JP5381395B2 - Rubber composition for tire tread - Google Patents
Rubber composition for tire tread Download PDFInfo
- Publication number
- JP5381395B2 JP5381395B2 JP2009151406A JP2009151406A JP5381395B2 JP 5381395 B2 JP5381395 B2 JP 5381395B2 JP 2009151406 A JP2009151406 A JP 2009151406A JP 2009151406 A JP2009151406 A JP 2009151406A JP 5381395 B2 JP5381395 B2 JP 5381395B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- silica
- rubber composition
- rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920001971 elastomer Polymers 0.000 title claims description 59
- 239000005060 rubber Substances 0.000 title claims description 59
- 239000000203 mixture Substances 0.000 title claims description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 90
- 239000000377 silicon dioxide Substances 0.000 claims description 44
- 239000006229 carbon black Substances 0.000 claims description 30
- 230000009477 glass transition Effects 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 17
- 238000001179 sorption measurement Methods 0.000 claims description 17
- 229920003244 diene elastomer Polymers 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 239000011593 sulfur Substances 0.000 claims description 15
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- XMOCLSLCDHWDHP-IUODEOHRSA-N epi-Gallocatechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@H]2O)=CC(O)=C(O)C(O)=C1 XMOCLSLCDHWDHP-IUODEOHRSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- 239000004902 Softening Agent Substances 0.000 claims description 6
- XMOCLSLCDHWDHP-SWLSCSKDSA-N (+)-Epigallocatechin Natural products C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC(O)=C(O)C(O)=C1 XMOCLSLCDHWDHP-SWLSCSKDSA-N 0.000 claims description 3
- 229930013915 (+)-catechin Natural products 0.000 claims description 3
- 235000007219 (+)-catechin Nutrition 0.000 claims description 3
- 229930013884 (+)-gallocatechin Natural products 0.000 claims description 3
- 235000007243 (+)-gallocatechin Nutrition 0.000 claims description 3
- PFTAWBLQPZVEMU-UKRRQHHQSA-N (-)-epicatechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-UKRRQHHQSA-N 0.000 claims description 3
- 229930013783 (-)-epicatechin Natural products 0.000 claims description 3
- 235000007355 (-)-epicatechin Nutrition 0.000 claims description 3
- LSHVYAFMTMFKBA-TZIWHRDSSA-N (-)-epicatechin-3-O-gallate Chemical compound O([C@@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=CC=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 LSHVYAFMTMFKBA-TZIWHRDSSA-N 0.000 claims description 3
- 229930014124 (-)-epigallocatechin gallate Natural products 0.000 claims description 3
- 235000004911 (-)-epigallocatechin gallate Nutrition 0.000 claims description 3
- LSHVYAFMTMFKBA-UHFFFAOYSA-N ECG Natural products C=1C=C(O)C(O)=CC=1C1OC2=CC(O)=CC(O)=C2CC1OC(=O)C1=CC(O)=C(O)C(O)=C1 LSHVYAFMTMFKBA-UHFFFAOYSA-N 0.000 claims description 3
- WMBWREPUVVBILR-UHFFFAOYSA-N GCG Natural products C=1C(O)=C(O)C(O)=CC=1C1OC2=CC(O)=CC(O)=C2CC1OC(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-UHFFFAOYSA-N 0.000 claims description 3
- VFSWRBJYBQXUTE-UHFFFAOYSA-N epi-Gallocatechin 3-O-gallate Natural products Oc1ccc2C(=O)C(OC(=O)c3cc(O)c(O)c(O)c3)C(Oc2c1)c4cc(O)c(O)c(O)c4 VFSWRBJYBQXUTE-UHFFFAOYSA-N 0.000 claims description 3
- 241001122767 Theaceae Species 0.000 claims 2
- 235000019241 carbon black Nutrition 0.000 claims 2
- 235000013616 tea Nutrition 0.000 description 42
- 244000269722 Thea sinensis Species 0.000 description 41
- 238000005096 rolling process Methods 0.000 description 17
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 description 15
- 235000005487 catechin Nutrition 0.000 description 15
- 238000001125 extrusion Methods 0.000 description 14
- 150000008442 polyphenolic compounds Chemical class 0.000 description 14
- 235000013824 polyphenols Nutrition 0.000 description 14
- 238000013329 compounding Methods 0.000 description 12
- 229920003048 styrene butadiene rubber Polymers 0.000 description 12
- 239000003921 oil Substances 0.000 description 10
- 235000019198 oils Nutrition 0.000 description 10
- 238000004073 vulcanization Methods 0.000 description 9
- 150000001765 catechin Chemical class 0.000 description 8
- -1 flavone glycosides Chemical class 0.000 description 8
- 229950001002 cianidanol Drugs 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229930003935 flavonoid Natural products 0.000 description 6
- 235000017173 flavonoids Nutrition 0.000 description 6
- 150000002215 flavonoids Chemical class 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000002542 deteriorative effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WMBWREPUVVBILR-WIYYLYMNSA-N (-)-Epigallocatechin-3-o-gallate Chemical compound O([C@@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=C(O)C=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-WIYYLYMNSA-N 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 235000012438 extruded product Nutrition 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 150000002206 flavan-3-ols Chemical class 0.000 description 3
- 229930003944 flavone Natural products 0.000 description 3
- 235000011949 flavones Nutrition 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-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
- CITFYDYEWQIEPX-UHFFFAOYSA-N Flavanol Natural products O1C2=CC(OCC=C(C)C)=CC(O)=C2C(=O)C(O)C1C1=CC=C(O)C=C1 CITFYDYEWQIEPX-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 235000006468 Thea sinensis Nutrition 0.000 description 2
- GAMYVSCDDLXAQW-AOIWZFSPSA-N Thermopsosid Natural products O(C)c1c(O)ccc(C=2Oc3c(c(O)cc(O[C@H]4[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O4)c3)C(=O)C=2)c1 GAMYVSCDDLXAQW-AOIWZFSPSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 235000011987 flavanols Nutrition 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 229920001194 natural rubber Polymers 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
- 239000003208 petroleum Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- VHBFFQKBGNRLFZ-UHFFFAOYSA-N vitamin p Natural products O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 VHBFFQKBGNRLFZ-UHFFFAOYSA-N 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- IABJHLPWGMWHLX-UHFFFAOYSA-N 3-(1,3-benzothiazol-2-yl)propyl-trimethoxysilane Chemical compound C1=CC=C2SC(CCC[Si](OC)(OC)OC)=NC2=C1 IABJHLPWGMWHLX-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000020279 black tea Nutrition 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920002770 condensed tannin Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- 150000002212 flavone derivatives Chemical class 0.000 description 1
- 150000002213 flavones Chemical class 0.000 description 1
- HVQAJTFOCKOKIN-UHFFFAOYSA-N flavonol Natural products O1C2=CC=CC=C2C(=O)C(O)=C1C1=CC=CC=C1 HVQAJTFOCKOKIN-UHFFFAOYSA-N 0.000 description 1
- 150000002216 flavonol derivatives Chemical class 0.000 description 1
- 235000011957 flavonols Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 235000009569 green tea Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 235000020333 oolong tea Nutrition 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- JPPLPDOXWBVPCW-UHFFFAOYSA-N s-(3-triethoxysilylpropyl) octanethioate Chemical compound CCCCCCCC(=O)SCCC[Si](OCC)(OCC)OCC JPPLPDOXWBVPCW-UHFFFAOYSA-N 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Description
本発明は、タイヤトレッド用ゴム組成物に関し、更に詳しくは、カーボンブラック及びシリカを配合したゴム組成物において、転がり抵抗性及び押出し成形性を悪化させることなく、耐摩耗性を向上するようにしたタイヤトレッド用ゴム組成物に関する。 The present invention relates to a rubber composition for tire treads, and more specifically, in a rubber composition containing carbon black and silica, the wear resistance is improved without deteriorating rolling resistance and extrusion moldability. The present invention relates to a rubber composition for a tire tread.
近年、高性能タイプの乗用車用空気入りタイヤには、グリップ性能を高度に向上させることが求められている。この対策としてトレッド用ゴム組成物に、ガラス転移温度が低く柔らかいゴムが配合されている。しかし、このような柔らかいゴム組成物は、耐摩耗性が低いという問題がある。 In recent years, high-performance type pneumatic tires for passenger cars are required to have a highly improved grip performance. As a countermeasure, a rubber having a low glass transition temperature and a soft rubber is blended in the rubber composition for tread. However, such a soft rubber composition has a problem of low wear resistance.
従来、ゴム組成物の耐摩耗性を向上するためには、カーボンブラックとシリカとを共に配合することが行なわれている。すなわち、小粒径のカーボンブラックを使用したり、カーボンブラックの配合量を多くしたりすることにより、柔らかいゴムの耐摩耗性を向上することができる。しかし、このようなゴム組成物は、ゴム粘度が増大すると共にカーボンブラックの混合性が悪化するため、押出し成形性及び転がり抵抗が悪化するという問題があった。同様に、シリカの配合量を多くした場合でも、ゴム粘度が増大し分散性が悪化する問題があった。特にシリカの分散性が悪いときには、耐摩耗性を改善する効果が得られない。 Conventionally, in order to improve the wear resistance of a rubber composition, carbon black and silica are blended together. That is, the wear resistance of soft rubber can be improved by using carbon black having a small particle diameter or increasing the amount of carbon black. However, such a rubber composition has a problem that extrudability and rolling resistance deteriorate because the rubber viscosity increases and the mixing property of carbon black deteriorates. Similarly, even when the amount of silica is increased, there is a problem that the rubber viscosity increases and the dispersibility deteriorates. In particular, when the dispersibility of silica is poor, the effect of improving the wear resistance cannot be obtained.
このシリカの分散性を改善するための対策として、シリカと共にシランカップリング剤を配合することが知られている（例えば、特許文献１参照）。しかし、シリカの分散性を一層向上させるためシランカップリング剤を増量すると早期加硫を起こすため、シリカ分散を改善することには限界があった。 As a measure for improving the dispersibility of silica, it is known that a silane coupling agent is blended together with silica (for example, see Patent Document 1). However, when the amount of the silane coupling agent is increased in order to further improve the dispersibility of silica, early vulcanization occurs, so there is a limit to improving silica dispersion.
また、シランカップリング剤を配合しても、カーボンブラック及びシリカを多量に配合した場合には、ゴム組成物の粘度を低減する作用は得られないため押出し成形性を改善することはできなかった。更に、カーボンブラックとシリカとを共に配合したゴム組成物は、押出し成形時に押出し成形体がシュリンクしやすく形状安定性に劣るという問題があるが、シランカップリング剤を配合してもこの問題は解決されない。したがって、転がり抵抗性及び押出し成形性を悪化させることなく、柔らかいゴム組成物の耐摩耗性を向上することは困難であった。 Moreover, even when a silane coupling agent was blended, when a large amount of carbon black and silica was blended, the effect of reducing the viscosity of the rubber composition could not be obtained, so the extrusion moldability could not be improved. . Furthermore, the rubber composition containing both carbon black and silica has the problem that the extruded product tends to shrink during extrusion molding and is inferior in shape stability, but this problem can be solved even if a silane coupling agent is added. Not. Therefore, it has been difficult to improve the wear resistance of the soft rubber composition without deteriorating rolling resistance and extrusion moldability.
本発明の目的は、カーボンブラック及びシリカを配合したゴム組成物において、転がり抵抗性及び押出し成形性を悪化させることなく、耐摩耗性を向上するようにしたタイヤトレッド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 a tire tread in which a rubber composition containing carbon black and silica is improved in wear resistance without deteriorating rolling resistance and extrusion moldability. It is in.
上記目的を達成する本発明のタイヤトレッド用ゴム組成物は、ガラス転移温度が−２５℃以下である芳香族ビニル共役ジエン共重合体を１０重量％以上含むジエン系ゴム１００重量部に対し、窒素吸着比表面積が１００〜１４０ｍ２／ｇであるカーボンブラックを５〜５０重量部、ＣＴＡＢ吸着比表面積が８０〜２５０ｍ２／ｇであるシリカを３０〜９０重量部配合し、かつ前記カーボンブラックとシリカとの合計量を４０〜１００重量部、茶抽出物を０．０１〜５重量部、軟化剤を３〜４０重量部配合すると共に、硫黄含有シランカップリング剤を前記シリカ配合量の２〜１５重量％配合したことを特徴とする。 The rubber composition for a tire tread of the present invention that achieves the above-mentioned object is obtained by adding nitrogen to 100 parts by weight of a diene rubber containing 10% by weight or more of an aromatic vinyl conjugated diene copolymer having a glass transition temperature of −25 ° C. or lower. 5-50 parts by weight of carbon black adsorption specific surface area of 100~140m 2 / g, CTAB adsorption specific surface area and silica 30-90 parts by compounding a 80~250m 2 / g, and the carbon black and silica 40 to 100 parts by weight, 0.01 to 5 parts by weight of tea extract, 3 to 40 parts by weight of softening agent, and 2 to 15 parts by weight of the sulfur-containing silane coupling agent. It is characterized by blending in weight percent.
茶抽出物は、（＋）−カテキン、（−）−エピカテキン、（＋）−ガロカテキン、（−）−エピガロカテキン、（−）−エピカテキンガレート及び（−）−エピガロカテキンガレートからなる群から選ばれる少なくとも１種であるとよい。また、硫黄含有シランカップリング剤を前記シリカ配合量の２〜１５重量％配合するとよい。 The tea extract consists of (+)-catechin, (−)-epicatechin, (+)-gallocatechin, (−)-epigallocatechin, (−)-epicatechin gallate and (−)-epigallocatechin gallate. It is good that it is at least one selected from the group. Moreover, it is good to mix | blend a sulfur containing silane coupling agent 2 to 15weight% of the said silica compounding quantity.
このタイヤトレッド用ゴム組成物は、空気入りタイヤの構成材料として好適に使用可能である。 This rubber composition for a tire tread can be suitably used as a constituent material of a pneumatic tire.
本発明のタイヤトレッド用ゴム組成物によれば、ガラス転移温度が−２５℃以下である芳香族ビニル共役ジエン共重合体を１０重量％以上含むジエン系ゴム１００重量部に対し、窒素吸着比表面積が１００〜１４０ｍ２／ｇであるカーボンブラックを５〜５０重量部、ＣＴＡＢ吸着比表面積が８０〜２５０ｍ２／ｇであるシリカを３０〜９０重量部配合し、かつカーボンブラックとシリカとの合計量を４０〜１００重量部、軟化剤を３〜４０重量部配合すると共に、硫黄含有シランカップリング剤をシリカ配合量の２〜１５重量％配合したことにより、カーボンブラックの配合量を制限しシリカの分散性を改善するので転がり抵抗性を悪化させることなく、柔らかいゴム組成物の耐摩耗性を高くする。また、茶抽出物０．０１〜５重量部を共に配合したことにより、シリカの分散性を一層向上すると共に、ゴム組成物の押出し成形時に押出し成形体がシュリンクするのを抑制するため、従来レベル以上の押出し成形性を達成可能にし、かつゴム組成物の低転がり抵抗性及び耐摩耗性を更に向上することができる。 According to the rubber composition for a tire tread of the present invention, the nitrogen adsorption specific surface area with respect to 100 parts by weight of a diene rubber containing 10% by weight or more of an aromatic vinyl conjugated diene copolymer having a glass transition temperature of −25 ° C. or less. the total amount of but 5 to 50 parts by weight of carbon black as a 100~140m 2 / g, CTAB adsorption specific surface area and silica 30-90 parts by compounding a 80~250m 2 / g, and the carbon black and silica 40 to 100 parts by weight, 3 to 40 parts by weight of a softening agent, and 2 to 15% by weight of the silica-containing amount of the sulfur-containing silane coupling agent, thereby limiting the amount of carbon black to be added. Since the dispersibility is improved, the wear resistance of the soft rubber composition is increased without deteriorating the rolling resistance. In addition, by blending together 0.01 to 5 parts by weight of the tea extract, the dispersibility of the silica is further improved, and the extrusion molded body is prevented from shrinking during the extrusion molding of the rubber composition. The above extrudability can be achieved, and the low rolling resistance and wear resistance of the rubber composition can be further improved.
本発明のタイヤトレッド用ゴム組成物において、ゴム成分にはジエン系ゴムが使用される。ジエン系ゴムとしては、ガラス転移温度が−２５℃以下である芳香族ビニル共役ジエン共重合体を必ず含むようにする。ガラス転移温度が−２５℃以下の芳香族ビニル共役ジエン共重合体を含むことにより、高性能タイヤのトレッドに要求されるグリップ性能を確保する。芳香族ビニル共役ジエン共重合体としては、例えばスチレンブタジエンゴム（ＳＢＲ）を例示することができる。スチレンブタジエンゴムの種類としては、上述したガラス転移温度を有するものであれば、溶液重合スチレンブタジエンゴム、乳化重合スチレンブタジエンゴムのいずれでもよい。また、スチレンブタジエンゴムは油展品でもよいが、油展ＳＢＲのガラス転移温度は、オイル成分を含まない状態におけるスチレンブタジエンゴムのガラス転移温度とする。 In the rubber composition for a tire tread of the present invention, a diene rubber is used as the rubber component. As the diene rubber, an aromatic vinyl conjugated diene copolymer having a glass transition temperature of −25 ° C. or lower is necessarily included. By including an aromatic vinyl conjugated diene copolymer having a glass transition temperature of −25 ° C. or lower, the grip performance required for the tread of a high-performance tire is ensured. Examples of the aromatic vinyl conjugated diene copolymer include styrene butadiene rubber (SBR). As a kind of styrene butadiene rubber, any of solution polymerization styrene butadiene rubber and emulsion polymerization styrene butadiene rubber may be used as long as it has the glass transition temperature described above. The styrene-butadiene rubber may be an oil-extended product, but the glass transition temperature of the oil-extended SBR is the glass transition temperature of the styrene-butadiene rubber in a state that does not contain an oil component.
芳香族ビニル共役ジエン共重合体のガラス転移温度は、−２５℃以下であり、好ましくは−２５℃〜−７０℃、より好ましくは−２５℃〜−６５℃にするとよい。なお、芳香族ビニル共役ジエン共重合体のガラス転移温度が低過ぎると、耐摩耗性能には優れるが、低温領域、特に−１０℃付近のｔａｎδが下がりすぎてウェットグリップ性能が低下するため、タイヤトレッドとして耐摩耗性能とグリップ性能とを両立できない。本発明において、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、低温側のベースラインと転移域の傾き（傾斜直線）とのそれぞれの延長線の交点の温度とする。 The glass transition temperature of the aromatic vinyl conjugated diene copolymer is −25 ° C. or lower, preferably −25 ° C. to −70 ° C., more preferably −25 ° C. to −65 ° C. In addition, if the glass transition temperature of the aromatic vinyl conjugated diene copolymer is too low, the wear resistance is excellent, but the tan δ in the low temperature region, particularly around −10 ° C., is too low and the wet grip performance is reduced. As a tread, it is impossible to achieve both wear resistance and grip performance. In the present invention, the glass transition temperature is measured by a differential scanning calorimetry (DSC) with a temperature increase rate of 20 ° C./minute, and a low temperature side baseline and a transition area slope (inclination straight line), respectively. The temperature at the intersection of the extension lines.
ジエン系ゴムにおけるガラス転移温度が−２５℃以下の芳香族ビニル共役ジエン共重合体の配合量は１０重量％以上、好ましくは１５〜１００重量％、より好ましくは２５〜１００重量％である。ガラス転移温度が−２５℃以下の芳香族ビニル共役ジエン共重合体の配合量が１０重量％未満であると、グリップ性能を確保するのが困難になる。 The blending amount of the aromatic vinyl conjugated diene copolymer having a glass transition temperature of −25 ° C. or less in the diene rubber is 10% by weight or more, preferably 15 to 100% by weight, and more preferably 25 to 100% by weight. When the blending amount of the aromatic vinyl conjugated diene copolymer having a glass transition temperature of −25 ° C. or lower is less than 10% by weight, it is difficult to ensure grip performance.
本発明において、ガラス転移温度が−２５℃以下の芳香族ビニル共役ジエン共重合体以外のジエン系ゴムとしては、天然ゴム、イソプレンゴム、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、ガラス転移温度が−２５℃より高いスチレン−ブタジエンゴム等が挙げられる。なかでも、ブタジエンゴム、天然ゴム、イソプレンゴムが好ましい。これらジエン系ゴムは、単独又は任意のブレンドとして使用することができる。 In the present invention, natural rubber, isoprene rubber, butadiene rubber, acrylonitrile-butadiene rubber, butyl rubber, glass transition temperature is-as the diene rubber other than the aromatic vinyl conjugated diene copolymer having a glass transition temperature of -25 ° C or lower. Examples thereof include styrene-butadiene rubber having a temperature higher than 25 ° C. Of these, butadiene rubber, natural rubber, and isoprene rubber are preferable. These diene rubbers can be used alone or as any blend.
本発明において、カーボンブラックは、前述した柔らかいゴム組成物の耐摩耗性を向上する。カーボンブラックの配合量は、ジエン系ゴム１００重量部に対し５〜５０重量部、好ましくは１０〜３０重量部である。カーボンブラックの配合量が５重量部未満の場合には、耐摩耗性が不足すると共に、ゴム強度を十分に高くすることができない。また、カーボンブラックの配合量が５０重量部を超えると、ゴムに対する混合性が悪化し、転がり抵抗及び押出し成形性が悪化する。 In the present invention, carbon black improves the wear resistance of the soft rubber composition described above. The compounding quantity of carbon black is 5-50 weight part with respect to 100 weight part of diene rubbers, Preferably it is 10-30 weight part. When the amount of carbon black is less than 5 parts by weight, the wear resistance is insufficient and the rubber strength cannot be sufficiently increased. Moreover, when the compounding quantity of carbon black exceeds 50 weight part, the mixing property with respect to rubber will deteriorate, and rolling resistance and extrusion moldability will deteriorate.
本発明において好適に使用するカーボンブラックは、窒素吸着比表面積（Ｎ２ＳＡ）が１００〜１４０ｍ２／ｇ、好ましくは１００〜１３０ｍ２／ｇである。カーボンブラックの窒素吸着比表面積が１００ｍ２／ｇ未満の場合には、耐摩耗性及びゴム強度を十分に高くすることができない。窒素吸着比表面積が１４０ｍ２／ｇを超えると転がり抵抗が悪化すると共に、ゴム粘度が高くなり押出し成形性が悪化する。カーボンブラックの窒素吸着比表面積（Ｎ２ＳＡ）は、ＪＩＳ Ｋ６２１７−２に準拠して求めるものとする。 The carbon black suitably used in the present invention has a nitrogen adsorption specific surface area (N 2 SA) of 100 to 140 m 2 / g, preferably 100 to 130 m 2 / g. When the nitrogen adsorption specific surface area of carbon black is less than 100 m 2 / g, the wear resistance and rubber strength cannot be sufficiently increased. When the nitrogen adsorption specific surface area exceeds 140 m 2 / g, the rolling resistance is deteriorated, the rubber viscosity is increased, and the extrusion moldability is deteriorated. The nitrogen adsorption specific surface area (N 2 SA) of carbon black is determined according to JIS K6217-2.
本発明において、シリカは、ゴム組成物の耐摩耗性を向上すると共に、ヒステリシスロス（ｔａｎδ）を小さくし、転がり抵抗を低減する。シリカの配合量は、ジエン系ゴム１００重量部に対し３０〜９０重量部、好ましくは４０〜８０重量部である。シリカの配合量が３０重量部未満では、ヒステリシスロス（ｔａｎδ）を小さくする効果が十分に得られない。また、シリカ配合量が９０重量部を超えると、混合時間が長くなるなどの加工性が悪化し好ましくない。 In the present invention, silica improves the wear resistance of the rubber composition, reduces hysteresis loss (tan δ), and reduces rolling resistance. The compounding quantity of a silica is 30-90 weight part with respect to 100 weight part of diene rubbers, Preferably it is 40-80 weight part. When the amount of silica is less than 30 parts by weight, the effect of reducing the hysteresis loss (tan δ) cannot be sufficiently obtained. On the other hand, if the amount of silica exceeds 90 parts by weight, the processability such as a longer mixing time is deteriorated.
本発明で使用するシリカは、ＣＴＡＢ吸着比表面積が好ましくは８０〜２５０ｍ２／ｇ、より好ましくは１００〜２００ｍ２／ｇであるとよい。シリカのＣＴＡＢ吸着比表面積が８０ｍ２／ｇ未満の場合には、破断強度が低下し、耐摩耗性能が悪化する。シリカのＣＴＡＢ吸着比表面積が２５０ｍ２／ｇを超えるとゴム粘度が高くなり押出し成形性が悪化する。シリカのＣＴＡＢ吸着比表面積は、ＡＳＴＭ−Ｄ３７６５−８０の規格に準拠して求めるものとする。 Silica used in the present invention, CTAB adsorption specific surface area is preferably 80~250m 2 / g, may more preferably at 100 to 200 m 2 / g. When the CTAB adsorption specific surface area of silica is less than 80 m 2 / g, the breaking strength decreases and the wear resistance performance deteriorates. When the CTAB adsorption specific surface area of silica exceeds 250 m 2 / g, the rubber viscosity increases and the extrusion moldability deteriorates. The CTAB adsorption specific surface area of silica shall be determined according to the standard of ASTM-D3765-80.
カーボンブラックとシリカの合計量は、ジエン系ゴム１００重量部に対し４０〜１００重量部、好ましくは５０〜９０重量部である。カーボンブラックとシリカの合計量が４０重量部未満の場合には、耐摩耗性を十分に高くすることができない。また、カーボンブラックとシリカの合計量が１００重量部を超えると、タイヤトレッド用ゴム組成物の粘度が増大し押出し成形性が悪化する。 The total amount of carbon black and silica is 40 to 100 parts by weight, preferably 50 to 90 parts by weight, based on 100 parts by weight of the diene rubber. When the total amount of carbon black and silica is less than 40 parts by weight, the wear resistance cannot be sufficiently increased. On the other hand, when the total amount of carbon black and silica exceeds 100 parts by weight, the viscosity of the rubber composition for a tire tread increases and the extrusion moldability deteriorates.
本発明において、硫黄含有シランカップリング剤は、ジエン系ゴムに対するシリカの分散性を向上する。シリカの分散性向上は、ゴム組成物の低転がり抵抗性及び耐摩耗性を向上する。硫黄含有シランカップリング剤の配合量はシリカ配合量の２〜１５重量％、好ましくは６〜１０重量％にするとよい。硫黄含有シランカップリング剤がシリカ配合量の２重量％未満の場合、シリカの分散が悪化し低転がり抵抗性と耐摩耗性とを両立することができない。硫黄含有シランカップリング剤が１５重量％を超える場合、ゴム組成物のスコーチタイムが短くなりすぎて早期加硫を起こしやすくなる。 In the present invention, the sulfur-containing silane coupling agent improves the dispersibility of silica with respect to the diene rubber. The improvement of the dispersibility of silica improves the low rolling resistance and wear resistance of the rubber composition. The compounding amount of the sulfur-containing silane coupling agent is 2 to 15% by weight, preferably 6 to 10% by weight of the silica compounding amount. When the sulfur-containing silane coupling agent is less than 2% by weight of the silica content, the dispersion of the silica is deteriorated, and it is impossible to achieve both low rolling resistance and wear resistance. When the sulfur-containing silane coupling agent exceeds 15% by weight, the scorch time of the rubber composition becomes too short and premature vulcanization tends to occur.
硫黄含有シランカップリング剤としては、シリカ配合のゴム組成物に使用可能なものであればよく、例えばビス−（３−トリエトキシシリルプロピル）テトラサルファイド、ビス（３−トリエトキシシリルプロピル）ジサルファイド、３−トリメトキシシリルプロピルベンゾチアゾールテトラサルファイド、γ−メルカプトプロピルトリエトキシシラン、３−オクタノイルチオプロピルトリエトキシシラン等を例示することができる。 The sulfur-containing silane coupling agent is not particularly limited as long as it can be used in a rubber composition containing silica, and examples thereof include bis- (3-triethoxysilylpropyl) tetrasulfide and bis (3-triethoxysilylpropyl) disulfide. , 3-trimethoxysilylpropylbenzothiazole tetrasulfide, γ-mercaptopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, and the like.
本発明において、茶抽出物は、シリカの分散性を一層向上する。シリカの分散性向上により低転がり抵抗性及び耐摩耗性を更に向上することができる。また、茶抽出物はゴム組成物のヒステリシスロス（６０℃におけるｔａｎδ）を小さする作用を行なうので、低転がり抵抗性を一層向上することができる。このため硫黄含有シランカップリング剤の配合量を抑制することができるので、シランカップリング剤に起因するゴム組成物の早期加硫を防止することができ成形加工性に優れる。更に、カーボンブラックとシリカとを共に配合した場合でも、タイヤトレッド用ゴム組成物を押出し成形したときに、押出し成形体がシュリンクするのを抑制することができる。したがって、カーボンブラック、シリカ及び硫黄含有シランカップリング剤を配合したゴム組成物のレベル以上の押出し成形性を達成可能にした。この理由は明らかではないが、茶抽出物はヒドロキシル基を多く含むためシリカ粒子に対する親和性が強いためと考えられる。 In the present invention, the tea extract further improves the dispersibility of silica. Low rolling resistance and wear resistance can be further improved by improving the dispersibility of silica. Moreover, since the tea extract acts to reduce the hysteresis loss (tan δ at 60 ° C.) of the rubber composition, the low rolling resistance can be further improved. For this reason, since the compounding quantity of a sulfur containing silane coupling agent can be suppressed, the early vulcanization | cure of the rubber composition resulting from a silane coupling agent can be prevented, and it is excellent in molding processability. Furthermore, even when carbon black and silica are blended together, it is possible to suppress shrinkage of the extruded product when the tire tread rubber composition is extruded. Therefore, it became possible to achieve extrudability exceeding the level of a rubber composition containing carbon black, silica and a sulfur-containing silane coupling agent. The reason for this is not clear, but it is considered that tea extract has a strong affinity for silica particles because it contains many hydroxyl groups.
茶抽出物の配合量は、ジエン系ゴム１００重量部に対し０．０１〜５重量部、好ましくは０．０３〜３重量部である。茶抽出物の配合量が０．０１重量部未満であると、所期の効果を得ることができない。また、茶抽出物の配合量が５重量部を超えると、却って充填剤の分散性を悪化させるため、耐摩耗性が悪化する。 The blending amount of the tea extract is 0.01 to 5 parts by weight, preferably 0.03 to 3 parts by weight based on 100 parts by weight of the diene rubber. If the blended amount of the tea extract is less than 0.01 parts by weight, the desired effect cannot be obtained. Moreover, since the dispersibility of a filler will be deteriorated on the contrary when the compounding quantity of a tea extract exceeds 5 weight part, abrasion resistance deteriorates.
本発明で使用する茶抽出物は、緑茶、烏龍茶、紅茶から選ばれる少なくとも１種からの抽出物であり、これらの茶葉又は茶葉の粉砕物から、水若しくは熱水、有機溶剤を抽出剤とし５〜６０℃の抽出温度で抽出するとよい。有機溶剤としては例えばメタノール、エタノール、イソプロパノール、酢酸エチル、グリセリンなどが例示される。これらの抽出剤は単独で使用してもよいし、複数を組み合わせて使用してもよい。 The tea extract used in the present invention is an extract from at least one selected from green tea, oolong tea, and black tea. From these tea leaves or ground tea leaves, water or hot water, an organic solvent is used as an extractant. Extraction may be performed at an extraction temperature of ˜60 ° C. Examples of the organic solvent include methanol, ethanol, isopropanol, ethyl acetate, glycerin and the like. These extractants may be used alone or in combination.
茶抽出物は、上記の抽出剤で抽出した画分を使用する。水若しくは熱水、有機溶剤で抽出したときは、その抽出液を茶抽出物としてそのまま使用してもよいが、取扱い性の観点からは、抽出液から噴霧乾燥や凍結乾燥等により水分を除去して粉末状にして使用するとよい。 For the tea extract, the fraction extracted with the above extractant is used. When extracted with water, hot water, or an organic solvent, the extract may be used as it is as a tea extract. However, from the viewpoint of handleability, water is removed from the extract by spray drying or freeze drying. It is recommended to use it in powder form.
本発明で使用する茶抽出物は、茶由来のポリフェノール類を含む。このポリフェノール類はフラボノイドを主成分とし、フラボノイドはフラボン、フラボノール、フラバノール、フラボン配糖体などが例示される。また、複数のフラボノイドが結合することにより縮合型タンニンが生成する。フラボノイドのうちフラバノールが、フラバン−３−オール骨格を有するカテキン類である。 The tea extract used in the present invention contains tea-derived polyphenols. These polyphenols are mainly composed of flavonoids, and examples of flavonoids include flavones, flavonols, flavanols, flavone glycosides, and the like. In addition, condensed tannins are generated by combining a plurality of flavonoids. Of the flavonoids, flavanols are catechins having a flavan-3-ol skeleton.
本発明において、茶抽出物に含まれるポリフェノール類をカテキン及びカテキン以外の茶ポリフェノール類に大別するものとする。カテキンとしては、例えば（＋）−カテキン、（−）−エピカテキン、（＋）−ガロカテキン、（−）−エピガロカテキン、（−）−エピカテキンガレート、（−）−エピガロカテキンガレート等が例示される。茶抽出物としては、上述の化合物からなる群から選ばれる少なくとも１種を含むものであればよい。茶抽出物は、とりわけカテキンを含むことが好ましく、茶抽出物中のカテキンの含有量は、好ましくは５重量％以上、より好ましくは５〜９０重量％にするとよい。カテキンの含有量が５重量％未満であると、所期の性能が十分に得られない。 In the present invention, the polyphenols contained in the tea extract are roughly classified into catechins and tea polyphenols other than catechins. Examples of catechin include (+)-catechin, (−)-epicatechin, (+)-gallocatechin, (−)-epigallocatechin, (−)-epicatechin gallate, (−)-epigallocatechin gallate, and the like. Illustrated. As a tea extract, what is necessary is just to contain at least 1 sort (s) chosen from the group which consists of the above-mentioned compound. The tea extract preferably contains catechin, and the catechin content in the tea extract is preferably 5% by weight or more, more preferably 5 to 90% by weight. If the content of catechin is less than 5% by weight, the desired performance cannot be obtained sufficiently.
また、カテキン以外の茶ポリフェノール類としては、カテキン以外の茶由来のフラボノイド類及びフラボノイド類以外の茶ポリフェノール類であるものとする。これら茶ポリフェノール類を含有することにより、カテキンだけを配合した場合よりもゴム中へのカテキンの分散性を良好にする。このためカテキンの作用効果をより高くすると共に、茶ポリフェノール類の作用効果との相乗効果が期待できる。 Further, tea polyphenols other than catechins are tea-derived flavonoids other than catechins and tea polyphenols other than flavonoids. By containing these tea polyphenols, the dispersibility of catechin in rubber is made better than when only catechin is blended. For this reason, while making the effect of catechin higher, a synergistic effect with the effect of tea polyphenols can be expected.
本発明に使用する茶抽出物は、上述した茶抽出物をそのまま使用してもよいし、他の天然化合物及び／又は界面活性剤を添加した混合物からなる添加剤として使用してもよい。天然化合物としては、例えばトコフェロール、アスコルビン酸、茶由来のポリフェノールを除いたポリフェノール、植物油、動物油等を例示することができる。界面活性剤としては、例えばモノグリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、ショ糖脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、プロピレングリコール脂肪酸エステル、ポリグリセリン縮合脂肪酸エステル等を例示することができる。 As the tea extract used in the present invention, the tea extract described above may be used as it is, or may be used as an additive comprising a mixture to which other natural compounds and / or surfactants are added. Examples of natural compounds include tocopherol, ascorbic acid, polyphenols excluding tea-derived polyphenols, vegetable oils, and animal oils. Examples of the surfactant include monoglycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, propylene glycol fatty acid ester, polyglycerin condensed fatty acid ester and the like. .
このような添加剤は市販されており、例えば太陽化学社製サンフェノンＤＫ（茶カテキンを７４重量％含む茶由来ポリフェノールを９２重量％、ミネラル，灰分などを８量％含む茶抽出物）、サンフラボンＨＧ（茶カテキンを７３重量％含む茶由来ポリフェノールを８９重量％、ミネラル，灰分などを１１量％含む茶抽出物）、サンカトールＮｏ１（茶カテキンを７０重量％含む茶由来ポリフェノールを１０重量％含有し、これを界面活性剤で処理したもの）等を例示することができる。 Such additives are commercially available, for example, Sun Chemical Co., Ltd. Sunphenon DK (92% by weight of tea-derived polyphenol containing 74% by weight of tea catechin, tea extract containing 8% by weight of minerals, ash, etc.), sun flavone HG (tea extract containing 73% by weight of tea catechins, tea extract containing 89% by weight, 11% by weight of minerals, ash, etc.), Sankator No1 (containing 10% by weight of tea-derived polyphenols containing 70% by weight of tea catechins) And those treated with a surfactant).
本発明において、軟化剤は、前述したガラス転移温度が−２５℃以下の芳香族ビニル共役ジエン共重合体を含むジエン系ゴムに基づくグリップ性能をより高いレベルに向上する。軟化剤の配合量は、ジエン系ゴム１００重量部に対し３〜４０重量部、好ましくは３〜３８重量部にする。軟化剤の配合量が３重量部未満であると、グリップ性能を確保することができない。また、軟化剤の配合量が４０重量部を超えると、耐摩耗性及び低転がり抵抗性が悪化する。なお、軟化剤は、タイヤトレッド用ゴム組成物中に含まれるすべての軟化剤であり、軟化剤の配合量とは、ジエン系ゴムが油展品であるときは油展された軟化剤成分（プロセス油又は伸展油）とゴム組成物に配合された軟化剤との合計量をいうものとする。 In the present invention, the softener improves the grip performance based on the diene rubber containing the above-described aromatic vinyl conjugated diene copolymer having a glass transition temperature of −25 ° C. or lower to a higher level. The blending amount of the softening agent is 3 to 40 parts by weight, preferably 3 to 38 parts by weight with respect to 100 parts by weight of the diene rubber. If the blending amount of the softening agent is less than 3 parts by weight, grip performance cannot be ensured. Moreover, when the compounding quantity of a softening agent exceeds 40 weight part, abrasion resistance and low rolling resistance will deteriorate. The softeners are all softeners contained in the rubber composition for tire treads. The blending amount of the softener is an oil-extended softener component (process) when the diene rubber is an oil-extended product. Oil or extender oil) and the total amount of softener blended in the rubber composition.
軟化剤としては、石油系軟化剤や植物油系軟化剤が挙げられ、石油系軟化剤としては例えばパラフィン系オイル、アロマ系オイル、ナフテン系オイルなどが例示される。なかでも、アロマオイルが好ましい。 Examples of the softener include petroleum-based softeners and vegetable oil-based softeners. Examples of petroleum-based softeners include paraffinic oil, aroma-based oil, and naphthenic oil. Of these, aroma oil is preferable.
本発明のタイヤトレッド用ゴム組成物には、前述した以外の充填剤、加硫剤、加硫促進剤、老化防止剤などのタイヤトレッド用ゴム組成物に一般的に使用される各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練してタイヤトレッド用ゴム組成物とし、加硫又は架橋するのに使用することができる。カーボンブラック及びシリカ以外の充填剤としては、例えば、シリカ、クレー、酸化チタン、タルク、炭酸カルシウム、水酸化アルミニウム、マイカ等が例示される。これらの添加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とすることができる。本発明のタイヤトレッド用ゴム組成物は、公知のゴム用混練機械、例えば、バンバリーミキサー、ニーダー、ロール等を使用して、上記各成分を混合することによって製造することができる。 In the tire tread rubber composition of the present invention, various additives generally used in tire tread rubber compositions such as fillers, vulcanizing agents, vulcanization accelerators and anti-aging agents other than those described above are used. These additives can be compounded and kneaded by a general method to obtain a rubber composition for a tire tread, which can be used for vulcanization or crosslinking. Examples of fillers other than carbon black and silica include silica, clay, titanium oxide, talc, calcium carbonate, aluminum hydroxide, mica and the like. As long as the amount of these additives is not contrary to the object of the present invention, a conventional general amount can be used. The rubber composition for a tire tread of the present invention can be produced by mixing each of the above components using a known rubber kneading machine such as a Banbury mixer, a kneader, or a roll.
本発明のタイヤトレッド用ゴム組成物は、転がり抵抗性及び押出し成形性を悪化させることなく、耐摩耗性を向上することができる。このタイヤトレッド用ゴム組成物は、レース用タイヤとしてだけでなく、グリップ性能に優れたタイプの乗用車用タイヤにも好適に使用することができる。これらの空気入りタイヤは、押出し成形性が優れるゴム組成物からなる形状安定性が向上した押出し成形体により構成されるため、品質安定性が優れると共に、耐摩耗性と低転がり抵抗性とを一層高いレベルで兼備することができる。 The rubber composition for a tire tread of the present invention can improve wear resistance without deteriorating rolling resistance and extrusion moldability. This rubber composition for tire treads can be suitably used not only as a tire for racing but also for a tire for passenger cars having excellent grip performance. Since these pneumatic tires are composed of an extruded molded body having improved shape stability made of a rubber composition having excellent extrudability, the quality stability is excellent, and wear resistance and low rolling resistance are further improved. Can be combined at a high level.
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１に示す配合からなる８種類のタイヤトレッド用ゴム組成物（実施例１〜３、比較例１〜５）を、それぞれ硫黄及び加硫促進剤を除く配合成分を秤量し、１.８Ｌのバンバリーミキサーで６分間混練し、温度１６０℃でマスターバッチを放出し室温冷却した。このマスターバッチを１.８Ｌのバンバリーミキサーに供し、硫黄及び加硫促進剤を加え混合し、タイヤトレッド用ゴム組成物を調製した。 Eight kinds of rubber compositions for tire treads (Examples 1 to 3 and Comparative Examples 1 to 5) each having the composition shown in Table 1 were weighed with respect to compounding ingredients excluding sulfur and a vulcanization accelerator, and 1.8 L The mixture was kneaded for 6 minutes with a Banbury mixer, and the master batch was discharged at a temperature of 160 ° C. and cooled at room temperature. The master batch was subjected to a 1.8 L Banbury mixer, and sulfur and a vulcanization accelerator were added and mixed to prepare a tire tread rubber composition.
得られた８種類のタイヤトレッド用ゴム組成物（実施例１〜３、比較例１〜５）を用いて下記の方法により押出し性を評価した。また、８種類のゴム組成物をそれぞれ所定形状の金型中で、１５０℃、３０分間加硫して試験片を作製し、下記に示す方法により、耐摩耗性及びｔａｎδを測定した。 Extrudability was evaluated by the following method using the obtained eight types of rubber compositions for tire treads (Examples 1 to 3, Comparative Examples 1 to 5). In addition, eight kinds of rubber compositions were each vulcanized at 150 ° C. for 30 minutes in a mold having a predetermined shape to prepare test pieces, and the wear resistance and tan δ were measured by the following methods.
押出し性
ＡＳＴＭ Ｄ２２３０に準拠して、ガーベイダイ試験を行なった。チューバー温度１００℃、スクリュー回転数４０ｒｐｍの条件で、約４０ｃｍの長さの未加硫状態の成形体を押出成形し２４時間静置した。押出し直後の長さ及び２４時間後の長さを測定し、長さの比（２４時間後の長さ／押出し直後の長さ）を計算した。得られた結果は、比較例１の長さの比を１００にする指数として表１に示した。この指数が大きいほど押出し成形体の寸法変化（シュリンク）が小さく押出し性が優れていることを意味する。
Extrudability A Garvey die test was conducted in accordance with ASTM D2230. Under the conditions of a tuber temperature of 100 ° C. and a screw rotation speed of 40 rpm, an unvulcanized molded body having a length of about 40 cm was extruded and allowed to stand for 24 hours. The length immediately after extrusion and the length after 24 hours were measured, and the length ratio (length after 24 hours / length immediately after extrusion) was calculated. The obtained results are shown in Table 1 as an index for setting the length ratio of Comparative Example 1 to 100. It means that the larger the index, the smaller the dimensional change (shrink) of the extruded product and the better the extrudability.
耐摩耗性
得られた試験片を、ＪＩＳ Ｋ６２６４に準拠して、ランボーン摩耗試験機（岩本製作所社製）を使用して、荷重４９Ｎ、スリップ率２５％、時間４分、室温の条件で摩耗量を測定した。得られた結果は、比較例１の摩耗量の逆数を１００とする指数として表１に示した。この指数が大きいほど耐摩耗性が優れることを意味する。
Abrasion resistance Abrasion amount of the obtained test piece in accordance with JIS K6264 using a Lambourn abrasion tester (manufactured by Iwamoto Seisakusho) under the conditions of load 49N, slip rate 25%, time 4 minutes, room temperature Was measured. The obtained results are shown in Table 1 as an index with the reciprocal of the wear amount of Comparative Example 1 as 100. Higher index means better wear resistance.
ｔａｎδ
得られた試験片の温度６０℃におけるｔａｎδ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の条件で測定した。得られた結果は、比較例１を１００とする指数として表１に示した。この指数が小さいほどヒステリシスロスが小さく低転がり抵抗性であることを意味する。
tan δ
Tan δ at a temperature of 60 ° C. of the obtained test piece 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 are shown in Table 1 as an index with Comparative Example 1 as 100. A smaller index means a smaller hysteresis loss and a lower rolling 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：乳化重合スチレンブタジエンゴム、ガラス転移温度−５２℃（日本ゼオン社製ＮＩＰＯＬ １７１２、ＳＢＲ１００重量部に対しアロマオイル３７．５重量部添加の油展品）
ＳＢＲ２：乳化重合スチレンブタジエンゴム、ガラス転移温度−２０℃（日本ゼオン社製ＮＩＰＯＬ ９５２９、ＳＢＲ１００重量部に対しアロマオイル５０重量部添加の油展品）
ＢＲ：ブタジエンゴム、日本ゼオン社製ＮＩＰＯＬ ＢＲ１２２０
カーボンブラック１：窒素吸着比表面積１２５ｍ２／ｇ（昭和キャボット社製Ｎ２３４）
カーボンブラック２：窒素吸着比表面積１４２ｍ２／ｇ（三菱化学社製ダイアブラックＡ）
シリカ：ＣＴＡＢ吸着比表面積１６０ｍ２／ｇ、ローディア社製Ｚｅｏｓｉｌ １１６５ＭＰ
カップリング剤：シランカップリング剤、デグッサ社製Ｓｉ６９
茶抽出物１：茶カテキンを７０重量％含む茶由来ポリフェノールを１０重量％含有しこれを界面活性剤で処理したもの、太陽化学社製サンカトールＮｏ１
茶抽出物２：茶カテキンを７４重量％含む茶由来ポリフェノールを９２重量％、ミネラル，灰分などを８量％含む茶抽出物、太陽化学社製サンフェノンＤＫ
アロマオイル：ジャパンエナジー社製プロセスＸ−１４０
酸化防止剤１：フレキシス社製ＳＡＮＴＯＦＬＥＸ ６ＰＰＤ
酸化防止剤２：フレキシス社製ＳＡＮＴＯＦＬＥＸ ３Ｃ
亜鉛華：正同化学工業社製酸化亜鉛３種
ステアリン酸：日油社製ビーズステアリン酸ＹＲ
加硫促進剤１：大内新興化学工業社製ノクセラーＤ−Ｇ
加硫促進剤２：大内新興化学工業社製ノクセラーＣＺ−Ｇ
硫黄：鶴見化学工業社製金華印油入微粉硫黄
In addition, the kind of raw material used in Table 1 is shown below.
SBR1: emulsion polymerization styrene butadiene rubber, glass transition temperature -52 ° C. (NIPOL 1712 manufactured by Nippon Zeon Co., Ltd., oil-extended product with 37.5 parts by weight of aroma oil added to 100 parts by weight of SBR)
SBR2: emulsion polymerization styrene butadiene rubber, glass transition temperature -20 ° C (NIPOL 9529 manufactured by Nippon Zeon Co., Ltd., oil-extended product with 50 parts by weight of aroma oil added to 100 parts by weight of SBR)
BR: butadiene rubber, NIPOL BR1220 manufactured by Nippon Zeon Co., Ltd.
Carbon black 1: Nitrogen adsorption specific surface area 125 m 2 / g (N234, Showa Cabot)
Carbon black 2: Nitrogen adsorption specific surface area 142 m 2 / g (Mitsubishi Chemical Corporation Dia Black A)
Silica: CTAB adsorption specific surface area 160 m 2 / g, Rhodia Zeosil 1165MP
Coupling agent: Silane coupling agent, Si69 manufactured by Degussa
Tea extract 1: 10% by weight of tea-derived polyphenol containing 70% by weight of tea catechin and treated with a surfactant, Taiyo Kagaku Sankator No1
Tea extract 2: Tea extract containing 92% by weight of polyphenol derived from tea containing 74% by weight of tea catechins and 8% by weight of minerals, ash, etc., Sunphenon DK manufactured by Taiyo Chemical Co., Ltd.
Aroma oil: Process X-140 manufactured by Japan Energy
Antioxidant 1: SANTOFLEX 6PPD manufactured by Flexis
Antioxidant 2: SANTOFLEX 3C manufactured by Flexis
Zinc Hana: Zinc Oxide 3 types manufactured by Shodo Chemical Industry Co., Ltd. Stearic Acid: Beads Stearic Acid YR manufactured by NOF Corporation
Vulcanization accelerator 1: Noxeller DG made by Ouchi Shinsei Chemical Co., Ltd.
Vulcanization accelerator 2: Noxeller CZ-G manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Sulfur: Fine powder sulfur with Jinhua seal oil manufactured by Tsurumi Chemical Co., Ltd.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009151406A JP5381395B2 (en) | 2008-06-30 | 2009-06-25 | Rubber composition for tire tread |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008169953 | 2008-06-30 | ||
| JP2008169953 | 2008-06-30 | ||
| JP2009151406A JP5381395B2 (en) | 2008-06-30 | 2009-06-25 | Rubber composition for tire tread |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010031261A JP2010031261A (en) | 2010-02-12 |
| JP5381395B2 true JP5381395B2 (en) | 2014-01-08 |
Family
ID=41736104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009151406A Expired - Fee Related JP5381395B2 (en) | 2008-06-30 | 2009-06-25 | Rubber composition for tire tread |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5381395B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2935440B1 (en) * | 2012-12-19 | 2016-10-12 | Bridgestone Corporation | Tyre portions highly impermeable to oxygen |
| JP6496218B2 (en) * | 2015-09-09 | 2019-04-03 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition for tire and pneumatic tire |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3301202B2 (en) * | 1994-03-18 | 2002-07-15 | 住友化学工業株式会社 | Method for producing vulcanized rubber excellent in hardness and dynamic elastic modulus |
| JPH11106569A (en) * | 1997-10-02 | 1999-04-20 | Erubu:Kk | Antibacterial rubber and antibacterial rubber latex |
| JP4741061B2 (en) * | 2000-09-07 | 2011-08-03 | 住友ゴム工業株式会社 | Rubber composition for tire tread |
| JP2005029590A (en) * | 2003-07-07 | 2005-02-03 | Bridgestone Corp | Natural rubber with reduced odor |
| JP2009138018A (en) * | 2007-12-03 | 2009-06-25 | Bridgestone Corp | Rubber composition and tire using the same |
| WO2009154118A1 (en) * | 2008-06-18 | 2009-12-23 | 株式会社ブリヂストン | Rubber composition and tires made by using the rubber composition |
| JP4572991B2 (en) * | 2008-06-30 | 2010-11-04 | 横浜ゴム株式会社 | Rubber composition for tire |
-
2009
- 2009-06-25 JP JP2009151406A patent/JP5381395B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010031261A (en) | 2010-02-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7897665B2 (en) | Tire rubber composition | |
| JP4572991B2 (en) | Rubber composition for tire | |
| JP5999167B2 (en) | Rubber composition for tire tread | |
| US8507582B2 (en) | Tire tread-use rubber composition | |
| JP5499689B2 (en) | Rubber composition for tire | |
| US9132699B2 (en) | Rubber composition for a tread comprising an unsaturated TPS | |
| JP5737324B2 (en) | Rubber composition for tire | |
| JP5382495B2 (en) | Rubber composition and pneumatic tire using the same | |
| JP5381396B2 (en) | Rubber composition for tire tread | |
| JP6420203B2 (en) | Method for producing rubber composition | |
| EP3237515B1 (en) | Reactive silica in epoxidized polybutadiene | |
| EP3828232A1 (en) | Rubber composition for tire tread and tire manufactured by using the same | |
| JP7159566B2 (en) | Rubber composition for tire | |
| JP2006188571A (en) | Rubber composition and tire formed out of the same | |
| JP5381395B2 (en) | Rubber composition for tire tread | |
| JP7215104B2 (en) | Rubber composition and pneumatic tire using the same | |
| EP3412716B1 (en) | Rubber composition for tires | |
| JP5998587B2 (en) | Rubber composition for tire and pneumatic tire using the same | |
| JP5401874B2 (en) | Rubber composition for tire | |
| JP5463734B2 (en) | Rubber composition for tire | |
| JP2010065103A (en) | Rubber composition for tire tread | |
| CN108794828B (en) | Rubber composition for tire and pneumatic tire | |
| JP2011068911A (en) | Rubber composition, and tire comprising the same | |
| JP7435718B2 (en) | Rubber composition for tires and tires | |
| JP7473825B2 (en) | Rubber composition for tires |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120524 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130823 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130903 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130916 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5381395 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |