JP2016033194A - Rubber composition for tire - Google Patents
Rubber composition for tire Download PDFInfo
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- JP2016033194A JP2016033194A JP2014156929A JP2014156929A JP2016033194A JP 2016033194 A JP2016033194 A JP 2016033194A JP 2014156929 A JP2014156929 A JP 2014156929A JP 2014156929 A JP2014156929 A JP 2014156929A JP 2016033194 A JP2016033194 A JP 2016033194A
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- weight
- aromatic vinyl
- parts
- rubber composition
- tire
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- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 229920001971 elastomer Polymers 0.000 title claims abstract description 44
- 239000005060 rubber Substances 0.000 title claims abstract description 44
- 229920001577 copolymer Polymers 0.000 claims abstract description 35
- 125000003118 aryl group Chemical group 0.000 claims abstract description 34
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000006229 carbon black Substances 0.000 claims abstract description 19
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 18
- 230000009477 glass transition Effects 0.000 claims abstract description 15
- 238000010521 absorption reaction Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims description 35
- 239000011347 resin Substances 0.000 claims description 35
- 239000004902 Softening Agent Substances 0.000 claims description 2
- 238000005299 abrasion Methods 0.000 abstract description 2
- JSNRRGGBADWTMC-UHFFFAOYSA-N (6E)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene Chemical compound CC(C)=CCCC(C)=CCCC(=C)C=C JSNRRGGBADWTMC-UHFFFAOYSA-N 0.000 description 38
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 238000013329 compounding Methods 0.000 description 15
- 229920003048 styrene butadiene rubber Polymers 0.000 description 14
- CXENHBSYCFFKJS-UHFFFAOYSA-N (3E,6E)-3,7,11-Trimethyl-1,3,6,10-dodecatetraene Natural products CC(C)=CCCC(C)=CCC=C(C)C=C CXENHBSYCFFKJS-UHFFFAOYSA-N 0.000 description 13
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- 238000002156 mixing Methods 0.000 description 11
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- JSNRRGGBADWTMC-QINSGFPZSA-N (E)-beta-Farnesene Natural products CC(C)=CCC\C(C)=C/CCC(=C)C=C JSNRRGGBADWTMC-QINSGFPZSA-N 0.000 description 9
- YSNRTFFURISHOU-UHFFFAOYSA-N beta-farnesene Natural products C=CC(C)CCC=C(C)CCC=C(C)C YSNRTFFURISHOU-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000003505 terpenes Chemical class 0.000 description 6
- 235000007586 terpenes Nutrition 0.000 description 6
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- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- -1 aromatic vinyl compound Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
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- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- RCJMVGJKROQDCB-UHFFFAOYSA-N 2-methylpenta-1,3-diene Chemical compound CC=CC(C)=C RCJMVGJKROQDCB-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 2
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- NSYRAUUZGRPOHS-BQYQJAHWSA-N (3E)-2-methylocta-1,3-diene Chemical compound CCCC\C=C\C(C)=C NSYRAUUZGRPOHS-BQYQJAHWSA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- HOXGZVUCAYFWGR-KQQUZDAGSA-N (3e,5e)-octa-1,3,5-triene Chemical compound CC\C=C\C=C\C=C HOXGZVUCAYFWGR-KQQUZDAGSA-N 0.000 description 1
- CORMBJOFDGICKF-UHFFFAOYSA-N 1,3,5-trimethoxy 2-vinyl benzene Natural products COC1=CC(OC)=C(C=C)C(OC)=C1 CORMBJOFDGICKF-UHFFFAOYSA-N 0.000 description 1
- QTYUSOHYEPOHLV-FNORWQNLSA-N 1,3-Octadiene Chemical compound CCCC\C=C\C=C QTYUSOHYEPOHLV-FNORWQNLSA-N 0.000 description 1
- VDNSZPNSUQRUMS-UHFFFAOYSA-N 1-cyclohexyl-4-ethenylbenzene Chemical compound C1=CC(C=C)=CC=C1C1CCCCC1 VDNSZPNSUQRUMS-UHFFFAOYSA-N 0.000 description 1
- WJNKJKGZKFOLOJ-UHFFFAOYSA-N 1-dodecyl-4-ethenylbenzene Chemical compound CCCCCCCCCCCCC1=CC=C(C=C)C=C1 WJNKJKGZKFOLOJ-UHFFFAOYSA-N 0.000 description 1
- OUSXYCTXXLYBGJ-UHFFFAOYSA-N 1-ethenyl-2,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C=C)C(C(C)C)=C1 OUSXYCTXXLYBGJ-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JHTICDZLXFNVKL-UHFFFAOYSA-N 1-ethenyl-4-(4-phenylbutyl)benzene Chemical compound C1=CC(C=C)=CC=C1CCCCC1=CC=CC=C1 JHTICDZLXFNVKL-UHFFFAOYSA-N 0.000 description 1
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 1
- VVTGQMLRTKFKAM-UHFFFAOYSA-N 1-ethenyl-4-propylbenzene Chemical compound CCCC1=CC=C(C=C)C=C1 VVTGQMLRTKFKAM-UHFFFAOYSA-N 0.000 description 1
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- JXBSHSBNOVLGHF-UHFFFAOYSA-N 10-cis-Dihydrofarnesen Natural products CC=C(C)CCC=C(C)CCC=C(C)C JXBSHSBNOVLGHF-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- BIOCRZSYHQYVSG-UHFFFAOYSA-N 2-(4-ethenylphenyl)-n,n-diethylethanamine Chemical compound CCN(CC)CCC1=CC=C(C=C)C=C1 BIOCRZSYHQYVSG-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- PDELBHCVXBSVPJ-UHFFFAOYSA-N 2-ethenyl-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(C=C)C(C)=C1 PDELBHCVXBSVPJ-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- DXFURPHVJQITAC-UHFFFAOYSA-N 4-benzyl-1-ethenyl-2-ethylbenzene Chemical compound C1=C(C=C)C(CC)=CC(CC=2C=CC=CC=2)=C1 DXFURPHVJQITAC-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 description 1
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
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- 229920002223 polystyrene Polymers 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
Description
本発明は、ドライグリップ性能と、耐久性および耐摩耗性を高いレベルで両立するようにしたタイヤ用ゴム組成物に関する。 The present invention relates to a rubber composition for tires that is compatible with dry grip performance, durability and wear resistance at a high level.
サーキット走行向けの競技用タイヤに求められる性能には、ドライグリップ性能が優れることに加え、タイヤ耐久性、耐摩耗性など多岐に亘る。優れたドライグリップ性能を得るために、トレッド用ゴム組成物に粒径の小さいカーボンブラックを多量に配合したり、ガラス転移温度が高いスチレンブタジエンゴムを配合したりすることが行われる。これにより、発熱が大きくなりドライグリップ性能が向上する。しかし、上述したゴム組成物は、高温状態になるとモジュラスやゴム強度が低下しやすくなる。このため、高速走行が長時間になると耐摩耗性が低下しトレッド表面の摩耗状態が悪化したり、熱ダレ現象によりドライグリップ性能が徐々に低下し、場合によってはブローアウトを起こすなどタイヤ耐久性が悪化する。一方、タイヤ耐久性を重視してゴム硬度を大きくしたり、発熱を抑制するためカーボンブラックの配合量を少なくするとドライグリップ性能が低下してしまう。 The performance required for racing tires for circuit running is not only excellent in dry grip performance, but also in tire durability and wear resistance. In order to obtain excellent dry grip performance, a large amount of carbon black having a small particle diameter is blended with a rubber composition for treads, or a styrene butadiene rubber having a high glass transition temperature is blended. This increases heat generation and improves dry grip performance. However, when the rubber composition described above is in a high temperature state, the modulus and rubber strength tend to decrease. For this reason, tire durability such as wear resistance decreases and wear conditions on the tread surface deteriorate when the high-speed driving is prolonged, and dry grip performance gradually deteriorates due to thermal sag phenomenon. Gets worse. On the other hand, if the rubber hardness is increased with emphasis on tire durability, or the amount of carbon black is decreased to suppress heat generation, the dry grip performance is degraded.
またドライグリップ性能を高くするため、スチレン−ブタジエン共重合体ゴムに特定の２種類のカーボンブラックおよび低分子量スチレン−ブタジエン共重合体を配合したタイヤトレッド用ゴム組成物が提案されている（例えば特許文献１参照）。しかし、需要者がサーキット走行向けの競技用タイヤに求めるドライグリップ性能、耐久性能および耐摩耗性能のレベルはより高く更なる改良が求められている。 In order to improve dry grip performance, a rubber composition for a tire tread in which two specific types of carbon black and a low molecular weight styrene-butadiene copolymer are blended with a styrene-butadiene copolymer rubber has been proposed (for example, patents). Reference 1). However, the level of dry grip performance, durability performance, and wear resistance performance that consumers demand for racing tires for circuit running is higher and further improvements are required.
本発明の目的は、ドライグリップ性能と、耐久性および耐摩耗性を従来以上に高いレベルで両立するようにしたタイヤ用ゴム組成物を提供することにある。 An object of the present invention is to provide a rubber composition for tires that is compatible with dry grip performance, durability and wear resistance at a higher level than before.
上記目的を達成する本発明のタイヤ用ゴム組成物は、ガラス転移温度が−３５℃以上である芳香族ビニル−共役ジエン系ゴムを含むジエン系ゴム１００重量部に対し、芳香族ビニル−ファルネセン共重合体を５〜１００重量部含む軟化剤成分を合計で５０重量部以上、窒素吸着比表面積が１５０〜４００ｍ2／ｇ、ＤＢＰ吸収量が１００〜２００ｃｍ3／１００ｇであるカーボンブラックを１０〜１８０重量部配合したことを特徴とする。 The rubber composition for a tire according to the present invention that achieves the above-mentioned object is obtained by adding aromatic vinyl-farnesene copolymer to 100 parts by weight of diene rubber containing aromatic vinyl-conjugated diene rubber having a glass transition temperature of −35 ° C. or higher. a softening agent component comprising 5 to 100 parts by weight of the polymer total 50 parts by weight or more, a nitrogen adsorption specific surface area of 150 to 400 m 2 / g, DBP absorption amount of carbon black is 100~200cm 3 / 100g 10~180 It is characterized by blending parts by weight.
本発明のタイヤ用ゴム組成物は、ガラス転移温度が−３５℃以上の芳香族ビニル−共役ジエン系ゴムを含むジエン系ゴム１００重量部に、芳香族ビニル−ファルネセン共重合体を５〜１００重量部含む軟化剤成分を合計で５０重量部以上、窒素吸着比表面積およびＤＢＰ吸収量が特定されたカーボンブラックを１０〜１８０重量部配合したので、ドライグリップ性能と、耐久性および耐摩耗性を従来レベル以上に向上することができる。 The rubber composition for tires of the present invention comprises 5 to 100 parts by weight of an aromatic vinyl-farnesene copolymer in 100 parts by weight of a diene rubber containing an aromatic vinyl-conjugated diene rubber having a glass transition temperature of −35 ° C. or higher. 50 parts by weight or more of the softener component including 10 parts by weight, and 10 to 180 parts by weight of carbon black with a specified nitrogen adsorption specific surface area and DBP absorption amount were blended, so that dry grip performance, durability and wear resistance were conventionally achieved It can be improved beyond the level.
前記軟化剤成分は、軟化点が１３０〜２００℃である樹脂を含むとよく、この樹脂の配合量は、前記ジエン系ゴム１００重量部に対し１０〜６０重量部であるとよい。前記軟化剤成分の合計中、前記芳香族ビニル−ファルネセン共重合体の重量分率が、０．２０〜０．６０であるとよい。 The softener component may include a resin having a softening point of 130 to 200 ° C., and the amount of the resin is preferably 10 to 60 parts by weight with respect to 100 parts by weight of the diene rubber. In the total of the softener components, the weight fraction of the aromatic vinyl-farnesene copolymer is preferably 0.20 to 0.60.
本発明のタイヤ用ゴム組成物をトレッド部に使用した空気入りタイヤは、ドライグリップ性能と、耐久性および耐摩耗性を従来以上に高いレベルで両立することができ、競技用空気入りタイヤとして好適である。 The pneumatic tire using the tire rubber composition of the present invention in the tread portion can achieve both dry grip performance, durability and wear resistance at a higher level than before, and is suitable as a pneumatic tire for competition. It is.
本発明のタイヤ用ゴム組成物は、そのゴム成分をジエン系ゴムで構成し、ジエン系ゴムとして、ガラス転移温度が−３５℃以上である芳香族ビニル−共役ジエン系ゴムを含む。芳香族ビニル−共役ジエン系ゴムとしては、スチレンブタジエンゴムが例示される。芳香族ビニル−共役ジエン系ゴムのガラス転移温度は−３５℃以上、好ましくは−３５〜−１０℃にする。芳香族ビニル−共役ジエン系ゴムのガラス転移温度を−３５℃以上にすることにより、ドライグリップ性能を高くすることができる。芳香族ビニル−共役ジエン系ゴムのガラス転移温度は示差走査熱量測定（ＤＳＣ）により２０℃／分の昇温速度条件によりサーモグラムを測定し、転移域の中点の温度とする。また芳香族ビニル−共役ジエン系ゴムがオイルを含む油展品であるときは、オイルを除いた芳香族ビニル−共役ジエン系ゴムのガラス転移温度とする。 The rubber composition for tires of the present invention comprises a diene rubber as a rubber component, and includes an aromatic vinyl-conjugated diene rubber having a glass transition temperature of −35 ° C. or higher as the diene rubber. Styrene butadiene rubber is exemplified as the aromatic vinyl-conjugated diene rubber. The glass transition temperature of the aromatic vinyl-conjugated diene rubber is −35 ° C. or higher, preferably −35 to −10 ° C. By setting the glass transition temperature of the aromatic vinyl-conjugated diene rubber to −35 ° C. or higher, the dry grip performance can be enhanced. The glass transition temperature of the aromatic vinyl-conjugated diene rubber is measured by a differential scanning calorimetry (DSC) under a heating rate condition of 20 ° C./min, and is set as the temperature at the midpoint of the transition region. When the aromatic vinyl-conjugated diene rubber is an oil-extended product containing oil, the glass transition temperature of the aromatic vinyl-conjugated diene rubber excluding the oil is used.
また芳香族ビニル−共役ジエン系ゴムの含有量は、ジエン系ゴム１００重量％中、好ましくは５０〜１００重量％、より好ましくは７５〜１００重量％であるとよい。 The content of the aromatic vinyl-conjugated diene rubber is preferably 50 to 100% by weight, more preferably 75 to 100% by weight in 100% by weight of the diene rubber.
本発明のタイヤ用ゴム組成物は、ガラス転移温度が−３５℃以上の芳香族ビニル−共役ジエン系ゴム以外に、他のジエン系ゴムを含むことができる。ジエン系ゴムとしては、例えば天然ゴム、イソプレンゴム、ブタジエンゴム、ガラス転移温度が−３５℃未満のスチレンブタジエンゴム、アクリロニトリルブタジエンゴム、ブチルゴム、クロロプレンゴム等を例示することができる。これらは、単独又は任意のブレンドとして使用することができる。上述した他のジエンゴムは、ジエン系ゴム１００重量％中、好ましくは０〜５０重量％、より好ましくは０〜２５重量％含有することができ、タイヤ耐久性および耐摩耗性を高くすることができる。 The rubber composition for tires of the present invention can contain other diene rubbers in addition to the aromatic vinyl-conjugated diene rubber having a glass transition temperature of −35 ° C. or higher. Examples of the diene rubber include natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber having a glass transition temperature of less than −35 ° C., acrylonitrile butadiene rubber, butyl rubber, and chloroprene rubber. These can be used alone or as any blend. The other diene rubbers mentioned above can be contained in 100% by weight of the diene rubber, preferably 0 to 50% by weight, more preferably 0 to 25% by weight, and the tire durability and wear resistance can be increased. .
本発明のタイヤ用ゴム組成物は、芳香族ビニル−ファルネセン共重合体を配合することにより、ドライグリップ性能、耐久性および耐摩耗性を向上することができ、とりわけドライグリップ性能を優れたものにすることができる。また芳香族ビニル−ファルネセン共重合体は、芳香族ビニル−共役ジエン系ゴムとの親和性が高く、かつ比較的高分子量であるとともに架橋性構造を有するため、加硫後にタイヤ用ゴム組成物の機械的特性を従来レベル以上に高くし、タイヤ耐久性や耐摩耗性を改良することができる。 The rubber composition for tires of the present invention can improve dry grip performance, durability and wear resistance by blending an aromatic vinyl-farnesene copolymer, and in particular, has excellent dry grip performance. can do. The aromatic vinyl-farnesene copolymer has a high affinity with the aromatic vinyl-conjugated diene rubber and has a relatively high molecular weight and a crosslinkable structure. The mechanical properties can be made higher than conventional levels, and the tire durability and wear resistance can be improved.
芳香族ビニル−ファルネセン共重合体とは、少なくとも芳香族ビニル化合物からなるモノマーおよびファルネセンからなるモノマーにより構成された共重合体である。ファルネセンからなるモノマーとしては、α−ファルネセン、β−ファルネセンが挙げられ、それぞれ単独または両者を組合せてモノマーとしてもよい。好ましくはβ−ファルネセンがよい。 The aromatic vinyl-farnesene copolymer is a copolymer composed of at least a monomer composed of an aromatic vinyl compound and a monomer composed of farnesene. Examples of the monomer comprising farnesene include α-farnesene and β-farnesene, and each may be used alone or in combination. Β-farnesene is preferable.
芳香族ビニル化合物からなるモノマーとしては、例えばスチレン、α−メチルスチレン、２−メチルスチレン、３−メチルスチレン、４−メチルスチレン、４−プロピルスチレン、４−ｔｅｒｔ−ブチルスチレン、４−シクロヘキシルルスチレン、４−ドデシルスチレン、２，４−ジメチルスチレン、２，４−ジイソプロピルスチレン、２，４，６−トリメチルスチレン、２−エチル−４−ベンジルスチレン、４−（フェニルブチル）スチレン、１−ビニルナフタレン、２−ビニルナフタレン、ビニルアントラセン、Ｎ，Ｎ−ジエチル−４−アミノエチルスチレン、ビニルピリジン、４−メトキシスチレン、モノクロロスチレン、ジクロロスチレン、ジビニルベンゼン等が例示される。なかでもスチレン、α−メチルスチレン、４−メチルスチレンが好ましい。 Examples of the monomer composed of an aromatic vinyl compound include styrene, α-methyl styrene, 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, 4-propyl styrene, 4-tert-butyl styrene, and 4-cyclohexyl styrene. 4-dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene , 2-vinylnaphthalene, vinylanthracene, N, N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, divinylbenzene and the like. Of these, styrene, α-methylstyrene, and 4-methylstyrene are preferable.
芳香族ビニル−ファルネセン共重合体の重量平均分子量は、特に制限されるものではないが、好ましくは２０００〜５０００００、より好ましくは８０００〜４５００００、更に好ましくは１５０００〜３０００００であるとよい。芳香族ビニル−ファルネセン共重合体の重量平均分子量が２０００未満であると、ゴム組成物の機械的強度が低下し、さらにゴム組成物からブリードアウトしやすくなる。また芳香族ビニル−ファルネセン共重合体の重量平均分子量が５０００００を超えると加工性が悪化する。 The weight average molecular weight of the aromatic vinyl-farnesene copolymer is not particularly limited, but is preferably 2000 to 500000, more preferably 8000 to 450,000, and still more preferably 15000 to 300000. When the weight average molecular weight of the aromatic vinyl-farnesene copolymer is less than 2000, the mechanical strength of the rubber composition is lowered, and further, bleeding out from the rubber composition becomes easy. Moreover, when the weight average molecular weight of an aromatic vinyl-farnesene copolymer exceeds 500,000, workability will deteriorate.
芳香族ビニル−ファルネセン共重合体の分子量分布（Ｍｗ／Ｍｎ；Ｍｗは重量平均分子量、Ｍｎは数平均分子量）は、好ましくは１．０〜４．０、より好ましくは１．０〜３．０、さらに好ましくは１．０〜２．０であるとよい。芳香族ビニル−ファルネセン共重合体の分子量分布がこのような範囲内であると、粘度のばらつきが小さくなる。本明細書において芳香族ビニル−ファルネセン共重合体の重量平均分子量Ｍｗおよび数平均分子量Ｍｎは、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により測定し標準ポリスチレン換算により求めるものとする。 The molecular weight distribution (Mw / Mn; Mw is the weight average molecular weight, Mn is the number average molecular weight) of the aromatic vinyl-farnesene copolymer is preferably 1.0 to 4.0, more preferably 1.0 to 3.0. More preferably, it is 1.0 to 2.0. When the molecular weight distribution of the aromatic vinyl-farnesene copolymer is within such a range, variation in viscosity becomes small. In the present specification, the weight average molecular weight Mw and the number average molecular weight Mn of the aromatic vinyl-farnesene copolymer are measured by GPC (gel permeation chromatography) and determined by standard polystyrene conversion.
芳香族ビニル−ファルネセン共重合体の溶融粘度は、好ましくは０．１〜３０００Ｐａ・ｓ、より好ましくは０．６〜２８００Ｐａ・ｓ、さらに好ましくは１．５〜２６００Ｐａ・ｓであるとよい。芳香族ビニル−ファルネセン共重合体の溶融粘度がこのような範囲内であると、ゴム組成物の混練が容易になりシリカの分散性が向上する。本明細書において、芳香族ビニル−ファルネセン共重合体の溶融粘度は、ブルックフィールド型粘度計により測定した３８℃における溶融粘度である。 The melt viscosity of the aromatic vinyl-farnesene copolymer is preferably 0.1 to 3000 Pa · s, more preferably 0.6 to 2800 Pa · s, and further preferably 1.5 to 2600 Pa · s. When the melt viscosity of the aromatic vinyl-farnesene copolymer is within such a range, the rubber composition is easily kneaded and the dispersibility of silica is improved. In this specification, the melt viscosity of the aromatic vinyl-farnesene copolymer is a melt viscosity at 38 ° C. measured by a Brookfield viscometer.
芳香族ビニル−ファルネセン共重合体は、芳香族ビニル化合物およびファルネセン以外の他のモノマーを含むことができ、他のモノマーとしては例えばブタジエン、イソプレン、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエン、２−メチル−１，３−ペンタジエン、１，３−ヘキサジエン、１，３−オクタジエン、１，３−シクロヘキサジエン、２−メチル−１，３−オクタジエン、１，３，７−オクタトリエン、ミルセン、クロロプレン等を例示することができる。芳香族ビニル−ファルネセン共重合体は、芳香族ビニル化合物からなるモノマーおよびファルネセンからなるモノマー、任意に他のモノマーを通常の方法で共重合することができ、例えば乳化重合法、溶液重合法を例示することができ、好ましくは溶液重合法で合成するとよい。 The aromatic vinyl-farnesene copolymer can contain an aromatic vinyl compound and other monomers other than farnesene. Examples of the other monomers include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1 , 3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7- Examples include octatriene, myrcene, chloroprene and the like. The aromatic vinyl-farnesene copolymer can be copolymerized with a monomer composed of an aromatic vinyl compound, a monomer composed of farnesene, and optionally other monomers by a conventional method. Examples include emulsion polymerization and solution polymerization. Preferably, it may be synthesized by a solution polymerization method.
本発明のタイヤ用ゴム組成物において、芳香族ビニル−ファルネセン共重合体の配合量は、ジエン系ゴム１００重量部に対し、５〜１００重量部、好ましくは１０〜８０重量部、より好ましくは１２〜７０重量部である。芳香族ビニル−ファルネセン共重合体の配合量が５重量部未満であると、ドライグリップ性能、タイヤ耐久性および耐摩耗性を改良する効果が十分に得られない。また芳香族ビニル−ファルネセン共重合体の配合量が１００重量部を超えると、耐久性が悪化してしまう。 In the rubber composition for tires of the present invention, the compounding amount of the aromatic vinyl-farnesene copolymer is 5 to 100 parts by weight, preferably 10 to 80 parts by weight, more preferably 12 parts per 100 parts by weight of the diene rubber. -70 parts by weight. When the blending amount of the aromatic vinyl-farnesene copolymer is less than 5 parts by weight, the effect of improving dry grip performance, tire durability and wear resistance cannot be sufficiently obtained. Moreover, when the compounding quantity of an aromatic vinyl-farnesene copolymer exceeds 100 weight part, durability will deteriorate.
本発明においてタイヤ用ゴム組成物は、上述した芳香族ビニル−ファルネセン共重合体を含む軟化剤成分を、ジエン系ゴム１００重量部に対し５０重量部以上、好ましくは５０〜１８０重量部、より好ましくは６０〜１６０重量部含む。軟化剤成分を５０重量部以上含むことにより、ドライグリップ性能を優れたものにすることができる。 In the present invention, the tire rubber composition contains 50 parts by weight or more, preferably 50 to 180 parts by weight, more preferably 50 parts by weight or more of the softener component containing the aromatic vinyl-farnesene copolymer. Contains 60 to 160 parts by weight. By including 50 parts by weight or more of the softener component, the dry grip performance can be improved.
また軟化剤成分中の芳香族ビニル−ファルネセン共重合体の重量分率は、好ましくは０．２０〜０．６０、より好ましくは０．２５〜０．５５、更に好ましくは０．３０〜０．５０であるとよい。芳香族ビニル−ファルネセン共重合体の重量分率を０．２０〜０．６０の範囲内にすることにより、ドライグリップ性能と、タイヤ耐久性および耐摩耗性とのバランスをより優れたものにすることができる。 The weight fraction of the aromatic vinyl-farnesene copolymer in the softener component is preferably 0.20 to 0.60, more preferably 0.25 to 0.55, and still more preferably 0.30 to 0.00. 50 is good. By making the weight fraction of the aromatic vinyl-farnesene copolymer in the range of 0.20 to 0.60, the balance between dry grip performance, tire durability and wear resistance is further improved. be able to.
本明細書において、軟化剤成分は芳香族ビニル−ファルネセン共重合体に加え、オイル、可塑剤、軟化剤、加工助剤、樹脂等を含む。芳香族ビニル−ファルネセン共重合体以外の軟化剤成分は、１つであっても複数を組合わせたものでもよい。またオイルはジエン系ゴムを製造するとき添加された油展成分、およびゴム組成物の調製時に添加するオイルであるものとする。樹脂としては、例えば石油系樹脂、芳香族系樹脂が例示される。 In the present specification, the softener component includes an oil, a plasticizer, a softener, a processing aid, a resin and the like in addition to the aromatic vinyl-farnesene copolymer. There may be one softener component other than the aromatic vinyl-farnesene copolymer, or a combination of a plurality of softener components. The oil is an oil-extended component added when the diene rubber is produced and an oil added when preparing the rubber composition. Examples of the resin include petroleum resins and aromatic resins.
石油系樹脂は、原油を蒸留、分解、改質などの処理をして得られた成分を重合して製造される芳香族系炭化水素樹脂あるいは飽和または不飽和脂肪族系炭化水素樹脂である。石油系樹脂として、例えばＣ５系石油樹脂（イソプレン、１，３−ペンタジエン、シクロペンタジエン、メチルブテン、ペンテンなどの留分を重合した脂肪族系石油樹脂）、Ｃ９系石油樹脂（α−メチルスチレン、ｏ−ビニルトルエン、ｍ−ビニルトルエン、ｐ−ビニルトルエンなどの留分を重合した芳香族系石油樹脂）、Ｃ５Ｃ９共重合石油樹脂などが例示される。 The petroleum-based resin is an aromatic hydrocarbon resin or a saturated or unsaturated aliphatic hydrocarbon resin produced by polymerizing components obtained by subjecting crude oil to treatment such as distillation, decomposition, and reforming. Examples of petroleum resins include C5 petroleum resins (aliphatic petroleum resins obtained by polymerizing fractions such as isoprene, 1,3-pentadiene, cyclopentadiene, methylbutene, and pentene), C9 petroleum resins (α-methylstyrene, o -Aromatic petroleum resin obtained by polymerizing fractions such as vinyltoluene, m-vinyltoluene, p-vinyltoluene), C5C9 copolymerized petroleum resin, and the like.
また芳香族系樹脂は、芳香族系炭化水素からなるセグメントを少なくとも１つ有する重合体であり、クマロン樹脂、フェノール樹脂、アルキルフェノール樹脂、テルペン系樹脂、ロジン系樹脂、ノボラック系樹脂、レゾール系樹脂などをあげることができる。なかでも芳香族変性テルペン樹脂が好ましい。これらの樹脂は、単独又は複数のブレンドとして使用することができる。なお上述したＣ９系石油樹脂は、芳香族系炭化水素樹脂であるが、本明細書では石油系樹脂に分類するものとする。 The aromatic resin is a polymer having at least one segment composed of an aromatic hydrocarbon, such as coumarone resin, phenol resin, alkylphenol resin, terpene resin, rosin resin, novolac resin, resole resin, etc. Can give. Of these, aromatic modified terpene resins are preferred. These resins can be used alone or as a blend. The C9 petroleum resin described above is an aromatic hydrocarbon resin, but is classified as a petroleum resin in this specification.
樹脂の軟化点は、特に制限されるものではないが、好ましくは１３０〜２００℃、より好ましくは１３５〜１８０℃であるとよい。樹脂の軟化点をこのような範囲内にすることにより、ドライグリップ性能を優れたものにすることができる。本明細書において、樹脂の軟化点は、ＪＩＳ Ｋ６２２０−１（環球法）に準拠し測定したものとする。 The softening point of the resin is not particularly limited, but is preferably 130 to 200 ° C, more preferably 135 to 180 ° C. By making the softening point of the resin within such a range, the dry grip performance can be made excellent. In this specification, the softening point of the resin is measured according to JIS K6220-1 (ring and ball method).
また樹脂の配合量は、上述した可塑剤成分の配合量を満たす限り特に制限されるものではないが、ジエン系ゴム１００重量部に対し、好ましくは１０〜６０重量部、より好ましくは１５〜５０重量部であるとよい。樹脂の配合量をこのような範囲内にすることにより、ドライグリップ性能をより優れたものにすることができる。 The blending amount of the resin is not particularly limited as long as the above-described blending amount of the plasticizer component is satisfied, but is preferably 10 to 60 parts by weight, more preferably 15 to 50 parts by weight based on 100 parts by weight of the diene rubber. It is good that it is a weight part. By making the compounding amount of the resin within such a range, the dry grip performance can be further improved.
本発明のタイヤ用ゴム組成物は、カーボンブラックを配合することにより、ドライグリップ性能を高くする。カーボンブラックの配合量は、ジエン系ゴム１００重量に対し１０〜１８０重量部、好ましくは５０〜１５０重量部である。カーボンブラックの配合量が１０重量部未満であると、ゴム組成物の補強性が十分に得られず、耐摩耗性が不足する。またカーボンブラックの配合量が１８０重量部を超えると、タイヤ耐久性および耐摩耗性が悪化する。 The rubber composition for tires of the present invention improves dry grip performance by blending carbon black. The compounding amount of carbon black is 10 to 180 parts by weight, preferably 50 to 150 parts by weight, based on 100 parts by weight of the diene rubber. If the blending amount of carbon black is less than 10 parts by weight, the rubber composition cannot be sufficiently reinforced and the wear resistance is insufficient. If the blending amount of carbon black exceeds 180 parts by weight, tire durability and wear resistance are deteriorated.
本発明で使用するカーボンブラックは、窒素吸着比表面積Ｎ2ＳＡが１５０〜４００ｍ2／ｇ、好ましくは１６５〜３８０ｍ2／ｇである。Ｎ2ＳＡが１５０ｍ2／ｇ未満であると、ゴム組成物の引張り破断特性、動的弾性率などの機械的特性が低下し、耐摩耗性が不足する虞がある。Ｎ2ＳＡが４００ｍ2／ｇを超えると、耐久性が悪化してします。Ｎ2ＳＡは、ＪＩＳ Ｋ６２１７−２に準拠して、測定するものとする。 The carbon black used in the present invention has a nitrogen adsorption specific surface area N 2 SA of 150 to 400 m 2 / g, preferably 165 to 380 m 2 / g. If N 2 SA is less than 150 m 2 / g, mechanical properties such as tensile rupture properties and dynamic elastic modulus of the rubber composition are lowered, and there is a possibility that the wear resistance is insufficient. If N 2 SA exceeds 400m 2 / g, durability will deteriorate. N 2 SA shall be measured according to JIS K6217-2.
またカーボンブラックのＤＢＰ吸収量は、１００〜２００ｃｍ3／１００ｇ、好ましくは１１０〜１８０ｃｍ3／１００ｇである。カーボンブラックのＤＢＰ吸収量が１００ｃｍ3／１００ｇ未満であると、耐久性が悪化する傾向がある。またＤＢＰ吸収量が２００ｃｍ3／１００ｇを超えると、グリップ性能が悪化する傾向がある。ＤＢＰ吸収量は、ＪＩＳ Ｋ６２１７−４に準拠して、測定するものとする。 The DBP absorption of carbon black is, 100~200cm 3 / 100g, preferably 110~180cm 3 / 100g. When the DBP absorption of carbon black is less than 100cm 3 / 100g, there is a tendency that the durability is deteriorated. Moreover, when DBP absorption exceeds 200 cm < 3 > / 100g, there exists a tendency for grip performance to deteriorate. The DBP absorption is measured according to JIS K6217-4.
本発明において、上記以外の他の配合剤を添加することができる。他の配合剤としては、カーボンブラック以外の他の補強性充填剤、加硫又は架橋剤、加硫促進剤、老化防止剤、液状ポリマー、熱硬化性樹脂、熱可塑性樹脂など、一般的に空気入りタイヤに使用される各種配合剤を例示することができる。これら配合剤の配合量は本発明の目的に反しない限り、従来の一般的な配合量にすることができる。また混練機としは、通常のゴム用混練機械、例えば、バンバリーミキサー、ニーダー、ロール等を使用することができる。 In the present invention, other compounding agents other than those described above can be added. Other compounding agents include generally reinforcing fillers other than carbon black, vulcanization or crosslinking agents, vulcanization accelerators, anti-aging agents, liquid polymers, thermosetting resins, thermoplastic resins, etc. Various compounding agents used for the tires can be exemplified. The compounding amounts of these compounding agents can be conventional conventional compounding amounts as long as they do not contradict the purpose of the present invention. Moreover, as a kneading machine, a normal rubber kneading machine, for example, a Banbury mixer, a kneader, a roll or the like can be used.
他の補強性充填剤としては、例えばシリカ、クレー、マイカ、タルク、炭酸カルシウム、水酸化アルミニウム、酸化アルミニウム、酸化チタン等を例示することができる。なかでもシリカが好ましい。 Examples of other reinforcing fillers include silica, clay, mica, talc, calcium carbonate, aluminum hydroxide, aluminum oxide, and titanium oxide. Of these, silica is preferable.
本発明のタイヤ用ゴム組成物は、乾燥路面を走行する競技用空気入りタイヤに使用するのが好適であり、ドライグリップ性能と、耐久性および耐摩耗性を従来以上に高いレベルで両立することができる。 The rubber composition for tires of the present invention is preferably used for a pneumatic tire for competition running on a dry road surface, and achieves both dry grip performance, durability and wear resistance at a higher level than before. Can do.
以下、実施例によって本発明を更に説明するが、本発明の範囲はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, the scope of the present invention is not limited to these Examples.
表２に示す配合剤を共通配合とし、表１に示す配合からなる１０種類のタイヤ用ゴム組成物（実施例１〜３、比較例１〜７）を、硫黄及び加硫促進剤を除く成分を、１.７Ｌの密閉式バンバリーミキサーで混練りし、所定時間の経過後、ミキサーから放出して室温冷却させた。これを１.７Ｌの密閉式バンバリーミキサーに投入し硫黄及び加硫促進剤を加えて混合することにより、タイヤ用ゴム組成物を調製した。なお表１のスチレンブタジエンゴム（ＳＢＲ１，ＳＢＲ２）の欄に、製品の配合量に加え、括弧内に油展成分を除く正味のＳＢＲの配合量を記載した。また表１に記載の「軟化剤成分の合計」は、ＳＢＲ１およびＳＢＲ２の油展成分、芳香族ビニル−ファルネセン共重合体、テルペン樹脂、低分子量ＳＢＲ並びにオイルの配合量の合計である。なお表２に記載した配合剤の配合量は、表１に記載したジエン系ゴム１００重量部に対する重量部で示した。 10 types of tire rubber compositions (Examples 1 to 3 and Comparative Examples 1 to 7) having the compounding composition shown in Table 2 as a common compounding composition and the composition shown in Table 1 except for sulfur and a vulcanization accelerator. Was kneaded with a 1.7 L hermetic Banbury mixer, and after a predetermined time, it was discharged from the mixer and allowed to cool to room temperature. This was put into a 1.7 L hermetic banbury mixer, and sulfur and a vulcanization accelerator were added and mixed to prepare a tire rubber composition. In addition, in the column of styrene butadiene rubber (SBR1, SBR2) in Table 1, in addition to the blending amount of the product, the blending amount of the net SBR excluding the oil-extended component is shown in parentheses. The “total softener component” described in Table 1 is the total of the blended amounts of the oil-extended component of SBR1 and SBR2, the aromatic vinyl-farnesene copolymer, the terpene resin, the low molecular weight SBR, and the oil. In addition, the compounding quantity of the compounding agent described in Table 2 was shown by the weight part with respect to 100 weight part of diene rubbers described in Table 1.
得られた１０種類のゴム組成物を所定の金型中で、１６０℃で３０分間プレス加硫してタイヤ用ゴム組成物からなる試験片を作製した。得られた試験片の１００℃のｔａｎδ（ドライグリップ性能）、３００％引張り応力（タイヤ耐久性）、および引張り破断強度（耐摩耗性）を以下の方法で評価した。 Ten types of the obtained rubber compositions were press vulcanized at 160 ° C. for 30 minutes in a predetermined mold to prepare a test piece made of a tire rubber composition. The obtained test piece was evaluated for tan δ (dry grip performance), 300% tensile stress (tire durability), and tensile rupture strength (wear resistance) at 100 ° C. by the following methods.
１００℃のｔａｎδ（ドライグリップ性能）
得られた試験片の動的粘弾性を、東洋精機製作所社製粘弾性スペクトロメーターを用いて、初期歪み１０％、振幅±２％、周波数２０Ｈｚの条件で、雰囲気温度１００℃におけるｔａｎδを測定した。得られた結果は、比較例１の値を１００とする指数で表わし表１の「ドライグリップ性能」の欄に示した。この指数が大きいほど１００℃のｔａｎδが大きく、タイヤにしたときドライグリップ性能が優れることを意味する。
100 ° C tan δ (dry grip performance)
With respect to the dynamic viscoelasticity of the obtained test piece, tan δ at an atmospheric temperature of 100 ° C. was measured using a viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho under the conditions of an initial strain of 10%, an amplitude of ± 2%, and a frequency of 20 Hz. . The obtained results were expressed as an index with the value of Comparative Example 1 being 100, and are shown in the “Dry Grip Performance” column of Table 1. The larger this index, the larger the tan δ at 100 ° C., which means that the dry grip performance is excellent when used as a tire.
３００％引張り応力（タイヤ耐久性）および引張り破断強度（耐摩耗性）
得られた試験片から、ＪＩＳ Ｋ６２５１に準拠してＪＩＳ３号ダンベル型試験片を切り出した。ＪＩＳ Ｋ６２５１に準拠し５００ｍｍ／分の引張り速度、雰囲気温度２３℃の条件で、３００％伸長時の引張り応力および引張り破断応力を測定した。得られた結果は、比較例１の値をそれぞれ１００とする指数として表１の「タイヤ耐久性」および「耐摩耗性」の欄にそれぞれ示した。タイヤ耐久性の指数が大きいほど３００％伸長時の引張り応力が大きく、タイヤ耐久性が優れることを意味する。耐摩耗性の指数が大きいほど引張り破断応力が大きく、耐摩耗性が優れることを意味する。
300% tensile stress (tire durability) and tensile strength at break (wear resistance)
A JIS No. 3 dumbbell-shaped test piece was cut out from the obtained test piece in accordance with JIS K6251. Based on JIS K6251, the tensile stress at 300% elongation and the tensile breaking stress were measured under the conditions of a tensile speed of 500 mm / min and an ambient temperature of 23 ° C. The obtained results are shown in the columns of “Tire Durability” and “Abrasion Resistance” in Table 1 as indices with the value of Comparative Example 1 as 100, respectively. The larger the tire durability index, the greater the tensile stress at 300% elongation, which means better tire durability. The larger the wear resistance index, the greater the tensile rupture stress and the better the wear resistance.
なお、表１において使用した原材料の種類を下記に示す。
・ＳＢＲ１：スチレンブタジエンゴム、日本ゼオン社製Ｎｉｐｏｌ １７３９、スチレンブタジエンゴム１００重量部にオイル成分３７．５重量部を配合した油展製品、ガラス転移温度が−３１℃、スチレン量が４１重量％、ビニル単位量が１４重量％
・ＳＢＲ２：スチレンブタジエンゴム、日本ゼオン社製Ｎｉｐｏｌ ９５４８、スチレンブタジエンゴム１００重量部にオイル成分３７．５重量部を配合した油展製品、ガラス転移温度が−３７℃、スチレン量が３６重量％、ビニル単位量が１４重量％
・カーボンブラック１：コロンビアンカーボン社製ＣＤ２０１９、窒素吸着比表面積が３４０ｍ2／ｇ、ＤＢＰ吸収量が１１８ｃｍ3／１００ｇ
・カーボンブラック２：東海カーボン社製シースト６、窒素吸着比表面積が１１９ｍ2／ｇ、ＤＢＰ吸収量が１１４ｃｍ3／１００ｇ
・ファルネセン共重合体：下記の合成例１により重合されたスチレンとβ−ファルネセンの共重合体、重量平均分子量が１００００、分子量分布が１．０６、溶融粘度が５．６Ｐａ・ｓ
・ファルネセン重合体：下記の合成例２により重合されたβ−ファルネセンの重合体、重量平均分子量が１４００００、分子量分布が１．２、溶融粘度が６９Ｐａ・ｓ
・低分子量ＳＢＲ：Ｃｒａｙ Ｖａｌｌｅｙ社製ＲＩＣＯＮ １００
・テルペン樹脂：芳香族変性テルペン樹脂、ヤスハラケミカル社製ＹＳポリスターＴ１４５、軟化点が１４５℃
・オイル：昭和シェル石油社製エキストラクト４号Ｓ、
In addition, the kind of raw material used in Table 1 is shown below.
SBR1: Styrene butadiene rubber, Nippon Zeon Nipol 1739, an oil-extended product in which 37.5 parts by weight of an oil component is blended with 100 parts by weight of styrene butadiene rubber, a glass transition temperature of −31 ° C., a styrene amount of 41% by weight, Vinyl unit amount is 14% by weight
SBR2: styrene butadiene rubber, Nipol 9548 manufactured by Nippon Zeon Co., Ltd., an oil-extended product in which 37.5 parts by weight of an oil component is blended with 100 parts by weight of styrene butadiene rubber, a glass transition temperature of −37 ° C., an amount of styrene of 36% by weight, Vinyl unit amount is 14% by weight
Carbon black 1: Columbian Carbon Co., Ltd. CD2019, nitrogen adsorption specific surface area of 340m 2 / g, DBP absorption amount of 118cm 3 / 100g
Carbon black 2: Tokai Carbon Co., Ltd. SEAST 6, nitrogen adsorption specific surface area of 119m 2 / g, DBP absorption amount of 114cm 3 / 100g
Farnesene copolymer: copolymer of styrene and β-farnesene polymerized in Synthesis Example 1 below, weight average molecular weight of 10,000, molecular weight distribution of 1.06, melt viscosity of 5.6 Pa · s
Farnesene polymer: a polymer of β-farnesene polymerized in Synthesis Example 2 below, a weight average molecular weight of 140000, a molecular weight distribution of 1.2, and a melt viscosity of 69 Pa · s.
Low molecular weight SBR: RICON 100 manufactured by Cray Valley
Terpene resin: Aromatic modified terpene resin, YS Polystar T145 manufactured by Yasuhara Chemical Co., Ltd., softening point 145 ° C.
-Oil: Extract No. 4 S manufactured by Showa Shell Sekiyu KK
合成例１（ファルネセン共重合体の重合）
窒素置換し乾燥させた耐圧容器に、溶媒としてシクロヘキサン１５００ｇ、開始剤としてｓｅｃ−ブチルリチウム（１０．５質量％シクロヘキサン溶液）１１２．６ｇを仕込み、５０℃に昇温した後、テトラヒドロフラン３ｇを添加し、予め調製したスチレンとβ−ファルネセンとの混合物（スチレン３４５ｇとβ−ファルネセン１１５５ｇとをボンベ内で混合）１５００ｇを１０ｍｌ／分で加えて１時間重合した。得られた重合反応液をメタノールで処理し、水を用いて重合反応液を洗浄した。洗浄後の重合反応液と水とを分離して、７０℃で１２時間乾燥することにより、スチレンとβ−ファルネセンのランダム共重合体（ファルネセン共重合体）を得た。
Synthesis Example 1 (Polymerization of farnesene copolymer)
In a pressure-resistant container that has been purged with nitrogen and dried, 1500 g of cyclohexane as a solvent and 112.6 g of sec-butyllithium (10.5 mass% cyclohexane solution) as an initiator are charged and heated to 50 ° C., and then 3 g of tetrahydrofuran is added. Then, 1500 g of a mixture of styrene and β-farnesene prepared in advance (mixing 345 g of styrene and 1155 g of β-farnesene in a cylinder) was added at 10 ml / min and polymerized for 1 hour. The obtained polymerization reaction liquid was treated with methanol, and the polymerization reaction liquid was washed with water. The polymerization reaction liquid after washing and water were separated and dried at 70 ° C. for 12 hours to obtain a random copolymer of styrene and β-farnesene (farnesene copolymer).
合成例２（ファルネセン重合体の重合）
窒素置換し、乾燥させた耐圧容器に、ヘキサン２７４ｇ、ｎ−ブチルリチウム（１７重量％ヘキサン溶液）１．２ｇを仕込み、５０℃に昇温した後、β−ファルネセン２７２ｇを加えて１時間重合した。得られた重合反応液にメタノールを添加後、重合反応液を水で洗浄した。水を分離して、重合反応液を７０℃で１２時間乾燥することにより、β−ファルネセンの重合体（ファルネセン重合体）を得た。
Synthesis example 2 (polymerization of farnesene polymer)
In a pressure vessel that was purged with nitrogen and dried, 274 g of hexane and 1.2 g of n-butyllithium (17 wt% hexane solution) were charged, and the temperature was raised to 50 ° C., followed by addition of 272 g of β-farnesene and polymerization for 1 hour. . After adding methanol to the obtained polymerization reaction solution, the polymerization reaction solution was washed with water. Water was separated, and the polymerization reaction solution was dried at 70 ° C. for 12 hours to obtain a β-farnesene polymer (farnesene polymer).
表２において使用した原材料の種類を下記に示す。
・ステアリン酸：日油社製ビーズステアリン酸ＹＲ
・酸化亜鉛：正同化学社製酸化亜鉛３種
・老化防止剤：フレキシス社製サントフレックス ６ＰＰＤ
・硫黄：鶴見化学工業社製金華印油入微粉硫黄
・加硫促進剤：ＣＢＳ、大内新興化学社製ノクセラーＣＺ−Ｇ
The types of raw materials used in Table 2 are shown below.
・ Stearic acid: NOF beads stearic acid YR
・ Zinc oxide: Three types of zinc oxide manufactured by Shodo Chemical Co., Ltd. ・ Anti-aging agent: Santoflex 6PPD manufactured by Flexis
・ Sulfur: Fine powdered sulfur with Jinhua seal oil manufactured by Tsurumi Chemical Industry Co., Ltd.
表１から明らかなように実施例１〜３により製造されたタイヤ用ゴム組成物は、ドライグリップ性能、タイヤ耐久性および耐摩耗性に優れることが確認された。 As is clear from Table 1, it was confirmed that the tire rubber compositions produced according to Examples 1 to 3 were excellent in dry grip performance, tire durability, and wear resistance.
比較例２のゴム組成物は、比較例１に比べ低分子量ＳＢＲおよびテルペン樹脂を減量したので、タイヤ耐久性および耐摩耗性が高くなるがドライグリップ性能が悪化する。 In the rubber composition of Comparative Example 2, since the low molecular weight SBR and the terpene resin were reduced as compared with Comparative Example 1, the tire durability and wear resistance were increased, but the dry grip performance was deteriorated.
比較例３のゴム組成物は、ＳＢＲ２のガラス転移温度が−３５℃未満であるので、ドライグリップ性能が悪化する。 Since the rubber composition of Comparative Example 3 has a glass transition temperature of SBR2 of less than −35 ° C., the dry grip performance is deteriorated.
比較例４のゴム組成物は、カーボンブラック２の窒素吸着比表面積が１５０ｍ2／ｇ未満であるで、ドライグリップ性能が悪化する。 Since the rubber composition of Comparative Example 4 has a nitrogen adsorption specific surface area of the carbon black 2 of less than 150 m 2 / g, the dry grip performance is deteriorated.
比較例５のゴム組成物は、カーボンブラック２の配合量が１８０重量部を超えるので、タイヤ耐久性および耐摩耗性が悪化する。 In the rubber composition of Comparative Example 5, since the compounding amount of the carbon black 2 exceeds 180 parts by weight, tire durability and wear resistance are deteriorated.
比較例６のゴム組成物は、軟化剤成分の合計が５０重量部未満であるので、ドライグリップ性能が悪化する。 In the rubber composition of Comparative Example 6, since the total amount of the softener components is less than 50 parts by weight, the dry grip performance is deteriorated.
比較例７のゴム組成物は、芳香族ビニル−ファルネセン共重合体の代わりに、ファルネセン重合体を配合したので、ドライグリップ性能が悪化する。 In the rubber composition of Comparative Example 7, since the farnesene polymer was blended instead of the aromatic vinyl-farnesene copolymer, the dry grip performance was deteriorated.
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| JP2019099656A (en) * | 2017-11-30 | 2019-06-24 | 住友ゴム工業株式会社 | Tire rubber composition |
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