JP5666352B2 - Ionomer composition for golf ball material and golf ball - Google Patents
Ionomer composition for golf ball material and golf ball Download PDFInfo
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- JP5666352B2 JP5666352B2 JP2011050525A JP2011050525A JP5666352B2 JP 5666352 B2 JP5666352 B2 JP 5666352B2 JP 2011050525 A JP2011050525 A JP 2011050525A JP 2011050525 A JP2011050525 A JP 2011050525A JP 5666352 B2 JP5666352 B2 JP 5666352B2
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- ionomer
- acid
- ethylene
- golf ball
- mass
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- 229920000554 ionomer Polymers 0.000 title claims description 78
- 239000000203 mixture Substances 0.000 title claims description 37
- 239000000463 material Substances 0.000 title claims description 29
- 239000002253 acid Substances 0.000 claims description 67
- 239000000539 dimer Substances 0.000 claims description 51
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 33
- 239000005977 Ethylene Substances 0.000 claims description 33
- 229920001577 copolymer Polymers 0.000 claims description 24
- 239000011777 magnesium Substances 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 19
- 229920012753 Ethylene Ionomers Polymers 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 238000005452 bending Methods 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 6
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 230000000740 bleeding effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- 229920005601 base polymer Polymers 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- -1 ethylhexyl Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 3
- CFQZKFWQLAHGSL-FNTYJUCDSA-N (3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e)-octadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoic acid Chemical compound OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C CFQZKFWQLAHGSL-FNTYJUCDSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000447 dimerizing effect Effects 0.000 description 2
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003784 tall oil Substances 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- VRWOEFJNMPHSTD-UHFFFAOYSA-N (2-octoxyphenyl)-phenylmethanone Chemical compound CCCCCCCCOC1=CC=CC=C1C(=O)C1=CC=CC=C1 VRWOEFJNMPHSTD-UHFFFAOYSA-N 0.000 description 1
- VNFXPOAMRORRJJ-UHFFFAOYSA-N (4-octylphenyl) 2-hydroxybenzoate Chemical compound C1=CC(CCCCCCCC)=CC=C1OC(=O)C1=CC=CC=C1O VNFXPOAMRORRJJ-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 description 1
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- FETUUKHOLDNMQO-UHFFFAOYSA-N 6-benzoyl-1-hydroxy-3-methoxycyclohexa-2,4-diene-1-carboxylic acid Chemical compound C1=CC(OC)=CC(O)(C(O)=O)C1C(=O)C1=CC=CC=C1 FETUUKHOLDNMQO-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- 235000019774 Rice Bran oil Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- SOGAXMICEFXMKE-UHFFFAOYSA-N alpha-Methyl-n-butyl acrylate Natural products CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ゴルフボール材料用アイオノマー組成物、及びこれを用いたゴルフボールに関する。 The present invention relates to an ionomer composition for a golf ball material and a golf ball using the same.
アイオノマーは、ベースポリマーであるエチレンと不飽和カルボン酸との共重合体の酸基（カルボキシル基）を金属イオンで中和した金属塩であり、その優れた強靭性と耐久性から、ゴルフボール用の材料として広く用いられている。 Ionomer is a metal salt in which the acid group (carboxyl group) of the copolymer of ethylene and unsaturated carboxylic acid, which is the base polymer, is neutralized with metal ions, and it is used for golf balls because of its excellent toughness and durability. It is widely used as a material.
このようなアイオノマーのうち、ベースポリマーにおける不飽和カルボン酸から誘導される構成単位の含有量（以下、酸含量ともいう。）が高く、金属イオンによる中和度の高いものは、剛性などの機械的特性に優れるが、溶融粘度が高く、流動性が低いため、成形加工が困難であるという問題がある。
特に、近年は、ゴルフボールの表皮材（カバー材ともいう。）の薄肉化が進んでいるため、アイオノマーの優れた機械的強度を維持しながら、流動性を改良することが強く望まれている。
Among such ionomers, those having a high content of structural units derived from an unsaturated carboxylic acid in the base polymer (hereinafter also referred to as acid content) and a high degree of neutralization with metal ions are used for machines such as rigidity. However, since the melt viscosity is high and the fluidity is low, the molding process is difficult.
In particular, in recent years, the skin material (also referred to as a cover material) of golf balls has been made thinner, so it is strongly desired to improve fluidity while maintaining the excellent mechanical strength of ionomers. .
上記状況に関連する技術として、不飽和カルボン酸から誘導される構成単位を所定の比率としたエチレン・不飽和カルボン酸共重合体のアイオノマーと分子量３５０以下のポリカルボン酸とを含むアイオノマー組成物が開示されており（例えば、特許文献１参照）、アイオノマーに分子量３５０以下のポリカルボン酸を含ませると、アイオノマーの機械的強度を損なわずに流動性が改良されるとされている。なお、ポリカルボン酸の量はアイオノマー１００質量部に対して９質量％以下である。 As a technique related to the above situation, there is an ionomer composition comprising an ionomer of an ethylene / unsaturated carboxylic acid copolymer having a predetermined proportion of structural units derived from an unsaturated carboxylic acid and a polycarboxylic acid having a molecular weight of 350 or less. It is disclosed (for example, refer to Patent Document 1), and if the ionomer contains a polycarboxylic acid having a molecular weight of 350 or less, the fluidity is improved without impairing the mechanical strength of the ionomer. In addition, the quantity of polycarboxylic acid is 9 mass% or less with respect to 100 mass parts of ionomers.
上記のようにポリカルボン酸を含むことで、アイオノマー組成物の流動性の改良効果が認められるところ、製造適性の観点から更なる改良効果が見込める技術に対する期待も大きい。 When the polycarboxylic acid is contained as described above, the improvement effect of the fluidity of the ionomer composition is recognized. However, there is a great expectation for a technique that can be further improved from the viewpoint of production suitability.
本発明は、添加成分のブリードアウトの発生を抑え、アイオノマーが本来有する機械的強度を保持すると共に、従来のアイオノマー組成物に比べ、更なる流動性を示すゴルフボール材料用のアイオノマー樹脂組成物、及び機械的強度に優れたゴルフボールを提供することを目的とし、該目的を達成することを課題とする。 The present invention suppresses the occurrence of bleed out of the additive component, retains the mechanical strength inherent to the ionomer, and further exhibits a fluidity compared to the conventional ionomer composition, an ionomer resin composition for golf ball materials, And it aims at providing the golf ball excellent in mechanical strength, and makes it a subject to achieve this objective.
前記課題を達成するための具体的手段は以下の通りである。即ち、第１の発明は、
＜１＞ エチレン・α，β−不飽和カルボン酸共重合体のナトリウム（Ｎａ）アイオノマーおよびマグネシウム（Ｍｇ）アイオノマーから選ばれるエチレン系アイオノマー（Ａ）と、ダイマー酸（Ｂ）とを含むゴルフボール材料用アイオノマー組成物である。
Specific means for achieving the above object are as follows. That is, the first invention is
<1> A golf ball material comprising an ethylene ionomer (A) selected from sodium (Na) ionomer and magnesium (Mg) ionomer of an ethylene / α, β-unsaturated carboxylic acid copolymer, and a dimer acid (B) It is an ionomer composition.
＜２＞ 前記＜１＞に記載のゴルフボール材料用アイオノマー組成物において、前記エチレン系アイオノマー（Ａ）１００質量部に対して、前記ダイマー酸（Ｂ）は０．１〜５０質量部の範囲で配合されているのが好ましい態様である。 <2> The ionomer composition for a golf ball material according to <1>, wherein the dimer acid (B) is in a range of 0.1 to 50 parts by mass with respect to 100 parts by mass of the ethylene ionomer (A). It is a preferable aspect that it is blended.
また、第２の発明は、
＜３＞ 前記＜１＞又は前記＜２＞に記載のゴルフボール材料用アイオノマー組成物を含むゴルフボールである。
In addition, the second invention,
<3> A golf ball comprising the ionomer composition for a golf ball material according to <1> or <2>.
本発明によれば、添加成分のブリードアウトの発生を抑え、アイオノマーが本来有する機械的強度を保持すると共に、従来のアイオノマー組成物に比べ、更なる流動性を示すゴルフボール材料用のアイオノマー樹脂組成物が提供される。また、
本発明によれば、機械的強度に優れたゴルフボールが提供される。
According to the present invention, an ionomer resin composition for a golf ball material that suppresses the occurrence of bleed-out of additive components, retains the mechanical strength inherent to ionomers, and exhibits further fluidity compared to conventional ionomer compositions. Things are provided. Also,
According to the present invention, a golf ball having excellent mechanical strength is provided.
以下、本発明のゴルフボール材料用アイオノマー組成物及びこれを用いたゴルフボールについて詳細に説明する。 Hereinafter, the ionomer composition for a golf ball material of the present invention and a golf ball using the same will be described in detail.
＜ゴルフボール材料用アイオノマー組成物＞
本発明のゴルフボール材料用アイオノマー組成物は、エチレン・α，β−不飽和カルボン酸共重合体のナトリウム（Ｎａ）アイオノマー、およびエチレン・α，β−不飽和カルボン酸共重合体のマグネシウム（Ｍｇ）アイオノマーから選ばれるエチレン系アイオノマー（Ａ）と、ダイマー酸（Ｂ）とを用いて構成され、必要に応じて、さらに添加剤等の他の成分が含有されてもよい。
<Ionomer composition for golf ball material>
The ionomer composition for golf ball materials of the present invention comprises a sodium (Na) ionomer of an ethylene / α, β-unsaturated carboxylic acid copolymer and a magnesium (Mg) of an ethylene / α, β-unsaturated carboxylic acid copolymer. ) It is comprised using the ethylene-type ionomer (A) chosen from an ionomer, and a dimer acid (B), and other components, such as an additive, may contain further as needed.
本発明においては、エチレン系アイオノマーとして、特にＮａ又はＭｇで中和されたアイオノマーを用い、これにダイマー酸を用いた構成にすると、亜鉛（Ｚｒ）中和アイオノマー等に比べ、曲げ剛性などに代表される機械的特性を大きく損なうことなく、成形時などに求められる流動性が著しく高められる。これにより、成形加工がより容易に行なえ、成形物の強度不足が懸念されることもない。 In the present invention, when an ionomer neutralized with Na or Mg is used as the ethylene-based ionomer, and dimer acid is used for the ionomer, it is representative of bending rigidity, etc., compared to zinc (Zr) neutralized ionomer. The fluidity required at the time of molding or the like is remarkably enhanced without greatly impairing the mechanical properties. As a result, the molding process can be performed more easily, and there is no concern about insufficient strength of the molded product.
［（Ａ）エチレン系アイオノマー］
本発明のゴルフボール材料用アイオノマー組成物（以下、単に「アイオノマー組成物」ともいう。）は、エチレン系アイオノマーの少なくとも一種を含有する。本発明におけるエチレン系アイオノマーは、エチレン由来の構成単位、及びα，β−不飽和カルボン酸に由来の構成単位を有するエチレン・α，β−不飽和カルボン酸共重合体の、酸基の少なくとも一部が、Ｎａ（ナトリウム）イオンまたはＭｇ（マグネシウム）により中和された樹脂である。
同じアイオノマーであっても、Ｚｎ（亜鉛）などの他の金属イオンで中和されたアイオノマーであると、本発明の目的を達成するには不充分である。
[(A) Ethylene ionomer]
The ionomer composition for golf ball material of the present invention (hereinafter also simply referred to as “ionomer composition”) contains at least one ethylene-based ionomer. The ethylene ionomer in the present invention contains at least one acid group of an ethylene / α, β-unsaturated carboxylic acid copolymer having a structural unit derived from ethylene and a structural unit derived from α, β-unsaturated carboxylic acid. Part is a resin neutralized with Na (sodium) ions or Mg (magnesium).
Even with the same ionomer, an ionomer neutralized with another metal ion such as Zn (zinc) is insufficient to achieve the object of the present invention.
エチレン系アイオノマーのベースポリマーとなる前記エチレン・α，β−不飽和カルボン酸共重合体において、α，β−不飽和カルボン酸から導かれる構成単位の含有割合は１〜３５質量％の範囲が好ましく、より好ましくは１０〜２０質量％の範囲である。また、エチレンから導かれる構成単位の含有割合としては、９９〜６５質量％の範囲が好ましく、より好ましくは９０〜８０質量％の範囲である。 In the ethylene / α, β-unsaturated carboxylic acid copolymer serving as the base polymer of the ethylene ionomer, the content of the structural unit derived from the α, β-unsaturated carboxylic acid is preferably in the range of 1 to 35% by mass. More preferably, it is the range of 10-20 mass%. Moreover, as a content rate of the structural unit guide | induced from ethylene, the range of 99-65 mass% is preferable, More preferably, it is the range of 90-80 mass%.
本発明におけるエチレン・α，β−不飽和カルボン酸共重合体は、エチレンとα，β−不飽和カルボン酸の二元共重合体のみならず、任意に他の単量体がランダム共重合された多元共重合体であってもよい。 The ethylene / α, β-unsaturated carboxylic acid copolymer in the present invention is not only a binary copolymer of ethylene and α, β-unsaturated carboxylic acid, but also other monomers are randomly copolymerized. Multi-component copolymers may also be used.
α，β−不飽和カルボン酸から導かれる構成単位の含有割合が１質量％以上であることは、この構成単位を積極的に含むことを意味し、α，β−不飽和カルボン酸の含有により透明性や金属接着性が良好になる。α，β−不飽和カルボン酸から導かれる構成単位の含有割合が３５質量％以下であると、実用的な耐熱性を維持できる。 When the content ratio of the structural unit derived from the α, β-unsaturated carboxylic acid is 1% by mass or more, it means that the structural unit is actively included, and the content of the α, β-unsaturated carboxylic acid is increased. Transparency and metal adhesion are improved. When the content of the structural unit derived from the α, β-unsaturated carboxylic acid is 35% by mass or less, practical heat resistance can be maintained.
前記α，β−不飽和カルボン酸としては、アクリル酸、メタクリル酸、マレイン酸、フマル酸、無水マレイン酸、マレイン酸モノエステルなどが挙げられ、特に、アクリル酸又はメタクリル酸が好ましい。 Examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, and maleic acid monoester, and acrylic acid or methacrylic acid is particularly preferable.
本発明において、エチレン系アイオノマーとしては、入手のしやすさの点から、エチレン・アクリル酸共重合体のＮａまたはＭｇアイオノマー、及びエチレン・メタクリル酸共重合体のＮａまたはＭｇアイオノマーが好ましい。具体的には、エチレン・アクリル酸共重合体のＮａアイオノマー、エチレン・メタクリル酸共重合体のＮａアイオノマー、エチレン・アクリル酸共重合体のＭｇアイオノマー、エチレン・メタクリル酸共重合体のＭｇアイオノマーを特に好ましい例として挙げることができる。 In the present invention, the ethylene ionomer is preferably an ethylene / acrylic acid copolymer Na or Mg ionomer and an ethylene / methacrylic acid copolymer Na or Mg ionomer from the viewpoint of availability. Specifically, Na ionomer of ethylene / acrylic acid copolymer, Na ionomer of ethylene / methacrylic acid copolymer, Mg ionomer of ethylene / acrylic acid copolymer, Mg ionomer of ethylene / methacrylic acid copolymer, in particular It can be mentioned as a preferred example.
本発明におけるアイオノマーが、エチレン及びα，β−不飽和カルボン酸に加えて更に他の単量体が共重合された多元共重合体である場合、共重合されてもよい他の単量体としては、酢酸ビニル、プロピオン酸ビニル等のビニルエステル、アクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸イソブチル、アクリル酸ｎブチル、アクリル酸イソオクチル、アクリル酸−２−エチルヘキシル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸イソブチル、マレイン酸ジメチル、マレイン酸ジエチル等のα・β−不飽和カルボン酸エステル、一酸化炭素などを例示することができる。
これらの単量体は、エチレン系アイオノマーの全質量に対して、例えば、０質量％超えて３０質量％以下、好ましくは０質量％超えて２０質量％以下、更に好ましくは、０質量％超えて１０質量％以下の範囲で共重合されていてもよい。
When the ionomer in the present invention is a multi-component copolymer obtained by copolymerizing other monomers in addition to ethylene and α, β-unsaturated carboxylic acid, as other monomers that may be copolymerized Are vinyl esters such as vinyl acetate and vinyl propionate, methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, nbutyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, methacryl Examples include α, β-unsaturated carboxylic acid esters such as ethyl acid, isobutyl methacrylate, dimethyl maleate, and diethyl maleate, and carbon monoxide.
These monomers are, for example, more than 0% by weight and less than 30% by weight, preferably more than 0% by weight and less than 20% by weight, more preferably more than 0% by weight, based on the total weight of the ethylene ionomer. It may be copolymerized within a range of 10% by mass or less.
前記α，β−不飽和カルボン酸エステルとしては、不飽和カルボン酸の炭素原子数１〜８のアルキルエステル、例えばアクリル酸アルキルエステル、メタクリル酸アルキルエステル、エタクリル酸アルキルエステル、クロトン酸アルキルエステル、フマル酸アルキルエステル、マレイン酸アルキルエステル、マレイン酸モノアルキルエステル、無水マレイン酸アルキルエステル、イタコン酸アルキルエステル及び無水イタコン酸アルキルエステルが挙げられる。これらのα，β−不飽和カルボン酸エステルから導かれる構成単位を含むと、エチレン・α，β−不飽和カルボン酸共重合体の柔軟性が向上するので好ましい。 Examples of the α, β-unsaturated carboxylic acid esters include alkyl esters of unsaturated carboxylic acids having 1 to 8 carbon atoms such as acrylic acid alkyl esters, methacrylic acid alkyl esters, ethacrylic acid alkyl esters, crotonic acid alkyl esters, fumarate. Examples include acid alkyl esters, maleic acid alkyl esters, maleic acid monoalkyl esters, maleic anhydride alkyl esters, itaconic acid alkyl esters and itaconic anhydride alkyl esters. It is preferable to include a structural unit derived from these α, β-unsaturated carboxylic acid esters because the flexibility of the ethylene / α, β-unsaturated carboxylic acid copolymer is improved.
前記アルキルエステルのアルキル部位としては、炭素原子数１〜１２のものを挙げることができ、より具体的には、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、セカンダリーブチル、２−エチルヘキシル、イソオクチル等のアルキル基を例示することができる。中でも、アルキル部位の炭素原子数が１〜８のアルキルエステルが好ましい。
前記α，β−不飽和カルボン酸エステルとしては、特に、アクリル酸又はメタクリル酸のメチルエステル、エチルエステル、ノルマルブチルエステル、イソブチルエステルが好ましい。
Examples of the alkyl moiety of the alkyl ester include those having 1 to 12 carbon atoms. More specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, 2- Examples of the alkyl group include ethylhexyl and isooctyl. Of these, alkyl esters having 1 to 8 carbon atoms in the alkyl moiety are preferred.
As the α, β-unsaturated carboxylic acid ester, acrylic acid or methacrylic acid methyl ester, ethyl ester, normal butyl ester, and isobutyl ester are particularly preferable.
本発明において、特に好ましいエチレン・α，β−不飽和カルボン酸・α，β−不飽和カルボン酸エステル共重合体としては、エチレン・（メタ）アクリル酸・（メタ）アクリル酸エステル共重合体であり、とりわけエチレン・（メタ）アクリル酸・アクリル酸メチル共重合体、エチレン・（メタ）アクリル酸・アクリル酸エチル共重合体、エチレン・（メタ）アクリル酸・アクリル酸ノルマルブチル共重合体、エチレン・（メタ）アクリル酸・アクリル酸イソブチル共重合体、エチレン・（メタ）アクリル酸・メタクリル酸メチル共重合体、エチレン・（メタ）アクリル酸・メタクリル酸エチル共重合体、エチレン・（メタ）アクリル酸・メタクリル酸ノルマルブチル共重合体、エチレン・メタアクリル酸イソブチル共重合体が挙げられる。 In the present invention, the ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer is particularly preferably an ethylene / (meth) acrylic acid / (meth) acrylic acid ester copolymer. Yes, ethylene / (meth) acrylic acid / methyl acrylate copolymer, ethylene / (meth) acrylic acid / ethyl acrylate copolymer, ethylene / (meth) acrylic acid / normal butyl acrylate copolymer, ethylene・ (Meth) acrylic acid / isobutyl acrylate copolymer, ethylene / (meth) acrylic acid / methyl methacrylate copolymer, ethylene / (meth) acrylic acid / ethyl methacrylate copolymer, ethylene / (meth) acrylic Examples thereof include an acid / normal butyl methacrylate copolymer and an ethylene / isobutyl methacrylate copolymer.
アイオノマーは、理論的には、共重合体中のカルボキシル基の１００％以下の範囲でナトリウム（Ｎａ）又はマグネシウム（Ｍｇ）の金属イオンによって中和される。通常は、８０％以下、好ましくは１０〜８０％を、更には１５〜６０％をＮａまたはＭｇの金属イオンで中和されたものが好適である。
また、本発明におけるエチレン系アイオノマーは、後述するダイマー酸との組成物になった場合の成形加工性、機械的強度などの観点から、ＪＩＳ Ｋ７２１０−１９９９に準拠した１９０℃、２１６０ｇ荷重でのメルトフローレート（ＭＦＲ）が０．００１〜５０ｇ／１０分であるものが好ましく、特には０．００５〜３０ｇ／１０分のものが好ましい。
The ionomer is theoretically neutralized by sodium (Na) or magnesium (Mg) metal ions in the range of 100% or less of the carboxyl groups in the copolymer. Usually, 80% or less, preferably 10 to 80%, more preferably 15 to 60%, neutralized with Na or Mg metal ions is suitable.
In addition, the ethylene ionomer in the present invention is a melt at 190 ° C. and 2160 g load in accordance with JIS K7210-1999 from the viewpoint of molding processability and mechanical strength when it becomes a composition with dimer acid described later. Those having a flow rate (MFR) of 0.001 to 50 g / 10 min are preferred, and those having a flow rate (0.005 to 30 g / 10 min) are particularly preferred.
前記エチレン系アイオノマーのベースポリマーであるエチレン・α，β−不飽和カルボン酸共重合体は、各重合成分を高温、高圧下にラジカル共重合することによって得ることができる。 The ethylene / α, β-unsaturated carboxylic acid copolymer, which is a base polymer of the ethylene ionomer, can be obtained by radical copolymerization of each polymerization component at high temperature and high pressure.
前記エチレン系アイオノマー（Ａ）は、α，β−不飽和カルボン酸から導かれる構成単位の含有割合が異なるものや中和度の異なるものを複数併用してもよく、更には金属種の異なるもの、即ちナトリウムとマグネシウムを併用しても構わない。また別には、本発明の目的を損なわない範囲で、亜鉛等のナトリウムとマグネシウム以外の他の金属種のエチレン系アイオノマーと併用しても構わない。 The ethylene ionomer (A) may be used in combination with a plurality of structural units derived from an α, β-unsaturated carboxylic acid, those having different proportions of neutralization, and those having different metal species. That is, sodium and magnesium may be used in combination. Alternatively, it may be used in combination with an ethylene ionomer of a metal species other than sodium and magnesium such as zinc within a range not impairing the object of the present invention.
［（Ｂ）ダイマー酸］
本発明のゴルフボール材料用アイオノマー組成物は、ダイマー酸の少なくとも１種を含有する。ダイマー酸は、不飽和脂肪酸の２分子又はそれ以上の分子が重合反応して得られる多価カルボン酸であって、通常２種類以上の混合物として得られ、混合物として各種の用途に供されている。また、ダイマー酸は、（好ましくは炭素原子数８〜２２の）直鎖状又は分岐状の不飽和脂肪酸を二量化することによって得られるものであり、その誘導体も含まれる。
[(B) Dimer acid]
The ionomer composition for a golf ball material of the present invention contains at least one dimer acid. Dimer acid is a polyvalent carboxylic acid obtained by polymerization reaction of two or more molecules of unsaturated fatty acid, and is usually obtained as a mixture of two or more types and used for various applications as a mixture. . The dimer acid is obtained by dimerizing a linear or branched unsaturated fatty acid (preferably having 8 to 22 carbon atoms), and derivatives thereof are also included.
ダイマー酸を前記エチレン系アイオノマー（Ａ）とともに含有することにより、アイオノマーの機械的強度を損なわずに、流動性が大幅に向上する。 By containing dimer acid together with the ethylene ionomer (A), the fluidity is greatly improved without impairing the mechanical strength of the ionomer.
ダイマー酸の誘導体としては、水素添加物などを挙げることができる。具体的には、前記ダイマー酸に水素化、別の表現では水素添加反応（水添ともいう）を付与して、含有される不飽和結合を還元した水添ダイマー酸などが使用できる。 Examples of the dimer acid derivative include a hydrogenated product. Specifically, a hydrogenated dimer acid obtained by hydrogenating the dimer acid, in other words a hydrogenation reaction (also referred to as hydrogenation) to reduce the unsaturated bond contained therein can be used.
ダイマー酸は、例えば、３−オクテン酸、１０−ウンデセン酸、オレイン酸、リノール酸、エライジン酸、パルミトレイン酸、リノレン酸、あるいはこれらの２種以上の混合物等を、あるいは工業的に入手可能なこれら不飽和カルボン酸の混合物であるトール油脂肪酸、大豆油脂肪酸、パーム油脂肪酸、米ぬか油脂肪酸、亜麻仁油脂肪酸などを原料としたものであってもよい。ダイマー酸としては、モノマー酸やトリマー酸を少量含有するものであってもよい。 The dimer acid may be, for example, 3-octenoic acid, 10-undecenoic acid, oleic acid, linoleic acid, elaidic acid, palmitoleic acid, linolenic acid, or a mixture of two or more thereof, or these which are commercially available The raw material may be a tall oil fatty acid, soybean oil fatty acid, palm oil fatty acid, rice bran oil fatty acid, linseed oil fatty acid or the like, which is a mixture of unsaturated carboxylic acids. The dimer acid may contain a small amount of monomer acid or trimer acid.
従来から、ダイマー酸は通常、モンモリロナイト系白土を触媒として用い、トール油脂肪酸などの不飽和脂肪酸を高温下で二量化して製造することができる。 Conventionally, dimer acid can usually be produced by dimerizing unsaturated fatty acid such as tall oil fatty acid at high temperature using montmorillonite clay as a catalyst.
ダイマー酸の例として、下記構造式（１）で表される鎖状ダイマー酸が挙げられる。 An example of the dimer acid is a chain dimer acid represented by the following structural formula (1).
前記構造式（１）で表される鎖状ダイマー酸のほかに、下記構造式（２）又は（３）で表される環状ダイマー酸を含む混合物などが得られる。 In addition to the chain dimer acid represented by the structural formula (1), a mixture containing a cyclic dimer acid represented by the following structural formula (2) or (3) is obtained.
工業的に入手可能なダイマー酸としては、例えば、ハリダイマー２００、３００（ハリマ化成（株）製）、ツノダイム２０５、３９５（築野食品工業（株）製）、エンポール１０２６、１０２８、１０６１、１０６２（コグニス（株）製）、水素化ダイマー酸として例えば、Ｄｉｍｅｒ ａｃｉｄ ｈｙｄｒｏｇｅｎａｔｅｄ（ＡＬＤＲＩＣＨ社製）、エンポール１００８、１０１２（コグニス（株）製）などが挙げられる。 Industrially available dimer acids include, for example, Halidimer 200 and 300 (manufactured by Harima Chemicals Co., Ltd.), Tsunodim 205 and 395 (manufactured by Tsukino Food Industry Co., Ltd.), Empor 1026, 1028, 1061, 1062 ( Examples of the hydrogenated dimer acid include Dimer acid hydrogenated (manufactured by ALDRICH), Empor 1008, 1012 (manufactured by Cognis Co., Ltd.), and the like.
これらのダイマー酸の中で、水素化ダイマー酸は、実質的に不飽和結合を有していない。このため、不飽和結合の存在に基づく熱や光に対する不安定性は小さいと予想される。したがって、極めて高い熱や光強度の強い環境下では、アイオノマー組成物に対する劣化や変色の可能性がより小さくなると期待できる。ここで、「実質的に不飽和結合を有しない」とする判断基準の一例として、ヨウ素価がある。ヨウ素価は、分子中における不飽和結合の量が前記の悪影響を起こしても実用上無視できる点で、５０以下、好ましくは３０以下、特に好ましくは１５以下の値が好ましい。 Among these dimer acids, hydrogenated dimer acid has substantially no unsaturated bond. For this reason, the instability to heat and light based on the presence of unsaturated bonds is expected to be small. Therefore, in an environment where the heat and light intensity are extremely high, it is expected that the possibility of deterioration or discoloration of the ionomer composition becomes smaller. Here, there is an iodine value as an example of a criterion for “substantially having no unsaturated bond”. The iodine value is preferably not more than 50, preferably not more than 30, particularly preferably not more than 15 in terms of practically negligible even if the amount of unsaturated bonds in the molecule causes the above-mentioned adverse effects.
本発明において、アイオノマー及びダイマー酸の合計量１００質量部に対するダイマー酸の含有比率は、０．１〜５０質量部の範囲が好ましい。ダイマー酸の含有比率が０．１質量部以上であることは、ダイマー酸を積極的に含むことを示し、アイオノマーの流動性が向上する。また、ダイマー酸の含有比率が５０質量部以下であると、アイオノマーの流動性を高めながら、ブリードアウト（滲み出し）の発生を抑えることができる。ブリードアウト（滲み出し）の発生を回避しながら、アイオノマーの流動性を高める観点から、ダイマー酸の含有比率は、１〜４０質量部の範囲がより好ましい。中でも、アイオノマー及びダイマー酸の合計量１００質量部に対するダイマー酸の含有比率としては、１〜３０質量部の範囲がより好ましく、１〜２５質量部の範囲がさらに好ましい。ダイマー酸の含有比率を３０質量部以下に抑えることで、ブリードアウト（滲み出し）の発生がより効果的に防止されると共に、透明で流動性に優れたアイオノマーを得ることができる。同様の理由から、ダイマー酸の含有比率は、さらに１〜２０質量部の範囲が好ましく、特に１〜１５質量部の範囲が好ましい。
更には、ダイマー酸の含有比率の下限値は、曲げ剛性の向上効果が大きい点で、２質量％、特には５質量％が望ましい。
In the present invention, the content ratio of dimer acid to 100 parts by mass of the total amount of ionomer and dimer acid is preferably in the range of 0.1 to 50 parts by mass. When the content ratio of the dimer acid is 0.1 part by mass or more, it indicates that the dimer acid is positively contained, and the fluidity of the ionomer is improved. Moreover, generation | occurrence | production of bleed-out (bleeding out) can be suppressed, improving the fluidity | liquidity of an ionomer as the content rate of a dimer acid is 50 mass parts or less. From the viewpoint of improving the flowability of the ionomer while avoiding the occurrence of bleeding out (bleeding out), the content ratio of the dimer acid is more preferably in the range of 1 to 40 parts by mass. Especially, as a content rate of dimer acid with respect to 100 mass parts of total amounts of ionomer and dimer acid, the range of 1-30 mass parts is more preferable, and the range of 1-25 mass parts is further more preferable. By suppressing the content ratio of the dimer acid to 30 parts by mass or less, occurrence of bleeding out (bleeding out) can be more effectively prevented, and an ionomer having transparency and excellent fluidity can be obtained. For the same reason, the content ratio of the dimer acid is further preferably in the range of 1 to 20 parts by mass, particularly preferably in the range of 1 to 15 parts by mass.
Furthermore, the lower limit value of the content ratio of the dimer acid is preferably 2% by mass, particularly 5% by mass in that the effect of improving the bending rigidity is great.
［他の成分］
本発明のアイオノマー組成物には、更に、紫外線吸収剤、光安定剤、酸化防止剤、老化防止剤、熱安定剤、滑剤、ブロッキング防止剤、可塑剤、粘着剤、無機充填剤、ガラス繊維、カーボン繊維などの強化繊維、顔料、染料、難燃剤、難燃助剤、発泡剤、発泡助剤などを含有してもよい。また、帯電防止剤を配合することもできる。
[Other ingredients]
The ionomer composition of the present invention further includes an ultraviolet absorber, a light stabilizer, an antioxidant, an anti-aging agent, a heat stabilizer, a lubricant, an anti-blocking agent, a plasticizer, an adhesive, an inorganic filler, glass fiber, Reinforcing fibers such as carbon fibers, pigments, dyes, flame retardants, flame retardant aids, foaming agents, foaming aids and the like may be contained. Moreover, an antistatic agent can also be mix | blended.
前記紫外線吸収剤としては、例えば、２−ヒドロキシ−４−メトキシベンゾフェノン、２，２’−ジヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−メトキシ−２−カルボキシベンゾフェノン、及び２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノンなどのベンゾフェノン系；２−（２’−ヒドロキシ−３’，５’−ジｔ−ブチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−５−メチルフェニル）ベンゾトリアゾール、及び２−（２’−ヒドロキシ−５−ｔ−オクチルフェニル）ベンゾトリアゾールなどのベンゾトリアゾール系；フェニルサリチレート及びｐ−オクチルフェニルサリチレートなどのサリチル酸エステル系のものが挙げられる。
前記光安定剤としては、例えばヒンダードアミン系のものが挙げられる。
前記酸化防止剤としては、各種ヒンダードフェノール系やホスファイト系のものが挙げられる。
Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2-carboxybenzophenone, and 2-hydroxy-4- benzophenone series such as n-octoxybenzophenone; 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5-methylphenyl) benzotriazole, and Examples include benzotriazoles such as 2- (2′-hydroxy-5-t-octylphenyl) benzotriazole; salicylic acid esters such as phenyl salicylate and p-octylphenyl salicylate.
Examples of the light stabilizer include hindered amines.
Examples of the antioxidant include various hindered phenols and phosphites.
＜ゴルフボール＞
本発明に係るゴルフボールは、上述したゴルフボール材料用アイオノマー組成物をゴルフボールの表皮材、中間層、コア材のいずれか、又は全てを構成する材料として保有する。
<Golf Ball>
The golf ball according to the present invention retains the above-described ionomer composition for a golf ball material as a material constituting any or all of the skin material, intermediate layer, and core material of the golf ball.
本発明に係るゴルフボールは、糸巻きボールであってもソリッドボールであってもよい。ソリッドボールとしては、ワンピースボール、ツーピースボールの他、３ピース、４ピースなどのマルチピースボールであってもよい。本発明に係るゴルフボールを製造する方法は、特に限定されず、常法に従い、射出成形や加圧成形などの方法を適宜採用することができる。 The golf ball according to the present invention may be a wound ball or a solid ball. The solid ball may be a one-piece ball or a two-piece ball, or a multi-piece ball such as a three-piece or a four-piece. The method for producing the golf ball according to the present invention is not particularly limited, and a method such as injection molding or pressure molding can be appropriately employed according to a conventional method.
本発明に係るゴルフボール材料用アイオノマー組成物は、表皮材のほかにも、中間層、コア材などの全てに適用可能である。その際、本発明に係るゴルフボール材料用アイオノマー組成物は、流動性が高く、ブリードアウトも抑えられているため、成形時にブリードアウト物が引き起こす発煙現象が防止される。さらに、表皮材の薄肉化に伴なうキャビティー容積の小さい成形でも、低い背圧で偏りなく均一に成形することが可能である。また、金型汚染を抑えることができるので、長時間に亘る連続成形が可能である。 The ionomer composition for a golf ball material according to the present invention can be applied to all of an intermediate layer, a core material, etc. in addition to a skin material. At that time, the ionomer composition for a golf ball material according to the present invention has high fluidity and suppresses bleed-out, so that the smoke generation phenomenon caused by the bleed-out product during molding is prevented. Furthermore, even when molding with a small cavity volume accompanying the thinning of the skin material, it is possible to mold uniformly with a low back pressure. Moreover, since mold contamination can be suppressed, continuous molding over a long time is possible.
本発明に係るゴルフボール材料用アイオノマー組成物は、アイオノマー本来の物性を保持しているため、反発弾性や剛性、耐摩耗性などの機械的特性に優れている。このようなアイオノマー組成物を表皮材、中間層、コア材のいずれか又は全てを構成する材料とするゴルフボールは、剛性、反発性、耐久性に優れることが期待される。 The ionomer composition for golf ball material according to the present invention retains the original physical properties of the ionomer, and therefore has excellent mechanical properties such as resilience, rigidity, and wear resistance. A golf ball having such an ionomer composition as a material constituting any or all of the skin material, the intermediate layer, and the core material is expected to be excellent in rigidity, resilience, and durability.
以下、本発明を実施例により更に具体的に説明するが、本発明はその主旨を越えない限り、以下の実施例に限定されるものではない。なお、特に断りのない限り、「部」は質量基準である。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.
以下に示す材料を用意した。
［アイオノマー］
・アイオノマー１：
エチレン・メタクリル酸共重合体（メタクリル酸由来の構成単位＝１５質量％）の亜鉛アイオノマー（中和度：５９％、ＭＦＲ（JIS K7210-1999に準拠（190℃、2160g荷重））：０．９ｇ／１０分）
・アイオノマー２：
エチレン・メタクリル酸共重合体（メタクリル酸由来の構成単位＝１５質量％）のナトリウムアイオノマー（中和度：５４％、ＭＦＲ（JIS K7210-1999に準拠（190℃、2160g荷重））：０．９ｇ／１０分）
・アイオノマー３：
エチレン・メタクリル酸共重合体（メタクリル酸由来の構成単位＝１５質量％）のマグネシウムアイオノマー（中和度：５４％、ＭＦＲ（JIS K7210-1999に準拠（190℃、2160g荷重））：０．７ｇ／１０分）
The following materials were prepared.
[Ionomer]
・ Ionomer 1:
Zinc ionomer of ethylene / methacrylic acid copolymer (constituent unit derived from methacrylic acid = 15% by mass) (neutralization degree: 59%, MFR (compliant with JIS K7210-1999 (190 ° C., 2160 g load))): 0.9 g / 10 minutes)
・ Ionomer 2:
Sodium ionomer of ethylene / methacrylic acid copolymer (constituent unit derived from methacrylic acid = 15 mass%) (neutralization degree: 54%, MFR (compliant with JIS K7210-1999 (190 ° C., 2160 g load))): 0.9 g / 10 minutes)
・ Ionomer 3:
Magnesium ionomer of ethylene / methacrylic acid copolymer (constituent unit derived from methacrylic acid = 15% by mass) (neutralization degree: 54%, MFR (compliant with JIS K7210-1999 (190 ° C., 2160 g load))): 0.7 g / 10 minutes)
［ダイマー酸］
・ダイマー酸１：
Ｄｉｍｅｒ ａｃｉｄ ｈｙｄｒｏｇｅｎａｔｅｄ（ＡＬＤＲＩＣＨ社製、平均分子量Ｍｎ：〜５７０、モノマー酸含有量：０．１質量％未満、トリマー酸含有量：０．１質量％未満、ヨウ素値：１０未満、密度０．９５ｇ／ｍｌ（２５℃）、酸価（acid number）：１９４〜１９８ｍｇ ＫＯＨ／ｇ）
[Dimer acid]
Dimer acid 1:
Dimer acid hydrogenated (manufactured by ALDRICH, average molecular weight Mn: ˜570, monomer acid content: less than 0.1% by mass, trimer acid content: less than 0.1% by mass, iodine value: less than 10, density 0.95 g / ml (25 ° C., acid number: 194 to 198 mg KOH / g)
（実験例１〜３）
用意したアイオノマー１〜３のそれぞれに、アイオノマー１００質量部に対して下記表１に示す量となるようにダイマー酸１を配合し、ラボプラストミル混練機（ツインスクリュー；東洋精機社製）にて、１８０℃、回転数５０ｍｉｎ−１で１０分間混合した。
混合して得られたアイオノマー組成物について、以下の評価を行なった。評価結果は、下記の表１及び図１〜図３に示す。
(Experimental Examples 1-3)
Each of the prepared ionomers 1 to 3 is blended with dimer acid 1 so as to have the amount shown in the following Table 1 with respect to 100 parts by mass of ionomer, and in a lab plast mill kneader (twin screw; manufactured by Toyo Seiki Co., Ltd.). , 180 ° C., and rotation speed 50 min −1 for 10 minutes.
The following evaluation was performed about the ionomer composition obtained by mixing. The evaluation results are shown in Table 1 below and FIGS.
（評価）
<１．流動性>
混合後、メルトフローレート（ＭＦＲ）を測定し、流動性の指標とした。このとき、ＭＦＲは、ＪＩＳ Ｋ７２１０−１９９９に準拠した方法により１９０℃、荷重２１６０ｇにて測定した。測定結果を下記表１に示す。ＭＦＲは、ダイマー酸を配合しない系の測定値を１００に規格化し、各配合量でのＭＦＲをこれに対する相対比で示した。
(Evaluation)
<1. Fluidity>
After mixing, the melt flow rate (MFR) was measured and used as an index of fluidity. At this time, MFR was measured at 190 ° C. and a load of 2160 g by a method based on JIS K7210-1999. The measurement results are shown in Table 1 below. MFR normalized the measured value of the system which does not mix | blend dimer acid to 100, and showed MFR in each compounding quantity by the relative ratio with respect to this.
<２．曲げ剛性率>
次に、得られた混合物を、加熱プレス（１６０℃）にてシート状にプレス成形し、１５０ｍｍ×１５０ｍｍ×２ｍｍのプレスシート（サンプルシート）を得た。このサンプルシートを用い、曲げ剛性率（オルゼン式に準拠）を測定した。オルゼン式の曲げ剛性率は、ＪＩＳ Ｋ７１０６に準拠した方法で測定した。測定結果を下記表１に示す。曲げ剛性率は、ダイマー酸を配合しない系の測定値を１００に規格化し、各配合量での曲げ剛性率をこれに対する相対比で示した。
<2. Flexural rigidity>
Next, the obtained mixture was press-molded into a sheet with a heating press (160 ° C.) to obtain a press sheet (sample sheet) of 150 mm × 150 mm × 2 mm. Using this sample sheet, the flexural rigidity (based on the Olsen method) was measured. The Orzen bending stiffness was measured by a method based on JIS K7106. The measurement results are shown in Table 1 below. The flexural rigidity was normalized to 100 for the system in which no dimer acid was blended, and the flexural rigidity at each blending amount was shown as a relative ratio thereto.
前記表１及び図１〜図３に示すように、ダイマー酸をＮａ中和またはＭｇ中和されたエチレン系アイオノマーと共に含有する本発明では、従来の組成に比べ、高い曲げ剛性率を達成しながら、良好な流動性を確保することができた。また、ダイマー酸のブリードアウトも認められなかった。
特に本発明では、図２〜図３に示すように、亜鉛中和のアイオノマーを用いた場合（図１の実験例１参照）に比べ、ダイマー酸の混合による流動性の改善効果が大きく、ダイマー酸の添加比率が２質量％以上、更には５質量％以上になるとその効果はより顕著であり、図１に示す実験例１のように曲げ剛性を大きく損なうこともなかった。
As shown in Table 1 and FIGS. 1 to 3, in the present invention containing dimer acid together with an ethylene ionomer that is Na-neutralized or Mg-neutralized, while achieving a high bending rigidity as compared with the conventional composition. Good fluidity could be secured. Also, no dimer acid bleed out was observed.
In particular, in the present invention, as shown in FIGS. 2 to 3, compared with the case where a zinc neutralized ionomer is used (see Experimental Example 1 in FIG. 1), the effect of improving fluidity by mixing dimer acid is large. When the addition ratio of the acid is 2% by mass or more, and further 5% by mass or more, the effect is more remarkable, and the bending rigidity is not greatly impaired as in Experimental Example 1 shown in FIG.
上記実施例では、エチレン系アイオノマー（Ａ）として前記アイオノマー２，３を、ダイマー酸（Ｂ）としてＤｉｍｅｒ ａｃｉｄ ｈｙｄｒｏｇｅｎａｔｅｄを用いた場合を中心に説明したが、これ以外の既述のエチレン系アイオノマー、ダイマー酸を用いた場合にも同様の結果が得られる。 In the above embodiment, the case where the ionomers 2 and 3 are used as the ethylene ionomer (A) and Dimer acid hydrogenated is used as the dimer acid (B) has been mainly described. Similar results are obtained when acids are used.
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