CN102526998A - Golf ball - Google Patents
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- CN102526998A CN102526998A CN2011104630209A CN201110463020A CN102526998A CN 102526998 A CN102526998 A CN 102526998A CN 2011104630209 A CN2011104630209 A CN 2011104630209A CN 201110463020 A CN201110463020 A CN 201110463020A CN 102526998 A CN102526998 A CN 102526998A
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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 a kind of big golf of flying distance of kicking off to bat, in more detail, relate to a kind of improvement of golf ball.
Background technology
When kicking off batting (driver shot) as prolongation for example there being the method for golf ball flight distance, uses the method for high bounce-back property ball, use to have the method for the ball of the hardness Hardness Distribution that the mind-set surface increases progressively from ball.The former has the effect that improves the golf initial velocity, and the latter has raising to hit angle, reduces the effect of rotating.Hit the high and low golf that rotates of angle, its flying distance can increase.
As improving the anti-flexible technology of ball, patent documentation 1～6 is for example arranged.A kind of solid golf ball with kernel is disclosed in the patent documentation 1,2; Said kernel has mixed zinc acrylate resin, the palmitic acid as the co-crosslinking auxiliary agent, stearic acid or myristic acid, the zinc oxide as the co-crosslinking auxiliary agent, reaction speed retarding agent as co-crosslinker with respect to rubber 100 weight portions.
A kind of solid golf ball that is obtained by rubber compsn is disclosed in the patent documentation 3; Said rubber compsn 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 acids slaine of 1～10 weight portion.
Patent documentation 5 discloses a kind of golf and constituent thereof; The composition of the foundation elasticity body of wherein, from contain the group that is constituted from polybutadiene and with other elastomeric mixed with polybutadiene thing, selecting, at least a slaine, radical initiator and the non-conjugated diene monomers of unsaturated monocarboxylic and being shaped.
Patent documentation 6 discloses a kind of manufacturing approach of golf; It is characterized in that; Mix unsaturated carboxylic acid and/or its slaine in the elastomeric material, process the masterbatch of unsaturated carboxylic acid and/or its slaine in advance, utilize this masterbatch to process the rubber compsn that contains said elastomeric material; Be that said unsaturated carboxylic acid and/or its slaine masterbatch contain following (A)～(C) with the heating shaping thing of this rubber compsn manufacture method of golf ball as the golf part.
(A) modified polybutadiene 20～100 quality %, its ethylene contents are 0～2% and cis 1, and the content that 4-combines accounts for more than 80%, and has reactive terminal, and its reactive terminal is formed by at 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
[above-mentioned numeral is 100 o'clock quality % with (A) and total metering (B).]
(C) unsaturated carboxylic acid and/or its slaine
For example, patent documentation 7～10 discloses a kind of ball with Hardness Distribution.Patent documentation 7 discloses a kind of double-deck golf; Wherein, At the ball that is formed by the rubber compsn that contains base material rubber, co-crosslinker and organic peroxide, in the double-deck golf that is constituted with shell, this ball is in the expression of JIS-C type hardness tester; To have core rigidities 1 be 58～73, the hardness 2 of 5～10mm is 65～75 apart from the center, the hardness 3 of 15mm is 74～82 apart from the center, case hardness 4 is 76～84 Hardness Distribution; Hardness 2 is roughly certain in hardness range, and other satisfies 1＜2＜3≤4 relation.
Patent documentation 8 discloses a kind of golf; Wherein, in the solid golf ball that possesses solid ball and the outer shell that coats it, said solid ball is formed by rubber compsn; In this rubber compsn; With respect to the cis-1 more than 60% that contains that contains 60～100 quality %, 4-combines, utilizes rubber substrate 100 mass parts of the synthetic polybutadiene rubber of rare earth element series catalysts, also contains organosulfur compound, unsaturated carboxylic acid or its slaine, inorganic fillers and the age resister of 0.1～5 mass parts; Simultaneously; The load of solid ball is 2.0～4.0mm from the deflection of initial stage load 10kgf during to final load 130kgf, and solid ball has Hardness Distribution as shown in the table.
[table 1]
| Solid ball Hardness Distribution | Shore D hardness |
| The center | 30～48 |
| The part of 4mm apart from the center | 34～52 |
| The part of 8mm apart from the |
40～58 |
| The part of 12mm (Q) apart from the center | 43～61 |
| Inside part (R) apart from |
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 the solid golf ball that possesses solid ball and the outer shell that coats it; Said solid ball is formed by rubber compsn, in this rubber compsn, with respect to the cis-1 more than 60% that contains that contains 60～100 mass parts; 4-combines, utilizes 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, the load of solid ball is 2.0～4.0mm from the deflection of initial stage load 10kgf during to final load 130kgf; And solid ball has Hardness Distribution as shown in the table.
[table 2]
| Solid ball Hardness Distribution | Shore D hardness |
| The center | 25～45 |
| The part of 5～10mm apart from the center | 39～58 |
| The part of 15mm apart from the center | 36～55 |
| The surface | 55～75 |
| Center and surperficial difference of |
20～50 |
Patent documentation 10 discloses a kind of multilayer solid golf ball; It is characterized in that; Have ball, be coated on ball embracing layer, be coated on embracing layer the intermediate layer, be coated on forming in the multilayer solid golf ball of shell of most indentures of intermediate layer on the surface; Said ball is that main material is processed with the elastomeric material; Increase gradually from center to the ball case hardness of ball; The difference of hardness on ball center and ball surface is shown in more than 15 with the JIS-C scale of hardness; And apart from the ball center cross section hardness mean value at position and the ball center of about 15mm be made as (I), when the cross section hardness of the position of 7.5mm is made as (II) apart from the ball center, two difference of hardness (I)-(II) with the JIS-C scale of hardness be shown in ± 2 in, the hardness of said embracing layer, intermediate layer and shell meets the condition of shell hardness＞intermediate layer hardness＞embracing layer hardness simultaneously.
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 is opened the 2008-212681 communique
Patent documentation 5: Japanese Patent Laid table 2008-523952 communique
Patent documentation 6: Japanese Patent Laid is opened the 2009-119256 communique
Patent documentation 7: japanese patent laid-open 6-154357 communique
Patent documentation 8: Japanese Patent Laid is opened the 2008-194471 communique
Patent documentation 9: Japanese Patent Laid is opened the 2008-194473 communique
Patent documentation 10: Japanese Patent Laid is opened the 2010-253268 communique
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide the big golf of a kind of flying distance of kicking off to bat.
The inventor is a purpose so that the excellent novel golf of flying quality to be provided; Proposed about " a kind of golf; it is characterized in that; have the spherical ball and the shell of the above said spherical ball of coating of one deck at least; said spherical ball is formed by rubber compsn, containing (a) base material rubber, (b) in the said rubber compsn is 3～8 α as the carbon number of co-crosslinker, beta-unsaturated carboxylic acid and/or its slaine, (c) cross-linked evocating agent, (d) carboxylate and (e) organosulfur compound; When (b) only contains carbon number as co-crosslinker is 3～8 α, and during beta-unsaturated carboxylic acid, said rubber compsn further contains (f) metallic compound; The content of said (d) carboxylate with respect to (a) base material rubber 100 mass parts, is more than 10 mass parts, discontented 40 mass parts " application (Japanese Patent Laid is willing to 2010-294589 number).
Japanese Patent Laid is willing to 2010-294589 number invention that relates to, and its Hardness Distribution mind-set surface from ball that will be intended to spherical ball roughly linearly increases.Because of ball Hardness Distribution mind-set surface from ball roughly linearly increases, and the outer amplitude crescendo of interior gentle structure just, cause rotation amount to descend, improved the performance of flying distance.The ball Hardness Distribution is the mind-set surface reason that increases of straight line roughly from ball, and following viewpoint is arranged.When ball was shaped, for the ball temperature inside, the ball central part was higher, then reduces near the ball surface.This is because the heat of reaction of cross-linking reaction is accumulated at the ball central part.When ball was shaped, said (d) carboxylate and (b) carbon number were 3～8 α, and the reacting metal salt of beta-unsaturated carboxylic acid produces the slaine of carboxylic acid.That is, (d) said carboxylate and carbon number are 3～8 α, and the slaine exchange cation of beta-unsaturated carboxylic acid, cut-out carbon number are 3～8 α, the metal corsslinking that the slaine of beta-unsaturated carboxylic acid produces.This cation exchange reaction takes place at the higher ball central part of ball temperature inside easily, then is difficult to gradually take place near the surface.In other words, the ball central part that is breaking at of metal corsslinking takes place easily, then becomes difficult gradually near the surface.Its result because the inner crosslink density of ball, the mind-set surface increases from ball, so think ball hardness, from ball the mind-set surface roughly straight line increase.
And the inventor is through further research, finds that through adopting (d) carbon number be 1～13 carboxylate, and the outer amplitude that softens in just of spherical ball is stronger than in the past, has reduced the rotation amount of kicking off to bat, thereby has accomplished the present invention.
Solve the means of problem
Golf of the present invention; It is characterized in that; Have the ball and the shell of the above said spherical ball of coating of one deck at least; Said spherical ball is formed by rubber compsn, and said rubber compsn contains (a) base material rubber, (b) as the carbon number of the co-crosslinker α between 3～8, and beta-unsaturated carboxylic acid and/or its slaine, (c) cross-linked evocating agent, (d) carbon number are 1～13 carboxylate; When (b) only contains carbon number between 3～8 α as co-crosslinker, during beta-unsaturated carboxylic acid, said rubber compsn further contains (e) metallic compound.The present invention is through aforesaid formation, and spherical ball is the amplitude grow of the just interior structure that softens outward, and the rotation amount of kicking off to bat reduction, flying distance increase.In addition, the spherical ball that the present invention the uses linearity meeting part of its ball Hardness Distribution sometimes reduces, and in this case, outer just interior gentle amplitude is stronger than in the past, and the rotation amount of kicking off to bat reduces.
Through adopting (d) carbon number is 1～13 carboxylic acid, spherical ball outer just in gentle amplitude than stronger in the past reason following consideration was arranged.As stated, carboxylic acid and carbon number are 3～8 α, the slaine exchange cation of beta-unsaturated carboxylic acid, and cutting off by carbon number is 3～8 α, the metal corsslinking that the slaine of beta-unsaturated carboxylic acid produces.Think that the effect of cutting off this metal corsslinking receives the influence that the carbon number that is added is 1～13 carboxylate molal quantity.Simultaneously, carbon number is that 1～13 carboxylate also works as the plasticizer of spherical ball.Adds the combined amount (quality) that carbon number is 1～13 carboxylate if increase institute, the whole meeting of ball is softened.This plasticization effect receive add the influence of the combined amount (quality) of carboxylic acid.Consider these effects, through using the carboxylic acid of carbon number few (molecular weight is little), compare during with the carboxylic acid that uses carbon number many (molecular weight is big), under the situation of 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 the action effect that cuts off metal corsslinking again.
The effect of invention
According to the present invention, a kind of big golf of flying distance of kicking off to bat can be provided.
Description of drawings
Fig. 1: show the sectional view that one of an embodiment of the present invention related golf part is cut open.
Fig. 2: the chart that shows the ball Hardness Distribution.
Fig. 3: the chart that shows the ball Hardness Distribution.
Fig. 4: the chart that shows the ball Hardness Distribution.
Fig. 5: the chart that shows the ball Hardness Distribution.
Fig. 6: the chart that shows the ball Hardness Distribution.
Fig. 7: the chart that shows the ball Hardness Distribution.
Fig. 8: the chart that shows the ball Hardness Distribution.
Fig. 9: the chart that shows the ball Hardness Distribution.
Figure 10: the chart that shows the ball Hardness Distribution.
Figure 11: the chart that shows the ball Hardness Distribution.
Figure 12: the chart that shows the ball Hardness Distribution.
The specific embodiment
Golf of the present invention; It is characterized in that; Have ball and the above shell that coats said spherical ball of one deck at least; Said spherical ball is formed by rubber compsn, and said rubber compsn contains (a) base material rubber, (b) as the carbon number of the co-crosslinker α between 3～8, and beta-unsaturated carboxylic acid and/or its slaine, (c) cross-linked evocating agent, (d) carbon number are 1～13 carboxylate; When (b) only contains carbon number between 3～8 α as co-crosslinker, during beta-unsaturated carboxylic acid, said rubber compsn further contains (e) metallic compound.
At first, (a) base material rubber that uses among 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 can use separately, also can more than 2 kinds and use.Wherein, contain more than the 40 quality %, more than the preferred 80 quality %, more preferably 90 quality % to the favourable cis-1 that rebounds, the high-cis polybutadiene that 4-combines is suitable especially.
Said high-cis polybutadiene, preferred 1, the content that the 2-vinyl combines is below 2 quality %, more preferably below the 1.7 quality %, further below the preferred 1.5 quality %.If 1, the content that the 2-vinyl combines is too much, bounce-back property can reduce sometimes.
Said high-cis polybutadiene; Material so that the rare earth element series catalysts is synthetic is advisable, particularly, and when use has been adopted as the neodymium series catalysts of the neodymium compound of group of the lanthanides row rare-earth element compound; Polymerization activity with excellence obtains 1; The 4-cis combines content height, 1, and 2-ethene combines the low polybutadiene rubber of content, thereby preferred.
Said high-cis polybutadiene, Mooney viscosity (ML
1+4(100 ℃)) preferred more than 30, more preferably more than 32, further preferred more than 35, preferred below 140, more preferably below 120, further preferred below 100, most preferably below 80.In addition, said Mooney viscosity (ML among the present invention
1+4(100 ℃)) be meant, be benchmark with JIS K6300, use the L rotor, the numerical value of under the condition of 1 minute preheating time, 4 minutes, 100 ℃ of rotor rotational times, being measured.
As said high-cis polybutadiene, its molecular weight distribution mw/mn (Mw: weight average molecular weight, Mn: number-average molecular weight) preferred more than 2.0; More preferably more than 2.2, further preferred more than 2.4, most preferably more than 2.6; Preferred below 6.0; More preferably below 5.0, further preferred below 4.0, most preferably below 3.4.The molecular weight distribution of high-cis polybutadiene (Mw/Mn) may reduce operability if too small, may reduce bounce-back property as if excessive.In addition, the molecular weight distribution, determined by gel permeation chromatography (Toso - Corporation, "HLC-8120GPC"), using a differential refractometer as a detector, column: GMHHXL (Tosoh - Corporation) Column temperature: 40 ℃, mobile phase: tetrahydrofuran under conditions determined based on standard polystyrene equivalent value, the calculated values.
Secondly, just (b) carbon number is 3～8 α, and beta-unsaturated carboxylic acid and/or its slaine describe.(b) carbon number is 3～8 α, and beta-unsaturated carboxylic acid and/or its slaine are to be mixed in the rubber compsn as co-crosslinker, through the strand of glycerol polymerization in base material rubber, play rubber molecule is carried out crosslinked effect.In the rubber compsn that uses among the present invention, only containing carbon number as co-crosslinker is 3～8 α, and during beta-unsaturated carboxylic acid, rubber compsn is as must further containing (e) metallic compound by composition.Because in rubber compsn; Through using in the metallic compound with carbon number is 3～8 α; Beta-unsaturated carboxylic acid, can obtain in fact with the carbon number that uses as co-crosslinker is 3～8 α, same effect during the beta-unsaturated carboxylic acid slaine.In addition, as co-crosslinker, carbon number is 3～8 α, beta-unsaturated carboxylic acid and slaine thereof and time spent, also can use (e) metallic compound as any composition.
As carbon number is 3～8 α, and beta-unsaturated carboxylic acid can be enumerated like acrylic acid, methacrylic acid, fumaric acid, maleic acid, butenoic acid etc.
As constituting carbon number is 3～8 α, and the metal of the slaine of beta-unsaturated carboxylic acid can be enumerated: 1 valence metal ions such as sodium, potassium, lithium; Bivalent metal ions such as magnesium, calcium, zinc, barium, cadmium; 3 valence metal ions such as aluminium; Other ion such as tin, zirconium.Said metal ingredient can use separately or as mixture more than 2 kinds.This wherein, as said metal ingredient, divalent metals such as preferably magnesium, calcium, zinc, barium, cadmium.Because through using carbon number is 3～8 α, the divalent metal salt of beta-unsaturated carboxylic acid generates metal corsslinking easily between rubber molecule.Particularly, as divalent metal salt, consider that from the bounce-back property height of resulting golf zinc acrylate resin is advisable.In addition, carbon number is 3～8 α, and beta-unsaturated carboxylic acid and/or its slaine can separately or make up more than 2 kinds and use.
(b) carbon number is 3～8 α; The content of beta-unsaturated carboxylic acid and/or its slaine is with respect to (a) base material rubber 100 mass parts; More than preferred 15 mass parts, more preferably more than 20 mass parts, below preferred 50 mass parts; More preferably below 45 mass parts, further below preferred 35 mass parts.(b) carbon number is 3～8 α; When the content of beta-unsaturated carboxylic acid and/or its slaine is discontented with 15 mass parts; In order to make the parts that form by rubber compsn have suitable hardness; State the amount of (c) cross-linked evocating agent after don't fail to increasing, will have the anti-flexible tendency that reduces golf like this.On the other hand, carbon number is 3～8 α, and the content of beta-unsaturated carboxylic acid and/or its slaine is if surpass 50 mass parts, and is then really up to the mark by the parts that rubber compsn forms, and might 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, be advisable with organic peroxide.Said organic peroxide specifically can be enumerated: cumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethyl-cyclohexane, 2,5-dimethyl-2,5-two (t-butylperoxy) hexane, di-tert-butyl peroxide etc.These organic peroxides can a kind use separately, also can more than 2 kinds and use.The preferred cumyl peroxide that uses in the middle of these.
(c) content of cross-linked evocating agent is with respect to (a) base material rubber 100 mass parts, more than preferred 0.2 mass parts, more preferably more than 0.5 mass parts, below preferred 5.0 mass parts, more preferably below 2.5 mass parts.When being discontented with 0.2 mass parts, too soft by the parts that rubber compsn forms, the bounce-back property of golf has the tendency of decline; If surpass 5.0 mass parts; Then by the parts that rubber compsn forms suitable hardness is arranged, be necessary to reduce the use amount of said (b) co-crosslinker, like this in order to guarantee; The bounce-back property of golf is not enough, and durability is worsened.
Then, just (d) carbon number is that 1～13 carboxylate describes.(d) carbon number that uses among the present invention is 1～13 carboxylate, so long as have the salt of the compound of carboxyl, just not special the qualification is 3～8 α but do not comprise (b) carbon number that uses as co-crosslinker, the salt of beta-unsaturated carboxylic acid.Think that (d) carbon number is 1～13 carboxylate, at the central part of ball, it was 3～8 α by (b) carbon number that cut-out is arranged, the effect of the metal corsslinking that the slaine of beta-unsaturated carboxylic acid produces when ball formed.
As said (d) carbon number is 1～13 carboxylate aliphatic carboxylate (being called for short " aliphatic acid " salt among the present invention sometimes).As said carbon number is 1～13 carboxylate, and preferred carbon number is 1～12 carboxylate.The carbon number of carboxylate reduces, and understands problems such as toxic or foul smell.In addition, carbon number is meant carboxylic acid composition's carbon number.
Said soap can be any one in saturated fat hydrochlorate, the unsaturated fatty acid salt, preferred saturated fat hydrochlorate.As the fatty acid composition concrete example of said 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.Said fatty acid composition can use separately or as mixture more than 2 kinds.As said 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, choose one wantonly.As metal ion, can enumerate like 1 valence metal ions such as sodium, potassium, lithium, silver; Divalent metal ions such as magnesium, calcium, zinc, barium, cadmium, copper, cobalt, nickel, manganese; 3 valence metal ions such as aluminium, iron; Other ions such as tin, zirconium, titanium.As the cation constituent of said carboxylate, preferred zinc ion.Said cation constituent can use separately or use as mixture more than 2 kinds.
Above-mentioned organic cation is the cation with carbochain.As above-mentioned organic cation, do not do special the qualification, can enumerate like the organic amine ion.As above-mentioned organic amine ion, can enumerate like primary amine ions such as stearylamine ion, hexyl amine ion, octyl amine ion, 2-DEHA ions; Secondary amine ions such as dodecyl (lauryl) amine ion, 18 (alkane) base (tristearin) amine ion; Tertiary amine ions such as trioctylphosphine amine ion; Quaternary ammonium ions such as dioctyl Dimethyl Ammonium ion, distearyl Dimethyl Ammonium ion etc.These organic cations can use separately, also can more than 2 kinds and use.In addition, carbon number is that the carbon number of 1～13 carboxylate is the carbon number among the carboxylic acid composition, and does not comprise the carbon number in the organic cation.
It as said (d) carbon number 1～13 carboxylate; Preferred caprylic acid (sad) (C8), n-nonanoic acid (C9), capric acid (capric acid) (C10) or the slaine of laurate (C12), further preferred caprylic acid (sad) (C8), capric acid (capric acid) (C10) and the zinc salt of laurate (C12).
Said (d) carbon number is that the content of 1～13 carboxylate is with respect to (a) base material rubber 100 mass parts; More than preferred 0.5 mass parts; More preferably more than 1.0 mass parts, further more than preferred 1.5 mass parts, below preferred 30 mass parts; More preferably below 25 mass parts, further below preferred 20 mass parts.If content is very few, and the effect of then adding (d) carbon number and be 1～13 carboxylate is insufficient, spherical ball outer just in gentle amplitude might diminish.In addition, if content is too much, resulting ball hardness might globality descend, and makes the reduction of bounce-back property.Moreover for improving the zinc acrylate resin that uses as the co-crosslinker dispersiveness to rubber, using carbon number sometimes is the surface that 1～13 carboxylate is handled zinc acrylate resin.So using with carbon number is 1～13 carboxylate when zinc acrylate resin is carried out surface treatment, among the present invention, is that the amount of 1～13 carboxylate is included in the middle of the content that (d) carbon number is 1～13 carboxylate as the carbon number of surface conditioning agent.For example; Using carbon number is that the surface treatment amount of 1～13 carboxylate is when being zinc acrylate resin 25 mass parts of 10 quality %; Carbon number is that the amount of 1～13 carboxylate is 2.5 mass parts; The amount of zinc acrylate resin is 22.5 mass parts, is the content of 1～13 carboxylate as (d) carbon number, then will 2.5 mass parts be calculated interior.
The rubber compsn that the present invention uses, only containing carbon number as co-crosslinker is 3～8 α, during beta-unsaturated carboxylic acid, as must further containing (e) metallic compound by composition.As above-mentioned (e) metallic compound, if in the ability with rubber compsn in (b) carbon number between 3～8 α, beta-unsaturated carboxylic acid, not special the qualification.As (e) above-mentioned metallic compound, can enumerate like metal hydroxides such as magnesium hydroxide, zinc hydroxide, calcium hydroxide, NaOH, lithium hydroxide, potassium hydroxide, Kocide SDs; Metal oxides such as magnesia, calcium oxide, zinc oxide, cupric oxide; 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 3～8 α, the beta-unsaturated carboxylic acid reaction forms metal corsslinking.In addition, through using zinc compound, can obtain the high golf of bounce-back property.Can be independent a kind use these (e) metallic compounds, also can more than 2 kinds and use.
The ball that the present invention uses preferably further contains (f) organosulfur compound with rubber compsn.Said ball is outside 1～13 the carboxylate at (d) carbon number with rubber compsn, and through using in the lump with (f) organosulfur compound, the sustainable straight of keeping the ball Hardness Distribution is linear, the control ball outer just in the amplitude of gentle structure.As (f) organosulfur compound; So long as contain the organic compound of sulphur atom at molecule; Then not special the qualification, can enumerate as: have mercapto (SH), perhaps number of sulfur atoms be 2～4 polythiaether key (S-S-,-S-S-S-or-S-S-S-S-) organic compound; Or their slaine (SM ,-S-M-S-,-S-M-S-S-,-S-S-M-S-S-,-S-M-S-S-S-etc., M is a metallic atom).In addition; (f) said organosulfur compound can be chosen one wantonly 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.As (f) organosulfur compound, can enumerate like benzenethiol class, thionaphthol class, multiple sulfides, thionothiolic acid class, dithiocarboxylic acid class, sulfenamide, thiuram (thiuram) class, dithiocar-bamate, thiazoles etc.Viewpoint based on the Hardness Distribution of spherical ball increases as (f) organosulfur compound, preferably has mercapto (organosulfur compound SH) or its slaine, preferred benzenethiol class, thionaphthol class or their slaine.As slaine, can enumerate like: sodium, lithium, potassium, copper (I), silver 1 valency slaines such as (I); Zinc, magnesium, calcium, strontium, barium, titanium (II), manganese (II), iron (II), cobalt (II), nickel (II), zirconium (II), tin divalent slaines such as (II).
As the benzenethiol class, can enumerate like benzenethiol; 4-fluoro thiophenol, 2,5-difluoro thiophenol, 2,4,5-trifluoro-benzene thiophenol, 2,4,5,6-phenyl tetrafluoride thiophenol, phenyl-pentafluoride thiophenol etc. are by the substituted benzenethiol class of fluorine; 2-chlorothio-phenol, 4-chlorothio-phenol, 2,4-thiophenol dichlorobenzene, 2,5-thiophenol dichlorobenzene, 2,4,5-trichloro-benzenes thiophenol, 2,4,5,6-tetrachlorobenzene thiophenol, reptazin etc. are by the substituted benzenethiol class of chlorine; 4-bromo thiophenol, 2,5-dibromobenzene thiophenol, 2,4,5-tribromo-benzene thiophenol, 2,4,5,6-tetrabromo-benzene thiophenol, phenyl-pentabromide thiophenol etc. are by the substituted benzenethiol class of bromine; 4-iodobenzene thiophenol, 2,5-diiodo-benzene thiophenol, 2,4,5-triiodo-benzene thiophenol, 2,4,5,6-tetraiodo-benzene thiophenol, pentaiodobenzene thiophenol etc. are by substituted benzenethiol class of iodine or their slaine.As slaine, preferred zinc salt.
As naphthyl mercaptan class (thionaphthol class); Can enumerate like 2-thionaphthol, 1-thionaphthol, 2-chloro-1-thionaphthol, 2-bromo-1-thionaphthol, 2-fluoro-1-thionaphthol, 2-cyanic acid-1-thionaphthol, 2-acetyl group-1-thionaphthol, 1-chloro-2-thionaphthol, 1-bromo-2-thionaphthol, 1-fluoro-2-thionaphthol, 1-cyanic acid-2-thionaphthol, 1-acetyl group-2-thionaphthol or their slaine preferred 1-thionaphthol, 2-thionaphthol and their zinc salt.
As sulfenamide is organosulfur compound, can enumerate as: just-cyclohexyl-2-[4-morpholinodithio sulfenamide, just-hydroxyl divinyl-2-[4-morpholinodithio sulfenamide, just-tert-butyl-2-[4-morpholinodithio sulfenamide.As thiuram is organic sulfur compound, can enumerate like tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylene thiuram tetrasulfide etc.As dithiocarbamates, can enumerate like 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 is organic sulfur compound; Can enumerate like 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), sodium salt, zinc salt, mantoquita or the cyclohexyl amine salt of 2-mercaptobenzothiazole, 2-(2; The 4-dinitrophenyl) mercaptobenzothiazoler, 2-(2,6-diethyl-4-morpholino sulphur) benzothiazole etc.
(f) said organosulfur compound can separately or mix more than two kinds and use.
(f) content of organosulfur compound is with respect to (a) base material rubber 100 mass parts, more than preferred 0.05 mass parts, more preferably more than 0.1 mass parts, below preferred 5.0 mass parts, more preferably below 2.0 mass parts.If be discontented with 0.05 mass parts, then can not get adding the effect of (f) organosulfur compound, might not can improve the bounce-back property of golf.In addition, if surpass 5.0 mass parts, the compress variation of resulting golf increases, and might reduce bounce-back property.
The rubber compsn that the present invention uses as required, can also add pigment, be used to adjust the additives such as filler, age resistor, peptizer, softening agent of weight etc.In addition, as stated, the rubber compsn that uses among the present invention, only containing carbon number as co-crosslinker is 3～8 α, during beta-unsaturated carboxylic acid, the preferred rubber composition further contains (e) metallic compound.
As the pigment that mixes in the rubber compsn, can enumerate like Chinese white, blue pigment, violet pigment etc.As said Chinese white, preferably use titanium oxide.Do not limit though the kind of titanium oxide is special,, preferably use rutile-type based on the good reason of covering property.In addition, the content of titanium oxide is with respect to (a) base material rubber 100 mass parts, more than preferred 0.5 mass parts, more preferably more than 2 mass parts, below preferred 8 mass parts, more preferably below 5 mass parts.
Rubber compsn contains Chinese white and blue pigment also is a preferred configuration.Blue pigment is to mix in order to make white seem more bright-coloured, can enumerate like ultramarine, cobalt blue, phthalocyanine blue etc.In addition, as said violet pigment, can enumerate like anthraquinone purple, dioxazine violet, crystal violet etc.
The content of said blue pigment is with respect to (a) base material rubber 100 mass parts, more than preferred 0.001 mass parts, more preferably more than 0.05 mass parts, below preferred 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 surpass 0.2 mass parts, then blue excessively, lost distinct white appearance.
As the filler that uses in the rubber compsn, mainly be in order to adjust weight, and the weight conditioning agent that mixes can mix as required as the resulting golf of final products.As said filler, can enumerate inorganic fillers such as zinc oxide, barium sulfate, calcium carbonate, magnesia, tungsten powder, molybdenum powder.The content of said filler is with respect to base material rubber 100 mass parts, more than preferred 0.5 mass parts, more preferably more than 1 mass parts, below preferred 30 mass parts, more preferably below 25 mass parts, further below preferred 20 mass parts.The content of filler then is difficult to adjustment weight if be discontented with 0.5 mass parts, if surpass 30 mass parts, then the percentage by weight of rubber constituent diminishes, has the anti-flexible tendency of reduction.
The content of said age resistor is with respect to (a) base material rubber 100 mass parts, more than preferred 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, more than preferred 0.1 mass parts, below 5 mass parts.
The rubber compsn that the present invention uses; Be that mixing (a) base material rubber, (b) carbon number are 3～8 α; Beta-unsaturated carboxylic acid and/or its slaine, (c) cross-linked evocating agent, (d) carbon number are 1～13 carboxylate and other additive as required, obtain through mixing.The method of mixing is not special to be limited, and for example can use known mullers such as mixing roller, Ben Baili banbury, kneader to carry out mixing.
The globose nucleus that golf of the present invention has can be through obtaining the rubber compsn after mixing at the metal die internal shaping.The temperature of spherical ball of being shaped is preferred more than 120 ℃, and is more preferably more than 150 ℃, further preferred more than 160 ℃, preferred below 170 ℃.Forming temperature is if surpass 170 ℃, and the ball case hardness has the tendency of reduction.In addition, the preferred 2.9MPa～11.8MPa of pressure during shaping.Preferred 10 minutes～60 minutes of curring time.
Above-mentioned spherical ball is on average divided the ball radius with 12.5% interval, measures the hardness of this average 9 points dividing, and these hardness with when the distance at ball center is mapped, are obtained the R of linear curve of approximation through least square method
2Preferably more than 0.95.R
2If more than 0.95, then the linearity of the Hardness Distribution of ball high, reduced the rotation amount of kicking off to bat, improved the performance of flying distance.
For the hardness of spherical ball, any radius of spherical ball is on average divided with 12.5% interval, measure the JIS-C hardness of these average 9 points dividing.That is, in distance be 9 the mensuration JIS-C of some places hardness at 0% (ball center), 12.5%, 25%, 37.5%, 50%, 62.5%, 75%, 87.5%, 100% (ball surface) apart from the ball center.Then, will by the JIS-C hardness of said determination as axis of ordinates, apart from the distance (%) at ball center as axis of abscissas, will measure the result and process chart as curve.Among the present invention, the linear curve of approximation R that obtains by this curve negotiating least square method
2Preferred more than 0.95.The R of the linear curve of approximation of obtaining through least square method
2It is the linear index of judging resultant curve.Among the present invention, R
2If more than 0.95, then mean this spherical ball Hardness Distribution roughly linearly.Use the golf of the spherical ball of Hardness Distribution straight wire, can reduce the rotation amount of kicking off to bat.Its result, the flying distance of kicking off to bat increases.The R of said linear curve of approximation
2More preferably more than 0.96.Through improving linearity, the flying distance of kicking off to bat can be bigger.
The difference of hardness of the case hardness Hs of said spherical ball and core rigidities Ho (Hs-Ho) is represented with JIS-C hardness, and is preferred more than 27, more preferably more than 28; Further preferred more than 30, preferred especially more than 31, most preferably more than 32; Preferred below 80, more preferably below 70, further preferred below 60.If ball surface is big with the difference of hardness at ball center, can obtain higher angle and low rotation, the golf that flying distance is big of hitting.
The core rigidities Ho of spherical ball representes with JIS-C hardness, and is preferred more than 30, more preferably more than 40, further preferred more than 45.The core rigidities Ho of spherical ball 30 o'clock with thumb down with JIS-C hardness is sometimes because of crossing the soft bounce-back property that reduces.In addition, the core rigidities Ho of spherical ball representes with JIS-C hardness, and is preferred below 70, more preferably below 65, further preferred below 60.Said core rigidities Ho representes with JIS-C hardness if surpass 70, tendency then really up to the mark, that the reduction touch is arranged.
The case hardness Hs of spherical ball representes with JIS-C hardness, and is preferred more than 76, more preferably more than 78, further preferred more than 80, preferred below 100, more preferably below 95.If represent with JIS-C hardness, the case hardness of said spherical ball is decided to be more than 76, it is soft excessively that then spherical ball can not become, and can obtain good bounce-back property.In addition, if represent with JIS-C hardness, the case hardness of said spherical ball is decided to be below 100, then spherical ball can be not really up to the mark, can obtain good touch.
The diameter of said spherical ball is more than the preferred 34.8mm, more preferably more than the 36.8mm, more than the further preferred 38.8mm, below the preferred 42.2mm, more preferably below the 41.8mm, below the further preferred 41.2mm, most preferably below the 40.8mm.The diameter of said spherical ball is if more than 34.8mm, and then the thickness of shell can be not blocked up, and bounce-back property can be better.On the other hand, the diameter of spherical ball is if below 42.2mm, and then shell can be not thin excessively, more can bring into play the function of shell.
Said spherical ball; When diameter is 34.8mm～42.2mm; Compress variation (towards the center amount of contraction of compression direction) till during load from the load condition of initial stage load 98N to final load 1275N is more than the preferred 2.0mm, more preferably more than the 2.8mm; Below the preferred 6.0mm, more preferably below the 5.0mm.Said compress variation is if more than 2.0mm, and then touch is better, if below 6.0mm, then 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 said resinous principle, can enumerate the thermoplastic polyurethane elastomer of peddling with trade name " エ ラ ス ト ラ Application (registration mark) " like: ionomer resin, BASF Japan (joint-stock company), 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 eastern レ デ ュ 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 said ionomer resin; Can enumerate as: alkene and carbon number are 3～8 α; Carboxyl at least a portion in the bipolymer of beta-unsaturated carboxylic acid is by the material that metal ion neutralized, and alkene and carbon number are 3～8 α, beta-unsaturated carboxylic acid and α; Carboxyl at least a portion of the terpolymer of beta-unsaturated carboxylic acid ester is by the material of metal ion neutralization, perhaps their mixture.As said alkene, preferred carbon number is 2～8 a alkene, can enumerate like ethene, propylene, butylene, amylene, hexene, heptene, octene etc., special optimal ethylene.As carbon number is 3～8 α, and beta-unsaturated carboxylic acid can be enumerated like acrylic acid, methacrylic acid, fumaric acid, maleic acid, butenoic acid etc., preferred especially acrylic acid or methacrylic acid.In addition, as α, the beta-unsaturated carboxylic acid ester can use like: the methyl esters of acrylic acid, methacrylic acid, fumaric acid, maleic acid etc., ethyl ester, propyl ester, positive butyl ester, isobutyl ester etc., special preferred acrylate and methacrylate.This wherein, as said 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 said ionomer resin is with the trade name example; Can enumerate that Mitsui デ ュ Port Application Port リ ケ ミ カ Le (joint-stock company) peddled " 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 the terpolymer ionomers resin ".
Further; The ionomer resin of peddling as デ ュ Port Application company; Can enumerate " サ-リ Application (Surlyn) (registration mark) (can enumerate 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. have 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. as the terpolymer ionomers resin) ".
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 the terpolymer ionomers resin) ".
In addition, the Na that is put down in writing in the bracket after the trade name of said ionomer resin, Zn, Li, Mg etc., represent they in the metal species of metal ion.Said ionomer resin can use separately, also can mix use more than 2 kinds.
The shell that constitutes golf ball of the present invention is used composition, as resinous principle, preferably contains thermoplastic polyurethane elastomer or ionomer resin.When using ionomer resin, preferably with thermoplastic styrene elastomer and usefulness.Shell is with the containing ratio of polyurethane in the composition resin composition or ionomer resin, more than the preferred 50 quality %, more preferably more than the 60 quality %, further more than the preferred 70 quality %.
Said shell is used composition; Except that 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 fluorescent whitening agents etc. such as pigment composition, zinc oxide, calcium carbonate and barium sulfate such as Chinese white (for example titanium oxide), blue pigment, red pigment.
The content of said Chinese white (for example titanium oxide) is with respect to resinous principle 100 mass parts that constitute shell, more than preferred 0.5 mass parts, more preferably more than 1 mass parts, below preferred 10 mass parts, more preferably below 8 mass parts.Through the content that makes Chinese white is more than 0.5 mass parts, can give casing covers property.In addition, if the content of Chinese white surpasses 10 mass parts, reduce the durability of the shell that obtains sometimes.
Said shell is preferably done suitably to set according to the golf performance of expectation with slab (slab) hardness of composition.For example, pay attention to flying distance apart from type golf the time, shell representes with Shore D hardness with the slab hardness of composition, and is preferred more than 50, more preferably more than 55, preferred below 80, more preferably below 70.Through the slab hardness of shell with composition is made as more than 50, 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, through the hardness of shell with composition is made as below 80, can obtain the golf of excellent in te pins of durability.In addition, when paying attention to controlled rotation (spin) type golf, shell is represented with Shore D hardness with the slab hardness of composition, preferably is discontented with 50, and is preferred more than 20, more preferably more than 25.Shell is represented with Shore D hardness with the slab hardness of composition; If be discontented with 50, resulting golf, it is through ball of the present invention; Seek high flying distanceization kick off bat in, rotation amount will improve, on the fruit mountain range, stop easily during Bail out.In addition, can improve the marresistance ability through slab hardness is made as more than 20.When a plurality of outer shell is arranged, constitute the slab hardness of each layer shell,, can be the same or different as long as within above-mentioned scope with composition.
Method as shaping golf ball of the present invention; Can enumerate as: be configured as the shell of hollow shelly, coat the method (preferably be configured as half shell of hollow shelly, coat the method for ball compression molding with 2 piece of half shell with composition) of ball compression molding with a plurality of shells again with composition by shell by shell; Perhaps, with the method for shell with composition direct injection molding forming on ball.
During the shaping shell, half shell is shaped and also can carries out through any means in compression forming method or the injection moulding method through compress moulding method, but suitable be compression forming method.Be configured as the condition of half shell with composition as the compression molding shell, can enumerate as: at the pressure more than the 1MPa, below the 20MPa, with respect to the temperature that begin flow of shell with composition, forming temperature is more than-20 ℃, below 70 ℃.Through setting said molding condition, can be configured as uniform half shell of thickness.As using the be shaped method of shell of half shell, can enumerate like the method that coats the ball compression molding with 2 piece of half shell.Be configured as the condition of shell as compression molding half shell, can enumerate as: more than 0.5MPa, the forming pressure below the 25MPa, with respect to the temperature that begin flow of shell with composition, forming temperature is more than-20 ℃, below 70 ℃.Through setting above-mentioned molding condition, can be configured as the uniform golf ball of outer casing thickness.
When the injection molding forming shell is configured as shell with composition, can use the shell of extruding resulting granules shape to carry out injection molding forming, perhaps, shells such as substrate resin composition and pigment mixed with drying of materials, directly injection molding forming with composition.Be shaped as shell and use lower mold, preferred use have hemispherical die cavity, have kick, the part of kick goes back the locking pin that double as can be advanced and retreat.The shaping of the shell that carries out through injection molding forming, through releasing locking pin, drop into ball and make its fixing after; Inject shell and use composition; Cool off, the shell that can be shaped is for example in the metal die with the good shape of pressure fixing of 9MPa～15MPa; 0.5 second～inject the shell be heated to 200 ℃～250 ℃ in 5 seconds use composition, in 10 seconds～60 seconds, cool off then and open mould.
During the shaping shell, form the pit that is called as indenture usually on the surface.Indenture total preferred is more than 200 below 500.When the 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 then is difficult to obtain the effect of indenture.Formed indenture shape (shape is seen on the plane), not special the qualification can be used separately or combination use circle, triangle roughly, quadrangle roughly, pentagon roughly, polygons such as hexagon roughly, other indefinite shape more than 2 kinds.
The thickness of said shell is below the preferred 4.0mm, more preferably below the 3.0mm, below the further preferred 2.0mm.The thickness of shell is if below 4.0mm, and the bounce-back property of resulting golf and touch can be better.The thickness of said shell is more than the preferred 0.3mm, more preferably more than the 0.5mm, more than the further preferred 0.8mm, more than the preferred especially 1.0mm.If the thickness of shell is discontented with 0.3mm, reduce the durability and the wearability of shell sometimes.During a plurality of outer shell, the aggregate thickness of a plurality of outer shells is preferably in above-mentioned scope.
With 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, surface treatment such as sandblast.In addition, also can be according to expectation, film or form mark.Said thickness of filming, not special the qualification is more than the preferred 5 μ m, more preferably more than the 7 μ m, below the preferred 50 μ m, more preferably below the 40 μ m, further below the preferred 30 μ m.Thickness is if discontented 5 μ m use because of lasting, and the easy abrasion of filming disappear, and surpass 50 μ m as if thickness, then can reduce the effect of indenture, thus the flying quality of reduction golf.
When golf of the present invention, diameter are 40mm～45mm, from the state of the load initial stage load 98N compress variation (to the amount of contraction of compression direction) when loading final load 1275N; Be preferably more than the 2.0mm, more preferably more than the 2.4mm, more than the further preferred 2.5mm; Most preferably more than the 2.8mm; Below the preferred 5.0mm, more preferably below the 4.5mm, below the further preferred 3.6mm.The golf of said compress variation more than 2.0mm, hardness is really up to the mark, and touch is good.On the other hand, be made as below the 5.0mm through compress variation, bounce-back property increases.
The structure of golf of the present invention, as long as have spherical ball and the above shell of the one deck that coats said spherical ball, just not special the qualification.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 spherical ball 4 and the shell 12 that coats spherical ball 4.Form a plurality of indentures 14 on the surface of this shell.On the surface of this golf 2, the part outside the 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.
Said spherical ball preferred single layer structure.The spherical ball of single layer structure, the noenergy loss can improve bounce-back property when catching a packet at the interface of sandwich construction.In addition, shell can be the above structure of one deck, also can have single layer structure, perhaps the sandwich construction more than at least two layers.As golf of the present invention, can enumerate like double-deck golf that the single layer enclosure that is disposed with coating said spherical ball by spherical ball constitutes; The multi-layer golf ball (containing three layers of golf) of shell more than 2 layers that has that spherical ball disposes with coating said spherical ball; Have spherical ball, be provided with around the said ball contain a rubber layer and coat the curled hair golf etc. of the said shell that contains a rubber layer and be provided with.The golf of above-mentioned arbitrary structures all is 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, so long as do not exceed the change of aim scope of the present invention, any embodiment is included within the scope of the present invention.
[evaluation method]
(1) compress variation (mm)
To ball or golf, when measuring its load from the load condition of initial stage load 98N to final load 1275N at the deflection (amount that ball or golf shrink on compression direction) of compression direction.
(2) rebound coefficient
With each ball or golf metal cylinder thing with the velocity shock 198.4g of 40m/ second, measure impact before and after, the speed of said 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 the rebound coefficient of its mean value as this ball or golf.In addition, rebound coefficient shows with the poor of rebound coefficient with golf (ball) No.11 in table 3～table 4, in table 5～table 6, shows with the poor of rebound coefficient with golf (ball) No.22.
(3) slab hardness (Shore D hardness)
Use shell to use composition,, process the thin slice that thickness is approximately 2mm, preserved for 2 weeks at 23 ℃ through injection molding forming.In order not measured the influence of substrate etc., to this thin slice,, use, that possess spring hardometer Shore D type, macromolecule gauge corporate system automatic durometer P1 type regulation according to ASTM-D2240 with state overlapping more than 3, measure.
(4) ball Hardness Distribution (JIS-C hardness)
Use possesses the automatic durometer P1 of spring hardometer JIS-C type macromolecule gauge corporate system type, and the JIS-C hardness of measuring the ball surface portion is as the ball case hardness.In addition, ball is cut into hemispherical, measure the center of section and from the center to the hardness of the distance of regulation.In addition, measure the hardness of 4 points from the center to the predetermined distance, calculate ball hardness through getting its mean value.
(5) kick off to bat flying distance (m) and rotation amount (rpm)
On the M/C of robot that swings of go Le Off ラ ボ ラ ト リ-corporate system; The ferrule system of loading onto W#1 rod (11 ° of SRI sports corporate system, XXIO S ロ Off ト); Hit golf second with bar head speed 40m/, measure golf rotary speed and flying distance (distance) after just hitting from the emission starting point to static place.Each golf is measured 12 times, gets the measured value of its mean value as this golf.In addition, just the rotary speed of the golf after the batting is measured through the golf that is hit is taken pictures continuously.Flying distance of kicking off to bat and rotation amount show with the difference with golf (ball) No.11 in table 3～table 4, in table 5～table 6, show with the difference with golf (ball) No.22.
[making of golf]
(1) making of ball
Through mixing roller, mixing rubber compsn of shown in table 3～table 6, sneaking into, have hemispherical die cavity in the lower mold with 170 ℃, 20 minutes heating and pressurizing, obtain the spherical ball of diameter 39.8mm.
[table 3]
[table 4]
[table 5]
[table 6]
BR730:JSR corporate system, high-cis polybutadiene (cis-1, content=96 quality % that 4-combines, 1, content=1.3 quality % that 2-ethene combines, Mooney viscosity (ML
1+4(100 ℃))=55, molecular weight distribution (Mw/Mn)=3)
Sanceler SR: three new chemical industrial company system zinc acrylate resins (10 quality % stearic acid face coat article)
The plumbous corporate system " silver-colored mountain range R " of zinc oxide: Dong Bangya
Barium sulfate: Sakai chemical company system " barium sulfate BD " is adjusted into 45.4g with the golf quality that finally obtains
2-thionaphthol (2-Thio naphthol): Tokyo changes into industrial group's system
Cumyl peroxide: day oily corporate system, " パ-Network ミ Le (registration mark) D (cumyl peroxide) "
Zinc octoate: three Tianjin and chemicals corporate system (purity is more than 99%)
Zinc laurate: three Tianjin and chemicals corporate system (purity is more than 99%)
Zinc tetradecanoate: day oily corporate system (purity is more than 90%)
Zinc stearate: with the pure medicine corporate system of light (purity is more than 99%)
(2) making of shell
Secondly,, push shell of sneaking into as shown in table 7 and use material, process the graininess shell and use composition through the twin shaft type extruder that mixes.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.The shell that obtains is used composition, on the spherical ball that obtains as stated above, carry out injection molding forming, process golf with spherical ball and the shell that coats said ball.
[table 7]
| Shell is used composition No. | A | B |
| Himilan?1605 | 50 | - |
| Himilan?1706 | 50 | - |
| Elastollan?XNY97A | - | 100 |
| |
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 ュ Port Application Port リ ケ ミ カ Le corporate system is an ionomer resin
Ha イ ミ ラ Application 1706 (Himilan 1706): the ethylene-methacrylic acid copolymer of the zinc ion neutralization of Mitsui デ ュ Port Application Port リ ケ ミ カ Le corporate system is an ionomer resin
エ ラ ス ト ラ Application XNY97A (Elastollan XNY97A): BASF Japanese firm heats the plasticity polyurethane elastomers
Can know from the result of table 3～6; Has the ball and the golf of the shell of the above said spherical ball of coating of one deck at least; Its flying distance of kicking off to bat is all big; The said ball of this golf contains (a) base material rubber, (b) as the carbon number of the co-crosslinker α between 3～8, and beta-unsaturated carboxylic acid and/or its slaine, (c) cross-linked evocating agent, (d) carbon number are 1～13 carboxylate.In such golf any one.
Utilizability on the industry
Golf of the present invention, the flying distance of kicking off to bat is big.
Claims (10)
1. a golf is characterized in that, has spherical ball and the above shell that coats said spherical ball of one deck at least, and said spherical ball is formed by rubber compsn,
It is 3～8 α as the carbon number of co-crosslinker that said rubber compsn contains (a) base material rubber, (b), and beta-unsaturated carboxylic acid and/or its slaine, (c) cross-linked evocating agent, (d) carbon number are 1～13 carboxylate;
When (b) only contains carbon number as co-crosslinker is 3～8 α, and during beta-unsaturated carboxylic acid, said rubber compsn further contains (e) metallic compound.
2. like the golf of claim 1 record, wherein, in the said rubber compsn, with respect to (a) base material rubber 100 mass parts, (d) carbon number that contains 0.5 mass parts～30 mass parts is 1～13 carboxylate.
3. like the golf of claim 1 or 2 records, wherein, the case hardness of said spherical ball and the difference of hardness of core rigidities are shown in more than 30 with the JIS-C scale of hardness.
4. like the golf of any record of claim 1～3, wherein, in the said rubber compsn, containing (b) is 3～8 α as the carbon number of co-crosslinker, the slaine of beta-unsaturated carboxylic acid.
5. like the golf of any record of claim 1～4, wherein, said (d) carbon number is that 1～13 carboxylate is a soap.
6. like the golf of claim 5 record, wherein, said soap is fatty acid zinc salt.
7. like the golf of any record of claim 1～6, wherein, said rubber compsn further contains (f) organosulfur compound.
8. like the golf of claim 7 record, wherein, said (f) organosulfur compound is benzenethiol class, diphenyl disulfide thing class, thionaphthol class, thiuram disulfides or their slaine.
9. like the golf of claim 7 or 8 records, wherein, in the said rubber compsn,, contain (f) organosulfur compound of 0.05 mass parts～5 mass parts with respect to (a) base material rubber 100 mass parts.
10. like the golf of any record of claim 1～9; Wherein, in the said rubber compsn, with respect to (a) base material rubber 100 mass parts; (b) carbon number that contains 15 mass parts～50 mass parts is 3～8 α, beta-unsaturated carboxylic acid and/or its slaine.
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010294589A JP5754938B2 (en) | 2010-12-29 | 2010-12-29 | Golf ball |
| JP2010-294589 | 2010-12-29 | ||
| JP2010294591A JP5697444B2 (en) | 2010-12-29 | 2010-12-29 | Golf ball |
| JP2010-294591 | 2010-12-29 | ||
| JP2010-294590 | 2010-12-29 | ||
| JP2010294590A JP5687053B2 (en) | 2010-12-29 | 2010-12-29 | Golf ball |
| JP2011-139904 | 2011-06-23 | ||
| JP2011-139902 | 2011-06-23 | ||
| JP2011139902 | 2011-06-23 | ||
| JP2011139904 | 2011-06-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102526998A true CN102526998A (en) | 2012-07-04 |
| CN102526998B CN102526998B (en) | 2015-05-06 |
Family
ID=46335782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110463020.9A Active CN102526998B (en) | 2010-12-29 | 2011-12-26 | Golf ball |
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| Country | Link |
|---|---|
| CN (1) | CN102526998B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104208848A (en) * | 2013-05-31 | 2014-12-17 | 邓禄普体育用品株式会社 | 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 |
-
2011
- 2011-12-26 CN CN201110463020.9A patent/CN102526998B/en active Active
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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104208848A (en) * | 2013-05-31 | 2014-12-17 | 邓禄普体育用品株式会社 | Golf ball |
| CN104208848B (en) * | 2013-05-31 | 2017-04-12 | 邓禄普体育用品株式会社 | golf ball |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102526998B (en) | 2015-05-06 |
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Address after: Kobe City, Hyogo Prefecture, Japan Central flank Bang Cho 3 chome 6 No. 9 Applicant after: Dunlop Sports Co., Ltd. Address before: Kobe City, Hyogo Prefecture, Japan Central flank Bang Cho 3 chome 6 No. 9 Applicant before: Sumitomo Rubber Ind. |
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