JP5322558B2 - Rubber composition for tire - Google Patents
Rubber composition for tire Download PDFInfo
- Publication number
- JP5322558B2 JP5322558B2 JP2008242762A JP2008242762A JP5322558B2 JP 5322558 B2 JP5322558 B2 JP 5322558B2 JP 2008242762 A JP2008242762 A JP 2008242762A JP 2008242762 A JP2008242762 A JP 2008242762A JP 5322558 B2 JP5322558 B2 JP 5322558B2
- Authority
- JP
- Japan
- Prior art keywords
- oil
- weight
- thermally expandable
- monomer
- rubber
- 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.)
- Active
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- 229920001971 elastomer Polymers 0.000 title claims description 46
- 239000005060 rubber Substances 0.000 title claims description 46
- 239000000203 mixture Substances 0.000 title claims description 39
- 239000003094 microcapsule Substances 0.000 claims description 45
- 239000000178 monomer Substances 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 15
- 229920003244 diene elastomer Polymers 0.000 claims description 8
- 239000011257 shell material Substances 0.000 claims description 8
- 150000002825 nitriles Chemical class 0.000 claims description 7
- 229920005992 thermoplastic resin Polymers 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 239000003921 oil Substances 0.000 description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000002775 capsule Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- -1 Aromatic divinyl compound Chemical class 0.000 description 6
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003302 ferromagnetic material Substances 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- SGVYKUFIHHTIFL-UHFFFAOYSA-N 2-methylnonane Chemical compound CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- ZNXKLRKQUSZVQY-UHFFFAOYSA-N 1,6-diisocyanatohexane ethyl carbamate 2-(phenoxymethyl)oxirane prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O.C1OC1COC1=CC=CC=C1.O=C=NCCCCCCN=C=O ZNXKLRKQUSZVQY-UHFFFAOYSA-N 0.000 description 1
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 1
- CZZVAVMGKRNEAT-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)CO.OCC(C)(C)C(O)=O CZZVAVMGKRNEAT-UHFFFAOYSA-N 0.000 description 1
- SNFRKUNAXTXJEN-UHFFFAOYSA-N 2,4-diisocyanato-1-methylbenzene ethyl carbamate [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound NC(=O)OCC.CC=1C(=CC(=CC1)N=C=O)N=C=O.C(C=C)(=O)OCC(COC(C=C)=O)(COC(C=C)=O)CO SNFRKUNAXTXJEN-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- RVBFWXYFXKDVKG-UHFFFAOYSA-N 2-ethoxyprop-2-enenitrile Chemical compound CCOC(=C)C#N RVBFWXYFXKDVKG-UHFFFAOYSA-N 0.000 description 1
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- UYSBPTPFKXYYIK-UHFFFAOYSA-N 4-methyl-2-methylidenepent-4-enenitrile Chemical compound CC(=C)CC(=C)C#N UYSBPTPFKXYYIK-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- GNULGOSSPWDTMD-UHFFFAOYSA-N NC(=O)OCC.C(CCCCCN=C=O)N=C=O.C(C=C)(=O)OCC(COC(C=C)=O)(COC(C=C)=O)CO Chemical compound NC(=O)OCC.C(CCCCCN=C=O)N=C=O.C(C=C)(=O)OCC(COC(C=C)=O)(COC(C=C)=O)CO GNULGOSSPWDTMD-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- RHPYPRAKWTXDFS-UHFFFAOYSA-N OC(=O)C=C.CCOC(N)=O.C1OC1COC1=CC=CC=C1.CC1=CC=C(N=C=O)C=C1N=C=O Chemical compound OC(=O)C=C.CCOC(N)=O.C1OC1COC1=CC=CC=C1.CC1=CC=C(N=C=O)C=C1N=C=O RHPYPRAKWTXDFS-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- WTFHMMSFTVPIDU-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate;5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1.C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C WTFHMMSFTVPIDU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
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- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- KIDIAQBVMKMQSF-UHFFFAOYSA-N benzoic acid;2,2-dimethylpropane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCC(C)(C)CO.OC(=O)C1=CC=CC=C1 KIDIAQBVMKMQSF-UHFFFAOYSA-N 0.000 description 1
- SQJJLIIRJIYBBO-UHFFFAOYSA-N benzoic acid;2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.CCC(CO)(CO)CO.OC(=O)C1=CC=CC=C1 SQJJLIIRJIYBBO-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
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- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
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- 238000007429 general method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
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- 239000003999 initiator Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000005147 toluenesulfonyl group Chemical group C=1(C(=CC=CC1)S(=O)(=O)*)C 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Description
本発明はタイヤ用ゴム組成物に関し、更に詳しくは氷上摩擦力を高めた、例えばタイヤトレッド用ゴム組成物において、経時的な硬度上昇などの性能低下を抑えたタイヤ用ゴム組成物に関する。 The present invention relates to a tire rubber composition, and more particularly to a tire rubber composition having an increased frictional force on ice, for example, a tire tread rubber composition that suppresses performance degradation such as increase in hardness over time.
スタッドレスタイヤのトレッドゴムに求められるゴムと氷の摩擦力を高める技術として、ジエン系ゴムに熱膨張性マイクロカプセルや熱膨張性黒鉛を配合する手法が既に考案されているが(特許文献1〜3)、更なるゴムと氷の摩擦力の向上が要望されており、また、トレッドゴムの経時による硬度上昇が、例えば2年目以降の性能低下を引き起こすという問題があった。 As a technique for increasing the frictional force between rubber and ice required for the tread rubber of a studless tire, a technique of blending a thermally expandable microcapsule or thermally expandable graphite with a diene rubber has been devised (Patent Documents 1 to 3). ), A further improvement in the frictional force between rubber and ice has been demanded, and the increase in the hardness of the tread rubber over time has caused the problem of, for example, a decrease in performance after the second year.
ところで、特許文献4には、ゴムマトリクスに、撥水性物質(シリコーンオイル等)を内包するカプセル粒子を配合してなるゴム組成物が開示されているが、このカプセルは熱膨張しないため、氷上摩擦力の向上が不十分であった。また、特許文献5には、熱膨張性マイクロカプセルを含むゴム組成物を製造するにあたり、熱膨張性マイクロカプセルの表面を予じめ油性物質で被覆処理することが記載されているが、上記のトレッドゴムの経時による硬度上昇が及ぼす性能低下の問題は未解決であった。 By the way, Patent Document 4 discloses a rubber composition in which capsule particles containing a water-repellent substance (silicone oil or the like) are blended in a rubber matrix. However, since this capsule does not thermally expand, friction on ice is disclosed. The improvement in power was insufficient. Patent Document 5 describes that the surface of a thermally expandable microcapsule is preliminarily coated with an oily substance in producing a rubber composition containing the thermally expandable microcapsule. The problem of performance degradation caused by the increase in hardness of the tread rubber over time has not been solved.
従って、本発明の目的は、ジエン系ゴムに、熱膨張性マイクロカプセルを配合したタイヤ用ゴム組成物の経時的な硬度上昇を抑制することにある。 Accordingly, an object of the present invention is to suppress the increase in hardness over time of a tire rubber composition in which a thermally expandable microcapsule is blended with a diene rubber.
本発明に従えば、(i)ジエン系ゴム100重量部並びに(ii)熱によって気化又は膨張して気体を発生させる物質及び非極性オイルを内包した熱膨張性マイクロカプセル0.5〜25重量部を含んでなり、前記熱膨張性マイクロカプセルの殻材がニトリル系単量体を40重量%以上含む単量体混合物を重合して得られる熱可塑性樹脂から構成されるタイヤ用ゴム組成物が提供される。 According to the present invention, (i) 100 parts by weight of a diene rubber, and (ii) 0.5 to 25 parts by weight of thermally expandable microcapsules enclosing a substance that generates gas by being vaporized or expanded by heat and nonpolar oil. A rubber composition for a tire comprising a thermoplastic resin obtained by polymerizing a monomer mixture containing 40% by weight or more of a nitrile monomer, wherein the shell material of the thermally expandable microcapsule comprises Is done.
本発明によれば、ジエン系ゴムに配合する熱膨張性マイクロカプセル中に非極性オイルを内包させることによって、タイヤと氷路面との摩擦により生じた水膜を除去し、ゴムと氷の摩擦力を効果的に高めつつ、且つカプセルに内包されたオイルが経時で徐々にゴム中にマイグレーションし、経時の硬度上昇を抑制することができる。 According to the present invention, the non-polar oil is encapsulated in the heat-expandable microcapsule blended with the diene rubber, thereby removing the water film caused by the friction between the tire and the icy road surface, and the frictional force between the rubber and ice. The oil contained in the capsule migrates gradually into the rubber over time, and the increase in hardness over time can be suppressed.
本発明者らは前記課題を解決すべく研究を進めた結果、ジエン系ゴムを含むゴム組成物に、熱膨張性マイクロカプセル中に非極性オイルを内包させることによって、経時的にカプセルの殻材からオイルがゴム中にマイグレーションし、経時の硬度上昇を抑制することに成功した。 As a result of researches to solve the above problems, the present inventors have made it possible to encapsulate a non-polar oil in a thermally expandable microcapsule in a rubber composition containing a diene-based rubber, thereby making the capsule shell material over time. The oil migrated into the rubber and successfully suppressed the increase in hardness over time.
本発明によれば、ジエン系ゴム100重量部に、熱によって気化又は膨張して気体を発生させる物質及び非極性オイルを内包した熱膨張性マイクロカプセル0.5〜25重量部、好ましくは1〜15重量部を配合したゴム組成物であって、前記熱膨張性マイクロカプセルの殻材がニトリル系単量体を40重量%以上含む単量体混合物を重合して得られる熱可塑性樹脂から構成されるゴム組成物によって前記目的を達成したものである。 According to the present invention, 0.5 to 25 parts by weight of a heat-expandable microcapsule containing a non-polar oil and a substance that generates a gas by vaporization or expansion by heat in 100 parts by weight of a diene rubber, preferably 1 to A rubber composition containing 15 parts by weight, wherein the shell material of the thermally expandable microcapsule is composed of a thermoplastic resin obtained by polymerizing a monomer mixture containing 40% by weight or more of a nitrile monomer. The rubber composition achieves the above object.
本発明のゴム組成物において、非極性オイルを内包した熱膨張性マイクロカプセルの配合量が少ないと氷上摩擦力と経時の硬度上昇が改善されないので好ましくなく、逆に多いと、氷上摩擦力と経時の硬度上昇は改善されるが耐摩耗性が低下するおそれがあるので好ましくない。 In the rubber composition of the present invention, if the amount of thermally expandable microcapsules encapsulating nonpolar oil is small, it is not preferable because the frictional force on ice and the increase in hardness over time are not improved. Although the increase in hardness is improved, it is not preferable because the wear resistance may be lowered.
本発明のゴム組成物に配合する熱膨張性マイクロカプセルにおいて、非極性オイルとしては、公知の、しかもゴム配合用として市販されている任意のナフテンオイル、パラフィンオイル及びアロマオイルを用いることができ、これらは単独又は任意の混合物として使用することができる。なおオイルが非極性でないとゴムに相溶せず、硬度上昇抑制効果が得られないので好ましくない。熱膨張性マイクロカプセル中の熱によって気化又は膨張して気体を発生させる物質と非極性オイルの合計重量に占める非極性オイルの重量分率は1〜20重量%であるのが好ましく、1.2〜10重量%であるのが更に好ましい。このオイル量と膨張率との間には適値があり、オイル量が少なすぎると効果が無く、逆に多すぎると膨張しにくくなり十分な氷上摩擦力が得られなくなるおそれがある。 In the thermally expandable microcapsules to be blended with the rubber composition of the present invention, as the nonpolar oil, any known naphthenic oil, paraffin oil and aroma oil which are commercially available for rubber blending can be used. These can be used alone or in any mixture. If the oil is not nonpolar, it will not be compatible with the rubber and the effect of suppressing the increase in hardness cannot be obtained, which is not preferable. The weight fraction of the nonpolar oil in the total weight of the nonpolar oil and the substance that is vaporized or expanded by heat in the thermally expandable microcapsule and the nonpolar oil is preferably 1 to 20% by weight, More preferably, it is 10 weight%. There is an appropriate value between the amount of oil and the expansion rate. If the amount of oil is too small, there is no effect. On the other hand, if the amount is too large, expansion is difficult and sufficient frictional force on ice may not be obtained.
本発明のゴム組成物に配合するジエン系ゴムはタイヤ用ゴム組成物として使用できる任意のジエン系ゴムを用いることができ、具体的には天然ゴム(NR)、ポリイソプレンゴム(IR)、ポリブタジエンゴム(BR)、スチレンブタジエン共重合体ゴム(SBR)、アクリロニトリル−ブタジエン共重合体ゴムなどをあげることができ、それらは単独又は任意のブレンドとして使用することができる。 As the diene rubber compounded in the rubber composition of the present invention, any diene rubber that can be used as a rubber composition for tires can be used. Specifically, natural rubber (NR), polyisoprene rubber (IR), polybutadiene can be used. Examples thereof include rubber (BR), styrene butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer rubber, and the like, and these can be used alone or as any blend.
本発明のゴム組成物に配合する熱膨張性マイクロカプセルは、熱によって気化又は膨張して気体を発生させる物質及び非極性オイルを内包した熱可塑性樹脂粒子を含む。 The heat-expandable microcapsules blended in the rubber composition of the present invention include thermoplastic resin particles encapsulating a substance that generates a gas by being vaporized or expanded by heat and a nonpolar oil.
本発明に用いる熱膨張性マイクロカプセルの殻材は、主成分となる単量体がニトリル系単量体(I)並びに分子中に不飽和二重結合とカルボキシル基を有する単量体(II)並びに必要に応じ、2以上の重合性二重結合を有する単量体(III)及び、膨張特性を調整するために前記単量体と共重合可能な単量体(IV)から重合した熱可塑性樹脂から構成される。この前記熱可塑性樹脂は、ニトリル系単量体(I)を40重量%以上、好ましくは40〜90重量%含んでなり、更に好ましくは50〜85重量%、特に好ましくは55〜70重量%含んでなる。この配合量が少ないと本発明の目的を達成するのが難しい。 The shell material of the thermally expandable microcapsule used in the present invention is composed of a nitrile monomer (I) as a main component monomer and a monomer (II) having an unsaturated double bond and a carboxyl group in the molecule. And, if necessary, a monomer (III) having two or more polymerizable double bonds, and a thermoplastic polymerized from the monomer (IV) copolymerizable with the monomer in order to adjust the expansion characteristics Consists of resin. This thermoplastic resin contains 40% by weight or more of nitrile monomer (I), preferably 40 to 90% by weight, more preferably 50 to 85% by weight, particularly preferably 55 to 70% by weight. It becomes. If the amount is small, it is difficult to achieve the object of the present invention.
本発明に用いる熱膨張性マイクロカプセルの殻材は、更に必要に応じ、分子中に不飽和二重結合とカルボキシル基を有する単量体(II)を7〜50重量%、好ましくは10〜45重量%、更に好ましくは15〜40重量%、
2以上の重合性二重結合を有する単量体(III)を0〜5重量%、好ましくは0.05〜5重量%、更に好ましくは0.2〜3重量%、膨張特性を調整するために共重合可能な単量体(IV)を0〜20重量%、好ましくは0〜15重量%、更に好ましくは1〜10重量%から、常法により重合して得ることができる。
The shell material of the thermally expandable microcapsule used in the present invention further contains, if necessary, 7 to 50% by weight, preferably 10 to 45%, of monomer (II) having an unsaturated double bond and a carboxyl group in the molecule. % By weight, more preferably 15-40% by weight,
0 to 5% by weight of monomer (III) having two or more polymerizable double bonds, preferably 0.05 to 5% by weight, more preferably 0.2 to 3% by weight, for adjusting the expansion characteristics The monomer (IV) copolymerizable with 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 1 to 10% by weight, can be obtained by polymerization according to a conventional method.
前記熱膨張性マイクロカプセルは、ゴムに配合されない状態において、加熱膨張させた膨張体に加重15MPa をかけた後の膨張体の体積保持率が好ましくは50%以上、更に好ましくは70〜100%の範囲であることが好ましい。 The heat-expandable microcapsules preferably have a volume retention of 50% or more, more preferably 70 to 100% after applying a load of 15 MPa to the expanded body heated and expanded in a state where it is not blended with rubber. A range is preferable.
本発明において使用することができるニトリル系単量体(I)としては、アクリロニトリル、メタクリロニトリル、α−クロルアクリロニトリル、α−エトキシアクリロニトリル、フマロニトリル又はこれらの任意の混合物等が例示されるが、アクリロニトリル及び/又はメタクリロニトリルが特に好ましい。 Examples of the nitrile monomer (I) that can be used in the present invention include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile, fumaronitrile, and any mixture thereof. And / or methacrylonitrile is particularly preferred.
本発明において必要に応じて使用することができる分子中に不飽和二重結合とカルボキシル基を有する単量体(II)としては、これらに限定されるものではないが例えば、アクリル酸(AA)、メタクリル酸(MAA)、イタコン酸、スチレンスルホン酸又はナトリウム塩、マレイン酸、フマル酸、シトラコン酸及びこれらの混合物が含まれる。この使用量が多過ぎると本発明の目的を達成することが難しくなるおそれがあり、逆に少な過ぎると高温領域における発泡性が低下するおそれがある。 The monomer (II) having an unsaturated double bond and a carboxyl group in the molecule that can be used as necessary in the present invention is not limited to these, but examples thereof include acrylic acid (AA). Methacrylic acid (MAA), itaconic acid, styrene sulfonic acid or sodium salt, maleic acid, fumaric acid, citraconic acid and mixtures thereof. If the amount used is too large, it may be difficult to achieve the object of the present invention. Conversely, if the amount used is too small, foamability in a high temperature region may be lowered.
本発明において必要に応じて使用することができる2以上の重合性二重結合を有する単量体(III)としては、これらに限定されるものではないが、例えば、ジビニルベンゼン、ジビニルナフタレン、などの芳香族ジビニル化合物、メタクリル酸アリル、トリアクリルホルマール、トリアリルイソシアネート、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、1,4−ブタンジオールジ(メタ)アクリレート、1,9−ノナンジオールジ(メタ)アクリレート、1,10−デカンジオールジ(メタ)アクリレート、PEG#200ジ(メタ)アクリレート、PEG#400ジ(メタ)アクリレート、PEG#600ジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、1,4−ブタンジオールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、1,9−ノナンジオールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、EO変性トリメチロールプロパントリ(メタ)アクリレート、グリセリンジ(メタ)アクリレート、ジメチロール−トリシクロデカンジ(メタ)アクリレート、ペンタエリスルトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスルトールヘキサ(メタ)アクリレート、ネオペンチルグリコールアクリル酸安息香酸エステル、トリメチロールプロパンアクリル酸安息香酸エステル、2−ヒドロキシ−3−アクリロイロキシプロピル(メタ)アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、2−ブチル−2−エチル−1,3−プロパンジオールジ(メタ)アクリレート、ポリテトラメチレングリコールジ(メタ)アクリレート、フェニルグリシジルエーテルアクリレートヘキサメチレンジイソシアネートウレタンプレポリマー、フェニルグリシジルエーテルアクリレートトルエンジイソシアネートウレタンプレポリマー、ペンタエリスリトールトリアクリレートヘキサメチレンジイソシアネートウレタンプレポリマー、ペンタエリスリトールトリアクリレートトルエンジイソシアネートウレタンプレポリマー、ペンタエリスリトールトリアクリレートイソホロンジイソシアネートウレタンプレポリマー等及びこれらの任意の混合物が含まれる。 The monomer (III) having two or more polymerizable double bonds that can be used as necessary in the present invention is not limited to these, and examples thereof include divinylbenzene, divinylnaphthalene, and the like. Aromatic divinyl compound, allyl methacrylate, triacryl formal, triallyl isocyanate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,4-butanediol di ( (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decandiol di (meth) acrylate, PEG # 200 di (meth) acrylate, PEG # 400 di (meth) acrylate, PEG # 600 di (Meth) acrylate, neo Nthyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, neopentyl glycol acrylic acid benzoate, trimethylolpropane acrylic acid benzoate, 2-hydroxy-3-acryloyloxypropyl (me ) Acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, polytetramethylene glycol di ( (Meth) acrylate, phenylglycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer, phenylglycidyl ether acrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate Isophorone diisocyanate Retanine prepolymers and the like and any mixtures thereof are included.
本発明において必要に応じて使用することができる、膨張特性を調整するための共重合可能な単量体(IV)としては、これらに限定されるものではないが、例えば、塩化ビニリデン、酢酸ビニル、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n−ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、t−ブチル(メタ)アクリレート、イソボルニル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、β−カルボキシエチルアクリレートなどの(メタ)アクリル酸エステル、スチレン、スチレンスルホン酸またはそのナトリウム塩、α−メチルスチレン、クロロスチレンなどスチレン系単量体、アクリルアミド、置換アクリルアミド、メタクリルアミド、置換メタクリルアミドなど、一般的なラジカル開始剤により重合反応が進行する単量体、及びこれらの任意の混合物である。 Examples of the copolymerizable monomer (IV) for adjusting the expansion property that can be used as necessary in the present invention are not limited to these, but examples thereof include vinylidene chloride and vinyl acetate. , Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth ) (Meth) acrylic acid esters such as acrylate and β-carboxyethyl acrylate, styrene, styrenesulfonic acid or its sodium salt, styrene monomers such as α-methylstyrene and chlorostyrene, acrylamide, substituted acrylamide, methacrylamide, substituted Metacri An amide, which is a common monomer polymerization reaction proceeds by a radical initiator, and any mixtures thereof.
上記単量体混合物を重合するのに使用できる重合開始剤としては、例えば以下の通りであるが、これに限定されるものではない。好ましくは、過酸化物化合物である過酸化ジアルキル、過酸化ジアシル、ペルオキシ酸エステル、ペルオキシジカーボネート及びアゾ化合物、かつ反応温度で好ましくは1〜25時間、更に好ましくは5〜20時間の半減期を有するものを使用して前記単量体混合物を懸濁重合することによって製造する。 Examples of the polymerization initiator that can be used to polymerize the monomer mixture are as follows, but are not limited thereto. Preferably, the peroxide compound is a dialkyl peroxide, a diacyl peroxide, a peroxy acid ester, a peroxydicarbonate and an azo compound, and preferably has a half-life of 1 to 25 hours, more preferably 5 to 20 hours at the reaction temperature. It is produced by subjecting the monomer mixture to suspension polymerization using what it has.
本発明において使用する熱膨張性マイクロカプセルは、従来の熱膨張性マイクロカプセルの作成方法が一般に用いられる。すなわち、水系における分散安定剤としては、シリカ、水酸化マグネシウムなどの無機微粒子が用いられる。その他に、分散安定補助剤としてジエタノールアミンと脂肪族ジカルボン酸の縮合生成物、ポリビニルピロリドン、メチルセルロール、ポリエチレンオキサイド、ポリビニルアルコール、各種乳化化剤などを用いることができる。 As the thermally expandable microcapsule used in the present invention, a conventional method for producing a thermally expandable microcapsule is generally used. That is, inorganic fine particles such as silica and magnesium hydroxide are used as an aqueous dispersion stabilizer. In addition, a condensation product of diethanolamine and aliphatic dicarboxylic acid, polyvinyl pyrrolidone, methyl cellulose, polyethylene oxide, polyvinyl alcohol, various emulsifying agents, and the like can be used as a dispersion stabilizing aid.
前記の熱により気化して気体を発生する物質としては、例えば、n−ブタン、イソブタン、n−ペンタン、イソペンタン、ネオペンタン、n−ヘキサン、イソヘキサン、n−ヘプタン、n−オクタン、イソオクタン、n−デカン、イソデカン、石油エーテルの如き炭化水素類、塩化メチル、塩化メチレン、ジクロロエチレン、トリクロロエタン、トリクロルエチレンの如き塩素化炭化水素のような液体、又は、アゾジカーボンアミド、ジニトロソペンタメチレンテトラミン、アゾビスイソブチロニトリル、トルエンスルホニルヒドラジド誘導体、芳香族スクシニルヒドラジド誘導体のような固体が挙げられる。 Examples of the substance that generates gas upon vaporization by heat include, for example, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isohexane, n-heptane, n-octane, isooctane, and n-decane. , Hydrocarbons such as isodecane, petroleum ether, liquids such as chlorinated hydrocarbons such as methyl chloride, methylene chloride, dichloroethylene, trichloroethane, trichloroethylene, or azodicarbonamide, dinitrosopentamethylenetetramine, azobisiso Examples thereof include solids such as butyronitrile, toluenesulfonyl hydrazide derivatives, and aromatic succinyl hydrazide derivatives.
本発明に用いる熱膨張性マイクロカプセルは、例えば、熱によって気化又は膨張して気体を発生する物質及び非極性オイルと、単量体(I)(必要に応じ更に単量体(II)〜単量体(IV))と、重合開始剤とを水性分散媒中に分散させ、懸濁重合することにより得られる。 The heat-expandable microcapsule used in the present invention includes, for example, a substance that generates a gas by being vaporized or expanded by heat, a nonpolar oil, a monomer (I) (and, if necessary, a monomer (II) to a simple substance). The monomer (IV)) and a polymerization initiator are dispersed in an aqueous dispersion medium and suspension polymerization is performed.
本発明において使用する熱膨張性マイクロカプセルは、強磁性体を実質的に含有しないことが好ましい。強磁性体を含有すると、強磁性を有するようになり、混合・押出し・成形工程において、熱膨張性マイクロカプセルが破壊された場合に、強磁性体による設備の汚染が発生することがある。なお、強磁性体を実質的に含有しないとは、強磁性体の重量割合が熱によって気化又は膨張して気体を発生する物質及び非極性オイルの合計の5重量%以下であることを意味し、好ましくは3重量%以下、より好ましくは1重量%以下、さらに好ましくは0.1重量%以下、最も好ましくは0重量%である。 The thermally expandable microcapsule used in the present invention preferably contains substantially no ferromagnetic material. When a ferromagnetic material is contained, the material becomes ferromagnetic and contamination of equipment due to the ferromagnetic material may occur when the thermally expandable microcapsules are destroyed in the mixing, extrusion, and molding process. The phrase “substantially free of ferromagnetic material” means that the weight ratio of the ferromagnetic material is 5% by weight or less of the total of the substances that generate gas by vaporizing or expanding by heat and the nonpolar oil. It is preferably 3% by weight or less, more preferably 1% by weight or less, still more preferably 0.1% by weight or less, and most preferably 0% by weight.
本発明の熱膨張性マイクロカプセルは混合・押出し・成形工程では膨張せず、好ましくは140〜180℃の温度、更に好ましくは150〜170℃の温度で、加硫の熱によって膨張させる。 The heat-expandable microcapsules of the present invention do not expand in the mixing / extrusion / molding process, and are preferably expanded by the heat of vulcanization at a temperature of 140 to 180 ° C., more preferably 150 to 170 ° C.
本発明に係るゴム組成物には、前記した成分に加えて、カーボンブラックやシリカなどの補強剤(フィラー)、加硫又は架橋剤、加硫又は架橋促進剤、各種オイル、老化防止剤、可塑剤などのタイヤ用、その他のゴム組成物用に一般的に配合されている各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量は本発明の目的に反しない限り、従来の一般的な配合量とすることができる。 In addition to the components described above, the rubber composition according to the present invention includes a reinforcing agent (filler) such as carbon black and silica, a vulcanization or crosslinking agent, a vulcanization or crosslinking accelerator, various oils, an anti-aging agent, a plasticizer. Various additives that are generally blended for tires such as additives and other rubber compositions can be blended, and these additives are kneaded into a composition by a general method to be vulcanized or crosslinked. Can be used to do. As long as the amount of these additives is not contrary to the object of the present invention, a conventional general amount can be used.
以下、実施例によって本発明を更に説明するが、本発明の範囲をこれらの実施例に限定するものでないことはいうまでもない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.
実施例1〜8及び比較例1
サンプルの調製
表I又は表IIに示す配合において、加硫促進剤、硫黄、熱膨張性マイクロカプセル、膨張黒鉛を除く成分を1.7リットルのバンバリーミキサーで5分間混練し、145℃に達したときに放出してマスターバッチを得た。このマスターバッチに、加硫促進剤、硫黄及び熱膨張性マイクロカプセルを70℃でオープンロールで混練し、ゴム組成物を得た。
Examples 1-8 and Comparative Example 1
Sample preparation In the formulation shown in Table I or Table II, ingredients other than the vulcanization accelerator, sulfur, thermally expandable microcapsules, and expanded graphite were kneaded in a 1.7 liter Banbury mixer for 5 minutes and reached 145 ° C. When released, a master batch was obtained. A vulcanization accelerator, sulfur, and thermally expandable microcapsules were kneaded with this master batch at 70 ° C. with an open roll to obtain a rubber composition.
次に得られたゴム組成物を15×15×0.2cmの金型中で170℃で10分間加硫して加硫ゴムシートを調製し、以下に示す試験法で加硫ゴムの物性を測定した。結果は比較例1の値を100として指数表示して表Iに示す。 Next, the obtained rubber composition was vulcanized in a 15 × 15 × 0.2 cm mold at 170 ° C. for 10 minutes to prepare a vulcanized rubber sheet. The physical properties of the vulcanized rubber were measured by the following test methods. It was measured. The results are shown in Table I as an index with the value of Comparative Example 1 being 100.
ゴム物性評価試験法
氷上摩擦力測定
各コンパウンドを加硫したシート状ゴム片を偏平円柱状の台ゴムにはりつけ、インサイドドラム型氷上摩擦試験機にて氷上摩擦係数を測定した(測定温度は−1.5℃、荷重5.5kg/cm3、ドラム回転速度は25km/h)。結果は比較例1の値を100として指数表示し、この数字が大きいほどゴムと氷の摩擦力が良好であることを示す。
Rubber physical property evaluation test method
Friction force measurement on ice A sheet-like rubber piece vulcanized with each compound was attached to a flat cylindrical base rubber, and the friction coefficient on ice was measured with an inside drum type on-ice friction tester (measurement temperature was -1.5 ° C, load 5.5 kg / cm 3 , drum rotation speed 25 km / h). The result is expressed as an index with the value of Comparative Example 1 being 100, and the larger this number, the better the frictional force between rubber and ice.
老化硬度上昇率
80℃及び、168時間の条件下に空気加熱老化処理を行い、老化処理前後における硬度をJIS K 6253に準拠して、測定し、[(老化後硬度−老化前硬度)/老化前硬度]×100を算出した。結果は比較例1の値を100として指数表示し、この数字が小さいほど経時の硬度上昇率が小さく良好であることを示す。
Aging process is performed by air-heating aging treatment under conditions of 80 ° C. and 168 hours, and the hardness before and after aging treatment is measured according to JIS K 6253, [(hardness after aging−hardness before aging) / aging. Pre-hardness] × 100 was calculated. The result is expressed as an index with the value of Comparative Example 1 being 100, and the smaller this number, the smaller the rate of increase in hardness over time, and the better.
・耐摩耗性:JIS K6264に準拠し、ランボーン摩耗試験機(岩本製作所(株)製)を使用して荷重6Kg(=49N)、スリップ率25%、時間4分、室温の条件で測定し摩耗減量を指数として示し、結果は比較例1を100として指数表示し、この数字が大きいほど耐偏摩耗性が良好であることを示す。 -Abrasion resistance: Abrasion measured in accordance with JIS K6264 using a Lambourn Abrasion Tester (Iwamoto Seisakusho Co., Ltd.) under the conditions of load 6Kg (= 49N), slip rate 25%, time 4 minutes, room temperature. The weight loss is shown as an index, and the result is shown as an index with Comparative Example 1 being 100. The larger this figure, the better the uneven wear resistance.
表I及びII脚注
NR:天然ゴムRSS#3
BR:日本ゼオン(株)製ポリブタジエンゴムNipol BR1220
カーボンブラック:東海カーボン(株)製カーボンブラックシースト6
シリカ:日本シリカ工業(株)製Nipsil AQ
Si69:デクサ社製SI69
酸化亜鉛:正同化学工業(株)製酸化亜鉛3種
ステアリン酸:日本油脂(株)製ビーズステアリン酸
老化防止剤:フレキシス社製6PPD
アロマオイル:富士興産(株)製アロマオイル
硫黄:鶴見化学工業(株)製金華印油入微粉硫黄
加硫促進剤:大内新興化学工業(株)製ノクセラー CZ−G
Table I and II Footnote NR: Natural rubber RSS # 3
BR: Nippon Zeon Co., Ltd. polybutadiene rubber Nipol BR1220
Carbon black: Carbon black seast 6 manufactured by Tokai Carbon Co., Ltd.
Silica: Nippon Sil AQ manufactured by Nippon Silica Industry Co., Ltd.
Si69: Dexa SI69
Zinc oxide: 3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd. Stearic acid: Beads stearic acid manufactured by Nippon Oil & Fats Co., Ltd. Anti-aging agent: 6PPD manufactured by Flexis
Aroma oil: Aroma oil manufactured by Fuji Kosan Co., Ltd. Sulfur: Fine powder sulfur containing Jinhua seal oil manufactured by Tsurumi Chemical Industry Co., Ltd. Vulcanization accelerator: Noxeller CZ-G manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
熱膨張性マイクロカプセルA:松本油脂製薬(株)製マイクロスフェアーF100D
熱膨張性マイクロカプセル(オイル内包)B〜F:以下の方法で製造して使用した。
Thermally expandable microcapsule A: Microsphere F100D manufactured by Matsumoto Yushi Seiyaku Co., Ltd.
Thermally expandable microcapsules (oil inclusion) BF: manufactured and used in the following manner.
熱膨張性マイクロカプセルB
水系成分として、固形分40%のコロイダルシリカ45g、ジエタノールアミン−アジピン酸縮合物1g、塩化ナトリウムを150g及びイオン交換水500gを混合後、pH3.5に調整して水系分散媒体を製造した。次いで、油系成分として、アクリロニトリル70g、メタクリロニトリル70g、メタクリル酸70g、エチレングリコールジメタクリレートを3g及びアゾビス(2,4−ジメチリルバレロニトリル)1gを混合して均一溶液の単量体混合物を調製した。この単量体混合物に、イソペンタン20g、2−メチルペンタン30gおよびアロマオイル0.5gを加え、オートクレーブに仕込み、水系分散媒体を更に仕込んだ。5分間700rpmで仕込み物を撹拌後、オートクレーブ内を窒素置換し、反応温度60℃で8時間反応させた。なお、反応圧力は0.5MPa、撹拌は350rpmで行った。この反応により得られた熱膨張性マイクロカプセルの熱膨張性分析を行った。すなわち、パーキンエルマー社製のTMA−7型を用いて、特開平11−002616号公報に記載の方法で膨張特性の分析を行ったところ、発泡開始温度は160℃、最大膨張温度は210℃であった。
Thermally expandable microcapsule B
As an aqueous component, 45 g of colloidal silica having a solid content of 40%, 1 g of diethanolamine-adipic acid condensate, 150 g of sodium chloride and 500 g of ion-exchanged water were mixed and adjusted to pH 3.5 to produce an aqueous dispersion medium. Next, as an oil component, 70 g of acrylonitrile, 70 g of methacrylonitrile, 70 g of methacrylic acid, 3 g of ethylene glycol dimethacrylate and 1 g of azobis (2,4-dimethylylvaleronitrile) are mixed to obtain a monomer mixture in a uniform solution. Prepared. To this monomer mixture, 20 g of isopentane, 30 g of 2-methylpentane and 0.5 g of aroma oil were added, and the mixture was charged into an autoclave, and an aqueous dispersion medium was further charged. After stirring the charged product at 700 rpm for 5 minutes, the inside of the autoclave was purged with nitrogen and reacted at a reaction temperature of 60 ° C for 8 hours. The reaction pressure was 0.5 MPa and stirring was performed at 350 rpm. Thermal expansion analysis of the thermal expansion microcapsules obtained by this reaction was performed. That is, when the expansion characteristics were analyzed by the method described in JP-A-11-002616 using a TMA-7 model manufactured by PerkinElmer, the foaming start temperature was 160 ° C., and the maximum expansion temperature was 210 ° C. there were.
熱膨張性マイクロカプセルC
アロマオイルの量を2.6gに変更した以外は、上記熱膨張性カプセルBと同様の手順で反応を行った。得られた熱膨張性マイクロカプセルの発泡開始温度は159℃、最大膨張温度は210℃であった。
Thermally expandable microcapsule C
The reaction was performed in the same procedure as the thermally expandable capsule B except that the amount of the aroma oil was changed to 2.6 g. The resulting thermally expandable microcapsule had a foaming start temperature of 159 ° C. and a maximum expansion temperature of 210 ° C.
熱膨張性マイクロカプセルD
アロマオイルの量を8.8gに変更した以外は、上記熱膨張性カプセルBと同様の手順で反応を行った。得られた熱膨張性マイクロカプセルの発泡開始温度は162℃、最大膨張温度は209℃であった。
Thermally expandable microcapsule D
The reaction was performed in the same procedure as that of the thermally expandable capsule B except that the amount of the aroma oil was changed to 8.8 g. The resulting thermally expandable microcapsule had a foaming start temperature of 162 ° C. and a maximum expansion temperature of 209 ° C.
熱膨張性マイクロカプセルE
アロマオイルの量を12.5gに変更した以外は、上記熱膨張性カプセルBと同様の手順で反応を行った。得られた熱膨張性マイクロカプセルの発泡開始温度は160℃、最大膨張温度は210℃であった。
Thermally expandable microcapsule E
The reaction was performed in the same procedure as that of the thermally expandable capsule B except that the amount of the aroma oil was changed to 12.5 g. The resulting thermally expandable microcapsule had a foaming start temperature of 160 ° C. and a maximum expansion temperature of 210 ° C.
熱膨張性マイクロカプセルF
熱膨張性マイクロカプセルCのアロマオイルをナフテンオイル(日本石油(株)製コウモレックス2号)に変更した以外は、上記熱膨張性マイクロカプセルCと同様の手順で反応を行った。得られた熱膨張性マイクロカプセルの発泡開始温度は155℃、最大膨張温度は215℃であった。
Thermally expandable microcapsule F
The reaction was performed in the same procedure as the above-described thermally expandable microcapsule C, except that the aroma oil of the thermally expandable microcapsule C was changed to naphthen oil (Koumo Rex No. 2 manufactured by Nippon Oil Corporation). The resulting thermally expandable microcapsule had a foaming start temperature of 155 ° C. and a maximum expansion temperature of 215 ° C.
本発明に従えば、配合する熱膨張性マイクロカプセル中に非極性オイルを内包させることによって、経時的にカプセルの殻材からオイルがゴム中にマイグレーションし、吸水に加えて経時の硬度上昇を抑制することができるので、空気入りタイヤのトレッド用、特に、スタッドレスタイヤ用のトレッドゴムなどとして使用するのに適している。 According to the present invention, the non-polar oil is encapsulated in the heat-expandable microcapsules to be blended, so that the oil migrates from the capsule shell material into the rubber over time and suppresses the increase in hardness over time in addition to water absorption. Therefore, it is suitable for use as a tread rubber for a pneumatic tire tread, particularly a studless tire.
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JP5534576B2 (en) * | 2009-07-08 | 2014-07-02 | 株式会社クレハ | Thermally expansible microsphere and method for producing the same, additive and molded article |
JP5474478B2 (en) * | 2009-09-30 | 2014-04-16 | 横浜ゴム株式会社 | Rubber composition |
JP5499728B2 (en) * | 2010-01-21 | 2014-05-21 | 横浜ゴム株式会社 | Rubber composition for tire tread |
JP5515867B2 (en) * | 2010-03-05 | 2014-06-11 | 横浜ゴム株式会社 | Rubber composition for tire tread and pneumatic tire using the same |
JP6318790B2 (en) * | 2014-04-07 | 2018-05-09 | 横浜ゴム株式会社 | Rubber composition for tire tread |
JP6442895B2 (en) * | 2014-07-18 | 2018-12-26 | 横浜ゴム株式会社 | Rubber composition for studless tire and studless tire using the same |
JP6435818B2 (en) * | 2014-12-03 | 2018-12-12 | 横浜ゴム株式会社 | Rubber composition and pneumatic tire using the same |
JP6721962B2 (en) * | 2015-10-15 | 2020-07-15 | Toyo Tire株式会社 | Rubber composition for tread and tire |
JP6701683B2 (en) * | 2015-11-17 | 2020-05-27 | 横浜ゴム株式会社 | Rubber composition and pneumatic tire using the same |
CN107141522A (en) * | 2017-05-24 | 2017-09-08 | 明光速耐德实心轮胎有限公司 | A kind of off-the-road tyre carcass sizing material and preparation method thereof |
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