JPS6397646A - Rubber composition for tire tread - Google Patents
Rubber composition for tire treadInfo
- Publication number
- JPS6397646A JPS6397646A JP24215386A JP24215386A JPS6397646A JP S6397646 A JPS6397646 A JP S6397646A JP 24215386 A JP24215386 A JP 24215386A JP 24215386 A JP24215386 A JP 24215386A JP S6397646 A JPS6397646 A JP S6397646A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- styrene
- weight
- butadiene copolymer
- parts
- 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.)
- Pending
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 57
- 239000005060 rubber Substances 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims description 20
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 23
- 239000006229 carbon black Substances 0.000 claims abstract description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001194 natural rubber Polymers 0.000 claims abstract description 9
- 238000010521 absorption reaction Methods 0.000 claims abstract description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000009826 distribution Methods 0.000 claims abstract description 7
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 6
- 244000043261 Hevea brasiliensis Species 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 3
- 239000012744 reinforcing agent Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 239000000446 fuel Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 4
- 229920001195 polyisoprene Polymers 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 229920003049 isoprene rubber Polymers 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 229940126062 Compound A Drugs 0.000 description 10
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 241000872198 Serjania polyphylla Species 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- JYGFTBXVXVMTGB-UHFFFAOYSA-N indolin-2-one Chemical compound C1=CC=C2NC(=O)CC2=C1 JYGFTBXVXVMTGB-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 description 2
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- -1 (2-naphthyllithium Chemical compound 0.000 description 1
- YBBLOADPFWKNGS-UHFFFAOYSA-N 1,1-dimethylurea Chemical compound CN(C)C(N)=O YBBLOADPFWKNGS-UHFFFAOYSA-N 0.000 description 1
- YLHUPYSUKYAIBW-UHFFFAOYSA-N 1-acetylpyrrolidin-2-one Chemical compound CC(=O)N1CCCC1=O YLHUPYSUKYAIBW-UHFFFAOYSA-N 0.000 description 1
- QYEMNJMSULGQRD-UHFFFAOYSA-N 1-methyl-2-quinolone Chemical compound C1=CC=C2C=CC(=O)N(C)C2=C1 QYEMNJMSULGQRD-UHFFFAOYSA-N 0.000 description 1
- RSQUAQMIGSMNNE-UHFFFAOYSA-N 1-methyl-3h-indol-2-one Chemical compound C1=CC=C2N(C)C(=O)CC2=C1 RSQUAQMIGSMNNE-UHFFFAOYSA-N 0.000 description 1
- GGYVTHJIUNGKFZ-UHFFFAOYSA-N 1-methylpiperidin-2-one Chemical compound CN1CCCCC1=O GGYVTHJIUNGKFZ-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZXLYYQUMYFHCLQ-UHFFFAOYSA-N 2-methylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(C)C(=O)C2=C1 ZXLYYQUMYFHCLQ-UHFFFAOYSA-N 0.000 description 1
- WLDMPODMCFGWAA-UHFFFAOYSA-N 3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione Chemical compound C1CCCC2C(=O)NC(=O)C21 WLDMPODMCFGWAA-UHFFFAOYSA-N 0.000 description 1
- QIKYZXDTTPVVAC-UHFFFAOYSA-N 4-Aminobenzamide Chemical compound NC(=O)C1=CC=C(N)C=C1 QIKYZXDTTPVVAC-UHFFFAOYSA-N 0.000 description 1
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 description 1
- QOVWSDOHZFBJSO-UHFFFAOYSA-N C=CC=C.C=CC=CC1=CC=CC=C1 Chemical compound C=CC=C.C=CC=CC1=CC=CC=C1 QOVWSDOHZFBJSO-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920004939 Cariflex™ Polymers 0.000 description 1
- 239000005065 High vinyl polybutadiene Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- QISSLHPKTCLLDL-UHFFFAOYSA-N N-Acetylcaprolactam Chemical compound CC(=O)N1CCCCCC1=O QISSLHPKTCLLDL-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- DFPAKSUCGFBDDF-ZQBYOMGUSA-N [14c]-nicotinamide Chemical compound N[14C](=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-ZQBYOMGUSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- TVFIYRKPCACCNL-UHFFFAOYSA-N furan-2-carboxamide Chemical compound NC(=O)C1=CC=CO1 TVFIYRKPCACCNL-UHFFFAOYSA-N 0.000 description 1
- BEBCJVAWIBVWNZ-UHFFFAOYSA-N glycinamide Chemical compound NCC(N)=O BEBCJVAWIBVWNZ-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QRWZCJXEAOZAAW-UHFFFAOYSA-N n,n,2-trimethylprop-2-enamide Chemical compound CN(C)C(=O)C(C)=C QRWZCJXEAOZAAW-UHFFFAOYSA-N 0.000 description 1
- GJTUWWUXLICYQX-UHFFFAOYSA-N n,n,n',n'-tetramethyloxamide Chemical compound CN(C)C(=O)C(=O)N(C)C GJTUWWUXLICYQX-UHFFFAOYSA-N 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- APRJFNLVTJWEPP-UHFFFAOYSA-M n,n-diethylcarbamate Chemical compound CCN(CC)C([O-])=O APRJFNLVTJWEPP-UHFFFAOYSA-M 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- IMNDHOCGZLYMRO-UHFFFAOYSA-N n,n-dimethylbenzamide Chemical compound CN(C)C(=O)C1=CC=CC=C1 IMNDHOCGZLYMRO-UHFFFAOYSA-N 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- FJEVKYZLIRAAKE-UHFFFAOYSA-N n,n-dimethylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC=CN=C1 FJEVKYZLIRAAKE-UHFFFAOYSA-N 0.000 description 1
- SLIKWWJXVUHCPJ-UHFFFAOYSA-N n-(dimethylazaniumyl)ethanimidate Chemical compound CN(C)NC(C)=O SLIKWWJXVUHCPJ-UHFFFAOYSA-N 0.000 description 1
- FHQADXALTZAVPY-UHFFFAOYSA-N n-acetyl-n-naphthalen-2-ylbenzamide Chemical compound C=1C=C2C=CC=CC2=CC=1N(C(=O)C)C(=O)C1=CC=CC=C1 FHQADXALTZAVPY-UHFFFAOYSA-N 0.000 description 1
- KBDYPDHUODKDRK-UHFFFAOYSA-N n-acetyl-n-phenylacetamide Chemical compound CC(=O)N(C(C)=O)C1=CC=CC=C1 KBDYPDHUODKDRK-UHFFFAOYSA-N 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- NCYVXEGFNDZQCU-UHFFFAOYSA-N nikethamide Chemical compound CCN(CC)C(=O)C1=CC=CN=C1 NCYVXEGFNDZQCU-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- CAZVNFHXWQYGPD-UHFFFAOYSA-N oxolane;potassium Chemical compound [K].C1CCOC1 CAZVNFHXWQYGPD-UHFFFAOYSA-N 0.000 description 1
- 229940012982 picot Drugs 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- JDVPQXZIJDEHAN-UHFFFAOYSA-N succinamic acid Chemical compound NC(=O)CCC(O)=O JDVPQXZIJDEHAN-UHFFFAOYSA-N 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明は、走行時のタイヤトレッド部の発熱が少なく、
低燃費性に優れ、しかも耐摩耗性と湿潤路面での制動性
および積雪・氷結路面での制動性を共に著しく改善した
、特に転がり抵抗性能に優れたトレッド用ゴム組成物に
関する。[Detailed Description of the Invention] [Technical Field of the Invention] The present invention provides a tire tread that generates less heat during driving,
The present invention relates to a rubber composition for a tread which is excellent in fuel efficiency, has significantly improved wear resistance, braking performance on wet road surfaces, and braking performance on snowy/icy road surfaces, and particularly has excellent rolling resistance performance.
近年、省資源、省エネルギーを目指す社会的要請のもと
に、自動車における低燃費性の要求が非常に高まってき
ている。このために、ガソリン消費の少ないエンジンの
開発など自動車本体の開発はもちろんのこと、エネルギ
ー損失の少ない低燃費タイヤの検討が急速に行われてき
た。In recent years, the demand for low fuel consumption in automobiles has increased significantly due to social demands for resource and energy conservation. For this reason, not only the development of automobiles themselves, such as engines that consume less gasoline, but also fuel-efficient tires that reduce energy loss have been rapidly investigated.
従来、低燃費タイヤのタイヤ材料用のゴムとしてヒステ
リシスロスの少ないゴム材料が求められ、なかでもタイ
ヤのヒステリシスロスの５０％以上を占めるといわれる
トレッド部には、ゴム成分としてヒステリシスロスの少
ない天然ゴム、ポリイソプレンゴム、ポリブタジェンゴ
ム、ガラス転移点（Ｔｇ ）の低いスチレン−ブタジエ
ン共重合体ゴム、およびこれらのブレンド物などが使用
されてきた。さらに、ゴム組成物としては、比較的粒子
径の大きいカーボンブランクを比較的少ない配合量で配
合し、かつ、アロマティックオイル等の軟化剤の配合量
もできるだけ少なくしたゴム組成物がこれまでは使用さ
れてきた。Conventionally, rubber materials with low hysteresis loss have been required as tire materials for fuel-efficient tires, and in particular, natural rubber with low hysteresis loss has been used as a rubber component in the tread section, which is said to account for more than 50% of the hysteresis loss in tires. , polyisoprene rubber, polybutadiene rubber, styrene-butadiene copolymer rubber with a low glass transition point (Tg), and blends thereof have been used. Furthermore, as for rubber compositions, rubber compositions that have been blended with a relatively small amount of carbon blank with a relatively large particle size and with as little amount of softeners such as aromatic oil as possible have been used up to now. It has been.
ところで、最近、タイヤに対してより多くの機能がいっ
そう高いレベルで求められるようになった。例えば、上
述のようにして開発された低燃費タイヤにおいて、その
低燃費性能を低下させることがなく、経済性の面からさ
らに優れた摩耗性能が、また、安全性の面からは湿潤路
面および積雪・氷結路面などの各種路面に対応できる高
い制動性能が強く望まれている。Incidentally, recently, tires have been required to have more functions at an even higher level. For example, the fuel-efficient tires developed as described above do not reduce their fuel-efficiency performance, have even better wear performance from an economic standpoint, and have better wear performance on wet roads and snow-covered roads from a safety standpoint.・High braking performance that can handle various road surfaces, including icy roads, is strongly desired.
しかし、上述したようにヒステリシスロスの少すい天然
ゴム、ポリイソプレンゴム、ポリブタジェンゴム、Ｔｇ
の低いスチレン−ブタジエン共重合体ゴムをトレンド部
に使用した場合には、特に湿潤路面での制動性（ウェッ
トスキッド抵抗性）が劣り、走行安定性が極端に低下し
てしまうという欠点があった。また、粒子径の大きなカ
ーボンブラックを使用した場合には、低燃費性能は優れ
るものの、湿潤路面での制動性および耐摩耗性といった
特性の低下が避けられなかった。さらに、これまでの低
燃費タイヤのトレッド部ゴムは、軟化剤の配合量を少な
くしているため低温になると硬くなり易く、このため積
雪や氷結した路面での制動性（アイスキッド抵抗性）も
十分に満足できるレベルには達していなかった。However, as mentioned above, natural rubber, polyisoprene rubber, polybutadiene rubber, Tg
When styrene-butadiene copolymer rubber with a low carbon content was used in the trend section, there was a drawback that the braking performance (wet skid resistance) was particularly poor on wet roads, resulting in an extremely low running stability. . Further, when carbon black with a large particle size is used, although the fuel efficiency performance is excellent, a decrease in properties such as braking performance on wet road surfaces and wear resistance is unavoidable. Furthermore, the tread rubber of conventional fuel-efficient tires contains a small amount of softener, so it tends to harden at low temperatures, which results in poor braking performance (ice skid resistance) on snowy or icy roads. It had not reached a level that was fully satisfactory.
一方、タイヤの低燃費性能とウェットスキッド抵抗性の
両特性を満足させる材料として、最近では１．２−ビニ
ル結合を５０％以上含有するいわゆる高ビニルポリブタ
ジェンゴムや高ビニルスチレン−ブタジエン共重合体ゴ
ムが提案されている。しかし、これらのゴムは、いずれ
も高いガラス転移点（Ｔｇ ）を有するため、耐摩耗性
に劣り、しかも低温で硬化し易く、積雪・氷結路面での
制動性能に著しく劣り、したがって上述したような全て
の特性を満たすにはやはり不十分である。On the other hand, recently, so-called high vinyl polybutadiene rubber containing 50% or more of 1,2-vinyl bonds and high vinyl styrene-butadiene copolymer rubber have been developed as materials that satisfy both the fuel efficiency and wet skid resistance characteristics of tires. A composite rubber has been proposed. However, all of these rubbers have a high glass transition point (Tg), so they have poor abrasion resistance, harden easily at low temperatures, and have significantly poor braking performance on snowy and icy roads. It is still insufficient to satisfy all the characteristics.
このように、現在では、低燃費性能、湿潤路面での高い
制動性、積雪・氷結路面での高い制動性といった特性を
全て満足するタイヤは提案されていない、特に、これま
では、路面が積雪や氷結のために滑り易くなる冬期にお
いては、低燃費タイヤを含む一般タイヤでは、これらの
路面における制動性が非常に小さく、スノータイヤの使
用を余儀なくされていた。しかし、使用者のタイヤ交換
にかける時間と手間はかなりのものであり、−ＦＩＱ夏
タイタイヤ記の３つの特性を満足するオールシーズン用
のタイヤの出現が非常に切望されている。As described above, currently no tire has been proposed that satisfies all of the characteristics of low fuel consumption, high braking performance on wet roads, and high braking performance on snowy and icy roads. In winter, when roads become slippery due to snow and ice, regular tires, including fuel-efficient tires, have very poor braking performance on these roads, forcing the use of snow tires. However, it takes a considerable amount of time and effort for users to change tires, and there is a strong desire for an all-season tire that satisfies the three characteristics of -FIQ summer tires.
本発明は、このような要求に応じるためになされたもの
であって、走行時のタイヤトレンド部の発熱が少なく、
低燃費性に優れ、しかも耐摩耗性と湿潤路面での制動性
および積雪・氷結路面での制動性を共に著しく改善した
、特に転がり抵抗性能に優れたトレッド用ゴム組成物を
・提供することを目的とする。この組成物は、夏冬を
問わず通期に亘って使用可能ないわゆるオールシーズン
用の空気入りタイヤのトレッド用として有用である。The present invention was made in order to meet these demands, and the present invention has been developed to reduce heat generation in the tire trend section during driving.
- To provide a rubber composition for a tread that is excellent in fuel efficiency, has significantly improved wear resistance and braking performance on wet road surfaces, and braking performance on snowy and icy roads, and has particularly excellent rolling resistance performance. purpose. This composition is useful as a tread for a so-called all-season pneumatic tire that can be used throughout the year, regardless of summer or winter.
Ｃ発明の構成〕
このため、本発明は、天然ゴムおよび／又はポリイソプ
レンゴム３０〜７０重量部、結合スチレン量が１０〜３
０重量％であってブタジェン部の１゜２−ビニル結合量
が３０〜８０％であるスチレン−ブタジエン共重合体ゴ
ム７０〜３０重量部含有し、ゴム分合計１００重量部で
あって、前記スチレン−ブタジエン共重合体ゴムには、
分子鎖末端或いは分子鎖中に下記式、
■
Ｃ−
−ｃ−Ｎ＜
０Ｈ（又はＳＨ）
で示される原子団が導入されており、補強剤として、比
表面積（ＮｚＳＡ）が７５〜９０ｒｒｒ／ｇ、ジブチル
フタレート吸油ｆ（Ｄ Ｂ Ｐ吸油量）が１００〜１５
０ ｍ／１００ｇ、遠心沈降法により測定される凝集体
分布の半値幅（ΔＤｓ ｔ）が６５〜９０ｍμであるカ
ーボンブランクを原料ゴム１００重量部に対し３０〜８
０重量部含有していることを特徴とするトレンド用ゴム
組成物を要旨とするものである。C Structure of the Invention] Therefore, the present invention uses 30 to 70 parts by weight of natural rubber and/or polyisoprene rubber and 10 to 3 parts by weight of bound styrene.
The styrene-butadiene copolymer rubber contains 70 to 30 parts by weight of 0% by weight and the amount of 1°2-vinyl bonds in the butadiene moiety is 30 to 80%, and the total rubber content is 100 parts by weight, and the styrene -Butadiene copolymer rubber has
An atomic group represented by the following formula: (1) C--c-N<0H (or SH) is introduced at the end of the molecular chain or into the molecular chain, and as a reinforcing agent, the specific surface area (NzSA) is 75 to 90rrr/g. , dibutyl phthalate oil absorption f (D B P oil absorption) is 100 to 15
0 m/100 g, and a carbon blank whose half width (ΔDs t) of aggregate distribution measured by centrifugal sedimentation is 65 to 90 mμ is added to 30 to 8 mμ per 100 parts by weight of raw rubber.
The gist of the present invention is a trendy rubber composition characterized in that it contains 0 parts by weight.
以下、本発明の構成について詳しく説明する。Hereinafter, the configuration of the present invention will be explained in detail.
（１） 本発明のトレッド用ゴム組成物は、天然ゴム
および／又はポリイソプレンゴム３０〜７０重量部と特
定のスチレン−ブタジエン共重合体ゴム７０〜３０重量
部含有するのである（ゴム分合計１００重量部）、この
範囲外の配合割合では、低燃費性、湿潤路面での制動性
、積雪・氷結路面での制動性のいずれかの特性が悪くな
るので好ましくないからである。ただし、他のジエン系
ゴム、例えば、ポリブタジェンゴム、アクリロニトリル
−ブタジェン共重合体ゴム、非変性スチレン−ブタジエ
ン共重合体ゴムなどを３０重量部以下含んでいてもよい
。(1) The rubber composition for a tread of the present invention contains 30 to 70 parts by weight of natural rubber and/or polyisoprene rubber and 70 to 30 parts by weight of a specific styrene-butadiene copolymer rubber (total rubber content 100 parts by weight). (parts by weight), a blending ratio outside this range is undesirable because any of the characteristics of fuel efficiency, braking performance on wet road surfaces, and braking performance on snowy/icy road surfaces will deteriorate. However, 30 parts by weight or less of other diene rubbers, such as polybutadiene rubber, acrylonitrile-butadiene copolymer rubber, unmodified styrene-butadiene copolymer rubber, etc., may be included.
ここで用いるスチレン−ブタジエン共重合体ゴムには、
分子鎖末端或いは分子鎖中に下記式で示される原子団が
導入されている。The styrene-butadiene copolymer rubber used here includes:
An atomic group represented by the following formula is introduced at the end of the molecular chain or into the molecular chain.
■
０Ｈ（又はＳＨ）
上記式（１）で示される原子団の導入は、下記式の結合
−ｃ−Ｎ＜
（式中Ｍは、０原子又はＳ原子を表わす）を有する化合
物（以下、化合物Ａと称する）をスチレン−ブタジエン
共重合体と反応させることによって行われる。■ 0H (or SH) The introduction of the atomic group represented by the above formula (1) is applied to a compound (hereinafter referred to as compound A) with a styrene-butadiene copolymer.
化合物Ａとしては、Ｎ、 Ｎ−ジメチルホルムアミド、
Ｎ、 Ｎ−ジエチルホルムアミド；Ｎ、Ｎ−ジエチルア
セトアミド；アミノアセトアミド、Ｎ。Compound A includes N,N-dimethylformamide,
N, N-diethylformamide; N, N-diethylacetamide; aminoacetamide, N.
Ｎ−ジメチル−Ｎ’、 Ｎ−ジメチルアミノアセトア
ミド、Ｎ−フェニルジアセトアミド：Ｎ、Ｎ−ジメチル
アクリルアミド、Ｎ、 Ｎ−ジメチルメタアクリルアミ
ド；プロピオンアミド、化Ｎ−ジメチルプロピオンアミ
ド；４−ピリジルアミド、Ｎ、 Ｎ−ジメチル−４−ピ
リジルアミド：Ｎ＋Ｎ−ジメチルベンズアミド、ｐ−ア
ミノベンズアミド、Ｎ’、 Ｎ’−（ｐ−ジメチルア
ミノ）ベンズアミド、Ｎ、 Ｎ−ジメチル−Ｎ’−（ｐ
−エチルアミノ）ベンズアミド、Ｎ−アセチル−Ｎ−２
−ナフチルベンズアミド；ニコチンアミド、Ｎ、 Ｎ−
ジエチルニコチンアミド；コハク酸アミド、マレイン酸
アミド、Ｎ、 Ｎ、 Ｎ’、 Ｎ−テトラメチルマレ
イン酸アミド；コハクイミド、マレイミド、Ｎ−メチル
マレイミド、Ｎ−メチルフタルイミド、１．２−シクロ
ヘキサンジカルボキシミド、Ｎ−メチル−・１，２−シ
クロヘキサンジカルボキシミド；オキサミド、２−フラ
ミド、Ｎ、 Ｎ、 Ｎ’、 Ｎ’−テトラメチルオキサ
ミド、Ｎ、 Ｎ−ジメチル−２−ワラミド：Ｎ。Ｎ−ジ
メチルー８−キノリンカルボキシアミド；Ｎ＋Ｎ−ジメ
チル−ｐ−アミノ−ベンザルアセトアミド、Ｎ、 Ｎ−
ジメチル−ＮＺＮ’−（ｐ−ジメチルアミノ）シンナミ
リデンアセトアミド；Ｎ、Ｎ−ジメチル−Ｎ’、 Ｎ’
−（２−ジメチルアミノ）ビニルアミド；Ｎ’−（２−
メチルアミノ）ビニルアミド；尿素、Ｎ、 Ｎ−ジメチ
ル尿素、Ｎ、 Ｎ、 Ｎ’、 Ｎ−テトラメチル尿素；
カルバミン酸メチル、Ｎ、 Ｎ−ジエチルカルバミン酸
メチル；ε−カプロラクタム、Ｎ−メチル−ε−カプロ
ラクタム、Ｎ−アセチル−ε−カプロラクタム、２−ピ
ロリドン、Ｎ−メチル−２−ピロリドン、Ｎ−アセチル
−２−ピロリドン、２−ピペリドン、Ｎ−メチル−２−
ピペリドン、２−キノロン、Ｎ−メチル−２−キノロン
、２−インドリノン、Ｎ−メチル−２−インドリノン；
イソシアヌル酸、Ｎ、 Ｎ’、 Ｎ’−）リメチルイソ
シアヌル酸等およびこれらの対応の含硫黄化合物が例示
できる。なかでも特に好ましい化合物゛は、窒素にアル
キル基が結合した化合物である。N-dimethyl-N', N-dimethylaminoacetamide, N-phenyldiacetamide: N,N-dimethylacrylamide, N,N-dimethylmethacrylamide; propionamide, N-dimethylpropionamide; 4-pyridylamide, N , N-dimethyl-4-pyridylamide: N+N-dimethylbenzamide, p-aminobenzamide, N', N'-(p-dimethylamino)benzamide, N, N-dimethyl-N'-(p
-ethylamino)benzamide, N-acetyl-N-2
- Naphthylbenzamide; Nicotinamide, N, N-
Diethylnicotinamide; succinic acid amide, maleic acid amide, N, N, N', N-tetramethylmaleic acid amide; succinimide, maleimide, N-methylmaleimide, N-methylphthalimide, 1,2-cyclohexanedicarboximide, N-methyl-1,2-cyclohexanedicarboximide; oxamide, 2-furamide, N, N, N', N'-tetramethyloxamide, N, N-dimethyl-2-waramide: N. N-dimethyl-8-quinolinecarboxamide; N+N-dimethyl-p-amino-benzalacetamide, N, N-
Dimethyl-NZN'-(p-dimethylamino)cinnamylideneacetamide;N,N-dimethyl-N',N'
-(2-dimethylamino)vinylamide;N'-(2-
methylamino) vinylamide; urea, N, N-dimethylurea, N, N, N', N-tetramethylurea;
Methyl carbamate, N,N-diethylcarbamate; ε-caprolactam, N-methyl-ε-caprolactam, N-acetyl-ε-caprolactam, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-acetyl-2 -pyrrolidone, 2-piperidone, N-methyl-2-
piperidone, 2-quinolone, N-methyl-2-quinolone, 2-indolinone, N-methyl-2-indolinone;
Examples include isocyanuric acid, N, N', N'-)limethylisocyanuric acid, and their corresponding sulfur-containing compounds. Among these, particularly preferred compounds are compounds in which an alkyl group is bonded to nitrogen.
前記式（１）で示される原子団が導入されたスチレン−
ブタジエン共重合体ゴムの製造方法としては、例えば、
（ａ）アルカリ金属基材触媒および／又はアルカリ土類
金属基材触媒を用いてスチレンとブタジェンとを重合さ
せ、重合反応が完了した溶液中に化合物Ａを添加する方
法、伽）スチレン−ブタジエン共重合体を適当な溶剤に
溶解させた溶液中で、該共重合体にアルカリ金属および
／又はアルカリ土類金属を付加させ、引き続き化合物Ａ
を添加して反応させる方法等が例示できる。Styrene into which the atomic group represented by the formula (1) is introduced -
As a method for producing butadiene copolymer rubber, for example,
(a) A method in which styrene and butadiene are polymerized using an alkali metal-based catalyst and/or an alkaline earth metal-based catalyst, and compound A is added to the solution after the polymerization reaction is completed. An alkali metal and/or alkaline earth metal is added to the copolymer in a solution in which the polymer is dissolved in a suitable solvent, and then compound A is added to the copolymer.
Examples include a method of adding and reacting.
この場合の重合反応および付加反応に使用されるアルカ
リ金属基材触媒は、リチウム、ルビジウム、セシウム等
の金属そのもの、或いはこれらの炭化水素化合物もしく
は極性化合物との錯体（例えば、ｎ−ブチルリチウム、
２−ナフチルリチウム、カリウム−テトラヒドロフラン
錯体、カリウム−ジェトキシエタン錯体等）である、ま
た、アルカリ土類金属基材触媒は、特開昭５１−１１５
５９０号、特開昭５２−９０９０号、特開昭５７−１０
０１４６号などに記載されているバリウム、ストロンチ
ウム、カルシウム等の化合物を主成分とする触媒系等が
例示できる。いずれの金属基材触媒も通常の溶液重合の
触媒として使用されるものでよく、特に制限されるもの
でない。In this case, the alkali metal-based catalyst used in the polymerization reaction and addition reaction is a metal itself such as lithium, rubidium, or cesium, or a complex of these metals with a hydrocarbon compound or a polar compound (for example, n-butyllithium,
(2-naphthyllithium, potassium-tetrahydrofuran complex, potassium-jethoxyethane complex, etc.), and alkaline earth metal-based catalysts are disclosed in JP-A-51-115
No. 590, JP-A-52-9090, JP-A-57-10
Examples include catalyst systems containing compounds such as barium, strontium, and calcium as main components, as described in No. 0146. Any metal-based catalyst may be used as a catalyst for normal solution polymerization, and is not particularly limited.
反応終了後、化合物Ａの導入された不飽和ゴム状重合体
は、メタノール等の凝固剤の添加、水蒸気によるストリ
ッピングなどの通常の分離方法を用いて反応溶液中から
回収される。得られた不飽和ゴム状重合体には、分子鎖
末端或いは分子鎖中に、
重合体分子鎖−ｄ−
−ｃ−Ｎ＜
０Ｂ （又はＳＨ）
なる原子団として化合物Ａが導入されている。After completion of the reaction, the unsaturated rubbery polymer into which Compound A has been introduced is recovered from the reaction solution using a conventional separation method such as addition of a coagulant such as methanol or stripping with steam. In the obtained unsaturated rubbery polymer, compound A is introduced at the end of the molecular chain or into the molecular chain as an atomic group such that the polymer molecular chain -d- -c-N<0B (or SH).
化合物Ａが導入される部位は、分子鎖の末端或いはそれ
以外の部位であってもよいが、好ましくは分子鎖の末端
である。分子鎖の末端がジェニル構造の共重合体と化合
物Ａとの反応で得られた重合体を使用することにより、
低燃費性の改善がさらに大となるからである。The site into which compound A is introduced may be at the end of the molecular chain or any other site, but is preferably at the end of the molecular chain. By using a polymer obtained by reacting a copolymer with a genyl structure at the end of the molecular chain with Compound A,
This is because the improvement in fuel efficiency becomes even greater.
スチレン−ブタジエン共重合体ゴムが前記式（１）で示
される原子団を分子鎖内に有していることが本発明の必
須の構成要件である。このスチレン−ブタジエン共重合
体ゴムを含有するゴム組成物は、前記式（Ｉ）で示され
る原子団を有さない通常のスチレン−ブタジエン共重合
体ゴムからなるゴム組成物に比べると著しく改善された
反発弾性を示す、したがって、このゴム組成物をトレン
ドに用いた空気入りタイヤは、他ノ特性を高いレベルに
維持しながら低燃費性を非常に改善することが可能とな
る。It is an essential component of the present invention that the styrene-butadiene copolymer rubber has an atomic group represented by the above formula (1) in its molecular chain. A rubber composition containing this styrene-butadiene copolymer rubber is significantly improved compared to a rubber composition containing an ordinary styrene-butadiene copolymer rubber that does not have the atomic group represented by formula (I). Therefore, pneumatic tires using this rubber composition can greatly improve fuel efficiency while maintaining other properties at high levels.
また、本発明で用いるスチレン−ブタジエン共重合体ゴ
ムは、結合スチレン量が１０〜３０重量％であり、また
、ブタジェン部の１．２−ビニル結合量が３０〜８０％
である。Furthermore, the styrene-butadiene copolymer rubber used in the present invention has a bound styrene content of 10 to 30% by weight, and a 1,2-vinyl bond content of the butadiene moiety of 30 to 80%.
It is.
結合スチレン量が１０重量％未満では、ゴム組成物のウ
ェットスキッド抵抗が低下し、湿潤路面におけるタイヤ
の制動性能を悪化させるので好ましくない。一方、３０
重量％を越えると、湿潤路面での制動性が大きくなる反
面、積雪・氷結路面での制動性および耐摩耗性が悪化す
るので好ましくない。If the amount of bound styrene is less than 10% by weight, the wet skid resistance of the rubber composition decreases, which deteriorates the braking performance of the tire on wet road surfaces, which is not preferable. On the other hand, 30
If it exceeds % by weight, the braking performance on wet road surfaces will increase, but the braking performance and abrasion resistance on snowy/icy road surfaces will deteriorate, which is not preferable.
１．２−ビニル結合量が３０％未満では湿潤路面での制
動性の改善効果が小さく、一方、８０％を越えると発熱
性が大きくなると共に氷結路面での制動性、耐摩耗性が
大幅に低下するため好ましくない。1. If the amount of 2-vinyl bond is less than 30%, the effect of improving braking performance on wet roads will be small; on the other hand, if it exceeds 80%, heat generation will increase, and braking performance and wear resistance on icy roads will be significantly reduced. This is not preferable because it lowers the temperature.
また、本発明で用いるスチレンーブタジエン共重合体ゴ
ムは、タイヤ製造時に良好な加工性を得るために、スズ
−ブタジェニル結合で結合された分岐状重合体を含んで
いてもよい。Further, the styrene-butadiene copolymer rubber used in the present invention may contain a branched polymer bonded with tin-butadienyl bonds in order to obtain good processability during tire manufacturing.
（２）また、本発明のトレッド用ゴム組成物は、補強剤
として、カーボンブラックを原料ゴム１００重量部に対
して３０〜８０重量部含有する。(2) The tread rubber composition of the present invention also contains 30 to 80 parts by weight of carbon black as a reinforcing agent based on 100 parts by weight of the raw rubber.
カーボンブラックの配合量が３０重量部未満では、タイ
ヤとして十分な湿潤路面での制動性、耐摩耗性が得られ
ない。一方、８０重量部を越えるとタイヤの低燃費性が
悪化し、加えて、トレッド部の硬度が低温で高（なるた
め氷結路面で滑り易くなり、好ましくないからである。If the blending amount of carbon black is less than 30 parts by weight, sufficient braking performance and wear resistance on wet road surfaces cannot be obtained as a tire. On the other hand, if it exceeds 80 parts by weight, the fuel efficiency of the tire deteriorates, and in addition, the hardness of the tread becomes high at low temperatures, making it easy to slip on icy roads, which is not preferable.
ここで用いるカーボンブラックの特性としては、窒素吸
着法による比表面積（Ｎ！ＳＡ）が７５〜９０ｍ”７ｇ
、ジブチルフタレート吸油量（ＤＢＰ吸油量）が１００
〜１５０ ｍｆ／１００ｇ、遠心沈降法により測定され
る凝集体分布の半値幅（ΔＤｓｔ）が６５〜９０ｍμで
あることが必要である。The characteristics of the carbon black used here include a specific surface area (N!SA) of 75 to 90 m"7g by nitrogen adsorption method.
, dibutyl phthalate oil absorption (DBP oil absorption) is 100
~150 mf/100 g, and the half width (ΔDst) of aggregate distribution measured by centrifugal sedimentation is required to be 65 to 90 mμ.
Ｎ！ＳＡが７５ｓ＋”７ｇ未満では、タイヤの低燃費性
に優れるものの、湿潤路面での制動性、耐摩耗性が著し
く悪化する。一方、ＮっＳＡが９０ａ＋”７ｇを越える
とタイヤの低燃費性が劣ることになるので好ましくない
。N! If the SA is less than 75s + 7g, the tire will have excellent fuel efficiency, but the braking performance and wear resistance on wet roads will deteriorate significantly. On the other hand, if the SA exceeds 90a + 7g, the tire will have poor fuel efficiency. This is not desirable because it will be inferior.
ＤＢＰ吸油量が１００ｄ／１００ ｇ未満では、タイヤ
の耐摩耗性が低下し、さらに操縦安定性が悪くなるので
好ましくない。１５０ｓＪ／１００ ｇを越えると、低
温でトレッド部が硬化し易く、積雪・氷結路面での制動
性が低下するので好ましくない。If the DBP oil absorption is less than 100 d/100 g, it is not preferable because the wear resistance of the tire decreases and the steering stability deteriorates. If it exceeds 150 sJ/100 g, the tread portion tends to harden at low temperatures and braking performance on snowy or icy roads decreases, which is not preferable.
ΔＤｓｔが６５ｍμ未満では耐摩耗性に優れるものの低
燃費性を改善できない、一方、９０ｍμを越えると低燃
費性は改善されるものの耐摩耗性の低下が避けられない
。良好な低燃費性と高い耐摩耗性を得るためにはΔＤｓ
ｔが６５〜９０ｍμの範囲にあることが必要である。When ΔDst is less than 65 mμ, the wear resistance is excellent, but fuel efficiency cannot be improved. On the other hand, when it exceeds 90 mμ, although the fuel efficiency is improved, a decrease in wear resistance is unavoidable. In order to obtain good fuel efficiency and high wear resistance, ΔDs
It is necessary that t be in the range of 65 to 90 mμ.
、本発明のゴム組成物は、通常のゴム工業で用いられる
配合剤である加硫剤、加硫促進剤、加硫助剤、老化防止
剤、軟化剤等を含んでいてもよい、また、本発明のゴム
組成物は、乗用車用タイヤをはじめ、トラック・バス用
タイヤなど全てのタイヤに適用できるものであり、タイ
ヤの種類には特に限定されるものではない。The rubber composition of the present invention may contain compounding agents commonly used in the rubber industry, such as a vulcanizing agent, a vulcanization accelerator, a vulcanization aid, an anti-aging agent, and a softening agent. The rubber composition of the present invention can be applied to all tires such as tires for passenger cars as well as tires for trucks and buses, and the type of tire is not particularly limited.
以下に実施例、比較例を示す。Examples and comparative examples are shown below.
実施例、比較例
ここで用いたスチレン−ブタジエン共重合体ゴム（Ｓ
Ｂ Ｒ）の特性を表１に、カーボンブラックの特性を表
２に示した。また、表３に実施例及び比較例について示
した（配合は重量部）。Examples and Comparative Examples The styrene-butadiene copolymer rubber (S
The properties of B R) are shown in Table 1, and the properties of carbon black are shown in Table 2. Further, Table 3 shows Examples and Comparative Examples (compounds are in parts by weight).
混合方法は表３に示した配合剤を１．１１のバンバリー
ミキサ−を使用して４分間混合し、ロールでイオウ及び
加硫促進剤を添加した。加硫は１６０℃×１５分でおこ
ない、リュプケ反撥弾性、ピコ摩耗および一１０℃の硬
度を測定した。リエブケ反撥弾性およびピコ摩耗は、そ
れぞれ比較例１を１００として指数で示した。リュプケ
反撥弾性は０℃、５０℃とも指数値が低いほどリュプケ
弾性の値が小さく、０℃の値が小さくなるとウェット性
能は良くなり、５０℃の値が大きくなると転勤抵抗が良
くなることを示している。ピコ摩耗は、耐摩耗性指数で
示し、数値が大きいほど耐摩耗性が良いことを示してい
る。−１θ℃の硬度は低温性能を示し、この配合におい
て７２以下であれば良好なスノー性が得られる注）
＄１．＄Ｉ Ｈ−ＮＭＲ法により測定。The mixing method was to mix the ingredients shown in Table 3 for 4 minutes using a 1.11 Banbury mixer, and then add sulfur and a vulcanization accelerator using a roll. Vulcanization was carried out at 160°C for 15 minutes, and Lübcke rebound, picot wear and hardness at -10°C were measured. Liebke rebound resilience and pico abrasion were each expressed as an index with Comparative Example 1 set as 100. The lower the index value of Lübke rebound elasticity at both 0°C and 50°C, the smaller the Lübcke elasticity value, which indicates that the smaller the value at 0°C, the better the wet performance, and the larger the value at 50°C, the better the transfer resistance. ing. Pico wear is expressed as a wear resistance index, and the larger the value, the better the wear resistance. A hardness of -1θ°C indicates low-temperature performance, and in this formulation, if it is 72 or less, good snow properties can be obtained Note) $1. Measured by $I H-NMR method.
＊３ 化合物ＡとしてＮ、Ｎ−ジメチルニコチンアミド
を使用。*3 N,N-dimethylnicotinamide was used as compound A.
＊４ 化合物ＡとしてＮ−メチル−２−ピロリドンを使
用。*4 N-methyl-2-pyrrolidone was used as compound A.
＊５ Ｃａｒｉｆｌｅｘ １２１５（シェルケミカル
）。*5 Cariflex 1215 (Shell Chemical).
（本頁以下余白） スーｌ 注） ＄６ ＡＳＴＭ Ｄ ３０３７の方法にて測定。(Margins below this page) Sue l note) $6 Measured using ASTM D 3037 method.
＊７ Ｊ Ｉｓ Ｋ ６２２１の方法にて測定。*7 Measured using the method of JIS K6221.
＊８ Δ３ｔの測定は、ディスクセントリフユージ（英
国Ｊｏｙｃｅ Ｌｏｅｂ１社製）を用いて次の方法によ
り測定、すなわち、
カーボンブラックを情秤し、２０容量エタノール水溶液
と界面活性剤とを加え、カーボンブラック濃度を５■／
１００ｃｃになるように超音波で分散させて試料溶
液を作製する０次にディスクセントリ
フユージの回転速度８０００ｒｐｍにおいて試料溶液０
．５−を蒸留水からなるスピン液１０−に注入し、−斉
に遠心沈降を開始させ、光沈降法によりストークス
径で換算された凝集体分布曲線を作成
し、そのヒストグラムにおける最多穎
度（最大吸光度）の〃のときの凝集体
の分布値を半値幅（Δｓｔ）とする。*8 Δ3t was measured by the following method using a disc centrifuge (manufactured by Joyce Loeb, UK). Namely, carbon black was weighed, 20 volumes of ethanol aqueous solution and a surfactant were added, and carbon black Increase the concentration to 5■/
Prepare a sample solution by dispersing it with ultrasonic waves so that it becomes 100 cc.
．． 5- is injected into a spin solution 10- consisting of distilled water, centrifugal sedimentation is simultaneously started, and an aggregate distribution curve converted to the Stokes diameter is created by the photo-sedimentation method. The distribution value of the aggregate when the absorbance) is taken as the half width (Δst).
＊９ ジーストＫＨ（東海カーボン）。*9 Geast KH (Tokai Carbon).
（本頁以下余白）
表３で１〜４および９〜１２に比較例および５〜８に実
施例を示した。比較例１〜４は、５ＢＲ−１又は５ＢＲ
−２の系にカーボンブラックＮ３３９を加えた系である
が、これに対し実施例５〜８ではＳＢＲは同じであるが
カーボンブラックをＮ３３９からＣＢ−１に変えている
。(Margin below this page) In Table 3, Comparative Examples 1 to 4 and 9 to 12 and Examples 5 to 8 are shown. Comparative Examples 1 to 4 are 5BR-1 or 5BR
This is a system in which carbon black N339 is added to the system of -2, but in contrast, in Examples 5 to 8, the SBR is the same but the carbon black is changed from N339 to CB-1.
実施例５〜８は、比較例１〜４に比較し０℃のリエブケ
反溌弾性は同じであるが、５０℃のリュプケ反撥弾性は
いずれも向上している。すなわち、本発明のカーボンブ
ラックを使用することによりウェット性能および他の性
能はかえずに転勤抵抗のみ改良することができる。Examples 5 to 8 have the same Liebke rebound properties at 0°C as compared to Comparative Examples 1 to 4, but all have improved Liebke rebound properties at 50°C. That is, by using the carbon black of the present invention, only the transfer resistance can be improved without changing the wet performance and other performances.
比較例９は分布が広いカーボンブランク、比較例１０は
ＮＡＳＡの値が小さいカーボンブラックを使用しており
、比較例１３はＤＢＰの値が小さいカーボンブラックを
使用しているが、実施例８に比較しピコ摩耗の値が小さ
く、耐摩耗性が低下している。比較例１１．１２に未変
性の５ＢＲ−３を使用しているが、実施例８に比較し５
０℃のリュプケ反撥弾性が小さく、転がり抵抗性能が悪
化している。Comparative Example 9 uses a carbon blank with a wide distribution, Comparative Example 10 uses carbon black with a small NASA value, and Comparative Example 13 uses carbon black with a small DBP value, but compared to Example 8. The pico wear value is small, and the wear resistance is low. Although unmodified 5BR-3 is used in Comparative Examples 11 and 12, 5BR-3 is used in comparison with Example 8.
The Lübcke rebound elasticity at 0°C is low, and the rolling resistance performance is poor.
以上のように変性Ｓ Ｂ Ｒ／Ｎ Ｒのブレンド系に上
記した特定のカーボンブラックを組み合わせることによ
り、ウェット性能、低温性能、耐摩耗性を高いレベルで
維持しながら、特に転勤抵抗性能を改善したトレッドコ
ンパウンドを得ることができる。As described above, by combining the above-mentioned specific carbon black with the modified SBR/NR blend system, it is possible to maintain high levels of wet performance, low-temperature performance, and abrasion resistance, while improving transfer resistance performance in particular. You can get tread compound.
以上説明したように本発明によれば、低燃費性に優れ、
しかも耐摩耗性と湿潤路面および積雪・氷結路面での制
動性を同時に満足するオールシーズン用の空気入りタイ
ヤのトレンド用として好適なゴム組成物を得ることがで
きる。As explained above, according to the present invention, it has excellent fuel efficiency and
Moreover, it is possible to obtain a rubber composition suitable for the trend of all-season pneumatic tires, which satisfies wear resistance and braking performance on wet road surfaces and snowy/icy road surfaces at the same time.
Claims (2)
７０重量部、結合スチレン量が１０〜３０重量％であっ
てブタジエン部の１，２−ビニル結合量が３０〜８０％
であるスチレン−ブタジエン共重合体ゴム７０〜３０重
量部含有し、ゴム分合計１００重量部であって、前記ス
チレン−ブタジエン共重合体ゴムには、分子鎖末端或い
は分子鎖中に下記式、 ▲数式、化学式、表等があります▼（又はＳＨ） で示される原子団が導入されており、(1) Natural rubber and/or polyisoprene rubber 30~
70 parts by weight, the amount of bound styrene is 10 to 30% by weight, and the amount of 1,2-vinyl bonds in the butadiene part is 30 to 80%.
The styrene-butadiene copolymer rubber contains 70 to 30 parts by weight of styrene-butadiene copolymer rubber, with a total rubber content of 100 parts by weight, and the styrene-butadiene copolymer rubber has the following formula at the end of the molecular chain or in the molecular chain: ▲ There are mathematical formulas, chemical formulas, tables, etc. An atomic group indicated by ▼ (or SH) has been introduced,
９０ｍ＾２／ｇ、ジブチルフタレート吸油量（ＤＢＰ吸
油量）が１００〜１５０ｍｌ／１００ｇ、遠心沈降法に
より測定される凝集体分布の半値幅（ΔＤｓｔ）が６５
〜９０ｍμであるカーボンブラックを原料ゴム１００重
量部に対し３０〜８０重量部含有していることを特徴と
するトレッド用ゴム組成物。(2) As a reinforcing agent, the specific surface area (N_2SA) is 75~
90m^2/g, dibutyl phthalate oil absorption (DBP oil absorption) is 100-150ml/100g, and the half-width of aggregate distribution (ΔDst) measured by centrifugal sedimentation is 65.
A rubber composition for a tread, comprising 30 to 80 parts by weight of carbon black having a particle diameter of 90 mμ based on 100 parts by weight of raw rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24215386A JPS6397646A (en) | 1986-10-14 | 1986-10-14 | Rubber composition for tire tread |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24215386A JPS6397646A (en) | 1986-10-14 | 1986-10-14 | Rubber composition for tire tread |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6397646A true JPS6397646A (en) | 1988-04-28 |
Family
ID=17085114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24215386A Pending JPS6397646A (en) | 1986-10-14 | 1986-10-14 | Rubber composition for tire tread |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6397646A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0232136A (en) * | 1988-07-21 | 1990-02-01 | Tokai Carbon Co Ltd | Carbon black for blending of tire tread rubber |
| JPH02129242A (en) * | 1988-11-10 | 1990-05-17 | Tokai Carbon Co Ltd | Carbon black for tire tread rubber |
-
1986
- 1986-10-14 JP JP24215386A patent/JPS6397646A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0232136A (en) * | 1988-07-21 | 1990-02-01 | Tokai Carbon Co Ltd | Carbon black for blending of tire tread rubber |
| JPH0637582B2 (en) * | 1988-07-21 | 1994-05-18 | 東海カーボン株式会社 | Carbon black for tire tread rubber |
| JPH02129242A (en) * | 1988-11-10 | 1990-05-17 | Tokai Carbon Co Ltd | Carbon black for tire tread rubber |
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