JP5597959B2 - Rubber composition for tire - Google Patents
Rubber composition for tire Download PDFInfo
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- JP5597959B2 JP5597959B2 JP2009210420A JP2009210420A JP5597959B2 JP 5597959 B2 JP5597959 B2 JP 5597959B2 JP 2009210420 A JP2009210420 A JP 2009210420A JP 2009210420 A JP2009210420 A JP 2009210420A JP 5597959 B2 JP5597959 B2 JP 5597959B2
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- silica
- weight
- rubber
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- rubber composition
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- 229920001971 elastomer Polymers 0.000 title claims description 41
- 239000005060 rubber Substances 0.000 title claims description 41
- 239000000203 mixture Substances 0.000 title claims description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 95
- 239000011347 resin Substances 0.000 claims description 49
- 229920005989 resin Polymers 0.000 claims description 49
- 239000000377 silicon dioxide Substances 0.000 claims description 47
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 39
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 35
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 20
- 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 claims description 20
- 229920003244 diene elastomer Polymers 0.000 claims description 20
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 20
- 150000003505 terpenes Chemical class 0.000 claims description 16
- 235000007586 terpenes Nutrition 0.000 claims description 16
- 239000002174 Styrene-butadiene Substances 0.000 description 26
- 238000002156 mixing Methods 0.000 description 18
- 238000005096 rolling process Methods 0.000 description 18
- 239000006087 Silane Coupling Agent Substances 0.000 description 9
- 239000006229 carbon black Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- -1 γ-mercaptopropyl Chemical group 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920003052 natural elastomer Polymers 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
- 239000008117 stearic acid Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- 150000000133 (4R)-limonene derivatives Chemical class 0.000 description 1
- HBKBEZURJSNABK-MWJPAGEPSA-N 2,3-dihydroxypropyl (1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(=O)OCC(O)CO HBKBEZURJSNABK-MWJPAGEPSA-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
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-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
- 239000011324 bead Substances 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 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
- 239000002904 solvent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 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
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 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
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、タイヤ用ゴム組成物に関し、さらに詳しくは、転がり抵抗及びグリップ性能を共に従来レベル以上に向上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 tire rubber composition, and more particularly to a tire rubber composition in which both rolling resistance and grip performance are improved to a conventional level or more.
一般に、空気入りタイヤのトレッド部に使用するタイヤ用ゴム組成物は、グリップ性能が優れていることに加え、転がり抵抗が小さく燃費性能に優れていることが求められている。グリップ性能を向上するためには、カーボンブラックなどの充填剤を増量することや、ガラス転移温度（Ｔｇ）が高いゴム又は樹脂を配合すること、粘着性付与樹脂を配合すること等が行われている。しかし、このような手段では、０℃のｔａｎδで評価可能なグリップ性能は向上するものの、６０℃のｔａｎδで評価可能な転がり抵抗が悪化するという問題があった。 In general, a tire rubber composition used for a tread portion of a pneumatic tire is required to have excellent rolling performance, low rolling resistance, and excellent fuel efficiency. In order to improve grip performance, increasing the amount of filler such as carbon black, blending rubber or resin having a high glass transition temperature (Tg), blending tackifying resin, etc. are performed. Yes. However, with such a means, the grip performance that can be evaluated with tan δ of 0 ° C. is improved, but the rolling resistance that can be evaluated with tan δ of 60 ° C. is deteriorated.
このため特許文献１は、末端変性ＳＢＲを含有したジエン系ゴムに、シリカ、極性官能基を有する脂環族石油樹脂及び芳香族変性テルペン樹脂等を配合したゴム組成物を提案している。しかし、このゴム組成物は、転がり抵抗を低減しながら、グリップ性能を向上する効果が必ずしも十分ではなく、さらなる改善の余地があった。 For this reason, Patent Document 1 proposes a rubber composition in which silica, an alicyclic petroleum resin having a polar functional group, an aromatic modified terpene resin, and the like are blended with a diene rubber containing terminal-modified SBR. However, this rubber composition is not necessarily sufficient in improving the grip performance while reducing rolling resistance, and there is room for further improvement.
本発明の目的は、転がり抵抗及びグリップ性能を共に従来レベル以上に向上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 a tire in which both rolling resistance and grip performance are improved to a conventional level or more.
上記目的を達成する本発明のタイヤ用ゴム組成物は、カルボキシル基により主鎖変性したスチレンブタジエンゴムを１０重量％以上含むジエン系ゴム１００重量部に対し、ＢＥＴ比表面積が７０〜３００ｍ2／ｇであるシリカを１０〜１２０重量部、ロジン系樹脂、テルペン系樹脂から選ばれる少なくとも１種の粘着性付与樹脂を１〜３０重量部配合したことを特徴とする。 The rubber composition for tires of the present invention that achieves the above object has a BET specific surface area of 70 to 300 m 2 / g with respect to 100 parts by weight of a diene rubber containing 10% by weight or more of a styrene butadiene rubber modified with a main chain by a carboxyl group. 10 to 120 parts by weight of silica, and 1 to 30 parts by weight of at least one tackifying resin selected from rosin resins and terpene resins are blended.
前記ジエン系ゴムがスチレンブタジエンゴムであるとよい。 The diene rubber may be styrene butadiene rubber .
また、本発明のタイヤ用ゴム組成物は、空気入りタイヤのトレッド部に好ましく使用することができる。 Moreover, the rubber composition for tires of this invention can be preferably used for the tread part of a pneumatic tire.
本発明のタイヤ用ゴム組成物は、カルボキシル基により主鎖変性したスチレンブタジエンゴムを１０重量％以上含むジエン系ゴム１００重量部に対し、ＢＥＴ比表面積が７０〜３００ｍ2／ｇであるシリカを１０〜１２０重量部、ロジン系樹脂、テルペン系樹脂から選ばれる少なくとも１種の粘着性付与樹脂を１〜３０重量部配合したことにより、カルボキシル基で主鎖変性したスチレンブタジエンゴムが、シリカに作用してその分散性を改良するので、転がり抵抗及びグリップ性能を共に従来レベル以上に向上することができる。 In the tire rubber composition of the present invention, 10 parts by weight of silica having a BET specific surface area of 70 to 300 m 2 / g with respect to 100 parts by weight of a diene rubber containing 10% by weight or more of a styrene butadiene rubber modified with a main chain by a carboxyl group. ~ 120 parts by weight , styrene butadiene rubber modified with a main chain with a carboxyl group acts on silica by blending 1 to 30 parts by weight of at least one tackifier resin selected from rosin resins and terpene resins. Therefore, both the rolling resistance and the grip performance can be improved over the conventional level.
本発明のタイヤ用ゴム組成物において、ゴム成分はジエン系ゴムであり、そのジエン系ゴムはカルボキシル基で主鎖変性したスチレンブタジエンゴム（以下、「カルボキシル基主鎖変性ＳＢＲ」という。）を必ず含むようにする。カルボキシル基主鎖変性ＳＢＲを配合することにより、ゴム組成物中のシリカの分散性を改良し、転がり抵抗（６０℃のｔａｎδ）及びグリップ性能（０℃のｔａｎδ）を共に従来レベル以上に向上させることが可能となる。 In the rubber composition for tires of the present invention, the rubber component is a diene rubber, and the diene rubber is necessarily a styrene butadiene rubber having a main chain modified with a carboxyl group (hereinafter referred to as “carboxyl main chain modified SBR”). To include. By compounding the carboxyl group main chain modified SBR, the dispersibility of silica in the rubber composition is improved, and both the rolling resistance (tan δ at 60 ° C.) and the grip performance (tan δ at 0 ° C.) are improved over conventional levels. It becomes possible.
本発明において使用するカルボキシル基主鎖変性ＳＢＲは、スチレンブタジエンゴムの主鎖を構成するポリブタジエンセグメントがカルボキシル基で変性されたもの或いはポリブタジエンセグメントがカルボキシル基を有する化合物と反応したものである。また、好ましくはポリブタジエンセグメントの末端を除くブタジエン単位とカルボキシル基を有する化合物とが反応したものであるとよい。ブタジエン単位としては、１，４結合、１，２結合のいずれでもよいが、１，２結合したブタジエン単位のビニル基が、カルボキシル基を有する化合物と反応しやすい。 The carboxyl group main chain-modified SBR used in the present invention is one in which the polybutadiene segment constituting the main chain of the styrene butadiene rubber is modified with a carboxyl group or the polybutadiene segment reacts with a compound having a carboxyl group. Moreover, it is preferable that the butadiene unit excluding the terminal of the polybutadiene segment reacts with a compound having a carboxyl group. The butadiene unit may be either 1,4 bond or 1,2 bond, but the vinyl group of the 1,2-bonded butadiene unit easily reacts with the compound having a carboxyl group.
本発明で使用するカルボキシル基主鎖変性ＳＢＲは、例えば特許文献１に記載された末端変性ＳＢＲと比べて、カルボキシル基の含有量を多くすることができる。すなわちカルボキシル基主鎖変性ＳＢＲは、極性が高いカルボキシル基を多量に含有するため、シリカに対する作用が強く、シリカの分散性を向上することができる。カルボキシル基主鎖変性ＳＢＲにおけるカルボキシル基の含有量は、好ましくは０．０３〜５重量％、より好ましくは０．１〜３重量％にするとよい。カルボキシル基の含有量が０．０３重量％未満であると、末端変性ＳＢＲとの差が少なくシリカの分散性を向上する効果が十分に得られない。また、カルボキシル基の含有量が５重量％を超えると、ＳＢＲとしては硬くなりすぎるため、混練に適さなくなる。 The carboxyl group main chain-modified SBR used in the present invention can increase the content of the carboxyl group as compared with the terminal-modified SBR described in Patent Document 1, for example. That is, the carboxyl group main chain-modified SBR contains a large amount of highly polar carboxyl groups, and thus has a strong effect on silica and can improve the dispersibility of silica. The carboxyl group content in the carboxyl group main chain-modified SBR is preferably 0.03 to 5% by weight, more preferably 0.1 to 3% by weight. When the carboxyl group content is less than 0.03% by weight, the difference from the terminal-modified SBR is small and the effect of improving the dispersibility of silica cannot be sufficiently obtained. On the other hand, when the content of the carboxyl group exceeds 5% by weight, the SBR becomes too hard and is not suitable for kneading.
カルボキシル基主鎖変性ＳＢＲは、通常の方法で製造することができる。また、適宜、市販品を入手し使用してもよい。カルボキシル基主鎖変性ＳＢＲの製造方法としては、例えば特開２０００−２５６５１３号公報に記載された方法を例示することができる。 The carboxyl group main chain-modified SBR can be produced by a usual method. Moreover, you may obtain and use a commercial item suitably. As a method for producing the carboxyl group main chain modified SBR, for example, the method described in JP-A No. 2000-256513 can be exemplified.
ジエン系ゴムにおけるカルボキシル基主鎖変性ＳＢＲの含有割合は、１０重量％以上、好ましくは１２〜１００重量％、より好ましくは１４〜１００重量％にする。カルボキシル基主鎖変性ＳＢＲがジエン系ゴム中の１０重量％未満であると、シリカの分散性を改良する効果が十分に得られない。なお、カルボキシル基主鎖変性ＳＢＲ及びジエン系ゴムは、オイル成分を含有してもよい。この場合、カルボキシル基主鎖変性ＳＢＲ及びジエン系ゴムの配合量は、オイル成分を除いた各ゴム成分の正味の配合量とする。 The content ratio of the carboxyl group main chain modified SBR in the diene rubber is 10% by weight or more, preferably 12 to 100% by weight, more preferably 14 to 100% by weight. When the carboxyl group main chain-modified SBR is less than 10% by weight in the diene rubber, the effect of improving the dispersibility of silica cannot be sufficiently obtained. The carboxyl group main chain modified SBR and the diene rubber may contain an oil component. In this case, the blending amount of the carboxyl group main chain modified SBR and the diene rubber is the net blending amount of each rubber component excluding the oil component.
本発明において、ジエン系ゴムはカルボキシル基主鎖変性ＳＢＲのみで構成してもよく、またカルボキシル基主鎖変性ＳＢＲと他のジエン系ゴムを共に用いてもよい。他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、スチレンブタジエンゴムから選ばれる少なくとも１種であるとよい。好ましくは天然ゴム、スチレンブタジエンゴム、ブタジエンゴムがよく更に好ましくはスチレンブタジエンゴムがよい。これら他のジエン系ゴムは、単独又は複数のブレンドとして配合することができる。 In the present invention, the diene rubber may be composed only of the carboxyl group main chain modified SBR, or the carboxyl group main chain modified SBR and another diene rubber may be used together. The other diene rubber may be at least one selected from natural rubber, isoprene rubber, butadiene rubber, and styrene butadiene rubber. Preferably natural rubber, styrene-butadiene rubber, more preferably butadiene rubber rather good good styrene-butadiene rubber. These other diene rubbers can be blended alone or as a plurality of blends.
本発明のゴム組成物は、シリカを配合することにより転がり抵抗（６０℃のｔａｎδ）を低減すると共に、グリップ性能、特にウェットグリップ性能（０℃のｔａｎδ）を高くする。ここで、６０℃のｔａｎδは、この値が小さいほど転がり抵抗が低く、また０℃のｔａｎδは、この値が大きいほどグリップ性能が高いものとして評価される。シリカとしては、ＢＥＴ比表面積が、７０〜３００ｍ２／ｇ、好ましくは８０〜２８０ｍ２／ｇのものを使用する。シリカのＢＥＴ比表面積が７０ｍ２／ｇ未満であると、フィラーとしての補強性が不十分となる。また、シリカのＢＥＴ比表面積が３００ｍ２／ｇを超えると、転がり抵抗の低減が困難になる。なお、本発明において、シリカのＢＥＴ比表面積は、ＡＳＴＭ Ｄ１９９３−０３に準拠して測定するものとする。 The rubber composition of the present invention reduces the rolling resistance (tan δ at 60 ° C.) and increases the grip performance, particularly wet grip performance (tan δ at 0 ° C.), by blending silica. Here, the tan δ at 60 ° C. is evaluated as the rolling resistance is lower as the value is smaller, and the tan δ at 0 ° C. is evaluated as the grip performance is higher as the value is larger. Silica having a BET specific surface area of 70 to 300 m 2 / g, preferably 80 to 280 m 2 / g is used. When the BET specific surface area of silica is less than 70 m 2 / g, the reinforcing property as a filler becomes insufficient. Moreover, when the BET specific surface area of a silica exceeds 300 m < 2 > / g, it will become difficult to reduce rolling resistance. In the present invention, the BET specific surface area of silica is measured according to ASTM D1993-03.
シリカの種類としては、通常タイヤ用ゴム組成物に配合されるシリカ、例えば湿式法シリカ、乾式法シリカあるいは表面処理シリカなどを使用することができる。 As the type of silica, silica that is usually blended in a tire rubber composition, such as wet method silica, dry method silica, or surface-treated silica, can be used.
また、シリカと共にシランカップリング剤を配合することにより、ジエン系ゴムに対するシリカの分散性を改良することができ好ましい。シランカップリング剤の配合量は、シリカの配合量に対し、好ましくは３〜１５重量％、より好ましくは４〜１０重量％にするとよい。シランカップリング剤の配合量が３重量％未満であると、シリカの分散性を十分に改良することができない。また、シランカップリング剤の配合量が１５重量％を超えると、シランカップリング剤同士が凝集・縮合してしまい、所望の効果を得ることができなくなる。 In addition, it is preferable to add a silane coupling agent together with silica to improve the dispersibility of silica in the diene rubber. The amount of the silane coupling agent is preferably 3 to 15% by weight, more preferably 4 to 10% by weight, based on the amount of silica. When the compounding amount of the silane coupling agent is less than 3% by weight, the dispersibility of silica cannot be sufficiently improved. Moreover, when the compounding quantity of a silane coupling agent exceeds 15 weight%, silane coupling agents will aggregate and condense, and it will become impossible to acquire a desired effect.
シランカップリング剤の種類としては、特に制限されるものではないが、硫黄含有シランカップリング剤が好ましい。硫黄含有シランカップリング剤としては、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。 Although it does not restrict | limit especially as a kind of silane coupling agent, A sulfur containing silane coupling agent is preferable. Examples of the sulfur-containing silane coupling agent include bis- (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, and γ-mercaptopropyl. Examples thereof include triethoxysilane and 3-octanoylthiopropyltriethoxysilane.
本発明のタイヤ用ゴム組成物は、さらに粘着性付与樹脂を配合することによりグリップ性能を一層高くする。また、ゴム組成物の混練・混合時におけるシリカの取り込み性を改良する。本発明のタイヤ用ゴム組成物は、カルボキシル基主鎖変性ＳＢＲを有するためシリカとの親和性が高くシリカの分散性が優れる。しかし、粒子径が微細なシリカは、混練・混合時の初期にシリカを投入したときに凝集しやすく、混練・混合が難しい。これに対し粘着性付与樹脂を配合することにより、シリカ投入時の取り込み性を改良し凝集を防ぐことができ、混練・混合時の作業性を向上する。 The rubber composition for tires of the present invention further enhances grip performance by blending a tackifying resin. Further, it improves the silica uptake during kneading and mixing of the rubber composition. The rubber composition for tires of the present invention has a carboxyl group main chain-modified SBR, and therefore has high affinity with silica and excellent silica dispersibility. However, silica having a fine particle diameter is likely to aggregate when silica is added at the initial stage of kneading and mixing, and is difficult to knead and mix. On the other hand, by incorporating a tackifying resin, it is possible to improve the uptake at the time of adding silica and prevent agglomeration and improve the workability at the time of kneading and mixing.
粘着性付与樹脂の配合量は、ジエン系ゴム１００重量部に対し１〜３０重量部、好ましくは２〜３０重量部である。粘着性付与樹脂の配合量が１重量部未満であると、グリップ性能を十分に高くすることができない。また、シリカの取り込み性を改良する効果が十分に得られない。粘着性付与樹脂の配合量が３０重量部を超えると、転がり抵抗が悪化するため好ましくない。なお、粘着性付与樹脂は軟化剤としての作用も行うため、粘着性付与樹脂の配合量に応じて、アロマオイル等の他の軟化剤の配合量を加減するとよい。 The amount of tackifying resin is from 1 to 30 wt parts against 100 parts by weight of the diene rubber, good Mashiku is 2 to 30 parts by weight. Grip performance cannot be made high enough that the compounding quantity of tackifying resin is less than 1 weight part. In addition, the effect of improving silica uptake cannot be sufficiently obtained. When the compounding amount of the tackifying resin exceeds 30 parts by weight, the rolling resistance is deteriorated, which is not preferable. In addition, since tackifying resin also acts as a softening agent, the blending amount of other softening agents such as aroma oil may be adjusted depending on the blending amount of the tackifying resin.
本発明において、粘着性付与樹脂とは、ゴム組成物への粘着付与性を有する樹脂であり、一般には分子量が数百から数千の熱可塑性樹脂で、上述したジエン系ゴムに配合することによって粘着性を付与する作用を行う。粘着性付与樹脂としては、例えば、テルペン系樹脂、ロジン系樹脂などの天然樹脂、石油系樹脂、石炭系樹脂、フェノール系樹脂、キシレン系樹脂などの合成樹脂が例示される。本発明のゴム組成物では、テルペン系樹脂および／またはロジン系樹脂を配合する。 In the present invention, the tackifying resin is a resin having tackifying properties to a rubber composition, and is generally a thermoplastic resin having a molecular weight of several hundred to several thousand, and is blended with the above-described diene rubber. Performs the action of imparting tackiness. Examples of the tackifying resin include natural resins such as terpene resins and rosin resins, and synthetic resins such as petroleum resins, coal resins, phenol resins, and xylene resins. In the rubber composition of the present invention, a terpene resin and / or a rosin resin is blended .
テルペン系樹脂としては、例えばα−ピネン樹脂、β−ピネン樹脂、リモネン樹脂、水添リモネン樹脂、ジペンテン樹脂、テルペンフェノール樹脂、テルペンスチレン樹脂、芳香族変性テルペン樹脂、水素添加テルペン樹脂等が挙げられる。ロジン系樹脂としては、例えばガムロジン、トール油ロジン、ウッドロジン、水素添加ロジン、不均化ロジン、重合ロジン、マレイン化ロジンおよびフマル化ロジン等の変性ロジン、これらのロジンのグリセリンエステル、ペンタエリスリトールエステル、メチルエステルおよびトリエチレングリコールエステルなどのエステル誘導体、並びにロジン変性フェノール樹脂、ロジン変性樹脂等が挙げられる。これらの中でも、テルペンフェノール樹脂、テルペンスチレン樹脂、芳香族変性テルペン樹脂、ロジンのエステル誘導体、ロジン変性樹脂、重合ロジンが好ましい。 Examples of the terpene resin include α-pinene resin, β-pinene resin, limonene resin, hydrogenated limonene resin, dipentene resin, terpene phenol resin, terpene styrene resin, aromatic modified terpene resin, hydrogenated terpene resin and the like. . Examples of rosin resins include gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin and modified rosin such as fumarinated rosin, glycerin ester of these rosin, pentaerythritol ester, Examples include ester derivatives such as methyl ester and triethylene glycol ester, and rosin-modified phenolic resins and rosin-modified resins. Among these, terpene phenol resin, terpene styrene resin, aromatic modified terpene resin, ester derivative of rosin, rosin modified resin, and polymerized rosin are preferable.
本発明のタイヤ用ゴム組成物に、カーボンブラックを配合することによりゴムの強度を高くする。カーボンブラックの配合量は、ジエン系ゴム１００重量部に対し好ましくは２〜７０重量部、より好ましくは３〜６０重量部にするとよい。カーボンブラックの配合量が２重量部未満の場合には、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７０重量部を超えると転がり抵抗が悪化する。 By adding carbon black to the tire rubber composition of the present invention, the strength of the rubber is increased. The compounding amount of carbon black is preferably 2 to 70 parts by weight, more preferably 3 to 60 parts by weight with respect to 100 parts by weight of the diene rubber. When the blending amount of carbon black is less than 2 parts by weight, the rubber strength cannot be sufficiently increased. On the other hand, if the blending amount of carbon black exceeds 70 parts by weight, rolling resistance is deteriorated.
また、シリカ以外の他の無機充填剤を配合してもよい。他の無機充填剤としては、例えばクレー、マイカ、タルク、炭酸カルシウム、水酸化アルミニウム、酸化アルミニウム等が例示される。 Moreover, you may mix | blend inorganic fillers other than a silica. Examples of other inorganic fillers include clay, mica, talc, calcium carbonate, aluminum hydroxide, and aluminum oxide.
タイヤ用ゴム組成物には、上述したカーボンブラック及び無機充填剤以外に、加硫又は架橋剤、加硫促進剤、老化防止剤、可塑剤、加工助剤、カップリング剤などのタイヤ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。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。このようなゴム組成物は、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 addition to the above-described carbon black and inorganic filler, the tire rubber composition includes tire rubber compositions such as a vulcanization or crosslinking agent, a vulcanization accelerator, an anti-aging agent, a plasticizer, a processing aid, and a coupling agent. Various additives generally used in products can be blended, and such additives can be kneaded by a general method to form a rubber composition, which can be used for vulcanization or crosslinking. 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. Such a rubber composition can be produced by mixing each of the above components using a known rubber kneading machine, for example, a Banbury mixer, a kneader, a roll or the like.
本発明のタイヤ用ゴム組成物は、空気入りタイヤのトレッド部として好適に使用することができる。また、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、転がり抵抗が小さく燃費性能が優れる。また、グリップ性能、特にウェットグリップ性能が高く、操縦安定性が優れる。 The tire rubber composition of the present invention can be suitably used as a tread portion of a pneumatic tire. Moreover, the pneumatic tire using the tire rubber composition of the present invention in the tread portion has low rolling resistance and excellent fuel efficiency. In addition, grip performance, particularly wet grip performance is high, and steering stability is excellent.
以下、実施例によって本発明をさらに説明するが、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９種類のタイヤ用ゴム組成物（実施例１〜４、参照例１，２、比較例１〜３）を、硫黄、加硫促進剤を除く成分を１.８Ｌの密閉型ミキサーで５分間混練し放出し室温冷却した。このマスターバッチに、硫黄、加硫促進剤を加えてオープンロールで混合することにより調整した。このときのシリカの取り込み性を下記に示す方法で評価した。 Nine kinds of tire rubber compositions (Examples 1 to 4, Reference Examples 1 and 2, and Comparative Examples 1 to 3) having the composition shown in Table 1 were added to 1.8 L of components excluding sulfur and a vulcanization accelerator. The mixture was kneaded for 5 minutes in a closed mixer, discharged, and cooled at room temperature. It adjusted by adding sulfur and a vulcanization accelerator to this masterbatch, and mixing with an open roll. The silica uptake at this time was evaluated by the following method.
シリカの取り込み性
上記９種類のタイヤ用ゴム組成物の密閉型ミキサーでの混練終了時において、放出されたゴム組成物におけるシリカの取り込み性を目視観察した。得られた結果は、下記に示す評価基準で判定し１〜５の評点を付け、表１に示した。
Silica uptake The silica uptake in the released rubber composition was visually observed at the end of kneading of the nine types of rubber compositions for tires in the closed mixer. The obtained results were determined according to the evaluation criteria shown below and given a score of 1 to 5, and are shown in Table 1.
１： シリカの取り込み性が悪い（比較的多量のシリカがポリマー中に混ざっていない）。
２： シリカの取り込み性がやや悪い（ポリマー中に混ざっていないシリカが目立つ）。
３： シリカの取り込み性は実用上問題がない（シリカがポリマー中にある程度分散しており、混ざっていないシリカが存在していない）。
４： シリカの取り込み性が良好（シリカがポリマー中に均一に近い形で分散している）。
５： シリカの取り込み性が優れる（シリカがポリマー中に完全に均一に分散している）。
1: The silica uptake is poor (a relatively large amount of silica is not mixed in the polymer).
2: Slightly poor silica uptake (silica that is not mixed in the polymer is noticeable).
3: Silica uptake has no practical problem (silica is dispersed to some extent in the polymer, and no unmixed silica is present).
4: Good uptake of silica (silica is dispersed in the polymer in a nearly uniform form).
5: Excellent silica uptake (silica is completely and uniformly dispersed in the polymer).
得られた９種類のタイヤ用ゴム組成物を所定形状の金型中で、１６０℃、２０分間プレス加硫して加硫ゴムサンプルを作製し、下記に示す方法でグリップ性能及び転がり抵抗を評価した。 Nine types of tire rubber compositions thus obtained were press vulcanized at 160 ° C. for 20 minutes in a mold having a predetermined shape to produce a vulcanized rubber sample, and the grip performance and rolling resistance were evaluated by the following methods. did.
グリップ性能及び転がり抵抗
得られた試験片の動的粘弾性をＪＩＳ Ｋ６３９４に準拠して、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、温度０℃及び６０℃のｔａｎδ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「グリップ性能」欄に０℃のｔａｎδを、「転がり抵抗」の欄に６０℃のｔａｎδを示した。グリップ性能の指数が大きいほど０℃のｔａｎδが大きくグリップ性能が優れることを意味する。また、転がり抵抗の指数が小さいほど６０℃のｔａｎδが低く、タイヤに使用したときの燃費性能が優れることを意味する。
Grip performance and rolling resistance Based on JIS K6394, the dynamic viscoelasticity of the obtained test piece was measured using a viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho Co., Ltd., with an initial strain of 10%, an amplitude of ± 2%, and a frequency of 20 Hz. Then, tan δ at temperatures of 0 ° C. and 60 ° C. was measured. The obtained results were indexed with the value of Comparative Example 1 being 100, respectively. In Table 1, “grip performance” column showed 0 ° C. tan δ, and “rolling resistance” column showed 60 ° C. tan δ. The larger the index of grip performance, the larger the tan δ at 0 ° C., and the better the grip performance. Further, the smaller the rolling resistance index, the lower the tan δ at 60 ° C., which means that the fuel efficiency when used in a tire is superior.
なお、表１において使用した原材料の種類を下記に示す。
・ＳＢＲ：スチレンブタジエンゴム、日本ゼオン社製Ｎｉｐｏｌ １７２３、ゴム成分１００重量部に対しオイル分３７．５重量部を含む油展品。
・変性ＳＢＲ１：カルボキシル基主鎖変性ＳＢＲ、スチレンブタジエンゴム（ＬＡＮＸＥＳＳ社製Ｂｕｎａ ＶＳＬ５０２５−０）を原料ゴムとして、その５００ｇを４リットルのシクロヘキサンに溶解させ、これに３−メルカプトプロピオン酸６．２５ｇおよびジラウロイルパーオキサイド０．２５ｇを加えて８０℃で５時間反応させた。その後、バルカノックス４０２０（バイエル社製）２．５ｇを加えて溶媒を除去し、乾燥させることによりカルボキシル基主鎖変性ＳＢＲ５０８ｇを調製した。得られたカルボキシル基主鎖変性ＳＢＲのカルボキシ基の含有量は０．２５重量％であった。このカルボキシル基主鎖変性ＳＢＲ１００重量部に対しオイル分３７．５重量部を添加・混合し油展することによりカルボキシル基主鎖変性ＳＢＲ（変性ＳＢＲ１）とした。
・変性ＳＢＲ２：Ｎ−メチルピロリドン基で末端を変性したＳＢＲ、Ｎ−メチルピロリドン基の含有量が０．０２重量％、日本ゼオン社製Ｎｉｐｏｌ ＮＳ１１６
・ＣＢ：カーボンブラック、東海カーボン社製シーストＫＨ
・シリカ：エボニックデグッサ社製ＵＬＴＲＡＳＩＬ ＶＮ３ＧＲ、ＢＥＴ比表面積１７１ｍ２／ｇ
・ロジン系樹脂：ロジン変性樹脂、ハリマ化成社製ハリタックＡＱ−９０Ａ
・テルペン系樹脂：芳香族変性テルペン樹脂、ヤスハラケミカル社製ＹＳレジンＴＯ−１２５
・オイル：昭和シェル石油社製エキストラクト４号Ｓ
・酸化亜鉛：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
・老化防止剤：フレキシス社製サントフレックス６ＰＰＤ
・ワックス：大内新興化学工業社製サンノック
・カップリング剤：シランカップリング剤、エボニックデグッサ社製Ｓｉ６９
・硫黄：鶴見化学工業社製金華印油入微粉硫黄
・加硫促進剤：大内新興化学工業社製ノクセラーＣＺ−Ｇ
In addition, the kind of raw material used in Table 1 is shown below.
-SBR: Styrene butadiene rubber, Nipol 1723 manufactured by Nippon Zeon Co., Ltd., an oil-extended product containing 37.5 parts by weight of oil with respect to 100 parts by weight of the rubber component.
-Modified SBR1: Carboxyl main chain modified SBR, styrene butadiene rubber (Buna VSL5025-0 manufactured by LANXESS) as a raw rubber, 500 g thereof was dissolved in 4 liters of cyclohexane, and 6.25 g of 3-mercaptopropionic acid and 0.25 g of dilauroyl peroxide was added and reacted at 80 ° C. for 5 hours. Thereafter, 2.5 g of Vulcanox 4020 (manufactured by Bayer) was added to remove the solvent, followed by drying to prepare 508 g of carboxyl group main chain modified SBR. The content of carboxy group in the obtained carboxyl group main chain-modified SBR was 0.25% by weight. A carboxyl group main chain modified SBR (modified SBR1) was obtained by adding and mixing 37.5 parts by weight of oil to 100 parts by weight of the carboxyl group main chain modified SBR and mixing and oil-extended.
-Modified SBR2: SBR whose terminal is modified with N-methylpyrrolidone group, the content of N-methylpyrrolidone group is 0.02% by weight, Nipol NS116 manufactured by ZEON Corporation
・ CB: Carbon black, Toast Carbon Co.
Silica: ULTRASIL VN3GR manufactured by Evonik Degussa, BET specific surface area of 171 m 2 / g
Rosin resin: rosin modified resin, Harima Chemical Co., Ltd. Haritac AQ-90A
Terpene resin: Aromatic modified terpene resin, YS resin TO-125 manufactured by Yasuhara Chemical Co., Ltd.
・ Oil: Extract No. 4 S manufactured by Showa Shell Sekiyu KK
・ Zinc oxide: 3 types of zinc oxide manufactured by Shodo Chemical Co., Ltd. ・ Stearic acid: Beads stearic acid YR manufactured by NOF Corporation
Anti-aging agent: Santoflex 6PPD manufactured by Flexis
・ Wax: Sunnock, manufactured by Ouchi Shinsei Chemical Co., Ltd.Coupling agent: Silane coupling agent, Si69, manufactured by Evonik Degussa
・ Sulfur: Fine powder sulfur with Jinhua seal oil manufactured by Tsurumi Chemical Co., Ltd. ・ Vulcanization accelerator: Noxeller CZ-G manufactured by Ouchi Shinsei Chemical Co., Ltd.
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| WO2011158509A1 (en) * | 2010-06-18 | 2011-12-22 | 横浜ゴム株式会社 | Tire rubber composition and pneumatic tire using same |
| JP5886610B2 (en) * | 2011-11-24 | 2016-03-16 | 住友ゴム工業株式会社 | Rubber composition and pneumatic tire |
| JP5798457B2 (en) * | 2011-11-24 | 2015-10-21 | 住友ゴム工業株式会社 | Rubber composition and pneumatic tire |
| JP6193581B2 (en) * | 2013-02-12 | 2017-09-06 | 住友ゴム工業株式会社 | Rubber composition for tire and pneumatic tire |
| US9969221B2 (en) | 2013-07-05 | 2018-05-15 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire |
| BR112015029725A8 (en) | 2013-11-21 | 2019-12-24 | Arizona Chemical Co Llc | composition of rubber and tire |
| DE112016001707B4 (en) * | 2015-04-13 | 2023-05-04 | The Yokohama Rubber Co., Ltd. | Rubber composition, vulcanized product and use |
| JP6790429B2 (en) * | 2016-04-11 | 2020-11-25 | 住友ゴム工業株式会社 | Pneumatic tires |
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| JPH09136996A (en) * | 1995-11-15 | 1997-05-27 | Bridgestone Corp | Pneumatic radial tire |
| JPH1087881A (en) * | 1996-09-17 | 1998-04-07 | Yokohama Rubber Co Ltd:The | Heavy-duty pneumatic tire |
| EP1000971B1 (en) * | 1998-11-16 | 2003-10-15 | Bayer Aktiengesellschaft | Rubber compositions consisting of solution-polymerised rubber containing carboxyl groups |
| WO2001092402A1 (en) * | 2000-05-26 | 2001-12-06 | Societe De Technologie Michelin | Rubber composition for use as tyre running tread |
| FR2854404B1 (en) * | 2003-04-29 | 2005-07-01 | Michelin Soc Tech | METHOD OF OBTAINING GRAFT ELASTOMER WITH FUNCTIONAL GROUPS ALONG THE CHAIN AND RUBBER COMPOSITIONS |
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| JP2007186567A (en) * | 2006-01-12 | 2007-07-26 | Yokohama Rubber Co Ltd:The | Rubber composition for tread of tire |
| JP2007321046A (en) * | 2006-05-31 | 2007-12-13 | Yokohama Rubber Co Ltd:The | Rubber composition and pneumatic tire |
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