CN102485295B - Golf ball - Google Patents
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- CN102485295B CN102485295B CN201110411898.8A CN201110411898A CN102485295B CN 102485295 B CN102485295 B CN 102485295B CN 201110411898 A CN201110411898 A CN 201110411898A CN 102485295 B CN102485295 B CN 102485295B
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Abstract
The object of the invention is to provide a golf ball having a long flying distance after being kicked off or being batted. The invention is characterized in that the golf ball is provided with a globular-shaped ball core and at least one layer of housing covered on the globular-shaped ball core. The globular-shaped ball core is constituted by rubber compositions, which contains (a) base material rubber,(b) alpha , beta-unsaturated carboxylic acid/or metal salt having 3-8 carbon atoms serving as co-crosslinker, (c) crosslinking initiator, (d) carboxylic acid having 1-14 carbon atoms. When only (b) only the alpha , beta-unsaturated carboxylic acid having the 3-8 carbon atoms serving as co-crosslinker, the rubber composition furthermore comprising (e) metal compositions.
Description
Technical field
The present invention relates to a kind of large golf of flying distance of kicking off to bat, in more detail, relate to a kind of improvement of golf ball.
Background technology
While kicking off to bat (driver shot) as prolongation, the method for golf ball flight distance, for example, have, and method, the use of the high bounce-back property of use ball have the method for the ball of the hardness hardness that mind-set surface increases progressively from ball distribution.The former is improved the effect of golf initial velocity, the effect that the latter is improved and hits angle, reduces rotation.The golf that hits the high and low rotation of angle, its flying distance can increase.
As improving the anti-flexible technology of ball, for example, there is patent documentation 1～6.A kind of solid golf ball with kernel is disclosed in patent documentation 1,2, described kernel, with respect to rubber 100 weight portions, has mixed zinc acrylate resin, the palmitic acid as co-crosslinking auxiliary agent, stearic acid or myristic acid, the zinc oxide as co-crosslinking auxiliary agent, reaction speed retarding agent as co-crosslinker.
A kind of solid golf ball being obtained by rubber composition is disclosed in patent documentation 3, described rubber composition is with respect to base material rubber 100 weight portions, the α that contains 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 documentation 4 discloses a kind of golf, it is characterized in that, packing material, organic peroxide, α in base material rubber, beta-unsaturated carboxylic acid and/or its slaine are essential component, using the cross moulding thing of the rubber composition that wherein mixed saturated or unrighted acid mantoquita as part.
Patent documentation 5 discloses a kind of golf and constituent thereof, the composition of the foundation elasticity body of wherein, selecting from contain the group forming from polybutadiene and with other elastomeric mixed with polybutadiene thing, at least one slaine, radical initiator and the non-conjugated diene monomers of unsaturated monocarboxylic and being shaped.
Patent documentation 6 discloses a kind of manufacture method of golf, it is characterized in that, in elastomeric material, mix unsaturated carboxylic acid and/or its slaine, make in advance the masterbatch of unsaturated carboxylic acid and/or its slaine, utilize this masterbatch to make the rubber composition that contains described elastomeric material, be to using the heating molding of this rubber composition as the manufacture method of golf ball of 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 there is 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
[the quality % that above-mentioned numeral be take (A) and total metering (B) is 100 o'clock.]
(C) unsaturated carboxylic acid and/or its slaine
For example, patent documentation 7～10 discloses a kind of ball that hardness distributes that has.Patent documentation 7 discloses a kind of double-deck golf, wherein, by containing base material rubber, the ball that the rubber composition of co-crosslinker and organic peroxide forms, in the double-deck golf forming with shell, this ball is in the expression of 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, the hardness that case hardness 4 is 76～84 distributes, hardness 2 is roughly certain in hardness range, and, other meets the relation of 1 < 2 < 3≤4.
Patent documentation 8 discloses a kind of golf, wherein, in possessing solid ball and coated its solid golf ball of outer shell, described solid ball is formed by rubber composition, in this rubber composition, with respect to more than 60% cis-1 that contains of containing 60～100 quality %, 4-combination, utilize rubber substrate 100 mass parts of the synthetic polybutadiene rubber of rare earth element series catalysts, the organosulfur compound that also contains 0.1～5 mass parts, unsaturated carboxylic acid or its slaine, inorganic fillers and age resister, simultaneously, from initial stage load 10kgf, the deflection during to final load 130kgf is 2.0～4.0mm to the load of solid ball, and, solid ball has hardness as shown in the table and distributes.
[table 1]
| Solid ball hardness distributes | Shore D hardness |
| Center | 30～48 |
| Part apart from center 4mm | 34～52 |
| Part apart from center 8mm | 40～58 |
| Part (Q) apart from center 12mm | 43～61 |
| Inner side part (R) apart from surface 2～3mm | 36～54 |
| Surface (S) | 41～59 |
| Difference of hardness [(Q)-(S)] | 1～10 |
| Difference of hardness [(S)-(R)] | 3～10 |
Patent documentation 9 discloses a kind of solid golf ball, in possessing solid ball and coated its solid golf ball of outer shell, described solid ball is formed by rubber composition, in this rubber composition, with respect to more than 60% cis-1 that contains of containing 60～100 mass parts, 4-combination, utilize rubber substrate 100 mass parts of the synthetic polybutadiene rubber of rare earth element series catalysts, also contain 0.1～5 mass parts organosulfur compound, unsaturated carboxylic acid or its slaine, inorganic fillers, simultaneously, from initial stage load 10kgf, the deflection during to final load 130kgf is 2.0～4.0mm to the load of solid ball, and, solid ball has hardness as shown in the table and distributes.
[table 2]
| Solid ball hardness distributes | Shore D hardness |
| Center | 25～45 |
| Part apart from center 5～10mm | 39～58 |
| Part apart from center 15mm | 36～55 |
| Surface | 55～75 |
| Center and surperficial difference of hardness | 20～50 |
Patent documentation 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, be coated on forming in the multilayer solid golf ball of shell of most indentures on surface of intermediate layer, described ball be take elastomeric material and is made as main material, from center to the ball case hardness of ball, increase gradually, the difference of hardness on ball center and ball surface is shown in more than 15 with JIS-C scale of hardness, and be made as (I) apart from the position of the about 15mm in ball center and the section hardness mean value at ball center, while being made as (II) apart from the section hardness of the position of ball center 7.5mm, two difference of hardness (I)-(II) with JIS-C scale of hardness be shown in ± 2 in, described embracing layer of while, the hardness of intermediate layer and shell meets the condition of shell hardness > intermediate layer hardness > embracing layer hardness.
Prior art
Patent documentation
Patent documentation 1: Japanese kokai publication sho 61-37178 communique
Patent documentation 2: Japanese kokai publication sho 61-113475 communique
Patent documentation 3: Japanese kokai publication sho 61-253079 communique
Patent documentation 4: Japanese Patent Laid-Open 2008-212681 communique
Patent documentation 5: the special table of Japan Patent 2008-523952 communique
Patent documentation 6: Japanese Patent Laid-Open 2009-119256 communique
Patent documentation 7: Japanese patent laid-open 6-154357 communique
Patent documentation 8: Japanese Patent Laid-Open 2008-194471 communique
Patent documentation 9: Japanese Patent Laid-Open 2008-194473 communique
Patent documentation 10: Japanese Patent Laid-Open 2010-253268 communique
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide a kind of large golf of flying distance of the batting of kicking off.
The inventor be take provides the Novel golf of flying quality excellence as object, proposed about " a kind of golf; it is characterized in that; there is spherical ball and the shell of coated described spherical ball more than one deck at least; described spherical ball is formed by rubber composition; containing (a) base material rubber, (b) in described rubber composition is the α of 3～8 as the carbon number of co-crosslinker, beta-unsaturated carboxylic acid and/or its slaine, (c) cross-linked evocating agent, (d) carboxylic acid and (e) organosulfur compound; When (b) only contains carbon number as co-crosslinker, be the α of 3～8, during beta-unsaturated carboxylic acid, described rubber composition further contains (f) metallic compound " application (No. 2011-045286, Japan Patent Patent).
The invention that Japan Patent Patent relates to for No. 2011-045286, its hardness distribution mind-set surface from ball that will be intended to spherical ball roughly linearly increases.Because ball hardness distribution mind-set surface from ball roughly linearly increases, and the amplitude crescendo of outer just interior soft structure, cause rotation amount decline, improved the performance of flying distance.The distribution of ball hardness is the mind-set surface reason that roughly straight line increases from ball, has following viewpoint.When ball is shaped, for the temperature of ball inside, ball central part is higher, near ball surface, reduces.This is because the heat of reaction of cross-linking reaction is accumulated at ball central part.When ball is shaped, described (d) carboxylic acid and (b) carbon number are the α of 3～8, beta-unsaturated carboxylic acid reacting metal salt, the slaine of generation carboxylic acid.That is, (d) described carboxylate and carbon number are the α of 3～8, the slaine exchange cation of 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.The ball central part that the temperature of this cation exchange reaction in ball inside is higher easily occurs, and near surface, is difficult to gradually occur.In other words, the ball central part that is breaking at of metal corsslinking easily occurs, and near surface, becomes gradually difficult.Its result because the crosslink density of ball inside mind-set surface from ball increases, so think ball hardness, from ball mind-set surface roughly straight line increase.
And the inventor after further study, finds by adopting the carboxylic acid that (d) carbon number is 1～14, the outer Amplitude Ratio soft in just of spherical ball is in the past stronger, has reduced the rotation amount of batting of kicking off, thereby has completed the present invention.
Solve the means of problem
Golf of the present invention, it is characterized in that, there is ball and the shell of coated described spherical ball more than one deck at least, described spherical ball is formed by rubber composition, described rubber composition contain (a) base material rubber, (b) as the carbon number of co-crosslinker the α between 3～8, the carboxylic acid that beta-unsaturated carboxylic acid and/or its slaine, (c) cross-linked evocating agent, (d) carbon number are 1～14; (b) as co-crosslinker, only contain carbon number between the α of 3～8, during beta-unsaturated carboxylic acid, further contain (e) metallic compound.The present invention is by formation as above, and spherical ball is the amplitude grow of just interior soft structure outward, and the rotation amount of the batting of kicking off reduces, flying distance increase.In addition, the linearity of the spherical ball that the present invention uses its ball hardness distribution sometimes can a part reduce, and in this case, outer just interior soft Amplitude Ratio is in the past stronger, and the rotation amount of the batting of kicking off reduces.
By adopting the aliphatic acid that (d) carbon number is 1～14, the outer Amplitude Ratio soft in just of spherical ball in the past stronger reason has following consideration.As mentioned above, carboxylic acid and carbon number are the α of 3～8, the slaine exchange cation of 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 of cutting off this metal corsslinking is subject to the impact that added carbon number is the molal quantity of 1～14 carboxylic acid.Meanwhile, the carboxylic acid that carbon number is 1～14 also works as the plasticizer of spherical ball.If increase adds carbon number and be the combined amount (quality) of 1～14 carboxylic acid, ball is whole to be understood and softens.This plasticization effect is subject to the impact of the combined amount (quality) of added carboxylic acid.Consider these effects, by using the carboxylic acid of carbon number few (molecular weight is little), with use carbon number many (molecular weight is large) carboxylic acid time compare, in the situation that identical combined amount (quality), addible molal quantity increase.That is, can, when the spherical ball integral body that suppresses to cause because of plasticization effect is softening, improve again the action effect that cuts off metal corsslinking.
The effect of invention
According to the present invention, can provide a kind of large golf of flying distance of kicking off to bat.
Accompanying drawing explanation
Fig. 1: show the sectional view that one of an embodiment of the present invention related golf part is cut open.
Fig. 2: show the chart that ball hardness distributes.
Fig. 3: show the chart that ball hardness distributes.
Fig. 4: show the chart that ball hardness distributes.
Fig. 5: show the chart that ball hardness distributes.
Fig. 6: show the chart that ball hardness distributes.
Fig. 7: show the chart that ball hardness distributes.
Fig. 8: show the chart that ball hardness distributes.
Fig. 9: show the chart that ball hardness distributes.
Figure 10: show the chart that ball hardness distributes.
Figure 11: show the chart that ball hardness distributes.
Figure 12: show the chart that ball hardness distributes.
Figure 13: show the chart that ball hardness distributes.
Figure 14: show the chart that ball hardness distributes.
Figure 15: show the chart that ball hardness distributes.
Figure 16: show the chart that ball hardness distributes.
Figure 17: show the chart that ball hardness distributes.
The specific embodiment
Golf of the present invention, it is characterized in that, there is spherical ball and the shell of coated described spherical ball more than one deck at least, described spherical ball is formed by rubber composition, described rubber composition contain (a) base material rubber, (b) as the carbon number of co-crosslinker the α between 3～8, the carboxylic acid that beta-unsaturated carboxylic acid and/or its slaine, (c) cross-linked evocating agent, (d) carbon number are 1～14; When (b) only contains carbon number between the α of 3～8 as co-crosslinker, during beta-unsaturated carboxylic acid, described rubber composition further contains (e) metallic compound.
First, (a) base material rubber using in the present invention is described.As (a) base material rubber, can use natural rubber and/or synthetic rubber, for example, can use polybutadiene rubber, natural rubber, polyisoprene rubber, styrene polybutadiene rubber, ethylene-propylene-diene rubber (EPDM) etc.These may be used alone, two or more kinds can also be used.Wherein, more than containing 40 quality %, preferably more than 80 quality %, more preferably the high-cis polybutadiene to the favourable cis-Isosorbide-5-Nitrae-combination that rebounds of 90 quality % is suitable especially.
Described high-cis polybutadiene, preferably 1, the content of 2-vinyl combination is below 2 quality %, more preferably below 1.7 quality %, further preferably below 1.5 quality %.If the content of 1,2-vinyl combination is too much, bounce-back property can reduce sometimes.
Described high-cis polybutadiene, with the material that rare earth element series catalysts is synthetic, be advisable, particularly, when use has adopted as the neodymium series catalysts of the neodymium compound of group of the lanthanides row rare-earth element compound, with excellent polymerization activity, obtain 1,4-cis is high in conjunction with content, 1,2-ethene is in conjunction with the low polybutadiene rubber of content, thereby preferably.
Described high-cis polybutadiene, Mooney viscosity (ML
1+4(100 ℃)) preferably more than 30, more preferably more than 32, further preferably more than 35, preferably below 140, more preferably below 120, further preferably below 100, most preferably below 80.In addition, said Mooney viscosity (ML in the present invention
1+4(100 ℃)) refer to, take JIS K6300 as benchmark, use L rotor, the numerical value of measuring under 1 minute preheating time, 4 minutes rotor time, the condition of 100 ℃.
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 below 6.0, more preferably below 5.0, further preferably below 4.0, most preferably below 3.4.The molecular weight distribution of high-cis polybutadiene (Mw/Mn), if too small, may reduce operability, if excessive, may fall low bounce.In addition, molecular weight distribution, by gel permeation chromatography (East ソ-company system, " HLC-8120GPC "), use differential refractometer as detector, GMHHXL (East ソ-company system), chromatogram column temperature chromatographic column:: 40 ℃, mobile phase: measuring under the condition of oxolane, is to using polystyrene standard as numerical value that scaled value was calculated.
Secondly, just (b) carbon number is the α of 3～8, and beta-unsaturated carboxylic acid and/or its slaine describe.(b) carbon number is the α of 3～8, and beta-unsaturated carboxylic acid and/or its slaine are to be mixed in rubber composition as co-crosslinker, by glycerol polymerization, in the strand of base material rubber, play the effect that rubber molecule is cross-linked.In the rubber composition using in the present invention, as co-crosslinker, only containing carbon number is the α of 3～8, and during beta-unsaturated carboxylic acid, rubber composition further contains (e) metallic compound 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 carbon number using as co-crosslinker is the α of 3～8, same effect 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, as any composition, also can use (e) metallic compound.
As carbon number, be the α of 3～8, beta-unsaturated carboxylic acid, can enumerate as acrylic acid, methacrylic acid, fumaric acid, maleic acid, butenoic acid etc.
As formation carbon number, be the α of 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; 3 valence metal ions such as aluminium; Other ion such as tin, zirconium.Described metal ingredient can be used 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 be the α of 3～8 by use carbon number, the divalent metal salt of beta-unsaturated carboxylic acid easily generates metal corsslinking between rubber molecule.Particularly, as divalent metal salt, from the bounce-back of resulting golf is high, consider, zinc acrylate resin is advisable.In addition, carbon number is the α of 3～8, beta-unsaturated carboxylic acid and/or its slaine, can be separately or two or more be used in combination.
(b) carbon number is the α of 3～8, the content of beta-unsaturated carboxylic acid and/or its slaine is with respect to (a) base material 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, for the parts that make to be formed by rubber composition have suitable hardness, don't fail to increase the amount of aftermentioned (c) cross-linked evocating agent, will have the anti-flexible tendency that reduces golf 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 surpasses 50 mass parts, the parts that 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 for crosslinked (a) base material rubber constituent.As (c) cross-linked evocating agent, with organic peroxide, be advisable.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 peroxide etc.These organic peroxides can a kind be used separately, also can two or more and use.In the middle of these, preferably use cumyl peroxide.
(c) content of cross-linked evocating agent is with respect to (a) base material 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 that formed by rubber composition are too soft, the bounce-back of golf has the tendency of decline, if surpass 5.0 mass parts,, for the parts that guarantee to be formed by rubber composition have suitable hardness, be necessary to reduce the use amount of described (b) co-crosslinker, like this, the bounce-back of golf is inadequate, likely makes durability worsen.
Then the carboxylic acid that, just (d) carbon number is 1～14 describes.The carboxylic acid that (d) carbon number using in the present invention is 1～14, so long as there is the compound that carbon number is 1～14 carboxyl, just being not particularly limited, is the α of 3～8 but do not comprise (b) carbon number using as co-crosslinker, beta-unsaturated carboxylic acid.Think the carboxylic acid that (d) carbon number is 1～14, when ball forms, at the central part of ball, 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.
(d) the carboxylic acid preferred aliphat carboxylic acid that described carbon number is 1～14 (being sometimes called for short " aliphatic acid " in the present invention).The carboxylic acid that is 1～14 as described carbon number, the carboxylic acid that preferably carbon number is 1～13, the carboxylic acid that more preferably carbon number is 1～12.The carbon number of carboxylic acid reduces, and understands the problems such as toxic or foul smell.
Described aliphatic acid can be any one in saturated fatty acid, unrighted acid, preferably saturated fatty acid.As the concrete example of described aliphatic acid, can enumerate as: butyric acid (C4), valeric acid (C5), caproic acid (C6), enanthylic acid (C7), caprylic acid (sad) (C8), pelargonic acid (C9), capric acid (capric acid) (C10), laurate (C12), myristic acid (C14), myristoleic acid (C14) etc.Described aliphatic acid can be used separately or as two or more mixture.As described aliphatic acid, preferably caprylic acid (sad) (C8), pelargonic acid (C9), capric acid (capric acid) (C10), laurate (C12), myristic acid (C14) and myristoleic acid (C14), further preferred caprylic acid (sad) (C8), capric acid (capric acid) (C10) and laurate (C12).
(d) content of the carboxylic acid that described carbon number is 1～14 is with respect to (a) base material 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 13 mass parts, more preferably below 12 mass parts, further preferably below 11 mass parts.If content is very few, the effect of adding the carboxylic acid that (d) carbon number is 1～14 is insufficient, and the outer just interior soft amplitude of spherical ball likely diminishes.In addition, if content is too much, resulting ball hardness likely can globality decline, and bounce-back property reduces.Moreover, for improving the zinc acrylate resin that uses as co-crosslinker to the dispersiveness of rubber, the surface of the carboxylic acid that is 1～14 with carbon number sometimes processing zinc acrylate resin.So use and take carboxylic acid that carbon number is 1～14 when zinc acrylate resin is carried out to surface treatment, in the present invention, the amount of the carboxylic acid that is 1～14 as the carbon number of surface conditioning agent is included in the middle of the content of the carboxylic acid that (d) carbon number is 1～14.For example, when the surface treatment amount of the carboxylic acid that use carbon number is 1～14 is zinc acrylate resin 25 mass parts of 10 quality %, carbon number is that the amount of 1～14 carboxylic acid is 2.5 mass parts, the amount of zinc acrylate resin is 22.5 mass parts, the content of the carboxylic acid that is 1～14 as (d) carbon number, will calculate 2.5 mass parts interior.
The rubber composition that the present invention uses, as co-crosslinker, only containing carbon number is the α of 3～8, during beta-unsaturated carboxylic acid, as must further containing (e) metallic compound by composition.As (e) above-mentioned 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 carbonated 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 reaction, forms metal corsslinking.In addition, by using zinc compound, can obtain the golf that bounce-back property is high.Can be independent a kind use these (e) metallic compounds, also can two or more and use.
The ball that the present invention uses preferably further contains (f) organosulfur compound with rubber composition.Outside the carboxylic acid that described ball is 1～14 with rubber composition at (d) carbon number, by using in the lump with (f) organosulfur compound, the sustainable roughly linearity that ball hardness distributes, the amplitude of the outer just interior soft structure of control ball of maintaining.As (f) organosulfur compound, so long as contain the organic compound of sulphur atom at molecule, be not particularly limited, can enumerate as the organic compound with the polythiaether key that mercapto (SH) or number of sulfur atoms are 2～4 (S-S-,-S-S-S-or-S-S-S-S-), 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 be 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, 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.The viewpoint that hardness based on spherical ball distributes and increases, as (f) organosulfur compound, preferably has organosulfur compound or its slaine of mercapto (SH), preferably benzenethiol class, thionaphthol class or their slaine.As slaine, can enumerate as 1 valency slaines such as: sodium, lithium, potassium, copper (I), silver (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 enumerate as benzenethiol; 4-fluoro thiophenol, 2,5-difluoro thiophenol, 2,4,5-trifluoro-benzene thiophenol, 2,4,5, the benzenethiol class that 6-phenyl tetrafluoride thiophenol, phenyl-pentafluoride thiophenol etc. are replaced by fluorine; 2-chlorothio-phenol, 4-chlorothio-phenol, 2,4-thiophenol dichlorobenzene, 2,5-thiophenol dichlorobenzene, 2,4,5-trichloro-benzenes thiophenol, 2,4,5, the benzenethiol class that 6-tetrachlorobenzene thiophenol, reptazin etc. are replaced by chlorine; 4-bromo thiophenol, 2,5-dibromobenzene thiophenol, 2,4,5-tribromo-benzene thiophenol, 2,4,5, the benzenethiol class that 6-tetrabromo-benzene thiophenol, phenyl-pentabromide thiophenol etc. are replaced by bromine; 4-iodobenzene thiophenol, 2,5-diiodo-benzene thiophenol, 2,4,5-triiodo-benzene thiophenol, 2,4,5, the benzenethiol class that 6-tetraiodo-benzene thiophenol, 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, the chloro-1-thionaphthol of 2-, the bromo-1-thionaphthol of 2-, the fluoro-1-thionaphthol of 2-, 2-cyano group-1-thionaphthol, 2-acetyl group-1-thionaphthol, the chloro-2-thionaphthol of 1-, the bromo-2-thionaphthol of 1-, the fluoro-2-thionaphthol of 1-, 1-cyano group-2-thionaphthol, 1-acetyl group-2-thionaphthol or their slaine, preferably 1-thionaphthol, 2-thionaphthol and their zinc salt.
As sulfenamide, be 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 the waste acyls of two hydroxylamine bases, be organic sulfur compound, can enumerate as the waste acyl list of tetramethyl two hydroxylamine bases sulphur, tetramethylthiuram disulfide, tetraethylthiuram disulfide, waste acyl two sulphur of the tetrabutyl two hydroxylamine bases, waste acyl four sulphur of two pentylidene two hydroxylamine bases 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, it is organic sulfur compound, can enumerate as 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), sodium salt, zinc salt, mantoquita and the cyclohexyl amine salt of 2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl) mercaptobenzothiazoler, 2-(2,6-diethyl-4-morpholino sulphur) benzothiazole etc.
Described (f) organosulfur compound can be used separately or two kinds of above mixing.
(f) content of organosulfur compound, with respect to (a) base material 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, the effect that can not get adding (f) organosulfur compound, the bounce-back that likely can not improve golf.In addition, if surpass 5.0 mass parts, the compress variation of resulting golf increases, and likely falls low bounce.
The rubber composition that the present invention uses, as required, can also add pigment, for adjusting the additives such as filler, age resistor, peptizer, softening agent of weight etc.In addition, as mentioned above, the rubber composition using in the present invention, as co-crosslinker, only containing carbon number is the α of 3～8, during beta-unsaturated carboxylic acid, preferred rubber composition is further containing (e) metallic compound.
As the pigment mixing 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 good reason of covering, preferably use rutile-type.In addition, the content of titanium oxide is with respect to (a) base material 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 is to mix in order 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 is with respect to (a) base material 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, blue not obvious, seem some yellowing, if surpass 0.2 mass parts, excessively blue, lost distinct white appearance.
As the filler using in rubber composition, be mainly in order to adjust the weight as the resulting golf of final products, and the weight conditioning agent mixing can mix as required.As described filler, can enumerate the inorganic fillers such as zinc oxide, barium sulfate, calcium carbonate, magnesia, tungsten powder, molybdenum powder.The content of described filler is with respect to base material 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, less than 0.5 mass parts, is difficult to adjust weight, if surpass 30 mass parts, the percentage by weight of rubber constituent diminishes, has the tendency of falling low bounce.
The content of described age resistor is with respect to (a) base material rubber 100 mass parts, preferably more than 0.1 mass parts, below 1 mass parts.In addition, the content of peptizer is with respect to (a) base material rubber 100 mass parts, preferably more than 0.1 mass parts, below 5 mass parts.
The rubber composition that the present invention uses, that mixing (a) base material rubber, (b) carbon number are the α of 3～8, the carboxylic acid that beta-unsaturated carboxylic acid and/or its slaine, (c) cross-linked evocating agent, (d) carbon number are 1～14 and as required other additive, obtain through mixing.The method of mixing is not particularly limited, and such as known mullers such as can using mixing roller, Ben Baili banbury, kneader, carries out mixing.
The globose nucleus that golf of the present invention has, can be by obtaining the rubber composition after mixing at metal die internal shaping.Be shaped the temperature of spherical ball preferably more than 120 ℃, more preferably more than 150 ℃, further preferably more than 160 ℃, preferably below 170 ℃.If forming temperature surpasses 170 ℃, ball case hardness has the tendency of reduction.In addition, the preferred 2.9MPa～11.8MPa of pressure during shaping.Be shaped hours preferably 10 minutes～60 minutes.
Above-mentioned spherical ball, on average divides ball radius, measures the hardness of this average 9 points dividing with 12.5% interval, these hardness when mapping to the distance at ball center, are obtained to the R of linear curve of approximation by least square method
2preferably more than 0.95.R
2if more than 0.95, linearity that hardness of ball distributes is high, reduced the rotation amount of kicking off to bat, improved the performance of flying distance.
Any radius of spherical ball is on average divided into 9 equal portions with 12.5% interval, measures this average 9 some JIS-C hardness of dividing.That is 9 some places that are, 0% (ball center), 12.5%, 25%, 37.5%, 50%, 62.5%, 75%, 87.5%, 100% (ball surface) in the distance apart from ball center 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 to chart as curve.In the present invention, the linear curve of approximation R being obtained by this curve negotiating least square method
2preferably more than 0.95.The R of the linear curve of approximation of obtaining by least square method
2it is the linear index of the resulting curve of judgement.In the present invention, R
2if more than 0.95, mean that the hardness of this spherical ball distributes roughly linearly.Use the hardness roughly golf of the spherical ball of linearity that distributes, can reduce the rotation amount of the batting of kicking off.Its result, the flying distance of the batting of kicking off increases.The R of described linear curve of approximation
2more preferably more than 0.96.By improving linearity, the flying distance of the batting of kicking off can be larger.
The difference of hardness of the case hardness Hs of described spherical ball and core rigidities Ho (Hs-Ho), represents with JIS-C hardness, preferably more than 27, more preferably more than 28, further preferably more than 30, preferably below 80, more preferably below 70, further preferably below 60.If ball surface is large with the difference of hardness at ball center, can obtains compared with high strike and go out angle and lower rotation, golf that flying distance is large.On the other hand, if difference of hardness is excessive, the durability of resulting golf reduces sometimes.
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 30 o'clock with thumb down with JIS-C hardness, sometimes because crossing the soft low bounce that falls.In addition, the core rigidities Ho of spherical ball, represents with JIS-C hardness, preferably below 70, more preferably below 65, further preferably below 60.If described core rigidities Ho represents to surpass 70 with JIS-C hardness, really up to the mark, have a tendency that reduces 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 below 100, more preferably below 95.If represent with JIS-C hardness, the case hardness of described spherical ball is decided to be more than 76, soft can not become excessively soft of spherical ball, can obtain good bounce-back.In addition, if represent with JIS-C hardness, the case hardness of described spherical ball is decided to be below 100, spherical ball can be not really up to the mark, can obtain good touch.
The diameter of described spherical ball, more than preferred 34.8mm, more preferably more than 36.8mm, further preferably more than 38.8mm, preferably below 42.2mm, more preferably below 41.8mm, below further preferred 41.2mm, most preferably below 40.8mm.If the diameter of described spherical ball is more than 34.8mm, the thickness of shell can be not blocked up, and bounce-back property can be better.On the other hand, if the diameter of spherical ball below 42.2mm, shell can be excessively not thin, more can bring into play the function of shell.
Described spherical ball, when diameter is 34.8mm～42.2mm, from the load condition of initial stage load 98N till the compress variation (towards the center amount of contraction of compression direction) during the load of final load 1275N, preferably more than 2.0mm, more preferably more than 2.8mm, preferably below 6.0mm, more preferably below 5.0mm.If described compress variation is more than 2.0mm, touch is better, if below 6.0mm, bounce-back property is better.
Golf ball of the present invention is to be formed with composition by the shell that contains resinous principle.As described resinous principle, can 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 ユ Port Application (joint-stock company) is peddled with trade name " Ha イ ト レ Le (registration mark) ", the thermoplastic styrene elastomer that Mitsubishi Chemical (joint-stock company) peddles with trade name " ラ バ ロ Application (registration mark) " etc.
As described ionomer resin, can enumerate as: alkene and carbon number are the α of 3～8, carboxyl at least a portion in the bipolymer of beta-unsaturated carboxylic acid is by material that metal ion neutralized, alkene and carbon number are the α of 3～8, beta-unsaturated carboxylic acid and α, the material that carboxyl at least a portion of the terpolymer of beta-unsaturated carboxylic acid ester is neutralized by metal ion, or their mixture.As described alkene, preferably carbon number is the alkene of 2～8, can enumerate as ethene, propylene, butylene, amylene, hexene, heptene, octene etc., particularly preferably ethene.As carbon number, be the α of 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 be used 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 ユ Port Application Port リ ケ ミ カ Le (joint-stock company) peddles " Ha イ ミ ラ Application (Himilan) (registration mark) (and 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., have Ha イ ミ ラ Application 1856 (Na), Ha イ ミ ラ Application 1855 (Zn) etc. as terpolymer ionomers resin ".
Further, the ionomer resin of peddling as デユポ Application company, 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., as terpolymer ionomers resin, there is サ-リ Application 8120 (Na), サ-リ Application 8320 (Na), サ-リ Application 9320 (Zn), サ-リ Application 6320 (Mg), HPF1000 (Mg), HPF2000 (Mg) etc.) ".
In addition, the ionomer resin of peddling as エ Network ソ Application モ-PVC Le chemistry (joint-stock company), 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, the Zn, Li, the Mg etc. that in bracket after the trade name of described ionomer resin, record, represent they in and the metal species of metal ion.Described ionomer resin can be used alone, and also can two or more mix use.
The shell composition that forms golf ball of the present invention, as resinous principle, preferably contains thermoplastic polyurethane elastomer or ionomer resin.While using ionomer resin, preferably with thermoplastic styrene elastomer use.Polyurethane in composition resin composition or the containing ratio of ionomer resin for shell, preferably more than 50 quality %, more preferably more than 60 quality %, further preferably more than 70 quality %.
Described shell composition, except above-mentioned resinous principle, in the scope of harmless shell performance, can also contain weight conditioning agent, dispersant, age resistor, ultra-violet absorber, light stabilizer, fluorescent material or the fluorescent whitening agents etc. such as pigment composition, zinc oxide, calcium carbonate and barium sulfate such as Chinese white (such as titanium oxide), blue pigment, red pigment.
The content of described Chinese white (for example titanium oxide) is with respect to resinous principle 100 mass parts that form 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, can give shell covering.In addition, if the content of Chinese white surpasses 10 mass parts, reduce sometimes the durability of the shell obtaining.
Slab (slab) hardness of composition for described shell, preferably does suitably to set according to the golf performance of expectation.For example, while paying attention to the distance type golf of flying distance, shell represents with Shore D hardness by the slab hardness of composition, preferably more than 50, more preferably more than 55, preferably below 80, more preferably below 70.By shell is made as more than 50 by the slab hardness of composition, when kicking off batting and iron slot, can obtain the golf that high strike goes out angle, low rotation, thereby improve flying distance.In addition, by shell is made as below 80 by the hardness of composition, can obtain the golf of excellent in te pins of durability.In addition, while paying attention to controlled rotation (spin) type golf, shell represents with Shore D hardness by the slab hardness of composition, is preferably discontented with 50, preferably more than 20, more preferably more than 25.Shell represents with Shore D hardness by the slab hardness of composition, if be discontented with 50, resulting golf, it is by ball of the present invention, in the batting of kicking off of seeking high flying distance, during Bail out, rotation amount on ridge easily stops raising, Guo.In addition, can, by slab hardness is made as more than 20, can improve marresistance energy.While having a plurality of outer shell, form the slab hardness of composition for each layer of shell, as long as within above-mentioned scope, can be the same or different.
Method as shaping golf ball of the present invention, can enumerate as: by shell with composition be configured as the shell of hollow shelly, again with the method for the coated ball compression molding of a plurality of shells (preferably by shell with composition be configured as half shell of hollow shelly, with the method for the coated ball compression molding of 2 piece of half shell), or, the method by shell with composition direct injection molding forming on ball.
By compress moulding method, during shaping shell, half shell is shaped and also can be undertaken by any means in compression forming method or injection moulding method, but suitable be compression forming method.As compression molding shell, with composition, be configured as the condition of half shell, can enumerate as the pressure more than 1MPa, below 20MPa, the mobile temperature that starts with respect to shell with composition, forming temperature is more than-20 ℃, below 70 ℃.By setting described molding condition, can be configured as half shell of even thickness.As the method for the shell that is shaped with half shell, can enumerate as: with the method for the coated ball compression molding of 2 piece of half shell.As compression molding half shell, be configured as the condition of shell, can enumerate as: more than 0.5MPa, the forming pressure below 25MPa, the mobile temperature that starts with respect to shell with composition, forming temperature is more than-20 ℃, below 70 ℃.By setting above-mentioned molding condition, can be configured as the uniform golf ball of outer casing thickness.
When injection molding forming shell is configured as shell with composition, can use the resulting granular shell of extruding to carry out injection molding forming with composition, or, by shell material dry mixed such as substrate resin composition and pigment, direct injection molding forming.As shell, be shaped and use lower mold, preferably use to there is hemispherical die cavity, with the part of kick, kick, also double as the locking pin that can advance and retreat.The shaping of the shell being undertaken by injection molding forming, by releasing locking pin, drop into ball and make its fixing after, inject shell composition, carry out coolingly, the shell that can be shaped, for example, in the metal die of the good shape of the pressure fixing with 9MPa～15MPa, the shell composition of injection heating to 200 ℃ in 0.5 second～5 seconds～250 ℃, then cooling in 10 seconds～60 seconds and open mould.
During shaping shell, conventionally on surface, form the pit that is called as indenture.The sum of indenture preferably 200 above below 500.When indenture sum is discontented with 200, be difficult to obtain the effect of indenture.In addition, if the sum of indenture surpasses 500, the size decreases of each indenture, is difficult to obtain the effect of indenture.Formed indenture shape (plane is seen shape), is not particularly limited, and can be used alone or two or more is used in combination circle, triangle roughly, quadrangle roughly, pentagon roughly, the polygons such as hexagon roughly, other indefinite shape.
The thickness of described shell, preferably below 4.0mm, more preferably below 3.0mm, further preferably below 2.0mm.If the thickness of shell is below 4.0mm, the bounce-back of resulting golf and touch can be better.The thickness of described shell, preferably more than 0.3mm, more preferably more than 0.5mm, further preferably more than 0.8mm, particularly preferably more than 1.0mm.If the thickness of shell is discontented with 0.3mm, reduce sometimes durability and the wearability of shell.During a plurality of outer shell, the aggregate thickness of a plurality of outer shells is preferably in above-mentioned scope.
By the golf main body of the shell that has been shaped, from metal die, take out, can be as required, preferably carry out deburring, clean, the surface treatment such as sandblast.In addition, also can, according to expectation, film or form mark.Described thickness of filming, is not particularly limited, preferably more than 5 μ m, more preferably more than 7 μ m, preferably below 50 μ m, more preferably below 40 μ m, further preferably below 30 μ m.If thickness is discontented with 5 μ m, because continuing to use, the easily abrasion of filming disappear, if thickness surpasses 50 μ m, can reduce the effect of indenture, thereby reduce the flying quality of golf.
Golf of the present invention, when diameter is 40mm～45mm, compress variation (to the amount of contraction of compression direction) from the state of load initial stage load 98N when loading final load 1275N, more than being preferably 2.0mm, more preferably more than 2.4mm, further preferably more than 2.5mm, most preferably more than 2.8mm, preferably below 5.0mm, more preferably below 4.5mm.The golf of described compress variation more than 2.0mm, hardness is really up to the mark, and touch is good.On the other hand, by compress variation, be made as below 5.0mm, bounce-back property increases.
The structure of golf of the present invention, as long as have shell 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 shows that one of embodiment of the present invention related golf 2 parts are cut open.Golf 2 has the shell 12 of spherical ball 4 and coated spherical ball 4.On the surface of this shell, form a plurality of indentures 14.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 has omitted the diagram of these layers.
Described spherical ball preferred single layer structure.The spherical ball of single layer structure, while catching a packet at the interface of sandwich construction, noenergy loss, can improve bounce-back.In addition, shell can be structure more than one deck, also can have single layer structure, or at least two layers of above sandwich construction.As golf of the present invention, can enumerate as: by spherical ball and coated as described in spherical ball and double-deck golf that the single layer enclosure that configures forms; The multi-layer golf ball (containing three layer golf balls) of 2 layers of above shell that there is spherical ball and coated described spherical ball and configure; Have spherical ball, at described ball, around arrange containing a silk rubber layer, and the curled hair golf of the coated described shell arranging containing silk rubber layer etc.The golf of above-mentioned arbitrary structures is all applicable to the present invention.
Embodiment
To the present invention, elaborate according to embodiment below, but the present invention is not defined to following embodiment, so long as do not exceed the change of aim scope of the present invention, within any embodiment is included in scope of the present invention.
[evaluation method]
(1) compress variation (mm)
To ball or golf, while measuring its load condition from initial stage load 98N to the load of final load 1275N at the deflection (amount that ball or golf shrink on compression direction) of compression direction.
(2) rebound coefficient
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 are respectively measured 12, get its mean value as the rebound coefficient of this ball or golf.In addition, rebound coefficient, in table 3～table 5, shows with the poor of the rebound coefficient with golf (ball) No.15.In table 6～table 8, with the poor of the rebound coefficient with golf (ball) No.31, show.
(3) slab hardness (Shore D hardness)
Use shell composition, by injection molding forming, make the thin slice that thickness is approximately 2mm, at 23 ℃, preserve 2 weeks.In order not measured the impact of substrate etc., to this thin slice, with 3 above overlapping states, use, macromolecule gauge company system automatic durometer P1 type regulation, that possess spring hardometer Shore D type according to ASTM-D2240, measure.
(4) ball hardness distribution (JIS-C hardness)
Use possesses the automatic durometer P1 of spring hardometer JIS-C type macromolecule gauge company's system type, measures the JIS-C hardness of ball surface part as ball case hardness.In addition, ball is cut into hemispherical, measures the center of section and from center to the hardness of the distance of regulation.In addition, measure the hardness of 4 points from center to predetermined distance, calculate its mean value.
(5) kick off to bat flying distance (m) and rotation amount (rpm)
Swinging on the M/C of robot of go Le Off ラ ボ ラ ト リ-company system, load onto ferrule W#1 rod processed (11 ° of SRI sports company system, XXIO S ロ Off ト), with bar head speed 40m/, hit golf second, measure golf ball spin speed and flying distance (distance from transmitting starting point to static place) after just hitting.Each golf is measured 12 times, gets its mean value as the measured value of this golf.In addition, the rotary speed of the golf after just having batted, by taking pictures continuously to measure to the golf being hit.Kick off flying distance and the rotation amount of batting, in table 3～table 5, to show with the poor of golf (ball) No.15, in table 6～table 8, to show with the poor of golf (ball) No.31.
[making of golf]
(1) making of ball
By mixing roller, mixing rubber composition of sneaking into as shown in table 3～table 8 with heating pressurization in 170 ℃, 20 minutes, obtains the spherical ball of diameter 39.8mm in having the upper lower mold of hemispherical die cavity.
[table 3]
[table 4]
[table 5]
[table 6]
[table 7]
[table 8]
BR730:JSR company system, high-cis polybutadiene (content=96 quality % of cis-Isosorbide-5-Nitrae-combination, the content=1.3 quality % of 1,2-ethene combination, Mooney viscosity (ML
1+4(100 ℃))=55, molecular weight distribution (Mw/Mn)=3)
Sanceler SR: San Xin chemical industrial company zinc acrylate resin processed (10 quality % stearic acid face coat product)
The plumbous company's system " silver-colored ridge R " of zinc oxide: Dong Bangya
Barium sulfate: Sakai chemical company system " barium sulfate BD ", is adjusted into 45.4g2-thionaphthol (2-Thio naphthol) by the golf quality finally obtaining: Tokyo changes into industrial group's system
Cumyl peroxide: You company system, " パ-Network ミ Le (registration mark) D (cumyl peroxide) "
Sad: Tokyo changes into industrial group's system (purity is more than 98%)
Capric acid: Tokyo changes into industrial group's system (purity is more than 98%)
Laurate: Tokyo changes into industrial group's system (purity is more than 98%)
Myristic acid: Tokyo changes into industrial group's system (purity is more than 98%)
Stearic acid: Tokyo changes into industrial group's system (purity is more than 98%)
(2) making of shell
Secondly, by the twin shaft type extruder that mixes, push shell material of sneaking into as shown in table 9, granulation shape 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 ℃ of heating.By the shell composition obtaining, on the spherical ball obtaining as stated above, carry out injection molding forming, make the golf of the shell with spherical ball and coated described ball.
[table 9]
| Shell composition No. | A | B |
| Himilan 1605 | 50 | - |
| Himilan 1706 | 50 | - |
| Elastollan XNY97A | - | 100 |
| Titanium oxide | 4 | 4 |
| Slab hardness (Shore D) | 65 | 47 |
Mix: mass parts
Ha イ ミ ラ Application 1605 (Himilan 1605): the ethylene-methacrylic acid copolymer of the sodium ion neutralization of Mitsui デ ユ Port Application ポリ ケミカル company system is ionomer resin
Ha イ ミ ラ Application 1706 (Himilan 1706): the ethylene-methacrylic acid copolymer of the zinc ion neutralization of Mitsui デ ユ Port Application ポリ ケミカル company system is ionomer resin
エ ラ ス ト ラ Application XNY97A (Elastollan XNY97A): BASF Japanese firm heats plasticity polyurethane elastomers
The golf being formed by rubber composition, there is ball and the shell of coated described spherical ball more than one deck at least, described rubber composition contain (a) base material rubber, (b) as the carbon number of co-crosslinker the α between 3～8, the carboxylic acid that beta-unsaturated carboxylic acid and/or its slaine, (c) cross-linked evocating agent, (d) carbon number are 1～14; When (b) only contains carbon number between the α of 3～8 as co-crosslinker, during beta-unsaturated carboxylic acid, described rubber composition further contains (e) metallic compound.Any one in such golf, its kick off batting rotation amount few, flying distance is large.
Utilizability in industry
Golf of the present invention, the flying distance of the batting of kicking off is large.
Claims (9)
1. a golf, is characterized in that, has spherical ball and the shell of the coated described spherical ball of one deck at least, and described spherical ball is formed by rubber composition,
It is the α of 3～8 as the carbon number of co-crosslinker that described rubber composition contains (a) base material rubber, (b), the carboxylic acid that beta-unsaturated carboxylic acid and/or its slaine, (c) cross-linked evocating agent, (d) carbon number are 1～14;
When (b) only contains carbon number as co-crosslinker, be the α of 3～8, during beta-unsaturated carboxylic acid, described rubber composition further contains (e) metallic compound.
2. the golf of recording as claim 1, wherein, in described rubber composition, with respect to (a) base material rubber 100 mass parts, the carboxylic acid that (d) carbon number that contains 0.5 mass parts～13 mass parts is 1～14.
3. the golf of recording as claim 1, wherein, the case hardness of described spherical ball and the difference of hardness of core rigidities are shown in more than 27 with JIS-C scale of hardness.
4. the golf of recording as claim 1, wherein, it is the α of 3～8 as the carbon number of co-crosslinker that described rubber composition contains (b), the slaine of beta-unsaturated carboxylic acid.
5. the golf of recording as claim 1, wherein, the carboxylic acid that (d) described carbon number is 1～14 is aliphatic acid.
6. the golf of recording as claim 1, wherein, described rubber composition further contains (f) organosulfur compound.
7. the golf of recording as claim 6, wherein, (f) described organosulfur compound is benzenethiol class, diphenyl disulfide compound class, thionaphthol class, thiuram disulfides or their slaine.
8. the golf of recording as claim 6, wherein, in described rubber composition, with respect to (a) base material rubber 100 mass parts, (f) organosulfur compound that contains 0.05 mass parts～5 mass parts.
9. the golf of recording as claim 1～8 any one, wherein, in described rubber composition, with respect to (a) base material rubber 100 mass parts, (b) carbon number that contains 15 mass parts～50 mass parts is the α of 3～8, beta-unsaturated carboxylic acid and/or its slaine.
Applications Claiming Priority (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010270767 | 2010-12-03 | ||
| JP2010-270767 | 2010-12-03 | ||
| JP2010-294590 | 2010-12-29 | ||
| JP2010-294591 | 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 |
| JP2011-045286 | 2011-03-02 | ||
| JP2011045286 | 2011-03-02 | ||
| JP2011-139901 | 2011-06-23 | ||
| JP2011-139903 | 2011-06-23 | ||
| JP2011139903A JP5975607B2 (en) | 2011-06-23 | 2011-06-23 | Golf ball |
| JP2011139901A JP5478561B2 (en) | 2011-06-23 | 2011-06-23 | Golf ball |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102485295A CN102485295A (en) | 2012-06-06 |
| CN102485295B true CN102485295B (en) | 2014-11-05 |
Family
ID=46150890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110411898.8A Active CN102485295B (en) | 2010-12-03 | 2011-12-02 | Golf ball |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102485295B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102586313B1 (en) * | 2015-09-10 | 2023-10-06 | 스미토모 고무 코교 카부시키카이샤 | Golf ball |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5605512A (en) * | 1994-09-20 | 1997-02-25 | Sumitomo Rubber Industries, Ltd. | Golf ball |
| AU4690597A (en) * | 1996-12-05 | 1998-06-11 | Sumitomo Rubber Industries, Ltd. | Solid golf ball |
| JP2002119613A (en) * | 2000-10-18 | 2002-04-23 | Sumitomo Rubber Ind Ltd | Solid 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 |
-
2011
- 2011-12-02 CN CN201110411898.8A patent/CN102485295B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5605512A (en) * | 1994-09-20 | 1997-02-25 | Sumitomo Rubber Industries, Ltd. | Golf ball |
| AU4690597A (en) * | 1996-12-05 | 1998-06-11 | Sumitomo Rubber Industries, Ltd. | Solid golf ball |
| JP2002119613A (en) * | 2000-10-18 | 2002-04-23 | Sumitomo Rubber Ind Ltd | Solid 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102485295A (en) | 2012-06-06 |
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