JP6434746B2 - ゴム組成物およびそれを用いたスタッドレスタイヤ - Google Patents
ゴム組成物およびそれを用いたスタッドレスタイヤ Download PDFInfo
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- JP6434746B2 JP6434746B2 JP2014170869A JP2014170869A JP6434746B2 JP 6434746 B2 JP6434746 B2 JP 6434746B2 JP 2014170869 A JP2014170869 A JP 2014170869A JP 2014170869 A JP2014170869 A JP 2014170869A JP 6434746 B2 JP6434746 B2 JP 6434746B2
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- 229920001971 elastomer Polymers 0.000 title claims description 79
- 239000005060 rubber Substances 0.000 title claims description 79
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- 229920002857 polybutadiene Polymers 0.000 claims description 122
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 37
- 238000009833 condensation Methods 0.000 claims description 29
- 230000005494 condensation Effects 0.000 claims description 29
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- 244000043261 Hevea brasiliensis Species 0.000 claims description 23
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- 150000002430 hydrocarbons Chemical group 0.000 claims description 17
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- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
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- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 7
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- 238000004898 kneading Methods 0.000 description 6
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 4
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- 238000003860 storage Methods 0.000 description 4
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 3
- WBUSESIMOZDSHU-UHFFFAOYSA-N 3-(4,5-dihydroimidazol-1-yl)propyl-triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN1CCN=C1 WBUSESIMOZDSHU-UHFFFAOYSA-N 0.000 description 3
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-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
- 238000005481 NMR spectroscopy Methods 0.000 description 3
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- XTOSZDRAGWRSBP-UHFFFAOYSA-N n,n-dimethyl-2-triethoxysilylethanamine Chemical compound CCO[Si](OCC)(OCC)CCN(C)C XTOSZDRAGWRSBP-UHFFFAOYSA-N 0.000 description 1
- RKOBOSOXEJGFTF-UHFFFAOYSA-N n,n-dimethyl-2-trimethoxysilylethanamine Chemical compound CO[Si](OC)(OC)CCN(C)C RKOBOSOXEJGFTF-UHFFFAOYSA-N 0.000 description 1
- QIOYHIUHPGORLS-UHFFFAOYSA-N n,n-dimethyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN(C)C QIOYHIUHPGORLS-UHFFFAOYSA-N 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- SULYJYHNLMOZIP-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)cyclohexanimine Chemical compound CCO[Si](OCC)(OCC)CCCN=C1CCCCC1 SULYJYHNLMOZIP-UHFFFAOYSA-N 0.000 description 1
- PHYRCSSYBSJTMI-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)ethanimine Chemical compound CCO[Si](OCC)(OCC)CCCN=CC PHYRCSSYBSJTMI-UHFFFAOYSA-N 0.000 description 1
- MPKNGASSKGJBSA-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)propan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)C MPKNGASSKGJBSA-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- DLAUQJZKDAKQGO-UHFFFAOYSA-N n-butyl-n-(3-triethoxysilylpropyl)butan-1-amine Chemical compound CCCCN(CCCC)CCC[Si](OCC)(OCC)OCC DLAUQJZKDAKQGO-UHFFFAOYSA-N 0.000 description 1
- DTPZJXALAREFEY-UHFFFAOYSA-N n-methyl-3-triethoxysilylpropan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCNC DTPZJXALAREFEY-UHFFFAOYSA-N 0.000 description 1
- DZNFWGVDYGAMJB-UHFFFAOYSA-K neodymium(3+);phosphate Chemical compound [Nd+3].[O-]P([O-])([O-])=O DZNFWGVDYGAMJB-UHFFFAOYSA-K 0.000 description 1
- 125000000449 nitro group Chemical class [O-][N+](*)=O 0.000 description 1
- CYCFYXLDTSNTGP-UHFFFAOYSA-L octadecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CYCFYXLDTSNTGP-UHFFFAOYSA-L 0.000 description 1
- OXOUKWPKTBSXJH-UHFFFAOYSA-J octadecanoate;titanium(4+) Chemical compound [Ti+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O OXOUKWPKTBSXJH-UHFFFAOYSA-J 0.000 description 1
- VRQWWCJWSIOWHG-UHFFFAOYSA-J octadecanoate;zirconium(4+) Chemical compound [Zr+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O VRQWWCJWSIOWHG-UHFFFAOYSA-J 0.000 description 1
- IJSWMXJWKNROSR-UHFFFAOYSA-N octane-1,1-diolate titanium(4+) Chemical compound [Ti+4].[Ti+4].CCCCCCCC([O-])[O-].CCCCCCCC([O-])[O-].CCCCCCCC([O-])[O-].CCCCCCCC([O-])[O-] IJSWMXJWKNROSR-UHFFFAOYSA-N 0.000 description 1
- GJYXGIIWJFZCLN-UHFFFAOYSA-N octane-2,4-dione Chemical compound CCCCC(=O)CC(C)=O GJYXGIIWJFZCLN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 125000001117 oleyl 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])=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 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000000087 stabilizing effect Effects 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
- 230000035882 stress Effects 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- KGKLLWHEYDUTBF-UHFFFAOYSA-J tetraiodorhenium Chemical compound I[Re](I)(I)I KGKLLWHEYDUTBF-UHFFFAOYSA-J 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- HFDOCGSUMLRQPF-UHFFFAOYSA-N titanium;2,2,2-tributoxyethyl 3-oxobutanoate Chemical compound [Ti].CCCCOC(OCCCC)(OCCCC)COC(=O)CC(C)=O HFDOCGSUMLRQPF-UHFFFAOYSA-N 0.000 description 1
- ZYBVXBFFLNCJIN-UHFFFAOYSA-N titanium;2,2,2-tripropoxyethyl 3-oxobutanoate Chemical compound [Ti].CCCOC(OCCC)(OCCC)COC(=O)CC(C)=O ZYBVXBFFLNCJIN-UHFFFAOYSA-N 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ZIYNWDQDHKSRCE-UHFFFAOYSA-N tricyclohexylalumane Chemical compound C1CCCCC1[Al](C1CCCCC1)C1CCCCC1 ZIYNWDQDHKSRCE-UHFFFAOYSA-N 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- FPBXRRDHCADTAL-UHFFFAOYSA-N triethoxy(3-nitropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC[N+]([O-])=O FPBXRRDHCADTAL-UHFFFAOYSA-N 0.000 description 1
- LENYMJLFWIMHEP-UHFFFAOYSA-N triethoxy(3-pyrrolidin-1-ylpropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN1CCCC1 LENYMJLFWIMHEP-UHFFFAOYSA-N 0.000 description 1
- SCONUHVNGPLTMV-UHFFFAOYSA-N triethoxy-[10-(2h-1,3-oxazol-3-yl)decyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCCCCCCCCN1COC=C1 SCONUHVNGPLTMV-UHFFFAOYSA-N 0.000 description 1
- ASAOXGWSIOQTDI-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSSCC[Si](OCC)(OCC)OCC ASAOXGWSIOQTDI-UHFFFAOYSA-N 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- RWJUTPORTOUFDY-UHFFFAOYSA-N triethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCOCC1CO1 RWJUTPORTOUFDY-UHFFFAOYSA-N 0.000 description 1
- PPLMQFARLJLZAO-UHFFFAOYSA-N triethyl(iodo)silane Chemical compound CC[Si](I)(CC)CC PPLMQFARLJLZAO-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- GCZKMPJFYKFENV-UHFFFAOYSA-K triiodogold Chemical compound I[Au](I)I GCZKMPJFYKFENV-UHFFFAOYSA-K 0.000 description 1
- QPPXVBLDIDEHBA-UHFFFAOYSA-N trimethoxy(3-nitropropyl)silane Chemical compound CO[Si](OC)(OC)CCC[N+]([O-])=O QPPXVBLDIDEHBA-UHFFFAOYSA-N 0.000 description 1
- NGLLPRYTJGRGEU-UHFFFAOYSA-N trimethoxy(3-pyrrolidin-1-ylpropyl)silane Chemical compound CO[Si](OC)(OC)CCCN1CCCC1 NGLLPRYTJGRGEU-UHFFFAOYSA-N 0.000 description 1
- JSXKIRYGYMKWSK-UHFFFAOYSA-N trimethoxy-[2-(2-trimethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CO[Si](OC)(OC)CCSSSSCC[Si](OC)(OC)OC JSXKIRYGYMKWSK-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- ZNXDCSVNCSSUNB-UHFFFAOYSA-N trimethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](OC)(OC)CCOCC1CO1 ZNXDCSVNCSSUNB-UHFFFAOYSA-N 0.000 description 1
- NQRACKNXKKOCJY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSCCC[Si](OC)(OC)OC NQRACKNXKKOCJY-UHFFFAOYSA-N 0.000 description 1
- JTTSZDBCLAKKAY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSSCCC[Si](OC)(OC)OC JTTSZDBCLAKKAY-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- FHAOCGKAMRAFMM-UHFFFAOYSA-N tris(2-ethylhexyl)alumane Chemical compound CCCCC(CC)C[Al](CC(CC)CCCC)CC(CC)CCCC FHAOCGKAMRAFMM-UHFFFAOYSA-N 0.000 description 1
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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Description
[1]天然ゴムおよびアルコキシシリル基を有する変性ブタジエンゴムを含むゴム成分、およびフィラーとしてのシリカを含有するゴム組成物であり、
前記変性ブタジエンゴムのシス1,4−結合含有率が97%以上、好ましくは98.5%以上、より好ましくは99.0%以上、さらに好ましくは99.2%以上であり、
ゴム成分中の天然ゴムおよび前記変性ブタジエンゴムの合計含有量が30〜100質量%、好ましくは60質量%以上、より好ましくは80質量%以上、さらに好ましくは100質量%であり、
前記シリカの含有量が、ゴム成分100質量部に対して15〜80質量部、好ましくは20質量部以上、より好ましくは25質量部以上、好ましくは70質量部以下、より好ましくは60質量部以下であり、
フィラー中のシリカの含有量が50質量%以上、好ましくは60質量%以上であり、かつ
前記変性ブタジエンゴムを前記シリカとのマスターバッチとして用いることにより得られるゴム組成物、
[2]前記変性ブタジエンゴムが、アルコキシシリル基以外の少なくとも1つの反応性基を有するアルコキシシラン化合物で変性された上記[1]記載のゴム組成物、
[3]前記変性ブタジエンゴムが、活性末端を有するシス1,4−結合含有量が98.5%以上のブタジエンゴムを用い、このブタジエンゴムの活性末端に、アルコキシシリル基以外の少なくとも1つの反応性基を有するアルコキシシラン化合物を導入させる変性反応を行う変性工程(A)、ならびに周期律表の4A族、2B族、3B族、4B族および5B族に含まれる元素のうち少なくとも1つの元素を含有する縮合触媒の存在下で、前記活性末端に導入されたアルコキシシラン化合物の残基を縮合反応させる縮合工程(B)を備え、前記ブタジエンゴムとして、下記(a)〜(c)成分の混合物を主成分とする触媒組成物の存在下で重合したブタジエンゴムを用いるブタジエンゴムの製造方法により得られたものである上記[1]または[2]記載のゴム組成物
(a)成分:ランタノイドの少なくともいずれか1つの元素を含有するランタノイド含有化合物、または前記ランタノイド含有化合物とルイス塩基との反応により得られる反応生成物
(b)成分:アルミノオキサン、および一般式(1):AlR1R2R3(式中、R1およびR2は、同一もしくは異なる炭素数1〜10の炭化水素基、または水素原子であり、R3は、R1およびR2と同一または異なる炭素数1〜10の炭化水素基である)で表される有機アルミニウム化合物よりなる群から選択される少なくとも1種
(c)成分:ヨウ化ケイ素化合物、ヨウ化炭化水素化合物またはヨウ素、
[4]上記[1]〜[3]のいずれかに記載のゴム組成物により形成されたトレッドを有するスタッドレスタイヤ
に関する。
(a)成分:ランタノイドの少なくともいずれか1つの元素を含有するランタノイド含有化合物、またはこのランタノイド含有化合物とルイス塩基との反応により得られる反応生成物
(b)成分:アルミノオキサン、および一般式(1):AlR1R2R3(式中、R1およびR2は、同一もしくは異なる炭素数1〜10の炭化水素基、または水素原子であり、R3は、R1およびR2と同一または異なる炭素数1〜10の炭化水素基である)で表される有機アルミニウム化合物よりなる群から選択される少なくとも一種
(c)成分:その分子構造中に少なくとも1個のヨウ素原子を含有するヨウ素含有化合物
(1)BRの合成
まず、シクロヘキサン2.4kg、1,3−ブタジエン300gを窒素置換された5Lオートクレーブに投入した。続いて、あらかじめ0.18mmolのバーサチック酸ネオジウム((a)成分)を含有するシクロヘキサン溶液、3.6mmolのメチルアルモキサン((b)成分)を含有するトルエン溶液、6.7mmolの水素化ジイソブチルアルミニウム((b)成分)を含有するトルエン溶液、および0.36mmolのトリメチルシリルアイオダイド((c)成分)を含有するトルエン溶液と、1,3−ブタジエン0.90mmolを30℃で60分間反応熟成させて得られる触媒組成物(ヨウ素原子/ランタノイド含有化合物(モル比)=2.0)を得ておき、この触媒組成物を上記オートクレーブに投入し、30℃で2時間、重合反応させて、BR溶液を得た。このBR溶液を次の(2)変性BRの合成に用いた。なお、投入した1,3−ブタジエンの反応転化率は、ほぼ100%であった。
カラム ;商品名「GMHHXL」、2本(東ソー(株)製)、
カラム温度 ;40℃
移動相 ;テトラヒドロフラン
流速 ;1.0ml/分
サンプル濃度 ;10mg/20ml
上記(1)で得られたBRの溶液に次の処理を行った。温度30℃に保持した重合体溶液に、1.71mmolの3−グリシドキシプロピルトリメトキシシランを含有するトルエン溶液を添加し、30分間反応させて反応溶液を得た。続いてこの反応溶液に、1.71mmolの3−アミノプロピルトリエトキシシランを含有するトルエン溶液を添加し、次いで1.28mmolのテトライソプロピルチタネートを含有するトルエン溶液を添加し、30分間攪拌した。その後、縮合反応を停止させるため、2,4−ジ−tert−ブチル−p−クレゾール1.5gを含むメタノール溶液を添加して、この溶液を変性重合体溶液とした(収量は、2.5kgであった)。続いて、この変性重合体溶液に、水酸化ナトリウムによりpH10に調整した水溶液20Lを添加し、110℃で2時間、脱溶媒とともに縮合反応させた。その後、110℃のロールで乾燥して、得られた乾燥物を変性BRとした。
式:[90℃の恒温槽で2日間保存した後のムーニー粘度(ML1+4、125℃)]
−[合成直後に測定したムーニー粘度(ML1+4、125℃)]
BR:日本ゼオン(株)製のBR1220(シス1,4−含有率96%)
変性BR:製造例1にて製造したもの
NR:RSS#3
カーボンブラック:三菱化学(株)製のダイアブラック(登録商標)N220(N2SA:114m2/g)
シリカ:エボニック・デグザ(Evonik Degussa)社製のULTRASIL(登録商標)VN3(N2SA:167m2/g、平均一次粒子径:15nm)
シランカップリング剤:エボニック・デグザ社製のSi75
酸化亜鉛:三井金属鉱業(株)製の亜鉛華1号
ステアリン酸:日本油脂(株)製のステアリン酸「椿」
オイル:(株)ジャパンエナジー製のプロセスX−140
老化防止剤:住友化学(株)製のアンチゲン6C(N−(1,3−ジメチルブチル)−N’−フェニル−p−フェニレンジアミン)
ワックス:大内新興化学工業(株)製のサンノックN
硫黄:軽井沢硫黄(株)製の粉末硫黄
加硫促進剤(1):大内新興化学工業(株)製のノクセラーCZ(N−シクロヘキシル−2−ベンゾチアゾリルスルフェンアミド)
加硫促進剤(2):大内新興化学工業(株)製のノクセラーD(N,N’−ジフェニルグアニジン)
表1の工程(I)に示す配合処方にしたがい、ゴム成分、シリカおよびその他の材料を入れ、1.7Lのバンバリーミキサーを用いて排出温度約150℃で5分間混練りすることによりマスターバッチを得た。
JIS K6253「加硫ゴムおよび熱可塑性ゴムの硬さ試験方法」に準じ、タイプA硬さ計にて0℃における試験用加硫ゴム組成物の硬度を測定した。下記の式により比較例1を100とする指数で示した。指数が小さいほど、硬度が低く低温特性に優れることを示す。結果を表1に示す。なお、100以下を性能目標値とする。
(硬度指数)=(測定硬度)/(比較例1の硬度)×100
試験用加硫ゴム組成物を、粘弾性スペクトロメーターVES((株)岩本製作所製)を用いて、温度−100〜100℃、動歪み0.5%の条件下で、tanδを測定し、得られたtanδ曲線のピーク値をTgとした。
試験用加硫ゴム組成物から、ミクロトームを用いて超薄切片を作成し、透過型電子顕微鏡を用いて観察した。各相モルホロジーは、コントラストの比較により確認することが可能であった。その結果、実施例、比較例では、BRとNRとの二相は互いに非相溶であることが確認された。
(BRを含む相中のシリカ存在量)/(シリカ配合量(質量部))×100 (式1)
(シリカ偏在率)/(比較例1のシリカ偏在率)×100 (式2)
実験例・比較例の冬用空気入りタイヤを用いて、下記の条件において氷上で実車性能を評価した。住友ゴム工業株式会社の北海道名寄テストコースを試験場所とした。氷上気温は−1℃〜−6℃であった。実施例および比較例のタイヤを国産2000ccのFR車に装着し、時速30km/hでロックブレーキを踏み停止させるまでに要した氷上の停止距離を測定した。そして比較例1を基準として、下記式から算出した。なお、100以上を性能目標値とする。
(氷上性能指数)=(比較例1の制動停止距離)/(測定停止距離)×100
LAT試験機(Laboratory Abration and Skid Tester)を用い、温度10℃、荷重40N、速度20km/h、スリップアングル10°、試験距離1000mの条件にて、各試験用加硫ゴム組成物の容積損失量を測定した。耐摩耗性能指数は、基準比較例の容積損失量を100としたときの相対値である。当該数値が大きいほど耐摩耗性に優れていることを示す。なお、100以上を性能目標値とする。
シート状の加硫ゴム試験片を粘弾性スペクトロメーターVES((株)岩本製作所製)を用いて、温度70℃、初期歪み10%、動歪み1%の条件下で各配合のtanδを100として、下記計算式により指数表示した。指数が小さいほど転がり抵抗性が優れることを示す。なお、100以下を性能目標値とする。
(低燃費性能指数)=(各配合のtanδ)/(比較例1のtanδ)×100
Claims (3)
- 天然ゴムおよびアルコキシシリル基を有する変性ブタジエンゴムを含むゴム成分、およびフィラーとしてのシリカを含有するゴム組成物であり、
前記変性ブタジエンゴムのシス1,4−結合含有率が97%以上であり、
前記変性ブタジエンゴムが、エポキシ基、イソシアネート基、カルボニル基およびシアノ基からなる群より選択されるアルコキシシリル基以外の少なくとも1つの反応性基を有するアルコキシシラン化合物で変性されたものであり、
ゴム成分中の天然ゴムおよび前記変性ブタジエンゴムの合計含有量が30〜100質量%であり、
前記シリカの含有量が、ゴム成分100質量部に対して15〜80質量部であり、
フィラー中のシリカの含有量が50質量%以上であり、かつ
前記変性ブタジエンゴムと前記シリカとが、前記変性ブタジエンゴムと前記シリカとを含むマスターバッチとして提供されている
ゴム組成物。 - 前記変性ブタジエンゴムが、下記(a)〜(c)成分の混合物を主成分とする触媒組成物の存在下で重合した、活性末端を有するシス1,4−結合含有量が98.5%以上のブタジエンゴムの、前記活性末端に導入された前記アルコキシシラン化合物の残基が、周期律表の4A族、2B族、3B族、4B族および5B族に含まれる元素のうち少なくとも1つの元素を含有する縮合触媒の存在下で縮合された変性ブタジエンゴムである請求項1記載のゴム組成物。
(a)成分:ランタノイドの少なくともいずれか1つの元素を含有するランタノイド含有化合物、または前記ランタノイド含有化合物とルイス塩基との反応により得られる反応生成物
(b)成分:アルミノオキサンン、および一般式(1):AlR1R2R3(式中、R1およびR2は、同一もしくは異なる炭素数1〜10の炭化水素基、または水素原子であり、R3は、R1およびR2と同一または異なる炭素数1〜10の炭化水素基である)で表される有機アルミニウム化合物よりなる群から選択される少なくとも1種
(c)成分:ヨウ化ケイ素化合物、ヨウ化炭化水素化合物またはヨウ素 - 請求項1または2記載のゴム組成物により形成されたトレッドを有するスタッドレスタイヤ。
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