JP2015218255A - Rubber composition for tire tread - Google Patents
Rubber composition for tire tread Download PDFInfo
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- JP2015218255A JP2015218255A JP2014102690A JP2014102690A JP2015218255A JP 2015218255 A JP2015218255 A JP 2015218255A JP 2014102690 A JP2014102690 A JP 2014102690A JP 2014102690 A JP2014102690 A JP 2014102690A JP 2015218255 A JP2015218255 A JP 2015218255A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 55
- 239000005060 rubber Substances 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- JSNRRGGBADWTMC-UHFFFAOYSA-N (6E)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene Chemical compound CC(C)=CCCC(C)=CCCC(=C)C=C JSNRRGGBADWTMC-UHFFFAOYSA-N 0.000 claims abstract description 85
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 59
- CXENHBSYCFFKJS-UHFFFAOYSA-N (3E,6E)-3,7,11-Trimethyl-1,3,6,10-dodecatetraene Natural products CC(C)=CCCC(C)=CCC=C(C)C=C CXENHBSYCFFKJS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- 229930009668 farnesene Natural products 0.000 claims abstract description 34
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 29
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 21
- 239000006229 carbon black Substances 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 abstract description 32
- 238000013329 compounding Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000006087 Silane Coupling Agent Substances 0.000 description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 description 9
- JSNRRGGBADWTMC-QINSGFPZSA-N (E)-beta-Farnesene Natural products CC(C)=CCC\C(C)=C/CCC(=C)C=C JSNRRGGBADWTMC-QINSGFPZSA-N 0.000 description 7
- YSNRTFFURISHOU-UHFFFAOYSA-N beta-farnesene Natural products C=CC(C)CCC=C(C)CCC=C(C)C YSNRTFFURISHOU-UHFFFAOYSA-N 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- JXBSHSBNOVLGHF-UHFFFAOYSA-N 10-cis-Dihydrofarnesen Natural products CC=C(C)CCC=C(C)CCC=C(C)C JXBSHSBNOVLGHF-UHFFFAOYSA-N 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 229920003049 isoprene rubber Polymers 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 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 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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)
Abstract
Description
本発明は、低転がり抵抗性およびウェット性能と、耐摩耗性とのバランスを従来レベル以上に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 a tire tread in which the balance between low rolling resistance and wet performance and wear resistance is improved to a level higher than conventional levels.
近年、空気入りタイヤに求められる性能は多岐にわたり、自動車の燃費性能を向上するため転がり抵抗を小さくすること、湿潤路面を走行するときの操縦安定性（ウェット性能）や耐摩耗性を高くすること等が求められている。低転がり抵抗性およびウェット性能を両立するためタイヤトレッド用ゴム組成物にシリカを配合することが行われている。しかしカーボンブラックの代わりにシリカを多量に配合すると、ゴム組成物の引張り破断特性が低下して耐摩耗性が悪化するという問題があった。 In recent years, the performance demanded of pneumatic tires has varied, and in order to improve the fuel efficiency of automobiles, the rolling resistance is reduced, and the driving stability (wet performance) and wear resistance when driving on wet road surfaces are increased. Etc. are required. In order to achieve both low rolling resistance and wet performance, silica is blended with a rubber composition for a tire tread. However, when a large amount of silica is blended in place of carbon black, there is a problem that the tensile rupture property of the rubber composition is lowered and the wear resistance is deteriorated.
特許文献１は、タイヤ用ゴム組成物にシリカとともに特定のシランカップリング剤およびアルキルトリエトキシシランを配合することを提案する。このゴム組成物は、低転がり抵抗性およびウェット性能を改良することができるが、耐摩耗性を改良するには至っていなかった。 Patent Document 1 proposes that a specific silane coupling agent and alkyltriethoxysilane are blended with a silica in a tire rubber composition. This rubber composition can improve the low rolling resistance and the wet performance, but has not yet improved the wear resistance.
本発明の目的は、低転がり抵抗性およびウェット性能と、耐摩耗性とのバランスを従来レベル以上に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 the balance between low rolling resistance and wet performance and wear resistance is improved to a level higher than the conventional level.
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、ジエン系ゴム１００重量部に対し、カーボンブラックを３〜２０重量部、シリカを６０〜１５０重量部、ファルネセン重合体を２〜１０重量部、炭素数３〜２０のアルキル基を有するアルキルトリエトキシシランを０．５〜８重量部配合するとともに、前記ファルネセン重合体およびアルキルトリエトキシシランの合計が２．５〜１８重量部であることを特徴とする。 The rubber composition for a tire tread of the present invention that achieves the above object is 3 to 20 parts by weight of carbon black, 60 to 150 parts by weight of silica, and 2 to 10 parts by weight of farnesene polymer with respect to 100 parts by weight of diene rubber. And 0.5 to 8 parts by weight of alkyltriethoxysilane having an alkyl group having 3 to 20 carbon atoms, and the total of the farnesene polymer and alkyltriethoxysilane is 2.5 to 18 parts by weight It is characterized by.
本発明のタイヤトレッド用ゴム組成物は、ジエン系ゴムに、カーボンブラック、シリカ、ファルネセン重合体およびアルキルトリエトキシシランを配合し、ファルネセン重合体およびアルキルトリエトキシシランの合計を限定するようにしたので、低転がり抵抗性およびウェット性能を高いレベルで両立しながら、耐摩耗を従来レベル以上に向上することができる。 In the tire tread rubber composition of the present invention, carbon black, silica, farnesene polymer and alkyltriethoxysilane are blended with diene rubber, and the total of farnesene polymer and alkyltriethoxysilane is limited. In addition, the wear resistance can be improved to a level higher than the conventional level while achieving both low rolling resistance and wet performance at a high level.
本発明のタイヤトレッド用ゴム組成物を、キャップトレッドに使用した空気入りタイヤは、低転がり抵抗性およびウェット性能を高いレベルで両立しながら、耐摩耗を従来レベル以上に向上することができる。 The pneumatic tire using the rubber composition for a tire tread of the present invention for a cap tread can improve wear resistance to a level higher than the conventional level while achieving both low rolling resistance and wet performance at a high level.
本発明のタイヤトレッド用ゴム組成物において、ゴム成分はジエン系ゴムからなる。ジエン系ゴムとして、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、アクリロニトリル−ブタジエンゴム、クロロプレンゴム、ブチルゴム、ニトリルゴム等を例示することができる。なかでもスチレンブタジエンゴム、ブタジエンゴム、天然ゴム、イソプレンゴムが好ましい。これらのジエン系ゴムは、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 rubber composition for a tire tread of the present invention, the rubber component is a diene rubber. Examples of the diene rubber include natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, and nitrile rubber. Of these, styrene butadiene rubber, butadiene rubber, natural rubber, and isoprene rubber are preferable. These diene rubbers can be used alone or as any blend.
ジエン系ゴムとしてスチレンブタジエンゴムを主成分にすることが好ましく、ジエン系ゴム１００重量％中、スチレンブタジエンゴムを好ましくは５０重量％以上、より好ましくは６０〜１００重量％含有するとよい。スチレンブタジエンゴムを主成分にすることにより、低転がり抵抗性およびウェット性能を高いレベルで兼備することができる。 As the diene rubber, a styrene butadiene rubber is preferably used as a main component, and the styrene butadiene rubber is preferably contained in an amount of 50% by weight or more, more preferably 60 to 100% by weight in 100% by weight of the diene rubber. By using styrene-butadiene rubber as a main component, low rolling resistance and wet performance can be combined at a high level.
スチレンブタジエンゴムとしては、例えば溶液重合スチレンブタジエンゴム（Ｓ−ＳＢＲ）、乳化重合スチレンブタジエンゴム（Ｅ−ＳＢＲ）、末端変性Ｓ−ＳＢＲ等を例示することができる。 Examples of the styrene butadiene rubber include solution polymerized styrene butadiene rubber (S-SBR), emulsion polymerized styrene butadiene rubber (E-SBR), and terminal-modified S-SBR.
ジエン系ゴムとしてブタジエンゴムを含むことが好ましく、耐摩耗性をより高くすることができる。 It is preferable to include butadiene rubber as the diene rubber, and the wear resistance can be further increased.
またジエン系ゴムとしてファルネセン重合体と親和性が高い天然ゴム、イソプレンゴムを含むことが好ましく、ゴム強度を高くすることができる。 The diene rubber preferably contains natural rubber or isoprene rubber having a high affinity with the farnesene polymer, so that the rubber strength can be increased.
本発明のタイヤトレッド用ゴム組成物は、カーボンブラックを配合することにより、耐摩耗性を高くする。カーボンブラックの配合量は、ジエン系ゴム１００重量に対し３〜２０重量部、好ましくは５〜１５重量部である。カーボンブラックの配合量が３重量部未満であると、ゴム組成物の補強性が十分に得られず、耐摩耗性が不足する。またカーボンブラックの配合量が２０重量部を超えると、転がり抵抗が大きくなる。 The rubber composition for a tire tread of the present invention increases wear resistance by blending carbon black. The compounding quantity of carbon black is 3-20 weight part with respect to 100 weight of diene rubber, Preferably it is 5-15 weight part. When the blending amount of carbon black is less than 3 parts by weight, the rubber composition cannot be sufficiently reinforced and the wear resistance is insufficient. If the blending amount of carbon black exceeds 20 parts by weight, rolling resistance increases.
本発明で使用するカーボンブラックは、窒素吸着比表面積Ｎ2ＳＡが好ましくは１００〜１７０ｍ2／ｇ、より好ましくは１３０〜１６０ｍ2／ｇであるとよい。Ｎ2ＳＡが１００ｍ2／ｇ未満であると、ゴム組成物の引張り破断特性、動的弾性率などの機械的特性が低下し、耐摩耗性が不足する虞がある。Ｎ2ＳＡが１７０ｍ2／ｇを超えると、転がり抵抗が大きくなる。Ｎ2ＳＡは、ＪＩＳ Ｋ６２１７−２に準拠して、測定するものとする。 The carbon black used in the present invention has a nitrogen adsorption specific surface area N 2 SA of preferably 100 to 170 m 2 / g, more preferably 130 to 160 m 2 / g. If N 2 SA is less than 100 m 2 / g, mechanical properties such as tensile rupture properties and dynamic elastic modulus of the rubber composition are lowered, and there is a possibility that the wear resistance is insufficient. When N 2 SA exceeds 170 m 2 / g, rolling resistance increases. N 2 SA shall be measured according to JIS K6217-2.
タイヤトレッド用ゴム組成物には、シリカを配合することにより、低転がり抵抗性およびウェット性能を両立する。シリカのＣＴＡＢ比表面積は好ましくは１４０〜２１０ｍ2／ｇ、より好ましくは１４０〜１６０ｍ2／ｇにするとよい。ＣＴＡＢ比表面積が１４０ｍ2／ｇ未満であると、ウェット性能が不足する。またＣＴＡＢ比表面積が２１０ｍ2／ｇを超えると、シリカの分散性が悪化し、耐摩耗性が低下する。シリカのＣＴＡＢ比表面積は、ＩＳＯ ５７９４により測定された値とする。 By incorporating silica into the tire tread rubber composition, both low rolling resistance and wet performance are achieved. The CTAB specific surface area of silica is preferably 140 to 210 m 2 / g, more preferably 140 to 160 m 2 / g. When the CTAB specific surface area is less than 140 m 2 / g, the wet performance is insufficient. On the other hand, when the CTAB specific surface area exceeds 210 m 2 / g, the dispersibility of silica deteriorates and the wear resistance decreases. The CTAB specific surface area of silica is a value measured according to ISO 5794.
本発明において、シリカの配合量は、ジエン系ゴム１００重量部に対し６０〜１５０重量部、好ましくは７０〜１２０重量部、より好ましくは７０〜１００重量部である。シリカの配合量が６０重量部未満であると、転がり抵抗を小さくしウェット性能を改良する効果が十分に得られない。またシリカの配合量が１５０重量部を超えると、耐摩耗性が低下すると共に転がり抵抗が大きくなる。 In this invention, the compounding quantity of a silica is 60-150 weight part with respect to 100 weight part of diene rubbers, Preferably it is 70-120 weight part, More preferably, it is 70-100 weight part. When the amount of silica is less than 60 parts by weight, the effect of reducing rolling resistance and improving wet performance cannot be obtained sufficiently. On the other hand, when the amount of silica exceeds 150 parts by weight, the wear resistance is lowered and the rolling resistance is increased.
本発明において、カーボンブラックおよびシリカを含む無機充填剤の配合量の合計は、特に制限されるものではないが、好ましくはジエン系ゴム１００重量部に対し６５〜１６０重量部、より好ましくは７０〜１３０重量部であるとよい。カーボンブラックおよびシリカを含む無機充填剤の合計が６５重量部未満であると、耐摩耗性およびウェット性能が不足する虞がある。またカーボンブラックおよびシリカを含む無機充填剤の合計が１６０重量部を超えると、転がり抵抗が大きくなる虞がある。 In the present invention, the total amount of the inorganic filler containing carbon black and silica is not particularly limited, but it is preferably 65 to 160 parts by weight, more preferably 70 to 100 parts by weight with respect to 100 parts by weight of the diene rubber. It may be 130 parts by weight. When the total amount of inorganic fillers including carbon black and silica is less than 65 parts by weight, wear resistance and wet performance may be insufficient. If the total amount of inorganic fillers containing carbon black and silica exceeds 160 parts by weight, rolling resistance may increase.
本発明では、シリカと共にシランカップリング剤を配合するとよい。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向上し、低転がり抵抗性およびウェット性能を改良する作用を高めることができる。 In this invention, it is good to mix | blend a silane coupling agent with a silica. By compounding a silane coupling agent, it is possible to improve the dispersibility of silica with respect to the diene rubber, and to enhance the action of improving low rolling resistance and wet performance.
シランカップリング剤の種類は、シリカ配合のゴム組成物に使用可能なものであれば特に制限されるものではないが、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の硫黄含有シランカップリング剤を例示することができる。 The type of the silane coupling agent is not particularly limited as long as it can be used for the rubber composition containing silica. For example, bis- (3-triethoxysilylpropyl) tetrasulfide, bis (3- Sulfur-containing silane coupling agents such as (triethoxysilylpropyl) disulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, γ-mercaptopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane can be exemplified. .
シランカップリング剤の配合量は、シリカの重量に対し、好ましくは３〜１５重量％を配合すると良く、より好ましくは５〜１０重量％にすると良い。シランカップリング剤の配合量がシリカ配合量の３重量％未満であるとシリカの分散を十分に改良することができない虞がある。シランカップリング剤の配合量がシリカ配合量の１５重量％を超えるとシランカップリング剤同士が縮合し、ゴム組成物における所望の硬度や強度を得ることができない。 The compounding amount of the silane coupling agent is preferably 3 to 15% by weight, more preferably 5 to 10% by weight, based on the weight of silica. If the compounding amount of the silane coupling agent is less than 3% by weight of the silica compounding amount, the silica dispersion may not be improved sufficiently. When the compounding amount of the silane coupling agent exceeds 15% by weight of the silica compounding amount, the silane coupling agents condense and the desired hardness and strength in the rubber composition cannot be obtained.
本発明のタイヤトレッド用ゴム組成物は、炭素数３〜２０のアルキル基を有するアルキルトリエトキシシランを配合することにより、シリカの凝集や、ゴム組成物の粘度上昇を抑制し、低転がり抵抗性、ウェット性能および耐摩耗性をより優れたものにすることができる。 The rubber composition for a tire tread of the present invention, by blending an alkyltriethoxysilane having an alkyl group having 3 to 20 carbon atoms, suppresses silica aggregation and viscosity increase of the rubber composition, and has low rolling resistance. In addition, wet performance and wear resistance can be further improved.
アルキルトリエトキシシランは、炭素数３〜２０、好ましくは炭素数７〜２０のアルキル基を有する。炭素数３〜２０のアルキル基として、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基が挙げられる。なかでもジエン系ゴムとの相溶性の観点から、炭素数８〜１０のアルキル基がより好ましく、オクチル基、ノニル基がさらに好ましい。 The alkyltriethoxysilane has an alkyl group having 3 to 20 carbon atoms, preferably 7 to 20 carbon atoms. As an alkyl group having 3 to 20 carbon atoms, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group Group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group. Among these, from the viewpoint of compatibility with the diene rubber, an alkyl group having 8 to 10 carbon atoms is more preferable, and an octyl group and a nonyl group are further preferable.
アルキルトリエトキシシランの配合量は、ジエン系ゴム１００重量部に対し０．５〜８重量部、より好ましくは２〜６重量部である。アルキルトリエトキシシランの配合量が０．５重量部未満であると、転がり抵抗が大きくなり耐摩耗性が低下する。またアルキルトリエトキシシランの配合量が８重量部を超えると、転がり抵抗が大きくなり耐摩耗性が低下する。 The compounding amount of the alkyltriethoxysilane is 0.5 to 8 parts by weight, more preferably 2 to 6 parts by weight with respect to 100 parts by weight of the diene rubber. When the blending amount of the alkyltriethoxysilane is less than 0.5 parts by weight, the rolling resistance increases and the wear resistance decreases. On the other hand, if the amount of alkyltriethoxysilane exceeds 8 parts by weight, rolling resistance increases and wear resistance decreases.
本発明のタイヤトレッド用ゴム組成物は、ファルネセン重合体を配合することにより、転がり抵抗を小さくし、耐摩耗性を高くすることができる。ファルネセン重合体は、ジエン系ゴムとの親和性が高く、かつ常温からタイヤトレッド用ゴム組成物の加工温度において液状で浸透性に優れることから、シリカの分散性を改良することができる。またファルネセン重合体は、比較的高分子量であるとともに架橋性構造を有するため、加硫後にタイヤトレッド用ゴム組成物の引張り破断特性を従来レベル以上に高くし、耐摩耗性を改良することができる。 The rubber composition for a tire tread of the present invention can reduce rolling resistance and increase wear resistance by blending a farnesene polymer. The farnesene polymer has a high affinity with the diene rubber, and is liquid and excellent in permeability from the normal temperature to the processing temperature of the rubber composition for a tire tread. Therefore, the dispersibility of silica can be improved. In addition, since the farnesene polymer has a relatively high molecular weight and a crosslinkable structure, the tensile rupture characteristics of the rubber composition for tire treads after vulcanization can be increased to a level higher than conventional levels, and the wear resistance can be improved. .
ファルネセン重合体とは、α−ファルネセンの重合体、β−ファルネセンの重合体またはα−ファルネセンおよびβ−ファルネセンの共重合体であり、好ましくはβ−ファルネセンの重合体であるとよい。またファルネセンの重合体は、α−ファルネセンおよび／またはβ−ファルネセンを由来とする構成単位が、好ましくは９０重量％以上、より好ましくは９５重量％以上、より好ましくは１００重量％であり、ブタジエン、イソプレン等の他のモノマー由来の構成単位を含んでもよい。 The farnesene polymer is a polymer of α-farnesene, a polymer of β-farnesene or a copolymer of α-farnesene and β-farnesene, and preferably a polymer of β-farnesene. Further, the polymer of farnesene has a constitutional unit derived from α-farnesene and / or β-farnesene, preferably 90% by weight or more, more preferably 95% by weight or more, more preferably 100% by weight, butadiene, A structural unit derived from another monomer such as isoprene may be included.
ファルネセン重合体の配合量は、ジエン系ゴム１００重量部に対し、２〜１０重量部、好ましくは２〜７重量部である。ファルネセン重合体の配合量が２重量部未満であると、低転がり抵抗性および耐摩耗性を改良する効果が十分に得られない。またファルネセン重合体の配合量が１０重量部を超えると、ウェット性能が低下する。 The blending amount of the farnesene polymer is 2 to 10 parts by weight, preferably 2 to 7 parts by weight with respect to 100 parts by weight of the diene rubber. If the blending amount of the farnesene polymer is less than 2 parts by weight, the effect of improving the low rolling resistance and wear resistance cannot be obtained sufficiently. Moreover, when the compounding quantity of a farnesene polymer exceeds 10 weight part, wet performance will fall.
ファルネセン重合体の重量平均分子量は、特に制限されるものではないが、好ましくは２０００〜２５０００、より好ましくは２５００〜２００００であるとよい。ファルネセン重合体の重量平均分子量が２０００未満であると、ゴム組成物のゴム硬度が低下し、さらにゴム組成物からブリードアウトしやすくなる。またファルネセン重合体の重量平均分子量が２５０００を超えると加工性が悪化する。 The weight average molecular weight of the farnesene polymer is not particularly limited, but is preferably 2000 to 25000, more preferably 2500 to 20000. When the weight average molecular weight of the farnesene polymer is less than 2,000, the rubber hardness of the rubber composition is lowered, and further, bleeding out from the rubber composition becomes easy. Moreover, when the weight average molecular weight of a farnesene polymer exceeds 25000, workability will deteriorate.
ファルネセン重合体の分子量分布（Ｍｗ／Ｍｎ；Ｍｗは重量平均分子量、Ｍｎは数平均分子量）は、好ましくは１．０〜２．０、より好ましくは１．０〜１．５、さらに好ましくは１．０〜１．３であるとよい。ファルネセン重合体の分子量分布がこのような範囲内であると、粘度のばらつきが小さくなる。本明細書においてファルネセン重合体の重量平均分子量Ｍｗおよび数平均分子量Ｍｎは、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により測定し標準ポリスチレン換算により求めるものとする。 The molecular weight distribution of the farnesene polymer (Mw / Mn; Mw is the weight average molecular weight, Mn is the number average molecular weight) is preferably 1.0 to 2.0, more preferably 1.0 to 1.5, and even more preferably 1. It is good that it is .0 to 1.3. When the molecular weight distribution of the farnesene polymer is within such a range, variation in viscosity is reduced. In the present specification, the weight average molecular weight Mw and the number average molecular weight Mn of the farnesene polymer are measured by GPC (gel permeation chromatography) and determined by standard polystyrene conversion.
ファルネセン重合体の溶融粘度は、好ましくは０．１〜３．５Ｐａ・ｓ、より好ましくは０．１〜２Ｐａ・ｓ、さらに好ましくは０．１〜１．５Ｐａ・ｓであるとよい。ファルネセン重合体の溶融粘度がこのような範囲内であると、ゴム組成物の混練が容易になりシリカの分散性が向上する。本明細書において、ファルネセン重合体の溶融粘度は、ブルックフィールド型粘度計により測定した３８℃における溶融粘度である。 The melt viscosity of the farnesene polymer is preferably 0.1 to 3.5 Pa · s, more preferably 0.1 to 2 Pa · s, and still more preferably 0.1 to 1.5 Pa · s. When the melt viscosity of the farnesene polymer is within such a range, the rubber composition is easily kneaded and the dispersibility of silica is improved. In this specification, the melt viscosity of the farnesene polymer is a melt viscosity at 38 ° C. measured by a Brookfield viscometer.
ファルネセン重合体は、通常の方法で合成することができ、例えば乳化重合法、溶液重合法を例示することができ、好ましくは溶液重合法で合成するとよい。 The farnesene polymer can be synthesized by an ordinary method, and examples thereof include an emulsion polymerization method and a solution polymerization method, and preferably a synthesis by a solution polymerization method.
本発明において、ファルネセン重合体の配合量Ａ（重量部）およびアルキルトリエトキシシランの配合量Ｂ（重量部）の合計（Ａ＋Ｂ）は、ジエン系ゴム１００重量部に対し２．５〜１８重量部、好ましくは５〜１５重量部である。ファルネセン重合体およびアルキルトリエトキシシランの合計（Ａ＋Ｂ）が２．５重量部未満であると、転がり抵抗を小さくし耐摩耗性を高くする効果が十分に得られない。また両者の合計（Ａ＋Ｂ）が１８重量部を超えると、ウェット性能が低下する。 In the present invention, the total amount (A + B) of the blending amount A (parts by weight) of the farnesene polymer and the blending amount B (parts by weight) of the alkyltriethoxysilane is 2.5 to 18 parts by weight with respect to 100 parts by weight of the diene rubber. The amount is preferably 5 to 15 parts by weight. When the sum of the farnesene polymer and the alkyltriethoxysilane (A + B) is less than 2.5 parts by weight, the effect of reducing the rolling resistance and increasing the wear resistance cannot be obtained sufficiently. On the other hand, if the total (A + B) of both exceeds 18 parts by weight, the wet performance decreases.
本発明のタイヤトレッド用ゴム組成物には、加硫又は架橋剤、加硫促進剤、各種オイル、老化防止剤、可塑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。本発明のタイヤトレッド用ゴム組成物は、通常のゴム用混練機械、例えば、バンバリーミキサー、ニーダー、ロール等を使用して、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。 The tire tread rubber composition of the present invention includes various additives generally used in tire rubber compositions such as vulcanization or crosslinking agents, vulcanization accelerators, various oils, anti-aging agents, and plasticizers. These additives can be compounded and kneaded by a general method to form a rubber composition, which can be vulcanized or crosslinked. 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 the above components using a normal 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、空気入りタイヤにおけるキャップトレッドに好適に使用することができ、低転がり抵抗性およびウェット性能と、耐摩耗性とのバランスを優れたものにすることができる。 The rubber composition for a tire tread of the present invention can be suitably used for a cap tread in a pneumatic tire, and can have an excellent balance between low rolling resistance and wet performance and wear resistance. .
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３に示す配合剤を共通配合とし、表１，２に示す配合からなる１３種類のゴム組成物（実施例１〜５、比較例１〜８）を調製するに当たり、それぞれ硫黄及び加硫促進剤を除く成分を秤量し、１.８Ｌの密閉型ミキサーで５分間混練した後、その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の密閉型ミキサーに供し、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得た。なお、表１，２において、変性Ｓ−ＳＢＲおよびＥ−ＳＢＲは油展品であるため、正味のゴム量を括弧内に併記した。また、表３の共通成分の配合量は、表１，２に示すジエン系ゴム１００重量部に対する重量部として記載した。 In preparing 13 kinds of rubber compositions (Examples 1 to 5 and Comparative Examples 1 to 8) having the composition shown in Tables 1 and 2 with the compounding agents shown in Table 3 as common formulations, sulfur and vulcanization acceleration were respectively used. The components excluding the agent were weighed and kneaded for 5 minutes with a 1.8 L closed mixer, and then the master batch was discharged and cooled at room temperature. This master batch was subjected to a 1.8 L closed mixer, and sulfur and a vulcanization accelerator were added and mixed to obtain a rubber composition for a tire tread. In Tables 1 and 2, since the modified S-SBR and E-SBR are oil-extended products, the net rubber amount is shown in parentheses. Moreover, the compounding quantity of the common component of Table 3 was described as a weight part with respect to 100 weight part of diene rubber shown to Table 1,2.
得られた１３種類のゴム組成物を所定の金型中で、１７０℃で１０分間プレス加硫してタイヤトレッド用ゴム組成物からなる加硫ゴムサンプルを作成した。得られた加硫ゴムサンプルを用いて、転がり抵抗（６０℃のｔａｎδ）を下記に示す方法により評価した。 Thirteen kinds of the obtained rubber compositions were press vulcanized at 170 ° C. for 10 minutes in a predetermined mold to prepare a vulcanized rubber sample comprising a rubber composition for a tire tread. Using the obtained vulcanized rubber samples, rolling resistance (tan δ at 60 ° C.) was evaluated by the method shown below.
転がり抵抗
得られた加硫ゴムサンプルの転がり抵抗を、発熱性の指標であることが知られている損失正接ｔａｎδ（６０℃）により評価した。ｔａｎδ（６０℃）は、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、温度６０℃の条件下で測定した。得られた結果は比較例１の値の逆数を１００とする指数として、表１，２に示した。ｔａｎδ（６０℃）の指数が大きいほど、特に指数が１０２以上であると、発熱が小さく空気入りタイヤにしたとき転がり抵抗が小さく燃費性能が優れることを意味する。
Rolling resistance The rolling resistance of the obtained vulcanized rubber samples was evaluated by a loss tangent tan δ (60 ° C.), which is known to be an index of heat generation. Tan δ (60 ° C.) was measured using a viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho under the conditions of an initial strain of 10%, an amplitude of ± 2%, a frequency of 20 Hz, and a temperature of 60 ° C. The obtained results are shown in Tables 1 and 2 as indices with the reciprocal of the value of Comparative Example 1 as 100. When the index of tan δ (60 ° C.) is larger, particularly when the index is 102 or more, it means that heat generation is small and rolling resistance is small when a pneumatic tire is used, and fuel efficiency is excellent.
得られた１３種類のゴム組成物をキャップトレッドに用いたサイズ（２２５／４０Ｒ１８）の空気入りタイヤを加硫成形した。それぞれの空気入りタイヤを用いて、ウェット性能および耐摩耗性を下記に示す方法により評価した。 A pneumatic tire having a size (225 / 40R18) using the obtained 13 kinds of rubber compositions as a cap tread was vulcanized. Using each pneumatic tire, wet performance and wear resistance were evaluated by the following methods.
ウェット性能
得られた空気入りタイヤをリムサイズ１８×８ＪＪのホイールに組付け、国産２．５リットルクラスの試験車両に装着し、空気圧２３０ｋＰａの条件で湿潤路面からなる１周２．６ｋｍのテストコースを実車走行させ、そのときの操縦安定性を専門パネラー３名による感応評価により採点した。得られた結果は比較例１を１００とする指数として、表１，２に示した。この指数が大きいほど、特に指数が１０２以上であると、湿潤路面におけるウェット操縦安定性が優れていることを意味する。
Wet performance The obtained pneumatic tire is assembled to a wheel with a rim size of 18 x 8 JJ, mounted on a domestic 2.5 liter class test vehicle, and a test course of 2.6 km per lap consisting of a wet road surface under the condition of air pressure 230 kPa. The vehicle was run, and the handling stability at that time was scored by a sensitive evaluation by three expert panelists. The obtained results are shown in Tables 1 and 2 as an index with Comparative Example 1 as 100. It means that the wet steering stability on a wet road surface is excellent when the index is larger, particularly when the index is 102 or more.
耐摩耗性
得られた空気入りタイヤをリムサイズ１８×８ＪＪのホイールに組付け、空気圧２３０ｋＰａを充填し国産２．５リットルクラスの試験車両に装着し、テストコースの１周５ｋｍの周回路の乾燥路面を速度８０ｋｍ／時で連続して１０周走行した。その後トレッド面における摩耗の状態を目視により観察し、比較例１を１００として点数付け評価した。得られた結果を表１，２に示した。評価の値が大きいほど耐摩耗性が良いことを示す。
Abrasion resistance The obtained pneumatic tire is assembled on a wheel with a rim size of 18 x 8 JJ, filled with air pressure of 230 kPa and mounted on a domestic 2.5 liter class test vehicle. For 10 laps continuously at a speed of 80 km / h. Thereafter, the state of wear on the tread surface was visually observed, and Comparative Example 1 was scored as 100. The obtained results are shown in Tables 1 and 2. It shows that abrasion resistance is so good that the value of evaluation is large.
なお、表１、２において使用した原材料の種類を下記に示す。
変性Ｓ−ＳＢＲ：末端変性された溶液重合スチレンブタジエンゴム、旭化成ケミカルズ社製Ｅ５８１、正味のゴム成分１００重量部に対し３７．５重量部の油展成分を含む油展品
Ｅ−ＳＢＲ：乳化重合スチレンブタジエンゴム、日本ゼオン社製Ｎｉｐｏｌ １７３９、正味のゴム成分１００重量部に対し３７．５重量部の油展成分を含む油展品
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：東海カーボン社製シーストＫＨ、窒素吸着比表面積が９０ｍ2／ｇ
シリカ：ローディア社製Ｚｅｏｘｉｌ １１６５ＭＰ、ＣＴＡＢ比表面積が１６０ｍ2／ｇ
カップリング剤：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、エボニックデグサ社製Ｓｉ６９
ファルネセン１：下記の合成例１により重合されたβ−ファルネセンの重合体、重量平均分子量が１４００００、分子量分布が１．２、溶融粘度が６９Ｐａ・ｓ
アルキルシラン：オクチルトリエトキシシラン、信越化学工業社製ＫＢＥ−３０８３
The types of raw materials used in Tables 1 and 2 are shown below.
Modified S-SBR: terminal-modified solution-polymerized styrene butadiene rubber, E581 manufactured by Asahi Kasei Chemicals Co., Ltd., oil-extended product E-SBR: emulsion-polymerized styrene containing 37.5 parts by weight of an oil-extended component with respect to 100 parts by weight of the net rubber component Butadiene rubber, Nipol 1739 manufactured by Nippon Zeon Co., Ltd. Oil-extended product BR containing 37.5 parts by weight of oil-extended component with respect to 100 parts by weight of the net rubber component: Butadiene rubber, Nipol BR1220 manufactured by Nippon Zeon Co., Ltd.
Carbon black: Seast KH manufactured by Tokai Carbon Co., Ltd., with a nitrogen adsorption specific surface area of 90 m 2 / g
Silica: Rhodia Zeoxil 1165MP, CTAB specific surface area of 160 m 2 / g
Coupling agent: bis- (3-triethoxysilylpropyl) tetrasulfide, Si69 manufactured by Evonik Degussa
Farnesene 1: β-farnesene polymer polymerized in Synthesis Example 1 below, weight average molecular weight of 140,000, molecular weight distribution of 1.2, melt viscosity of 69 Pa · s
Alkylsilane: Octyltriethoxysilane, Shin-Etsu Chemical Co., Ltd. KBE-3083
合成例１（ファルネセン１の重合）
窒素置換し、乾燥させた耐圧容器に、ヘキサン２７４ｇ、ｎ−ブチルリチウム（１７重量％ヘキサン溶液）１．２ｇを仕込み、５０℃に昇温した後、β−ファルネセン２７２ｇを加えて１時間重合した。得られた重合反応液にメタノールを添加後、重合反応液を水で洗浄した。水を分離して、重合反応液を７０℃で１２時間乾燥することにより、β−ファルネセンの重合体（ファルネセン１）を得た。
Synthesis example 1 (polymerization of farnesene 1)
In a pressure vessel that was purged with nitrogen and dried, 274 g of hexane and 1.2 g of n-butyllithium (17 wt% hexane solution) were charged, and the temperature was raised to 50 ° C., followed by addition of 272 g of β-farnesene and polymerization for 1 hour. . After adding methanol to the obtained polymerization reaction solution, the polymerization reaction solution was washed with water. Water was separated, and the polymerization reaction solution was dried at 70 ° C. for 12 hours to obtain a β-farnesene polymer (farnesene 1).
なお、表３において使用した原材料の種類を下記に示す。
アロマオイル：昭和シェル石油社製エキストラクト４号Ｓ
ステアリン酸：千葉脂肪酸社製ビーズステアリン酸
老化防止剤：住友化学社製アンチゲン６Ｃ
ワックス：大内新興化学工業社製サンノック
酸化亜鉛：正同化学工業社製酸化亜鉛３種
硫黄：鶴見化学工業社製金華印油入微粉硫黄（硫黄の含有量が９５．２４重量％）
加硫促進剤１：大内新興化学工業社製ノクセラーＣＺ−Ｇ
加硫促進剤２：大内新興化学工業社製ノクセラーＤ
In addition, the kind of raw material used in Table 3 is shown below.
Aroma oil: Showa Shell Sekiyu Extract 4 S
Stearic acid: Chiba Fatty Acid Co., Ltd. Beads stearic acid anti-aging agent: Sumitomo Chemical Antigen 6C
Wax: Sannok Zinc Oxide manufactured by Ouchi Shinsei Chemical Industry Co., Ltd .: Zinc Oxide 3 types produced by Shodo Chemical Industry Co., Ltd.
Vulcanization accelerator 1: Noxeller CZ-G manufactured by Ouchi Shinsei Chemical Co., Ltd.
Vulcanization accelerator 2: Noxeller D made by Ouchi Shinsei Chemical Co., Ltd.
表１から明らかなように実施例１〜５のゴム組成物は、低転がり抵抗性、ウェット性能および耐摩耗性が従来レベル以上に向上することが確認された。 As is clear from Table 1, it was confirmed that the rubber compositions of Examples 1 to 5 were improved in the low rolling resistance, wet performance and wear resistance to the conventional level or more.
比較例１のゴム組成物は、ファルネセン重合体を配合しない基準となる配合である。
比較例２のゴム組成物は、カーボンブラックを配合しないので、耐摩耗性が悪化した。
比較例３のゴム組成物は、カーボンブラックを配合量が２０重量部を超えるので転がり抵抗が大きくなり、耐摩耗性が悪化した。
The rubber composition of Comparative Example 1 is a reference composition that does not contain a farnesene polymer.
Since the rubber composition of Comparative Example 2 did not contain carbon black, the wear resistance deteriorated.
In the rubber composition of Comparative Example 3, since the blending amount of carbon black exceeds 20 parts by weight, the rolling resistance is increased and the wear resistance is deteriorated.
比較例４のゴム組成物は、シリカの配合量が６０重量部未満であるのでウェット性能が悪化した。比較例５のゴム組成物は、シリカの配合量が１５０重量部を超えるので転がり抵抗が大きくなり、耐摩耗性が悪化した。 In the rubber composition of Comparative Example 4, the wet performance deteriorated because the compounding amount of silica was less than 60 parts by weight. In the rubber composition of Comparative Example 5, since the compounding amount of silica exceeded 150 parts by weight, the rolling resistance increased and the wear resistance deteriorated.
比較例６のゴム組成物は、アルキルトリエトキシシランを配合しないので、転がり抵抗が大きくなり、耐摩耗性が悪化した。
比較例７のゴム組成物は、アルキルトリエトキシシランの配合量が８重量部を超えるので転がり抵抗が大きくなり、耐摩耗性が悪化した。
比較例８のゴム組成物は、ファルネセン重合体およびアルキルトリエトキシシランの配合量の合計（Ａ＋Ｂ）が１８を超えるのでウェット性能が悪化した。
Since the rubber composition of Comparative Example 6 did not contain alkyltriethoxysilane, the rolling resistance increased and the wear resistance deteriorated.
In the rubber composition of Comparative Example 7, since the compounding amount of alkyltriethoxysilane exceeded 8 parts by weight, the rolling resistance increased and the wear resistance deteriorated.
In the rubber composition of Comparative Example 8, since the total amount (A + B) of the farnesene polymer and the alkyltriethoxysilane exceeds 18, the wet performance deteriorated.
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