JPS63205335A - Rubber composition for tread - Google Patents
Rubber composition for treadInfo
- Publication number
- JPS63205335A JPS63205335A JP62035778A JP3577887A JPS63205335A JP S63205335 A JPS63205335 A JP S63205335A JP 62035778 A JP62035778 A JP 62035778A JP 3577887 A JP3577887 A JP 3577887A JP S63205335 A JPS63205335 A JP S63205335A
- 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.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 67
- 239000005060 rubber Substances 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000006229 carbon black Substances 0.000 claims abstract description 11
- 229920001194 natural rubber Polymers 0.000 claims abstract description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 7
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- 239000012744 reinforcing agent Substances 0.000 claims description 3
- 241000872198 Serjania polyphylla Species 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 15
- 238000005299 abrasion Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000002787 reinforcement Effects 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 229940126062 Compound A Drugs 0.000 description 8
- 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 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 238000005096 rolling process Methods 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
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 102220489978 Protein LTV1 homolog_N25A_mutation Human genes 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
- 230000007423 decrease 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
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 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
- 239000012488 sample solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- -1 2-naphthyllithium Chemical compound 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-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
- 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
- TYOGEBUAZMRGQP-UHFFFAOYSA-N 3-(4-aminophenyl)-n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=CC1=CC=C(N)C=C1 TYOGEBUAZMRGQP-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
- 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
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-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
- 229910000831 Steel Inorganic materials 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
- 150000001408 amides Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 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
- 230000008859 change Effects 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
- 238000011161 development 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
- 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
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid 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
- 238000005259 measurement Methods 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
- 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
- CXBLJKFKCLWTJR-UHFFFAOYSA-N n,n-dimethylfuran-2-carboxamide Chemical compound CN(C)C(=O)C1=CC=CO1 CXBLJKFKCLWTJR-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
- MBHINSULENHCMF-UHFFFAOYSA-N n,n-dimethylpropanamide Chemical compound CCC(=O)N(C)C MBHINSULENHCMF-UHFFFAOYSA-N 0.000 description 1
- SXFKGLXJEKJXEW-UHFFFAOYSA-N n,n-dimethylquinoline-8-carboxamide Chemical compound C1=CN=C2C(C(=O)N(C)C)=CC=CC2=C1 SXFKGLXJEKJXEW-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
- CAZVNFHXWQYGPD-UHFFFAOYSA-N oxolane;potassium Chemical compound [K].C1CCOC1 CAZVNFHXWQYGPD-UHFFFAOYSA-N 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
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 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
- 150000003440 styrenes Chemical class 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
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Tires In General (AREA)
- 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（、
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ッ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 having 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 comparatively small amount of carbon black, which has a relatively large particle size, and have as little amount of softeners such as aromatic oils 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ない天然
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ッド部
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
ーボンブラン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 a styrene-butadiene copolymer rubber with a low carbon content was used in the tread, the braking performance (wet skid resistance), especially on wet roads, was poor, resulting in an extremely low running stability. . Further, when a carbon blank with a large particle size is used, although the fuel efficiency is excellent, properties such as braking performance on a wet road surface and abrasion resistance are inevitably deteriorated. 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 high glass transition points (Tg), so they have poor abrasion resistance, are easy to harden at low temperatures, and have significantly poor braking performance on snowy and icy roads, so 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、一般夏タイ
ヤで上記の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。Thus, at present, no tire has been proposed that satisfies all of the characteristics of low fuel consumption, high braking performance on wet road surfaces, and high braking performance on snowy and icy roads. Particularly in the winter, when roads become slippery due to snow and ice, conventional tires, including fuel-efficient tires, have very poor braking performance on these surfaces, 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 above three characteristics while being a regular summer tire.
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 such demands, and the present invention has been developed to reduce heat generation in the tire tread portion during driving.
The purpose of the present invention is 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 particularly has excellent rolling resistance performance. shall be. 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.
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２０〜８０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１０〜８０％であるスチレン−ブタジエン共重合体ゴ
ム８０〜２０重量部を含有し、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り
■
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、Ｉ
Ａ＝６０〜７０、Ｎ２５Ａ／ＩＡ ＝ １．１８〜１，
４０、ΔＤｓｏ（ＤＳｔ） ＝７０〜１３０ｍμ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
ム組成物を要旨とするものである。Therefore, in the present invention, the content of natural rubber and/or polyisoprene rubber is 20 to 80 parts by weight, and the amount of bound styrene is 10 to 3 parts by weight.
It contains 80 to 20 parts by weight of a styrene-butadiene copolymer rubber in which the amount of 1°2-vinyl bonds in the butadiene moiety is 0% by weight and 10 to 80%, and the total rubber content is 100 parts by weight, and the above-mentioned Styrene-butadiene copolymer rubber has an atomic group represented by the following formula, C--C-N-OH (or SH) introduced at the end of the molecular chain or into the molecular chain, and as a reinforcing agent, I
A=60~70, N25A/IA=1.18~1,
40, ΔDso(DSt) = 30 to 130 mμ of carbon black to 100 parts by weight of raw rubber
The gist of the invention is a rubber composition for a tread, characterized in that it contains 80 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.
（１１本発明のトレッド用ゴム組成物は、天然ゴム（Ｎ
ｉｌ）および／又はポリイソプレンゴム（Ｉｔ？）２０
〜８０重量部と特定のスチレン−ブタジエン共重合体ゴ
ム８０〜２０重量部含有するのである（ゴム分合計１０
０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。(11 The rubber composition for tread of the present invention is made of natural rubber (N
il) and/or polyisoprene rubber (It?) 20
~80 parts by weight and 80 to 20 parts by weight of a specific styrene-butadiene copolymer rubber (total rubber content: 10 parts by weight).
0 parts by weight). This is because 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, other diene rubbers, such as polybutadiene rubber,
It may contain 30 parts by weight or less of acrylonitrile-butadiene copolymer rubber, unmodified styrene-butadiene copolymer rubber, and the like.
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（Ｉ）で示される原子団の導入は、下記式の結合
−Ｃ−Ｎ＜
Ｉ
台
（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 (I) is carried out in a compound (hereinafter referred to as , 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；アミノアセト了ミド、ＮｌＮ−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、Ｎ、 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−フラミド；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−Ｎ
′。Compound A includes N,N-dimethylformamide,
N, N-diethylformamide; N, N-diethylacetamide; aminoacetamide, NlN-dimethyl-
N',N'-dimethylaminoacetamide, N-phenyldiacetamide; N,N-dimethylacrylamide, N,N-dimethylmethacrylamide; Propionamide, N,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-furamide; N,N-dimethyl-8-
Quinolinecarboxamide; N,N-dimethyl-p-amino-benzalacetamide, N,N-dimethyl-N
'.
Ｎ’−（ｐ′−ジメチルアミノ）シンナミリデンアセト
アミドｉＮ、Ｎ−ジメチル−Ｎ’、 Ｎ’−（２−ジ
メチルアミノ）ビニルアミドｉ 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
リトン、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'-(p'-dimethylamino)cinnamylideneacetamide iN, N-dimethyl-N', N'-(2-dimethylamino)vinylamide i N'-(2-methylamino)vinylamide; urea, N, N '-dimethylurea, N, N, N', N'-tetramethylurea; methyl carbamate, N,N-methyl 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-piperitone, 2-quinolone, N-methyl-2-quinolone, 2
Examples include -indolinone, N-methyl-2-indolinone; isocyanuric acid, N, N', N"-)limethylisocyanuric acid, and their corresponding sulfur-containing compounds. Among these, particularly preferred compounds are It is a compound in which groups are bonded.
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、山）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 of the polymer 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.). In addition, 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−Ｃ−
■
−Ｃ−Ｎり
■
ＯＨ（又はＳ■）
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 consisting of (1) polymer molecular chain -C- (2) -C-N, (2) OH (or S). has been done.
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末端或いは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
ム組成物をトレッドに用いた空気入りタイヤは、他の特
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) at the end of the molecular chain or within the molecular chain. This styrene
The rubber composition containing the butadiene copolymer rubber is a conventional styrene rubber composition containing no atomic group represented by the formula (I).
It exhibits significantly improved impact resilience compared to rubber compositions made of butadiene copolymer rubber. Therefore, a pneumatic tire using this rubber composition in its tread can greatly improve fuel efficiency while maintaining other properties at a high level.
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１０〜８０％
である。Further, 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 10 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１０％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 10%, 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−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.
カーボンブランクの配合量が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くなるた
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 amount of carbon blank is less than 30 parts by weight, sufficient braking performance and wear resistance on wet road surfaces as a tire cannot be obtained. 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 increases at low temperatures, making it easy to slip on icy roads, which is undesirable.
ここで用いるカーボンブラックの特性としては、ヨウ素
吸着量（ＩＡ） ＝６０〜７０、窒素比表面積（１’ｈ
Ｓ＾）とヨウ素吸着量（Ｉ八）との比（ＮＡＳＡ／ＩＡ
） ＝１．１８〜１．４０、ΔＤｓｏ（Ｄｓｔ） −７
０〜１３０ｎｌであることが必要である。The characteristics of the carbon black used here include iodine adsorption amount (IA) = 60 to 70, nitrogen specific surface area (1'h
Ratio between S^) and iodine adsorption amount (I8) (NASA/IA
) = 1.18 to 1.40, ΔDso(Dst) −7
It needs to be 0 to 130 nl.
ＩＡが６０未満では耐摩耗性が著しく低下することとな
り、一方、７０を超えると低燃費性が悪化するので好ま
しくない。If IA is less than 60, wear resistance will be significantly reduced, while if it exceeds 70, fuel efficiency will deteriorate, which is not preferable.
Ｎ２５ＡＩＩＡ比はカーボンブランクの表面活性度の尺
度と考えられ、この値が大のとき活性が高い。Ｎ２５Ａ
／Ｔ＾が１．１８未満では充分な耐摩耗性、低燃費性が
得られず、また、１．４０を超えるとカーボンブランク
製造時に造粒が困難となり、ゴムの混練性が著しく劣る
こととなるので好ましくない。The N25AIIA ratio is considered to be a measure of the surface activity of the carbon blank, and when this value is large, the activity is high. N25A
If /T^ is less than 1.18, sufficient wear resistance and fuel efficiency cannot be obtained, and if it exceeds 1.40, granulation becomes difficult during carbon blank production and the kneading properties of the rubber are significantly deteriorated. This is not desirable.
ΔＤｓｏ（ＤＳｔ）は、カーボンブラックの粒子の粒度
分布半値幅で、分布の尺度となる。ΔＤｓｏ（Ｄｓｔ）
が７０ｍμ未満では低燃費性が悪化し、一方、１３０ｍ
μを超えると耐摩耗性が低下する。ΔDso(DSt) is the half width of the particle size distribution of carbon black particles, and is a measure of the distribution. ΔDso(Dst)
If it is less than 70 mμ, fuel efficiency deteriorates;
When μ is exceeded, wear resistance decreases.
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、トランク・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. Further, the rubber composition of the present invention can be applied to all tires such as tires for passenger cars as well as tires for trunks and buses, and the type of tires 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（ＳＢ
Ｒ）の特性を表１に、カーボンブランク（ＣＢ）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 (SB
Table 1 shows the properties of R), and Table 2 shows the properties of the carbon blank (CB). 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１．７１のバンバリー
ミキサ−を使用して４分間部合し、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、３００％引張応力、リュプケ反撥弾性、ウェット
スキッド抵抗およびピコ摩耗を測定した。リュプケ反撥
弾性は０℃、６０℃゛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、６０℃の値が大きくなると転勤抵抗が低く
なることを示している。ピコ摩耗は、摩耗量で示し、数
値が小さいほど耐摩耗性が良いことを示している。The mixing method was to mix the ingredients shown in Table 3 for 4 minutes using a 1.71 Banbury mixer, and then add sulfur and a vulcanization accelerator using a roll. Vulcanization was performed at 160° C. for 15 minutes, and 300% tensile stress, Lübcke rebound, wet skid resistance, and pico abrasion were measured. The lower the index value of the Lübcke rebound elasticity is at both 0°C and 60°C, the smaller the Lübcke elasticity is, the smaller the value at 0°C, the better the wet performance, and the larger the value at 60°C, the lower the transfer resistance. It shows. Pico wear is expressed as the amount of wear, and the smaller the value, the better the wear resistance.
表 １ ＝ 表 ２ ＊ ｌ ＪＩＳ Ｋ ６２２１の方法にて測定。Table 1 = Table 2 *Measured using the method of JIS K 6221.
＊ ２ ＪＩＳ Ｋ ６２２１の方法にて測定。*2 Measured using the method of JIS K 6221.
＊３ ΔＤｓｏ（Ｄｓｔ）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、カーボンブランクを精秤し、２０容量エタノール水
溶液と界面活性剤とを
加え、カーボンブランク濃度を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。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０．５１１を蒸溜水からなるスピン液１０ＴＢｌ
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
る最多頻度（最大吸光度）の２のとき
の凝集体の分布値を半値幅ΔＤｓｏ（Ｄｓｔ）とする。*3 ΔDso (Dst) was measured by the following method using a disc centrifuge (manufactured by Joyce Loeb 1, UK). That is, a sample solution is prepared by accurately weighing a carbon blank, adding 20 volumes of an aqueous ethanol solution and a surfactant, and dispersing the carbon blank using ultrasonic waves so that the carbon blank concentration becomes 5 cm/100 cc. Next, at a rotation speed of 8000 rpm of the disk centrifuge, 10 TBl of the sample solution was mixed with 10 TBl of a spin liquid consisting of distilled water.
- Injected into the histogram, simultaneously start centrifugal sedimentation, create an aggregate distribution curve converted to Stokes diameter by photoprecipitation method, and calculate the aggregate distribution value when the highest frequency (maximum absorbance) is 2 in the histogram. is the half width ΔDso(Dst).
（来夏以下余白）
表 ３
表３から、本発明のカーボンブラック（ＣＢ−３、ＣＢ
−４）を使用することによりウェットスキッド抵抗性、
耐摩耗性を低下させずに反撥弾性が向上することが判る
。(Blank below next summer) Table 3 From Table 3, carbon black of the present invention (CB-3, CB
-4) Wet skid resistance by using
It can be seen that the rebound resilience is improved without reducing the abrasion resistance.
つぎに、比較例２および実施例３のゴム組成物をそれぞ
れトレッドゴムとして用いた１４５５Ｒ１２サイズのタ
イヤで転勤抵抗を試験した。この結果を下記表４に指数
で示す。この場合、転勤抵抗の試験は、タイヤ空気圧１
．７ｋｇ／ｃＪで直径１７０７ｍのスチールドラム上で
速度６０ｋｍ／ｈにて測定した。Next, rolling resistance was tested on 1455R12 size tires using the rubber compositions of Comparative Example 2 and Example 3 as tread rubber. The results are shown in Table 4 below as an index. In this case, the transfer resistance test is performed at a tire pressure of 1
．． Measurements were made at a speed of 60 km/h on a steel drum with a diameter of 1707 m at 7 kg/cJ.
表４から、本発明のゴム組成物（実施例３）の場合が転
勤抵抗が低いことが判る。Table 4 shows that the rubber composition of the present invention (Example 3) has low transfer resistance.
表４
以上のように変性ＳＢＲ／ＮＲ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。Table 4 As shown above, by combining the above-mentioned specific carbon black with the modified SBR/NR blend system, a tread with particularly improved rolling resistance performance while maintaining high levels of wet performance, low-temperature performance, and wear resistance. You can get the compound.
以上説明したように本発明によれば、ポリマーとしてカ
ーボンブランクとの相互作用が高いＳＢＲを用い、カー
ボンブラックとして活性の高いものを組合わせて用いる
ことで、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ッド用として好適な
ゴム組成物を得ることができる。As explained above, according to the present invention, SBR, which has a high interaction with carbon blank, is used as a polymer, and carbon black, which has high activity, is used in combination, resulting in excellent fuel efficiency and wear resistance. It is possible to obtain a rubber composition suitable for use in the tread of an all-season pneumatic tire, which satisfies both braking performance on wet road surfaces and snowy/icy road surfaces.
Claims (2)
８０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１０〜８０％
であるスチレン−ブタジエン共重合体ゴム８０〜２０重
量部を含有し、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▼ で示される原子団が導入されており、(1) Natural rubber and/or polyisoprene rubber 20~
80 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 10 to 80%.
The styrene-butadiene copolymer rubber contains 80 to 20 parts by weight of a 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.▼ The atomic groups shown are introduced,
ＩＡ＝１．１８〜１．４０、ΔＤ＿５＿０（Ｄｓｔ）＝
７０〜１３０ｍμであるカーボンブラックを原料ゴム１
００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, IA=60-70, N_2SA/
IA=1.18~1.40, ΔD_5_0(Dst)=
Carbon black with a diameter of 70 to 130 mμ is used as raw material rubber 1
A rubber composition for a tread, characterized in that the rubber composition contains 30 to 80 parts by weight per 00 parts by weight.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62035778A JP2613043B2 (en) | 1987-02-20 | 1987-02-20 | Rubber composition for tread |
| KR1019880001759A KR960004675B1 (en) | 1987-02-20 | 1988-02-19 | Rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62035778A JP2613043B2 (en) | 1987-02-20 | 1987-02-20 | Rubber composition for tread |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63205335A true JPS63205335A (en) | 1988-08-24 |
| JP2613043B2 JP2613043B2 (en) | 1997-05-21 |
Family
ID=12451356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62035778A Expired - Lifetime JP2613043B2 (en) | 1987-02-20 | 1987-02-20 | Rubber composition for tread |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2613043B2 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5922940A (en) * | 1982-07-29 | 1984-02-06 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread |
| JPS5989339A (en) * | 1982-11-13 | 1984-05-23 | Bridgestone Corp | Rubber composition for tire |
| JPS61231037A (en) * | 1985-04-05 | 1986-10-15 | Bridgestone Corp | Rubber composition for tire tread |
| JPS6227442A (en) * | 1985-07-29 | 1987-02-05 | Nippon Erasutomaa Kk | Improved rubber composition for tire |
| JPS6250349A (en) * | 1985-08-30 | 1987-03-05 | Nippon Erasutomaa Kk | Improved conjugated diene rubber composition for tire |
-
1987
- 1987-02-20 JP JP62035778A patent/JP2613043B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5922940A (en) * | 1982-07-29 | 1984-02-06 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread |
| JPS5989339A (en) * | 1982-11-13 | 1984-05-23 | Bridgestone Corp | Rubber composition for tire |
| JPS61231037A (en) * | 1985-04-05 | 1986-10-15 | Bridgestone Corp | Rubber composition for tire tread |
| JPS6227442A (en) * | 1985-07-29 | 1987-02-05 | Nippon Erasutomaa Kk | Improved rubber composition for tire |
| JPS6250349A (en) * | 1985-08-30 | 1987-03-05 | Nippon Erasutomaa Kk | Improved conjugated diene rubber composition for tire |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2613043B2 (en) | 1997-05-21 |
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