell composition, preferably does suitably setting according to the golf performance expected.Such as, when paying attention to the distance type golf of flying distance, the shell slab hardness of composition represents with Shore D hardness, preferably more than 50, more preferably more than 55, preferably less than 80, more preferably less than 70.By the slab hardness of shell composition is set to more than 50, when kicking off batting and iron slot, the golf that high strike goes out angle, low rotation can be obtained, thus improve flying distance.In addition, by the hardness of shell composition is set to less than 80, the golf of excellent in te pins of durability can be obtained.In addition, when paying attention to rotation (spin) the type golf of controlling, the shell slab hardness of composition represents with Shore D hardness, preferably discontented 50, preferably more than 20, more preferably more than 25.The shell slab hardness of composition represents with Shore D hardness, if discontented 50, the golf obtained, it is by ball of the present invention, while the batting of kicking off seeking high flying distance, during Bail out, rotation amount by raising, easily stop on fruit ridge.In addition, by slab hardness is set to more than 20, scratch resistance performance can be improved.When having multiple outer shell, form the slab hardness of each layer shell composition, as long as within above-mentioned scope, can be the same or different.
As the method for shaping golf ball of the present invention, can enumerate as: by shell composition be configured as hollow shelly shell, again with the method for multiple shell coated ball compression molding (preferably by shell composition be configured as hollow shelly half shell, with the method for 2 piece of half coated ball compression molding of shell), or, by the method for shell composition direct injection molding forming on ball.
By compress moulding method during outer profiled shell, half shell is shaped and also can be undertaken by any means in compression forming method or injection moulding method, but desirably compression forming method.Be configured as the condition of half shell as compression molding shell composition, can enumerate as: at the pressure of more than 1MPa, below 20MPa, relative to shell composition start flow temperature, forming temperature is more than-20 DEG C, less than 70 DEG C.By setting described molding condition, uniform half shell of thickness can be configured as.Carry out the method for outer profiled shell as use half shell, can enumerate as: with the method for 2 piece of half coated ball compression molding of shell.Be configured as the condition of shell as compression molding half shell, can enumerate as: with more than 0.5MPa, the forming pressure of below 25MPa, relative to shell composition start flow temperature, forming temperature is more than-20 DEG C, less than 70 DEG C.By setting above-mentioned molding condition, the uniform golf ball of outer casing thickness can be configured as.
Injection molding forming shell composition and when being configured as shell, the granular shell composition that extruding can be used to obtain carries out injection molding forming, or, by shell material dry mixed such as substrate resin composition and pigment, direct injection molding forming.Be shaped as shell and use lower mold, preferably use has hemispherical die cavity, also doubles as with a part for kick, kick the locking pin that can retreat.The shaping of the shell undertaken by injection molding forming, by releasing locking pin, drop into ball and make its fixing after, inject shell composition, cool, can outer profiled shell, such as, with in the metal die of the good shape of the pressure fixing of 9MPa ~ 15MPa, the shell composition of injection heating to 200 DEG C in 0.5 second ~ 5 seconds ~ 250 DEG C, then cooled and opens mould in 10 seconds ~ 60 seconds.
During outer profiled shell, usually form the pit being called as indenture on surface.The sum of indenture preferably more than 200 less than 500.During discontented 200 of indenture sum, be difficult to the effect obtaining indenture.In addition, if the sum of indenture is more than 500, then the size of each indenture diminishes, and is difficult to the effect obtaining indenture.The indenture shape (plane sees shape) formed, be not particularly limited, can be used alone or two or more combinationally uses polygon, other indefinite shapes such as circle, triangle roughly, quadrangle roughly, pentagon roughly, hexagon roughly.
The thickness of described shell, preferred below 4.0mm, more preferably below 3.0mm, further preferred below 2.0mm.If the thickness of shell is at below 4.0mm, the least and touch of the golf obtained can be better.The thickness of described shell, preferred more than 0.3mm, more preferably more than 0.5mm, further preferred more than 0.8mm, particularly preferably more than 1.0mm.If the thickness of shell is discontented with 0.3mm, reduce durability and the wearability of shell sometimes.During multiple outer shell, the aggregate thickness of multiple outer shell is preferably in above-mentioned scope.
By the golf main body of the shell that has been shaped, take out from metal die, can as required, preferably carry out deburring, clean, the surface treatment such as sandblasting.In addition, also can according to expectation, film or formation mark.The thickness of described film, is not particularly limited, preferably more than 5 μm, more preferably more than 7 μm, preferably less than 50 μm, more preferably less than 40 μm, preferably less than 30 μm further.If discontented 5 μm of thickness, because continuing to use, film easily wears away disappearance, if thickness is more than 50 μm, then can reduce the effect of indenture, thus reduces the flying quality of golf.
Golf of the present invention, when diameter is 40mm ~ 45mm, compress variation (amount of contraction to compression direction) during from the state of load initial stage load 98N to load final load 1275N, be preferably more than 2.0mm, more preferably more than 2.4mm, further preferred more than 2.5mm, most preferably more than 2.8mm, preferred below 5.0mm, more preferably below 4.5mm, further preferred below 3.6mm.Described compress variation is at the golf of more than 2.0mm, and hardness is really up to the mark, and touch is good.On the other hand, be set to below 5.0mm by compress variation, leastly increase.
The structure of golf of the present invention, as long as the shell with more than one deck of spherical ball and coated described spherical ball, is just not particularly limited.Fig. 1 is the model sectional view that one of display embodiment of the present invention involved golf 2 part is cut open.Golf 2 has the shell 12 of spherical ball 4 and coated spherical ball 4.Multiple indenture 14 is formed on the surface of this shell.On the surface of this golf 2, the part outside indenture 14 is the scope of attack (land) 16.This golf 2, is provided with dope layer and mark layer in the outside of shell 12, but eliminates the diagram of these layers.
Described spherical ball preferred single layer structure.The spherical ball of single layer structure, when the interface of sandwich construction catches a packet, noenergy loss, can improve least.In addition, shell can be the structure of more than one deck, also can have single layer structure, or the sandwich construction of more than at least two layers.As golf of the present invention, can enumerate as: by spherical ball and coated as described in the two-piece golf ball that forms of spherical ball and the single layer enclosure configured; There is spherical ball and coated described spherical ball and the multi-layer golf ball (containing three layer golf balls) of more than the 2 layers shells configured; Have spherical ball, arrange around described ball containing silk rubber layer, and the curled hair golf etc. of the coated described shell arranged containing silk rubber layer.The golf of above-mentioned arbitrary structures is all applicable to the present invention.
Embodiment
To elaborate to the present invention according to embodiment below, but the present invention is not defined to following embodiment, as long as do not exceed the change of present inventive concept scope, any embodiment is included within scope of the present invention.
[evaluation method]
(1) compress variation (mm)
To ball or golf, measure it from the load condition of initial stage load 98N to the deflection (amount that ball or golf shrink on compression direction) at compression direction during the load of final load 1275N.
(2) rebound coefficient
With each ball or golf with the metal cylinder thing of the velocity shock 198.4g of 40m/ second, measure before and after impacting, the speed of described cylinder and ball or golf, from each speed and quality, calculates the rebound coefficient of ball or golf.Each ball or golf respectively measure 12, get the rebound coefficient of its mean value as this ball or golf.In addition, rebound coefficient, the difference with the rebound coefficient with golf (ball) No.11 in table 3 ~ table 4 shows, and the difference with the rebound coefficient with golf (ball) No.22 in table 5 ~ table 6 shows.
(3) slab hardness (Shore D hardness)
Use shell composition, by injection molding forming, make the thin slice that thickness is approximately 2mm, preserve 2 weeks at 23 DEG C.In order to not by the impact measuring substrate etc., to this thin slice, with more than 3 overlapping states, use according to ASTM-D2240 regulation, possess spring durometer Shore D type, macromolecule gauge Inc. automatic durometer P1 type, measure.
(4) ball hardness distribution (JIS-C hardness)
Use possesses spring hardometer JIS-C type macromolecule gauge Inc. automatic durometer P1 type, measures the JIS-C hardness of ball surface portion as ball case hardness.In addition, ball is cut into hemispherical, measure section center and from center to the hardness of distance of regulation.In addition, measuring the hardness of 4 points from center to predetermined distance, calculating ball hardness by getting its mean value.
(5) to kick off batting flying distance (m) and rotation amount (rpm)
Swing on robot M/C in go Le Off ラ ボ ラ ト リ-Inc., load onto ferrule W#1 rod (SRI sports Inc., XXIO S ロ Off ト 11 °), hitting golf second with bar head speed 40m/, measuring the golf ball spin speed after just hitting and flying distance (from launching the distance of starting point to static place).Each golf measures 12 times, gets the measured value of its mean value as this golf.In addition, the rotary speed of the golf just after batting, by measuring being taken pictures continuously by the golf hit.Kick off bat flying distance and rotation amount, in table 3 ~ table 4 with golf (ball) No.11 difference show, in table 5 ~ table 6 with golf (ball) No.22 differ from show.
[making of golf]
(1) making of ball
By mixing roller, the mixing rubber composition be mixed into as shown in table 3 ~ table 6, with heating pressurization in 170 DEG C, 20 minutes in the upper lower mold with hemispherical die cavity, obtains the spherical ball of diameter 39.8mm.
[table 3]
[table 4]
[table 5]
[table 6]
BR730:JSR Inc., high-cis polybutadiene (content=96 quality % of cis-Isosorbide-5-Nitrae-combination, the content=1.3 quality % that 1,2-ethene combines, Mooney viscosity (ML
1+4(100 DEG C))=55, molecular weight distribution (Mw/Mn)=3)
New chemical industrial company's zinc acrylate resin (10 quality % stearic acid surface coating product) of Sanceler SR: three
The plumbous Inc. " silver-colored ridge R " of zinc oxide: Dong Bangya
Barium sulfate: the golf Mass adjust-ment finally obtained is 45.4g by Sakai chemical company system " barium sulfate BD "
2-thionaphthol (2-Thio naphthol): Tokyo changes into industrial group's system
Cumyl peroxide: You Inc., " パ-Network ミ Le (registration mark) D (cumyl peroxide) "
Zinc octoate: three Tianjin and Chemical Company's system (purity more than 99%)
Zinc laurate: three Tianjin and Chemical Company's system (purity more than 99%)
Zinc tetradecanoate: You Inc. (purity more than 90%)
Zinc stearate: with Guang Chun medicine Inc. (purity more than 99%)
(2) making of shell
Secondly, to be mixed type extruder by twin shaft, extrude the shell material be mixed into as shown in table 7, make graininess shell composition.Extruding is carried out with the condition of spiral footpath 45mm, revolution speed of screw 200rpm, spiral L/D=35.Mixture in the mould position of extruder with 150 ~ 230 DEG C of heating.By the shell composition obtained, the spherical ball obtained as stated above carries out injection molding forming, make the golf of the shell with spherical ball and coated described ball.
[table 7]
Shell composition No. | A | B |
Himilan 1605 | 50 | - |
Himilan 1706 | 50 | - |
Elastollan XNY97A | - | 100 |
Titanium oxide | 4 | 4 |
Slab hardness (Shore D) | 65 | 47 |
Mixing: mass parts
The ethylene-methacrylic acid copolymer system ionomer resin of the sodium ion neutralization of Ha イ ミ ラ Application 1605 (Himilan 1605): Mitsui デ ュ Port Application Port リ ケ ミ カ Le Inc.
The ethylene-methacrylic acid copolymer system ionomer resin of the zinc ion neutralization of Ha イ ミ ラ Application 1706 (Himilan 1706): Mitsui デ ュ Port Application Port リ ケ ミ カ Le Inc.
エ ラ ス ト ラ Application XNY97A (Elastollan XNY97A): BASF Japanese firm thermoplastic polyurethane elastomers
From the result of table 3 ~ 6, there is the golf of the shell of ball and the coated described spherical ball at least more than one deck, its flying distance of kicking off to bat is all large, the described ball of this golf contains (a) substrate rubber, (b) as the carbon number of co-crosslinker between the α of 3 ~ 8, and beta-unsaturated carboxylic acid and/or its slaine, (c) cross-linked evocating agent, (d) carbon number are the carboxylate of 1 ~ 13.Any one in such golf.
Utilizability in industry
Golf of the present invention, the flying distance of kicking off to bat is large.
Claims (10)
1. a golf, is characterized in that, have the shell of spherical ball and at least coated described spherical ball of one deck, described spherical ball is formed by rubber composition,
Described rubber composition contains the α that (a) substrate rubber, (b) as the carbon number of co-crosslinker are 3 ~ 8, and beta-unsaturated carboxylic acid and/or its slaine, (c) cross-linked evocating agent, (d) carbon number are the carboxylate of 1 ~ 13;
When (b) only contains as co-crosslinker the α that carbon number is 3 ~ 8, during beta-unsaturated carboxylic acid, described rubber composition is further containing (e) metallic compound;
In described rubber composition, relative to (a) substrate rubber 100 mass parts, (b) carbon number containing 15 mass parts ~ 50 mass parts is the α of 3 ~ 8, beta-unsaturated carboxylic acid and/or its slaine, (c) cross-linked evocating agent of 0.2 mass parts ~ 5 mass parts, (d) carbon number of 0.5 mass parts ~ 30 mass parts is the carboxylate of 1 ~ 13.
2., as the golf that claim 1 is recorded, wherein, in described rubber composition, relative to (a) substrate rubber 100 mass parts, (d) carbon number containing 1.5 mass parts ~ 20 mass parts is the carboxylate of 1 ~ 13.
3., as the golf that claim 1 is recorded, wherein, the described case hardness of spherical ball and the difference of hardness of core rigidities are shown in more than 30 with JIS-C scale of hardness.
4., as the golf that claim 1 is recorded, wherein, in described rubber composition, be the α of 3 ~ 8 as the carbon number of co-crosslinker containing (b), the slaine of beta-unsaturated carboxylic acid.
5. as the golf that claim 1 is recorded, wherein, described (d) carbon number is the carboxylate of 1 ~ 13 is soap.
6., as the golf that claim 5 is recorded, wherein, described soap is fatty acid zinc salt.
7. as the golf that claim 1 is recorded, wherein, described rubber composition is further containing (f) organosulfur compound.
8., as the golf that claim 7 is recorded, wherein, described (f) organosulfur compound is benzenethiol class, diphenyl disulfide compound class, thionaphthol class, thiuram disulfides class or their slaine.
9. as the golf that claim 7 is recorded, wherein, in described rubber composition, relative to (a) substrate rubber 100 mass parts, (f) organosulfur compound containing 0.05 mass parts ~ 5 mass parts.
10. as the golf of claim 1 ~ 9 any one record, wherein, in described rubber composition, relative to (a) substrate rubber 100 mass parts, (b) carbon number containing 20 mass parts ~ 45 mass parts is the α of 3 ~ 8, beta-unsaturated carboxylic acid and/or its slaine.
Applications Claiming Priority (10)
Application Number | Priority Date | Filing Date | Title |
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JP2010-294590 | 2010-12-29 | ||
JP2010294591A JP5697444B2 (en) | 2010-12-29 | 2010-12-29 | Golf ball |
JP2010294590A JP5687053B2 (en) | 2010-12-29 | 2010-12-29 | Golf ball |
JP2010-294591 | 2010-12-29 | ||
JP2010294589A JP5754938B2 (en) | 2010-12-29 | 2010-12-29 | Golf ball |
JP2010-294589 | 2010-12-29 | ||
JP2011-139902 | 2011-06-23 | ||
JP2011139904 | 2011-06-23 | ||
JP2011-139904 | 2011-06-23 | ||
JP2011139902 | 2011-06-23 |
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CN102526998A CN102526998A (en) | 2012-07-04 |
CN102526998B true CN102526998B (en) | 2015-05-06 |
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CN201110463020.9A Active CN102526998B (en) | 2010-12-29 | 2011-12-26 | Golf ball |
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JP6406834B2 (en) * | 2013-05-31 | 2018-10-17 | 住友ゴム工業株式会社 | Golf ball |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5605512A (en) * | 1994-09-20 | 1997-02-25 | Sumitomo Rubber Industries, Ltd. | Golf ball |
CN101534908A (en) * | 2006-12-20 | 2009-09-16 | 宇部兴产株式会社 | Rubber composition for golf ball and golf ball |
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2011
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5605512A (en) * | 1994-09-20 | 1997-02-25 | Sumitomo Rubber Industries, Ltd. | Golf ball |
CN101534908A (en) * | 2006-12-20 | 2009-09-16 | 宇部兴产株式会社 | Rubber composition for golf ball and golf ball |
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