JP2016065017A - Organic silane and rubber composition using the same - Google Patents
Organic silane and rubber composition using the same Download PDFInfo
- Publication number
- JP2016065017A JP2016065017A JP2014195069A JP2014195069A JP2016065017A JP 2016065017 A JP2016065017 A JP 2016065017A JP 2014195069 A JP2014195069 A JP 2014195069A JP 2014195069 A JP2014195069 A JP 2014195069A JP 2016065017 A JP2016065017 A JP 2016065017A
- Authority
- JP
- Japan
- Prior art keywords
- group
- skeleton
- formula
- mass
- organosilane
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229920001971 elastomer Polymers 0.000 title claims description 33
- 239000005060 rubber Substances 0.000 title claims description 33
- UAHWPYUMFXYFJY-UHFFFAOYSA-N myrcene group Chemical group CC(=CCCC(C=C)=C)C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- CXENHBSYCFFKJS-UHFFFAOYSA-N farnesene group Chemical group C=CC(C)=CCC=C(C)CCC=C(C)C CXENHBSYCFFKJS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 51
- 150000001282 organosilanes Chemical class 0.000 claims description 31
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- 229920003244 diene elastomer Polymers 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- OPFTUNCRGUEPRZ-QLFBSQMISA-N (-)-beta-elemene Chemical group CC(=C)[C@@H]1CC[C@@](C)(C=C)[C@H](C(C)=C)C1 OPFTUNCRGUEPRZ-QLFBSQMISA-N 0.000 abstract description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 24
- 239000005977 Ethylene Substances 0.000 description 24
- 239000006087 Silane Coupling Agent Substances 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- JSNRRGGBADWTMC-UHFFFAOYSA-N (6E)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene Chemical compound CC(C)=CCCC(C)=CCCC(=C)C=C JSNRRGGBADWTMC-UHFFFAOYSA-N 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000011256 inorganic filler Substances 0.000 description 8
- 229910003475 inorganic filler Inorganic materials 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- -1 silane compound Chemical class 0.000 description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000012763 reinforcing filler Substances 0.000 description 7
- 239000002174 Styrene-butadiene Substances 0.000 description 6
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 150000003505 terpenes Chemical group 0.000 description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 238000004438 BET method Methods 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 5
- 235000002597 Solanum melongena Nutrition 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 229930009668 farnesene Natural products 0.000 description 5
- QHDRKFYEGYYIIK-UHFFFAOYSA-N isovaleronitrile Chemical compound CC(C)CC#N QHDRKFYEGYYIIK-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 125000005370 alkoxysilyl group Chemical group 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 125000002625 beta-farnesene group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229920003049 isoprene rubber Polymers 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- OPFTUNCRGUEPRZ-UHFFFAOYSA-N (+)-beta-Elemen Natural products CC(=C)C1CCC(C)(C=C)C(C(C)=C)C1 OPFTUNCRGUEPRZ-UHFFFAOYSA-N 0.000 description 2
- DVNPFNZTPMWRAX-UHFFFAOYSA-N 2-triethoxysilylethanethiol Chemical compound CCO[Si](CCS)(OCC)OCC DVNPFNZTPMWRAX-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- JSNRRGGBADWTMC-QINSGFPZSA-N (E)-beta-Farnesene Natural products CC(C)=CCC\C(C)=C/CCC(=C)C=C JSNRRGGBADWTMC-QINSGFPZSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- DQMRXALBJIVORP-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(C)CCCS DQMRXALBJIVORP-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- OFLUYMXTEHNVBB-UHFFFAOYSA-N 3-trimethoxysilylsulfanylpropane-1-thiol Chemical compound CO[Si](OC)(OC)SCCCS OFLUYMXTEHNVBB-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 0 CC(CS*SC=*C)C1CC(C(C)CS*(*)*)C(C)(CCS*[*+])CC1 Chemical compound CC(CS*SC=*C)C1CC(C(C)CS*(*)*)C(C)(CCS*[*+])CC1 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- 125000000891 alpha-farnesene group Chemical group 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- YSNRTFFURISHOU-UHFFFAOYSA-N beta-farnesene Natural products C=CC(C)CCC=C(C)CCC=C(C)C YSNRTFFURISHOU-UHFFFAOYSA-N 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 125000003783 beta-pinene group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- QDUJKDRUFBJYSQ-OAHLLOKOSA-N elemene Chemical group CC(C)C1=CC(=C(C)C)CC[C@@]1(C)C=C QDUJKDRUFBJYSQ-OAHLLOKOSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000005065 mining Methods 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000014366 other mixer Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- AQSMLSJHYWHNRT-UHFFFAOYSA-N s-(3-trimethoxysilylpropyl) propanethioate Chemical compound CCC(=O)SCCC[Si](OC)(OC)OC AQSMLSJHYWHNRT-UHFFFAOYSA-N 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940052367 sulfur,colloidal Drugs 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 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
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- PTRSAJDNBVXVMV-UHFFFAOYSA-N triethoxy-[4-(4-triethoxysilylbutyldisulfanyl)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCCSSCCCC[Si](OCC)(OCC)OCC PTRSAJDNBVXVMV-UHFFFAOYSA-N 0.000 description 1
- JQBSHJQOBJRYIX-UHFFFAOYSA-N trimethoxy-[2-(2-trimethoxysilylethyldisulfanyl)ethyl]silane Chemical compound CO[Si](OC)(OC)CCSSCC[Si](OC)(OC)OC JQBSHJQOBJRYIX-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
- 230000004580 weight loss Effects 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、新規な有機シラン、及びそれを用いたゴム組成物、更には空気入りタイヤに関するものである。 The present invention relates to a novel organosilane, a rubber composition using the same, and a pneumatic tire.
一般にゴム組成物には、補強剤としてカーボンブラックやシリカなどの補強性フィラーが配合される。補強性フィラーは、充填量を多くすると、ゴム中での分散不良などの問題が生じやすい。そのため、補強性フィラーとゴムとの双方に反応する種々のシランカップリング剤が用いられている。しかし、従来のシランカップリング剤では、低発熱性と耐摩耗性をバランスよく改良することは難しく、補強性フィラーの分散性の更なる改良が認められる。 Generally, a reinforcing filler such as carbon black or silica is blended in the rubber composition as a reinforcing agent. When the filling amount of the reinforcing filler is increased, problems such as poor dispersion in rubber tend to occur. Therefore, various silane coupling agents that react with both the reinforcing filler and rubber are used. However, with conventional silane coupling agents, it is difficult to improve the low heat build-up and wear resistance in a well-balanced manner, and further improvement in the dispersibility of the reinforcing filler is recognized.
特許文献1及び2には、シリカなどの無機充填剤を含むゴム組成物の物理特性と摩耗特性のバランスを改良するために用いる硫黄含有シランカップリング剤として、シラン化コアポリスルフィド化合物が開示されている。また、特許文献3には、シリカ等の白色強化充填剤のためのシランカップリング剤として、多岐構造を持つチオ置換シラン又はそのオリゴマー状加水分解物からなるものが開示されている。また、特許文献4には、ビニルエーテル基を有する化合物でメルカプトシランをブロックしてなるシランカップリング剤が開示されている。しかしながら、これらの有機シランはテルペン骨格を有するものではなく、分子中にモノスルフィド結合を有するとともにテルペン骨格の構造を持つ有機シランは知られていなかった。 Patent Documents 1 and 2 disclose silanized core polysulfide compounds as sulfur-containing silane coupling agents used to improve the balance between physical properties and wear properties of rubber compositions containing inorganic fillers such as silica. Yes. Patent Document 3 discloses a silane coupling agent for a white reinforcing filler such as silica, which is composed of a thio-substituted silane having various structures or an oligomer hydrolyzate thereof. Patent Document 4 discloses a silane coupling agent obtained by blocking mercaptosilane with a compound having a vinyl ether group. However, these organosilanes do not have a terpene skeleton, and organic silanes having a monosulfide bond in the molecule and a terpene skeleton structure have not been known.
本発明は、新規な有機シランを提供することを目的とする。 An object of the present invention is to provide a novel organosilane.
本発明に係る有機シランは、下記一般式(1)で表される化合物又はその混合物である。 The organosilane according to the present invention is a compound represented by the following general formula (1) or a mixture thereof.
本発明に係るゴム組成物は、ジエン系ゴム100質量部に対して、シリカ30〜120質量部と、前記有機シランをシリカ質量に対して2〜20質量%配合してなるものである。本発明に係る空気入りタイヤは、該ゴム組成物を用いてなるものである。 The rubber composition according to the present invention is obtained by blending 30 to 120 parts by mass of silica and 2 to 20% by mass of the above organosilane with respect to 100 parts by mass of diene rubber. The pneumatic tire according to the present invention is formed using the rubber composition.
本発明に係る有機シランであると、分子中にモノスルフィド結合を持つことにより、ジエン系ゴムとの親和性を高めることができる。また、ピネン骨格、ミルセン骨格、ファルネセン骨格又はエレメン骨格といったテルペン骨格の構造を持つことによりジエン系ゴムとの相溶性を高めることができる。そのため、ジエン系ゴム中でのシリカ等のフィラーの分散性を高めることができる。 When the organosilane according to the present invention has a monosulfide bond in the molecule, the affinity with the diene rubber can be increased. Moreover, compatibility with a diene rubber can be improved by having a terpene skeleton structure such as a pinene skeleton, a myrcene skeleton, a farnesene skeleton, or an elementene skeleton. Therefore, the dispersibility of fillers, such as a silica, in diene rubber can be improved.
以下、本発明の実施に関連する事項について詳細に説明する。 Hereinafter, matters related to the implementation of the present invention will be described in detail.
本実施形態に係る有機シランは、上記一般式(1)で表されるシラン化合物又はその混合物であり、分子中にモノスルフィド結合とアルコキシシリル基を有する。 The organosilane according to this embodiment is a silane compound represented by the above general formula (1) or a mixture thereof, and has a monosulfide bond and an alkoxysilyl group in the molecule.
式(1)中、R1、R2及びR3は、それぞれ独立に、炭素数1〜3のアルキル基又は炭素数1〜3のアルコキシ基であり、少なくとも1つはアルコキシ基である。アルキル基としては、例えば、メチル基又はエチル基が好ましい。アルコキシ基としては、例えば、メトキシ基又はエトキシ基が好ましい。R1、R2及びR3は、好ましくは2つ以上がアルコキシ基であり、更に好ましくは3つともアルコキシ基である。すなわち、−SiR1R2R3で表されるアルコキシシリル基は、アルキルジアルコキシシリル基又はトリアルコキシシリル基であることが好ましく、より好ましくは、トリエトキシシリル基又はトリメトキシシリル基などのトリアルコキシシリル基である。 In formula (1), R 1 , R 2 and R 3 are each independently an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and at least one is an alkoxy group. As the alkyl group, for example, a methyl group or an ethyl group is preferable. As the alkoxy group, for example, a methoxy group or an ethoxy group is preferable. Two or more of R 1 , R 2 and R 3 are preferably alkoxy groups, and more preferably all three are alkoxy groups. That is, the alkoxysilyl group represented by -SiR 1 R 2 R 3 is preferably an alkyl dialkoxysilyl group or a trialkoxysilyl group, more preferably a triethoxysilyl group or a trimethoxysilyl group. An alkoxysilyl group.
式(1)において、nは2〜4の整数である。従って、−CnH2n−は、炭素数2〜4のアルキレン基(アルカンジイル基)を示し、具体的には、エチレン基、プロピレン基、ブチレン基が挙げられ、これらは直鎖状でも分岐状であってもよい。 In Formula (1), n is an integer of 2-4. Accordingly, —C n H 2n — represents an alkylene group having 2 to 4 carbon atoms (alkanediyl group), and specific examples thereof include an ethylene group, a propylene group, and a butylene group, which are linear or branched. It may be a shape.
式(1)において、Aは、ピネン骨格を有する基、ミルセン骨格を有する基、ファルネセン骨格を有する基、又はエレメン骨格を有する基である。これらはテルペン骨格を持つ点で共通するものであり、ジエン系ゴムとの相溶性向上に寄与する。後述するように、本実施形態の有機シランは、これらのテルペン類の炭素−炭素二重結合とメルカプトシランのメルカプト基とのエン−チオール反応により合成することができるので、Aは、ピネン、ミルセン、ファルネセン又はエレメンの炭素−炭素二重結合にメルカプト基が付加したときのSを除いた構造を持つ炭化水素基であり、アルキル基などの置換基を有するものでもよい。 In Formula (1), A is a group having a pinene skeleton, a group having a myrcene skeleton, a group having a farnesene skeleton, or a group having an elementene skeleton. These are common in that they have a terpene skeleton, and contribute to improving compatibility with diene rubbers. As will be described later, since the organosilane of this embodiment can be synthesized by an ene-thiol reaction between the carbon-carbon double bond of these terpenes and the mercapto group of mercaptosilane, A represents pinene, myrcene. , A hydrocarbon group having a structure excluding S when a mercapto group is added to the carbon-carbon double bond of farnesene or element, and may have a substituent such as an alkyl group.
ピネン骨格を有する基としては、β−ピネン骨格を有する基が好ましく、具体的には下記式(2)で表される1価の基が好ましい。 The group having a pinene skeleton is preferably a group having a β-pinene skeleton, and specifically, a monovalent group represented by the following formula (2) is preferable.
ミルセン骨格を有する基としては、α−ミルセン骨格を有する基でもよく、β−ミルセン骨格を有する基でもよい。好ましくは、下記式(3-1)〜(3-3)で表される基から選択される少なくとも1種である、β−ミルセン骨格を有する1価又は2価の基である。 The group having a myrcene skeleton may be a group having an α-myrcene skeleton or a group having a β-myrcene skeleton. Preferably, it is a monovalent or divalent group having a β-myrcene skeleton, which is at least one selected from the groups represented by the following formulas (3-1) to (3-3).
ファルネセン骨格を有する基としては、α−ファルネセン骨格を有する基でもよく、β−ファルネセン骨格を有する基でもよい。好ましくは、下記式(4-1)〜(4-3)で表される基から選択される少なくとも1種である、β−ファルネセン骨格を有する1価又は2価の基である。 The group having a farnesene skeleton may be a group having an α-farnesene skeleton or a group having a β-farnesene skeleton. Preferably, it is a monovalent or divalent group having a β-farnesene skeleton, which is at least one selected from the groups represented by the following formulas (4-1) to (4-3).
エレメン骨格を有する基としては、α−エレメン骨格を有する基でもよく、β−エレメン骨格を有する基でもよい。好ましくは、下記式(5-1)〜(5-7)で表される基から選択される少なくとも1種である、β−エレメン骨格を有する1価、2価又は3価の基である。 The group having an elemental skeleton may be a group having an α-elemene skeleton or a group having a β-elemene skeleton. Preferably, it is a monovalent, divalent or trivalent group having a β-elemene skeleton, which is at least one selected from the groups represented by the following formulas (5-1) to (5-7).
本実施形態に係る有機シランは、上記ピネン骨格、ミルセン骨格、ファルネセン骨格又はエレメン骨格のいずれか1種のみを有する化合物又は混合物(例えば、上記式(1-3-1)と(1-3-2)の混合物)でもよく、また、異種のテルペン骨格を有するものを2種以上組み合わせた混合物であってもよい。 The organosilane according to this embodiment is a compound or mixture (for example, the above formulas (1-3-1) and (1-3-) having only one of the pinene skeleton, myrcene skeleton, farnesene skeleton, and elemental skeleton. 2) or a combination of two or more types having different terpene skeletons.
本実施形態に係る有機シランは、好ましくはエン−チオール反応により合成することができる。詳細には、下記一般式(6)で表される化合物(式中のR1、R2、R3及びnは、上記式(1)と同じ。)と、ピネン、ミルセン、ファルネセン及びエレメンから選択される少なくとも1種とを、反応させることにより合成することができる。 The organosilane according to this embodiment can be synthesized preferably by an ene-thiol reaction. Specifically, from a compound represented by the following general formula (6) (wherein R 1 , R 2 , R 3 and n are the same as those in the above formula (1)), pinene, myrcene, farnesene and element It can synthesize | combine by making at least 1 sort (s) selected react.
式(6)の化合物としては、公知の種々のメルカプトシランカップリング剤を用いることができ、具体例としては、(3−メルカプトプロピル)トリエトキシシラン、(3−メルカプトプロピル)トリメトキシシラン、(3−メルカプトプロピル)メチルジメトキシシラン、(3−メルカプトプロピル)ジメチルメトキシシラン、又は、メルカプトエチルトリエトキシシランなどが挙げられる。 As the compound of the formula (6), various known mercaptosilane coupling agents can be used. Specific examples include (3-mercaptopropyl) triethoxysilane, (3-mercaptopropyl) trimethoxysilane, ( Examples include 3-mercaptopropyl) methyldimethoxysilane, (3-mercaptopropyl) dimethylmethoxysilane, or mercaptoethyltriethoxysilane.
エン−チオール反応に際しては、ラジカル発生剤を反応触媒として用いることが好ましい。紫外線(UV)を照射することによるラジカル反応でもよい。ラジカル発生剤としては、アゾ化合物、有機過酸化物などが挙げられ、熱によりラジカルが発生するものや光照射によりラジカルが発生するものが含まれる。アゾ化合物の例としては、アゾビスイソブチロニトリル(AIBN)、1,1’−アゾビス(シクロヘキサンカルボニトリル)(ABCN)などが挙げられる。有機過酸化物の例としては、ジ−tert−ブチルペルオキシド、tert−ブチルヒドロペルオキシド、過酸化ベンゾイル、メチルエチルケトンペルオキシドなどが挙げられる。 In the ene-thiol reaction, it is preferable to use a radical generator as a reaction catalyst. It may be a radical reaction by irradiating with ultraviolet rays (UV). Examples of the radical generator include azo compounds and organic peroxides, and those that generate radicals by heat and those that generate radicals by light irradiation are included. Examples of the azo compound include azobisisobutyronitrile (AIBN), 1,1′-azobis (cyclohexanecarbonitrile) (ABCN), and the like. Examples of the organic peroxide include di-tert-butyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, and methyl ethyl ketone peroxide.
エン−チオール反応は、より詳細には、式(6)で表される化合物と、ピネン、ミルセン、ファルネセン及びエレメンの何れか少なくとも1種と、ラジカル発生剤を、トルエンなどの有機溶剤とともに混合し、ラジカルが発生する条件に保持することにより行うことができる。特に限定するものではないが、反応温度は50〜120℃であることが好ましい。 More specifically, in the ene-thiol reaction, a compound represented by formula (6), at least one of pinene, myrcene, farnesene, and element, and a radical generator are mixed with an organic solvent such as toluene. , By maintaining the conditions under which radicals are generated. Although it does not specifically limit, it is preferable that reaction temperature is 50-120 degreeC.
本実施形態に係る有機シランは、無機材料と有機材料を結合させるカップリング剤として用いることができる。該有機シランは、モノスルフィド結合(−C−S−C−)を分子内に有しており、この部分が熱により開裂してジエン系ゴムと反応するか、又は少なくともモノスルフィド結合を有することでジエン系ゴムとの親和性が向上するものと考えられる。また、該有機シランは、ピネン骨格、ミルセン骨格、ファルネセン骨格又はエレメン骨格を持つことによりジエン系ゴムとの相溶性が高い。更に、該有機シランは、アルコキシシリル基を分子内に有しており、この部分がシリカなどの無機フィラーと反応することができる。そのため、ジエン系ゴムと無機フィラーを結合させることができるので、ゴム組成物においてシランカップリング剤として用いることにより、無機フィラーの分散性を向上させて、ゴム組成物の特性を改良することができる。また、モノスルフィド結合を持つものであるため、スコーチが生じにくく、耐スコーチ性能を向上することもできる。 The organosilane according to this embodiment can be used as a coupling agent that binds an inorganic material and an organic material. The organosilane has a monosulfide bond (—C—S—C—) in the molecule, and this part is cleaved by heat to react with the diene rubber, or at least has a monosulfide bond. It is thought that the affinity with the diene rubber is improved. The organosilane has a high compatibility with a diene rubber because it has a pinene skeleton, a myrcene skeleton, a farnesene skeleton, or an elementene skeleton. Further, the organosilane has an alkoxysilyl group in the molecule, and this portion can react with an inorganic filler such as silica. Therefore, since the diene rubber and the inorganic filler can be combined, the dispersibility of the inorganic filler can be improved and the characteristics of the rubber composition can be improved by using it as a silane coupling agent in the rubber composition. . Moreover, since it has a monosulfide bond, scorch is unlikely to occur and the scorch resistance can be improved.
本実施形態に係るゴム組成物は、ゴム成分であるジエン系ゴムに対し、補強性フィラーとしてのシリカとともに、上記有機シランを配合してなるものである。 The rubber composition according to the present embodiment is obtained by blending the organosilane with silica as a reinforcing filler with respect to a diene rubber that is a rubber component.
上記ジエン系ゴムとしては、例えば、天然ゴム(NR)、合成イソプレンゴム(IR)、ブタジエンゴム(BR)、スチレンブタジエンゴム(SBR)、ニトリルゴム(NBR)、クロロプレンゴム(CR)、ブチルゴム(IIR)、スチレン−イソプレン共重合体ゴム、ブタジエン−イソプレン共重合体ゴム、スチレン−イソプレン−ブタジエン共重合体ゴム等が挙げられ、これらはいずれか1種単独で又は2種以上組み合わせて用いることができる。これらの中でも、NR、BR及びSBRからなる群から選択された少なくとも1種であることが好ましい。 Examples of the diene rubber include natural rubber (NR), synthetic isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), nitrile rubber (NBR), chloroprene rubber (CR), and butyl rubber (IIR). ), Styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, and the like. These may be used alone or in combination of two or more. . Among these, at least one selected from the group consisting of NR, BR and SBR is preferable.
また、これらのジエン系ゴムとしては、主鎖中又は末端が変性された変性ジエン系ゴムであってもよく、例えば、NR、IR、BR、SBRの主鎖中又は末端が、アルコキシ基、カルボニル基、水酸基、アミノ基及びエポキシ基などの少なくとも1種の官能基(シリカのシラノール基と相互作用のある官能基)で変性されていてもよい。かかる変性ジエン系ゴムの含有量は、特に限定されず、例えば、ジエン系ゴム中に占める割合が10質量%以上でもよく、また30質量%以上でもよく、ゴム成分を変性ジエン系ゴムのみで構成してもよい。 Further, these diene rubbers may be modified diene rubbers whose main chain or terminal is modified. For example, the main chain or terminal of NR, IR, BR, SBR is an alkoxy group, carbonyl It may be modified with at least one functional group such as a group, a hydroxyl group, an amino group, and an epoxy group (a functional group that interacts with a silanol group of silica). The content of the modified diene rubber is not particularly limited. For example, the proportion in the diene rubber may be 10% by mass or more, or 30% by mass or more, and the rubber component is composed only of the modified diene rubber. May be.
上記補強性フィラーとしてのシリカとしては、特に限定されないが、湿式シリカ(含水ケイ酸)が好ましい。シリカのコロイダル特性も、特に限定されないが、BET法による窒素吸着比表面積(BET)が150〜250m2/gであるものが好ましく用いられ、より好ましくは180〜230m2/gである。なお、シリカのBETはISO 5794に記載のBET法に準拠し測定される。 The silica as the reinforcing filler is not particularly limited, but wet silica (hydrous silicic acid) is preferable. Colloidal properties of the silica is also not particularly limited, a nitrogen absorption specific surface area by the BET method (BET) is 150 to 250 2 / g is preferably used, more preferably 180~230m 2 / g. The BET of silica is measured according to the BET method described in ISO 5794.
シリカの配合量は、上記ジエン系ゴム100質量部に対して、30〜120質量部であることが好ましく、より好ましくは40〜100質量部である。 It is preferable that the compounding quantity of a silica is 30-120 mass parts with respect to 100 mass parts of said diene rubbers, More preferably, it is 40-100 mass parts.
本実施形態に係るゴム組成物において、フィラーとしては、上記シリカの他、カーボンブラック、酸化チタン、ケイ酸アルミニウム、クレー、又は、タルクなどの各種無機フィラーを併用してもよい。これらは2種以上組み合わせて用いてもよい。これらの中でも、シリカと併用するフィラーとしてはカーボンブラックが好ましい。なお、シリカを含む無機フィラーの総配合量は、上記ジエン系ゴム100質量部に対して、30〜180質量部であることが好ましく、より好ましくは40〜150質量部であり、更に好ましくは50〜120質量部である。他の無機フィラーを併用する場合、シリカを主成分とすること、すなわち、無機フィラーの50質量%以上がシリカであることが好ましい。 In the rubber composition according to the present embodiment, as the filler, various inorganic fillers such as carbon black, titanium oxide, aluminum silicate, clay, or talc may be used in combination in addition to the silica. Two or more of these may be used in combination. Among these, carbon black is preferable as a filler used in combination with silica. In addition, it is preferable that the total compounding quantity of the inorganic filler containing a silica is 30-180 mass parts with respect to 100 mass parts of said diene rubbers, More preferably, it is 40-150 mass parts, More preferably, it is 50. -120 parts by mass. When other inorganic fillers are used in combination, it is preferable that silica is the main component, that is, 50% by mass or more of the inorganic filler is silica.
上記有機シランの配合量は、シリカ質量に対して2〜20質量%であることが好ましい。すなわち、該有機シランの配合量は、シリカ100質量部に対して2〜20質量部である。このような配合量とすることにより、その添加効果を十分に発揮することができる。有機シランの配合量は、より好ましくは、シリカ質量の5〜15質量%である。 The amount of the organic silane is preferably 2 to 20% by mass with respect to the silica mass. That is, the compounding quantity of this organosilane is 2-20 mass parts with respect to 100 mass parts of silica. By setting it as such a compounding quantity, the addition effect can fully be exhibited. The amount of the organic silane is more preferably 5 to 15% by mass of the silica mass.
本実施形態に係るゴム組成物において、シランカップリング剤としては、上記式(1)で表される有機シランのみでもよいが、これとともに他のシランカップリング剤を併用してもよい。他のシランカップリング剤としては、特に限定されず、例えば、ビス(3−トリエトキシシリルプロピル)テトラスルフィド、ビス(3−トリエトキシシリルプロピル)ジスルフィド、ビス(2−トリエトキシシリルエチル)テトラスルフィド、ビス(4−トリエキトシシリルブチル)ジスルフィド、ビス(3−トリメトキシシリルプロピル)テトラスルフィド、ビス(2−トリメトキシシリルエチル)ジスルフィドなどのスルフィドシランカップリング剤; (3−メルカプトプロピル)トリメトキシシラン、(3−メルカプトプロピル)トリエトキシシラン、(3−メルカプトプロピル)メチルジメトキシシラン、メルカプトエチルトリエトキシシランなどのメルカプトシランカップリング剤; 3−オクタノイルチオ−1−プロピルトリエトキシシラン、3−プロピオニルチオプロピルトリメトキシシランなどの保護化メルカプトシランカップリング剤などが挙げられ、これらは2種以上を組合せて用いてもよい。このように他のシランカップリング剤を併用する場合、シランカップリング剤の総配合量は、シリカ質量の3〜20質量%であることが好ましく、より好ましくは5〜15質量%である。なお、他のシランカップリング剤を併用する場合、上記式(1)の有機シランを主成分とすること、すなわち、シランカップリング剤の50質量%以上が該有機シランであることが好ましい。 In the rubber composition according to the present embodiment, as the silane coupling agent, only the organic silane represented by the above formula (1) may be used, but another silane coupling agent may be used in combination therewith. Other silane coupling agents are not particularly limited. For example, bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) tetrasulfide , Sulfide silane coupling agents such as bis (4-triethoxysilylbutyl) disulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) disulfide; (3-mercaptopropyl) trimethoxy Mercaptosilane coupling agents such as silane, (3-mercaptopropyl) triethoxysilane, (3-mercaptopropyl) methyldimethoxysilane, mercaptoethyltriethoxysilane; 3-octanoylthio-1-propyltri Examples thereof include protected mercaptosilane coupling agents such as ethoxysilane and 3-propionylthiopropyltrimethoxysilane, and these may be used in combination of two or more. Thus, when using another silane coupling agent together, it is preferable that the total compounding quantity of a silane coupling agent is 3-20 mass% of silica mass, More preferably, it is 5-15 mass%. In addition, when using together another silane coupling agent, it is preferable that the organic silane of said Formula (1) is made into a main component, ie, 50 mass% or more of a silane coupling agent is this organic silane.
本実施形態に係るゴム組成物には、上記の各成分の他に、オイル、亜鉛華、ステアリン酸、老化防止剤、ワックス、加硫剤、加硫促進剤など、ゴム組成物において一般に使用される各種添加剤を配合することができる。上記加硫剤としては、粉末硫黄、沈降硫黄、コロイド硫黄、不溶性硫黄、高分散性硫黄などの硫黄成分が挙げられ、特に限定するものではないが、その配合量は、ジエン系ゴム100質量部に対して0.1〜10質量部であることが好ましく、より好ましくは0.5〜5質量部である。 The rubber composition according to the present embodiment is generally used in rubber compositions such as oil, zinc white, stearic acid, anti-aging agent, wax, vulcanizing agent, and vulcanization accelerator in addition to the above components. Various additives can be blended. Examples of the vulcanizing agent include sulfur components such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Although not particularly limited, the blending amount thereof is 100 parts by mass of diene rubber. It is preferable that it is 0.1-10 mass parts with respect to it, More preferably, it is 0.5-5 mass parts.
実施形態に係るゴム組成物は、通常に用いられるバンバリーミキサーやニーダー、ロール等の混合機を用いて、常法に従い混練し作製することができる。すなわち、第一混合段階で、ゴム成分に対し、フィラーとともに、加硫剤及び加硫促進剤を除く他の添加剤を添加混合し、次いで、得られた混合物に、最終混合段階で加硫剤及び加硫促進剤を添加混合してゴム組成物を調製することができる。 The rubber composition according to the embodiment can be prepared by kneading according to a conventional method using a commonly used Banbury mixer, kneader, roll, or other mixer. That is, in the first mixing stage, other additives except the vulcanizing agent and the vulcanization accelerator are added and mixed with the rubber component in the first mixing stage, and then the vulcanizing agent is added to the obtained mixture in the final mixing stage. And a rubber composition can be prepared by adding and mixing a vulcanization accelerator.
このようにして得られたゴム組成物は、タイヤ用、防振ゴム用、コンベアベルト用などの各種ゴム部材に用いることができる。好ましくは、タイヤ用として用いることであり、乗用車用、トラックやバスの大型タイヤなど各種用途、サイズの空気入りタイヤのトレッド部、サイドウォール部、ビード部、タイヤコード被覆用ゴムなどタイヤの各部位に適用することができる。すなわち、該ゴム組成物は、常法に従い、例えば、押出加工によって所定の形状に成形され、他の部品と組み合わせた後、例えば140〜180℃で加硫成形することにより、空気入りタイヤを製造することができる。これらの中でも、タイヤのトレッド用配合として用いることが特に好ましい。 The rubber composition thus obtained can be used for various rubber members for tires, vibration-proof rubbers, conveyor belts and the like. Preferably, it is used for tires, for various applications such as passenger cars, large tires for trucks and buses, tread parts, side wall parts, bead parts, tire cord covering rubber, etc. Can be applied to. That is, according to a conventional method, the rubber composition is molded into a predetermined shape by, for example, extrusion, and combined with other parts, and then vulcanized and molded at, for example, 140 to 180 ° C. to produce a pneumatic tire. can do. Among these, it is particularly preferable to use as a tire tread formulation.
以下、本発明の実施例を示すが、本発明はこれらの実施例に限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
<有機シランの合成>
[合成例1]
β-ピネン(東京化成工業(株)製)50g、(3−メルカプトプロピル)トリエトキシシラン(東京化成工業(株)製)83.1g、2,2’−アゾビス(イソブチルニトリル)(和光純薬工業(株)製)3.50gおよびトルエン100mLをナスフラスコ内で混合し、窒素ガスで30分間バブリングした後、60℃で3時間反応させた。その後、反応溶液を濃縮し、122gの無色透明の液体が得られた(収率:92質量%)。下記NMRの結果から、生成物が下記式(10)で表される化合物(有機シラン1)であることを同定した。
<Synthesis of organosilane>
[Synthesis Example 1]
β-pinene (manufactured by Tokyo Chemical Industry Co., Ltd.) 50 g, (3-mercaptopropyl) triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) 83.1 g, 2,2′-azobis (isobutylnitrile) (Wako Pure Chemical Industries, Ltd.) Kogyo Co., Ltd. (3.50 g) and toluene (100 mL) were mixed in an eggplant flask, bubbled with nitrogen gas for 30 minutes, and reacted at 60 ° C. for 3 hours. Thereafter, the reaction solution was concentrated to obtain 122 g of a colorless and transparent liquid (yield: 92% by mass). From the result of the following NMR, it was identified that the product was a compound (organosilane 1) represented by the following formula (10).
1H NMR (400MHz CDCl3, δ in ppm):
1.21 (t, 9H, -Si-(O-CH2-CH 3 )3), 3.83 (q, 6H, -Si-(O-CH 2 -CH3)3), 0.56 (t, 2H, -CH 2 -Si-(O-CH2-CH3)3), 1.62 (m, 2H, -S-CH2-CH 2 -CH2-Si-), 2.60 (t, 2H, -S-CH 2 -CH2-CH2-Si-), 2.23-2.48 (m, 2H, -CH 2 -S-), 1.68 (m, 1H, cyclohexane CH), 1.38-1.63 (m, 2H, cyclohexane CH 2 ), 1.45-1.55 (m, 2H, cyclohexane CH 2 ), 1.20-1.45 (m, 2H, cyclohexane CH 2 ), 3.71 (m, 1H, cyclohexane CH), 3.81 (m, 1H, cyclohexane CH), 0.89 (s, 6H, methyl -(CH 3 )2).
13C NMR (400MHz CDCl3, δ in ppm):
18.4 (-Si-(O-CH2-CH3)3), 58.4 (-Si-(O-CH2-CH3)3), 15.6 (-CH2-Si-(O-CH2-CH3)3), 16.8 (-S-CH2-CH2-CH2-Si-), 36.7 (-S-CH2-CH2-CH2-Si-), 39.1 (-CH2-S-), 41.1 (cyclohexane CH),30.6 (cyclohexane CH2), 27.9 (cyclohexane CH2), 29.3 (cyclohexane CH2), 41.0 (cyclohexane CH), 48.7 (cyclohexane CH), 38.4 (cyclohexane C), 25.1 (methyl -(CH3)2).
1 H NMR (400MHz CDCl 3 , δ in ppm):
1.21 (t, 9H, -Si- (O-CH 2 -C H 3 ) 3 ), 3.83 (q, 6H, -Si- (OC H 2 -CH 3 ) 3 ), 0.56 (t, 2H, -C H 2 -Si- (O-CH 2 -CH 3 ) 3 ), 1.62 (m, 2H, -S-CH 2 -C H 2 -CH 2 -Si-), 2.60 (t, 2H, -SC H 2 -CH 2 -CH 2 -Si-), 2.23-2.48 (m, 2H, -C H 2 -S-), 1.68 (m, 1H, cyclohexane C H ), 1.38-1.63 (m, 2H, cyclohexane C H 2 ), 1.45-1.55 (m, 2H, cyclohexane C H 2 ), 1.20-1.45 (m, 2H, cyclohexane C H 2 ), 3.71 (m, 1H, cyclohexane C H ), 3.81 (m, 1H, cyclohexane C H ), 0.89 (s, 6H, methyl-(C H 3 ) 2 ).
13 C NMR (400 MHz CDCl 3 , δ in ppm):
18.4 (-Si- (O-CH 2 -C H 3 ) 3 ), 58.4 (-Si- (O- C H 2 -CH 3 ) 3 ), 15.6 ( -C H 2 -Si- (O-CH 2 -CH 3 ) 3 ), 16.8 (-S-CH 2 - C H 2 -CH 2 -Si-), 36.7 (-S- C H 2 -CH 2 -CH 2 -Si-), 39.1 ( -C H 2 -S-), 41.1 (cyclohexane C H), 30.6 (cyclohexane C H 2 ), 27.9 (cyclohexane C H 2 ), 29.3 (cyclohexane C H 2 ), 41.0 (cyclohexane C H), 48.7 (cyclohexane C H) , 38.4 (cyclohexane C ), 25.1 (methyl-( C H 3 ) 2 ).
[合成例2]
β-ミルセン(東京化成工業(株)製)50g、(3−メルカプトプロピル)トリエトキシシラン(東京化成工業(株)製)87.5g、2,2’−アゾビス(イソブチルニトリル)(和光純薬工業(株)製)1.75gおよびトルエン100mLをナスフラスコ内で混合し、窒素ガスで30分間バブリングした後、60℃で3時間反応させた。その後、反応溶液を濃縮し、131gの淡黄色の液体が得られた(収率:95質量%)。下記NMRの結果から、生成物が下記式(11)で表される化合物と下記式(12)で表される化合物との混合物(有機シラン2)であることを同定した。
[Synthesis Example 2]
β-myrcene (manufactured by Tokyo Chemical Industry Co., Ltd.) 50 g, (3-mercaptopropyl) triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) 87.5 g, 2,2′-azobis (isobutylnitrile) (Wako Pure Chemical Industries, Ltd.) 1.75 g (manufactured by Kogyo Co., Ltd.) and 100 mL of toluene were mixed in an eggplant flask, bubbled with nitrogen gas for 30 minutes, and reacted at 60 ° C. for 3 hours. Thereafter, the reaction solution was concentrated to obtain 131 g of a pale yellow liquid (yield: 95% by mass). From the following NMR results, it was identified that the product was a mixture (organosilane 2) of a compound represented by the following formula (11) and a compound represented by the following formula (12).
有機シラン2-(11)
1H NMR (400MHz CDCl3, δ in ppm):
1.21 (t, 9H, -Si-(O-CH2-CH 3 )3), 3.83 (q, 6H, -Si-(O-CH 2 -CH3)3), 0.56 (t, 2H, -CH 2 -Si-(O-CH2-CH3)3), 1.62 (m, 2H, -S-CH2-CH 2 -CH2-Si-), 2.42 (m, 2H, -S-CH 2 -CH2-CH2-Si-), 2.48 (m, 2H, -CH2-CH 2 -S-), 2.33 (m, 2H, -CH 2 -CH2-S-), 4.82 (s, 1H, 1-ethylene H), 4.57 (s, 1H, 1-ethylene H), 2.00 (s, 2H, -CH 2 -CH2-), 2.00 (s, 2H, -CH2-CH 2-), 5.20 (s, 1H, 1-ethylene H), 1.70 (m, 3H, methyl -CH 3 ), 1.82 (m, 3H, methyl -CH 3 ).
13C NMR (400MHz CDCl3, δ in ppm):
18.4 (-Si-(O-CH2-CH3)3), 58.4 (-Si-(O-CH2-CH3)3), 15.6 (-CH2-Si-(O-CH2-CH3)3), 16.8 (-S-CH2-CH2-CH2-Si-), 36.5 (-S-CH2-CH2-CH2-Si-), 31.3 (-CH2-CH2-S-), 40.3 (-CH2-CH2-S-), 148.6 (1-ethylene C=CH2), 109.2 (1-ethylene C=CH2), 27.7 (-CH2-CH2-), 26.4 (-CH2-CH2-), 123.5 (1-ethylene CH=C), 132.0 (1-ethylene CH=C), 18.6(methyl -CH3), 24.6(methyl -CH3).
Organosilane 2- (11)
1 H NMR (400MHz CDCl 3 , δ in ppm):
1.21 (t, 9H, -Si- (O-CH 2 -C H 3 ) 3 ), 3.83 (q, 6H, -Si- (OC H 2 -CH 3 ) 3 ), 0.56 (t, 2H, -C H 2 -Si- (O-CH 2 -CH 3 ) 3 ), 1.62 (m, 2H, -S-CH 2 -C H 2 -CH 2 -Si-), 2.42 (m, 2H, -SC H 2 -CH 2 -CH 2 -Si-), 2.48 (m, 2H, -CH 2 -C H 2 -S-), 2.33 (m, 2H, -C H 2 -CH 2 -S-), 4.82 (s , 1H, 1-ethylene H ), 4.57 (s, 1H, 1-ethylene H ), 2.00 (s, 2H, -C H 2 -CH 2- ), 2.00 (s, 2H, -CH 2 -C H 2 -), 5.20 (s, 1H, 1-ethylene H ), 1.70 (m, 3H, methyl -C H 3 ), 1.82 (m, 3H, methyl -C H 3 ).
13 C NMR (400 MHz CDCl 3 , δ in ppm):
18.4 (-Si- (O-CH 2 -C H 3 ) 3 ), 58.4 (-Si- (O- C H 2 -CH 3 ) 3 ), 15.6 ( -C H 2 -Si- (O-CH 2 -CH 3 ) 3 ), 16.8 (-S-CH 2 - C H 2 -CH 2 -Si-), 36.5 (-S- C H 2 -CH 2 -CH 2 -Si-), 31.3 (-CH 2 -C H 2 -S-), 40.3 ( -C H 2 -CH 2 -S-), 148.6 (1-ethylene C = CH 2 ), 109.2 (1-ethylene C = C H 2 ), 27.7 ( -C H 2 -CH 2- ), 26.4 (-CH 2 - C H 2- ), 123.5 (1-ethylene C H = C), 132.0 (1-ethylene CH = C ), 18.6 (methyl- C H 3 ), 24.6 (methyl- C H 3 ).
有機シラン2-(12)
1H NMR (400MHz CDCl3, δ in ppm):
1.21 (t, 9H, -Si-(O-CH2-CH 3 )3), 3.83 (q, 6H, -Si-(O-CH 2 -CH3)3), 0.56 (t, 2H, -CH 2 -Si-(O-CH2-CH3)3), 1.62 (m, 2H, -S-CH2-CH 2 -CH2-Si-), 2.60 (m, 2H, -S-CH 2 -CH2-CH2-Si-), 2.29-2.54 (m, 2H, CH-CH 2 -S-), 2.35 (m, 1H, CH-CH2-S-), 5.70 (m, 1H, 1-ethylene H), 5.03 (s, 1H, 1-ethylene H), 5.07 (s, 1H, 1-ethylene H), 1.31 (m, 2H, -CH2-CH 2 -), 1.94 (m, 2H, -CH 2 -CH2-), 5.20 (s, 1H, 1-ethylene H), 1.70 (m, 3H, methyl -CH 3 ), 1.82 (m, 3H, methyl -CH 3 ).
13C NMR (400MHz CDCl3, δ in ppm):
18.4 (-Si-(O-CH2-CH3)3), 58.4 (-Si-(O-CH2-CH3)3), 15.6 (-CH2-Si-(O-CH2-CH3)3), 16.8 (-S-CH2-CH2-CH2-Si-), 36.8 (-S-CH2-CH2-CH2-Si-), 36.5 (CH-CH2-S-), 40.8 (CH-CH2-S-), 138.9 (1-ethylene CH=CH2), 114.5 (1-ethylene CH=CH2), 33.9 (-CH2-CH2-), 26.0 (-CH2-CH2-), 124.7 (1-ethylene CH=C), 131.3 (1-ethylene CH=C), 18.6(methyl -CH3), 24.6(methyl -CH3).
Organosilane 2- (12)
1 H NMR (400MHz CDCl 3 , δ in ppm):
1.21 (t, 9H, -Si- (O-CH 2 -C H 3 ) 3 ), 3.83 (q, 6H, -Si- (OC H 2 -CH 3 ) 3 ), 0.56 (t, 2H, -C H 2 -Si- (O-CH 2 -CH 3 ) 3 ), 1.62 (m, 2H, -S-CH 2 -C H 2 -CH 2 -Si-), 2.60 (m, 2H, -SC H 2 -CH 2 -CH 2 -Si-), 2.29-2.54 (m, 2H, CH-C H 2 -S-), 2.35 (m, 1H, C H -CH 2 -S-), 5.70 (m, 1H , 1-ethylene H ), 5.03 (s, 1H, 1-ethylene H ), 5.07 (s, 1H, 1-ethylene H ), 1.31 (m, 2H, -CH 2 -C H 2- ), 1.94 (m , 2H, -C H 2 -CH 2- ), 5.20 (s, 1H, 1-ethylene H ), 1.70 (m, 3H, methyl -C H 3 ), 1.82 (m, 3H, methyl -C H 3 ) .
13 C NMR (400 MHz CDCl 3 , δ in ppm):
18.4 (-Si- (O-CH 2 -C H 3 ) 3 ), 58.4 (-Si- (O- C H 2 -CH 3 ) 3 ), 15.6 ( -C H 2 -Si- (O-CH 2 -CH 3 ) 3 ), 16.8 (-S-CH 2 - C H 2 -CH 2 -Si-), 36.8 (-S- C H 2 -CH 2 -CH 2 -Si-), 36.5 (CH- C H 2 -S-), 40.8 ( C H-CH 2 -S-), 138.9 (1-ethylene C H = CH 2 ), 114.5 (1-ethylene CH = C H 2 ), 33.9 (-CH 2 - C H 2- ), 26.0 ( -C H 2 -CH 2- ), 124.7 (1-ethylene C H = C), 131.3 (1-ethylene CH = C ), 18.6 (methyl- C H 3 ), 24.6 (methyl -C H 3 ).
[合成例3]
β-ミルセン(東京化成工業(株)製)50g、(3−メルカプトプロピル)トリエトキシシラン(東京化成工業(株)製)175.0g、2,2’−アゾビス(イソブチルニトリル)(和光純薬工業(株)製)3.50gおよびトルエン200mLをナスフラスコ内で混合し、窒素ガスで30分間バブリングした後、60℃で3時間反応させた。その後、反応溶液を濃縮し、203gの淡黄色の液体が得られた(収率:90質量%)。下記NMRの結果から、生成物が下記式(13)で表される化合物(有機シラン3)であることを同定した。
[Synthesis Example 3]
β-Myrcene (manufactured by Tokyo Chemical Industry Co., Ltd.) 50 g, (3-mercaptopropyl) triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) 175.0 g, 2,2′-azobis (isobutylnitrile) (Wako Pure Chemical Industries, Ltd.) (Industry Co., Ltd.) 3.50 g and toluene 200 mL were mixed in an eggplant flask, bubbled with nitrogen gas for 30 minutes, and reacted at 60 ° C. for 3 hours. Thereafter, the reaction solution was concentrated to obtain 203 g of a pale yellow liquid (yield: 90% by mass). From the following NMR results, it was identified that the product was a compound (organosilane 3) represented by the following formula (13).
1H NMR (400MHz CDCl3, δ in ppm):
1.21 (t, 18H, (-Si-(O-CH2-CH 3 )3)2), 3.83 (q, 12H, (-Si-(O-CH 2 -CH3)3)2), 0.56 (t, 2H, -CH 2 -Si-(O-CH2-CH3)3), 1.62 (m, 2H, -S-CH2-CH 2 -CH2-Si-), 2.60 (m, 2H, -S-CH 2 -CH2-CH2-Si-),2.23-2.48 (m, 2H, CH-CH 2 -S-), 0.56 (t, 2H, -CH 2 -Si-(O-CH2-CH3)3), 1.62 (m, 2H, -S-CH2-CH 2 -CH2-Si-), 2.42 (m, 2H, -S-CH 2 -CH2-CH2-Si-), 2.60 (m, 2H, CH-CH2-CH 2 -S-), 1.58 (m, 2H, CH-CH 2-CH2-S-), 1.57 (m, 1H, CH-CH2-CH2-S-), 1.53 (m, 2H, -CH2-CH 2-CH) , 1.94 (m, 2H, -CH 2-CH2-CH), 5.20 (m, 1H, 1-ethylene H), 1.70 (m, 3H, methyl -CH 3 ) , 1.82 (m, 3H, methyl -CH 3 )
13C NMR (400MHz CDCl3, δ in ppm):
18.4 ((-Si-(O-CH2-CH3)3)2, 58.4 ((-Si-(O-CH2-CH3)3)2, 15.6 (-CH2-Si-(O-CH2-CH3)3), 16.8 (-S-CH2-CH2-CH2-Si-), 36.7 (-S-CH2-CH2-CH2-Si-), 40.7 (CH-CH2-S-), 15.6 (-CH2-Si-(O-CH2-CH3)3), 16.8 (-S-CH2-CH2-CH2-Si-), 36.4 (-S-CH2-CH2-CH2-Si-), 30.3 (CH-CH2-CH2-S-), 31.3 (CH-CH2-CH2-S-), 36.5 (CH-CH2-CH2-S-), 34.0 (-CH2-CH2-CH), 24.0 (-CH2-CH2-CH), 124.7 (1-ethylene CH=C), 131.3 (1-ethylene CH=C), 18.6(methyl -CH3), 24.6(methyl -CH3).
1 H NMR (400MHz CDCl 3 , δ in ppm):
1.21 (t, 18H, (-Si- (O-CH 2 -C H 3 ) 3 ) 2 ), 3.83 (q, 12H, (-Si- (OC H 2 -CH 3 ) 3 ) 2 ), 0.56 ( t, 2H, -C H 2 -Si- (O-CH 2 -CH 3 ) 3 ), 1.62 (m, 2H, -S-CH 2 -C H 2 -CH 2 -Si-), 2.60 (m, 2H, -SC H 2 -CH 2 -CH 2 -Si-), 2.23-2.48 (m, 2H, CH-C H 2 -S-), 0.56 (t, 2H, -C H 2 -Si- (O -CH 2 -CH 3 ) 3 ), 1.62 (m, 2H, -S-CH 2 -C H 2 -CH 2 -Si-), 2.42 (m, 2H, -SC H 2 -CH 2 -CH 2- Si-), 2.60 (m, 2H, CH-CH 2 -C H 2 -S-), 1.58 (m, 2H, CH-C H 2 -CH 2 -S-), 1.57 (m, 1H, C H -CH 2 -CH 2 -S-), 1.53 (m, 2H, -CH 2 -C H 2 -CH), 1.94 (m, 2H, -C H 2 -CH 2 -CH), 5.20 (m, 1H , 1-ethylene H ), 1.70 (m, 3H, methyl -C H 3 ), 1.82 (m, 3H, methyl -C H 3 )
13 C NMR (400 MHz CDCl 3 , δ in ppm):
18.4 ((-Si- (O-CH 2 -C H 3 ) 3 ) 2 , 58.4 ((-Si- (O- C H 2 -CH 3 ) 3 ) 2 , 15.6 ( -C H 2 -Si- ( O-CH 2 -CH 3 ) 3 ), 16.8 (-S-CH 2 - C H 2 -CH 2 -Si-), 36.7 (-S- C H 2 -CH 2 -CH 2 -Si-), 40.7 (CH- C H 2 -S-), 15.6 ( -C H 2 -Si- (O-CH 2 -CH 3 ) 3 ), 16.8 (-S-CH 2 - C H 2 -CH 2 -Si-) , 36.4 (-S- C H 2 -CH 2 -CH 2 -Si-), 30.3 (CH-CH 2 - C H 2 -S-), 31.3 (CH- C H 2 -CH 2 -S-), 36.5 ( C H-CH 2 -CH 2 -S-), 34.0 (-CH 2 - C H 2 -CH), 24.0 ( -C H 2 -CH 2 -CH), 124.7 (1-ethylene C H = C ), 131.3 (1-ethylene CH = C ), 18.6 (methyl- C H 3 ), 24.6 (methyl- C H 3 ).
[合成例4]
β-ファルネセン(Sigma-Aldrich製)50g、(3−メルカプトプロピル)トリエトキシシラン(東京化成工業(株)製)116.7g、2,2’−アゾビス(イソブチルニトリル)(和光純薬工業(株)製)2.33gおよびトルエン200mLをナスフラスコ内で混合し、窒素ガスで30分間バブリングした後、60℃で3時間反応させた。その後、反応溶液を濃縮し、151gの淡黄色の液体が得られた(収率:91質量%)。下記NMRの結果から、生成物が下記式(14)で表される化合物(有機シラン4)であることを同定した。
[Synthesis Example 4]
β-farnesene (manufactured by Sigma-Aldrich) 50 g, (3-mercaptopropyl) triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) 116.7 g, 2,2′-azobis (isobutylnitrile) (Wako Pure Chemical Industries, Ltd.) 2) 2.33 g and toluene 200 mL were mixed in an eggplant flask, bubbled with nitrogen gas for 30 minutes, and reacted at 60 ° C. for 3 hours. Thereafter, the reaction solution was concentrated to obtain 151 g of a pale yellow liquid (yield: 91% by mass). From the NMR results below, it was identified that the product was a compound represented by the following formula (14) (organosilane 4).
1H NMR (400MHz CDCl3, δ in ppm):
1.21 (t, 18H, (-Si-(O-CH2-CH 3 )3)2), 3.83 (q, 12H, (-Si-(O-CH 2 -CH3)3)2), 0.56 (t, 2H, -CH 2 -Si-(O-CH2-CH3)3), 1.62 (m, 2H, -S-CH2-CH 2 -CH2-Si-), 2.60 (m, 2H, -S-CH 2 -CH2-CH2-Si-),2.23-2.48 (m, 2H, CH-CH 2 -S-), 0.56 (t, 2H, -CH 2 -Si-(O-CH2-CH3)3), 1.62 (m, 2H, -S-CH2-CH 2 -CH2-Si-), 2.42 (m, 2H, -S-CH 2 -CH2-CH2-Si-), 2.60 (m, 2H, CH-CH2-CH 2 -S-), 1.58 (m, 2H, CH-CH 2-CH2-S-), 1.57 (m, 1H, CH-CH2-CH2-S-), 1.53 (m, 2H, -CH2-CH 2-CH), 1.94 (m, 2H, -CH 2-CH2-CH), 5.20 (m, 1H, 1-ethylene H), 1.79 (m, 3H, methyl -CH 3 ), 2.00 (s, 2H, -CH2-CH 2-C=), 2.00 (s, 2H, -CH 2-CH2-C=), 5.20 (m, 1H, 1-ethylene H), 1.70 (m, 3H, methyl -CH 3 ), 1.82 (m, 3H, methyl -CH 3 )
13C NMR (400MHz CDCl3, δ in ppm):
18.4 ((-Si-(O-CH2-CH3)3)2, 58.4 ((-Si-(O-CH2-CH3)3)2, 15.6 (-CH2-Si-(O-CH2-CH3)3), 16.8 (-S-CH2-CH2-CH2-Si-), 36.7 (-S-CH2-CH2-CH2-Si-), 40.7 (CH-CH2-S-), 15.6 (-CH2-Si-(O-CH2-CH3)3), 16.8 (-S-CH2-CH2-CH2-Si-), 36.4 (-S-CH2-CH2-CH2-Si-), 30.3 (CH-CH2-CH2-S-), 31.3 (CH-CH2-CH2-S-), 36.5 (CH-CH2-CH2-S-), 34.0 (-CH2-CH2-CH), 24.0 (-CH2-CH2-CH), 124.7 (1-ethylene CH=C), 135.0 (1-ethylene CH=C), 16.4(methyl -CH3), 39.7 (-CH2-CH2-C=), 26.4 (-CH2-CH2-C=), 123.5 (1-ethylene CH=C), 132.0 (1-ethylene CH=C), 18.6(methyl -CH3), 24.6(methyl -CH3).
1 H NMR (400MHz CDCl 3 , δ in ppm):
1.21 (t, 18H, (-Si- (O-CH 2 -C H 3 ) 3 ) 2 ), 3.83 (q, 12H, (-Si- (OC H 2 -CH 3 ) 3 ) 2 ), 0.56 ( t, 2H, -C H 2 -Si- (O-CH 2 -CH 3 ) 3 ), 1.62 (m, 2H, -S-CH 2 -C H 2 -CH 2 -Si-), 2.60 (m, 2H, -SC H 2 -CH 2 -CH 2 -Si-), 2.23-2.48 (m, 2H, CH-C H 2 -S-), 0.56 (t, 2H, -C H 2 -Si- (O -CH 2 -CH 3 ) 3 ), 1.62 (m, 2H, -S-CH 2 -C H 2 -CH 2 -Si-), 2.42 (m, 2H, -SC H 2 -CH 2 -CH 2- Si-), 2.60 (m, 2H, CH-CH 2 -C H 2 -S-), 1.58 (m, 2H, CH-C H 2 -CH 2 -S-), 1.57 (m, 1H, C H -CH 2 -CH 2 -S-), 1.53 (m, 2H, -CH 2 -C H 2 -CH), 1.94 (m, 2H, -C H 2 -CH 2 -CH), 5.20 (m, 1H , 1-ethylene H ), 1.79 (m, 3H, methyl -C H 3 ), 2.00 (s, 2H, -CH 2 -C H 2 -C =), 2.00 (s, 2H, -C H 2 -CH 2 -C =), 5.20 (m, 1H, 1-ethylene H ), 1.70 (m, 3H, methyl -C H 3 ), 1.82 (m, 3H, methyl -C H 3 )
13 C NMR (400 MHz CDCl 3 , δ in ppm):
18.4 ((-Si- (O-CH 2 -C H 3 ) 3 ) 2 , 58.4 ((-Si- (O- C H 2 -CH 3 ) 3 ) 2 , 15.6 ( -C H 2 -Si- ( O-CH 2 -CH 3 ) 3 ), 16.8 (-S-CH 2 - C H 2 -CH 2 -Si-), 36.7 (-S- C H 2 -CH 2 -CH 2 -Si-), 40.7 (CH- C H 2 -S-), 15.6 ( -C H 2 -Si- (O-CH 2 -CH 3 ) 3 ), 16.8 (-S-CH 2 - C H 2 -CH 2 -Si-) , 36.4 (-S- C H 2 -CH 2 -CH 2 -Si-), 30.3 (CH-CH 2 - C H 2 -S-), 31.3 (CH- C H 2 -CH 2 -S-), 36.5 ( C H-CH 2 -CH 2 -S-), 34.0 (-CH 2 - C H 2 -CH), 24.0 ( -C H 2 -CH 2 -CH), 124.7 (1-ethylene C H = C ), 135.0 (1-ethylene CH = C ), 16.4 (methyl- C H 3 ), 39.7 (-CH 2 - C H 2 -C =), 26.4 ( -C H 2 -CH 2 -C =), 123.5 (1-ethylene C H = C), 132.0 (1-ethylene CH = C ), 18.6 (methyl- C H 3 ), 24.6 (methyl- C H 3 ).
[合成例5]
β-エレメン(Sigma-Aldrich製)10g、(3−メルカプトプロピル)トリエトキシシラン(東京化成工業(株)製)35.0g、2,2’−アゾビス(イソブチルニトリル)(和光純薬工業(株)製)0.70gおよびトルエン200mLをナスフラスコ内で混合し、窒素ガスで30分間バブリングした後、60℃で3時間反応させた。その後、反応溶液を濃縮し、39.6gの無色透明の液体が得られた(収率:88質量%)。下記NMRの結果から、生成物が下記式(15)で表される化合物(有機シラン5)であることを同定した。
[Synthesis Example 5]
β-elemene (manufactured by Sigma-Aldrich) 10 g, (3-mercaptopropyl) triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) 35.0 g, 2,2′-azobis (isobutylnitrile) (Wako Pure Chemical Industries, Ltd.) )) 0.70 g and 200 mL of toluene were mixed in an eggplant flask, bubbled with nitrogen gas for 30 minutes, and reacted at 60 ° C. for 3 hours. Thereafter, the reaction solution was concentrated to obtain 39.6 g of a colorless and transparent liquid (yield: 88% by mass). From the NMR results shown below, it was identified that the product was a compound represented by the following formula (15) (organosilane 5).
1H NMR (400MHz CDCl3, δ in ppm):
1.21 (t, 27H, (-S-CH2-CH2-CH2-Si-(O-CH2-CH 3 )3)3), 3.83 (q, 18H, (-S-CH2-CH2-CH2-Si-(O-CH 2 -CH3)3)3), 0.56 (t, 6H, (-S-CH2-CH2-CH 2 -Si-(O-CH2-CH3)3)3), 1.62 (m, 6H, (-S-CH2-CH 2 -CH2-Si-(O-CH2-CH3)3)3), 2.42-2.60 (m, 6H, (-S-CH 2 -CH2-CH2-Si-(O-CH2-CH3)3)3), 2.60 (m, 2H, -CH2-CH 2 -S-), 1.52 (m, 2H, -CH 2 -CH2-S-), 0.70 (m, 3H, methyl -CH 3 ), 2.23-2.48 (m, 2H, -CH-CH 2 -S-), 1.67 (m, 1H, -CH-CH2-S-), 0.93 (m, 3H, methyl -CH 3 ), 2.23-2.48 (m, 2H, -CH-CH 2 -S-), 1.67 (m, 1H, -CH-CH2-S-), 0.93 (m, 3H, methyl -CH 3 ), 1.31-1.56 (m, 2H, cyclohexane CH 2 ), 1.38-1.63 (m, 2H, cyclohexane CH 2 ), 1.20-1.45 (m, 2H, cyclohexane CH 2 ), 1.04 (m, 1H, cyclohexane CH), 1.24 (m, 1H, cyclohexane CH)
13C NMR (400MHz CDCl3, δ in ppm):
18.4 (((-Si-(O-CH2-CH3)3)3), 58.4 (((-Si-(O-CH2-CH3)3)3), 15.6 ((-S-CH2-CH2-CH2-Si-(O-CH2-CH3)3)3), 16.8 ((-S-CH2-CH2-CH2-Si-(O-CH2-CH3)3)3), 36.7 ((-S-CH2-CH2-CH2-Si-(O-CH2-CH3)3)3), 28.8 (CH2-CH2-S-), 40.7 (CH2-CH2-S-), 19.9 (methyl -CH3), 41.9 (CH-CH2-S-), 31.7 (CH-CH2-S-), 15.5 (methyl -CH3), 41.3 (CH-CH2-S-), 36.4 (CH-CH2-S-), 14.9 (methyl -CH3), 34.0 (cyclohexane C), 40.4 (cyclohexane CH2), 23.5 (cyclohexane CH2), 39.9 (cyclohexane CH), 25.4 (cyclohexane CH2), 53.3 (cyclohexane CH).
1 H NMR (400MHz CDCl 3 , δ in ppm):
1.21 (t, 27H, (-S-CH 2 -CH 2 -CH 2 -Si- (O-CH 2 -C H 3 ) 3 ) 3 ), 3.83 (q, 18H, (-S-CH 2 -CH 2 -CH 2 -Si- (OC H 2 -CH 3 ) 3 ) 3 ), 0.56 (t, 6H, (-S-CH 2 -CH 2 -C H 2 -Si- (O-CH 2 -CH 3 3 ) 3 ), 1.62 (m, 6H, (-S-CH 2 -C H 2 -CH 2 -Si- (O-CH 2 -CH 3 ) 3 ) 3 ), 2.42-2.60 (m, 6H, (-SC H 2 -CH 2 -CH 2 -Si- (O-CH 2 -CH 3 ) 3 ) 3 ), 2.60 (m, 2H, -CH 2 -C H 2 -S-), 1.52 (m, 2H, -C H 2 -CH 2 -S-), 0.70 (m, 3H, methyl -C H 3 ), 2.23-2.48 (m, 2H, -CH-C H 2 -S-), 1.67 (m, 1H, -C H -CH 2 -S-), 0.93 (m, 3H, methyl -C H 3 ), 2.23-2.48 (m, 2H, -CH-C H 2 -S-), 1.67 (m, 1H , -C H -CH 2 -S-), 0.93 (m, 3H, methyl -C H 3 ), 1.31-1.56 (m, 2H, cyclohexane C H 2 ), 1.38-1.63 (m, 2H, cyclohexane C H 2 ), 1.20-1.45 (m, 2H, cyclohexane C H 2 ), 1.04 (m, 1H, cyclohexane C H ), 1.24 (m, 1H, cyclohexane C H )
13 C NMR (400 MHz CDCl 3 , δ in ppm):
18.4 (((-Si- (O- CH 2 - C H 3) 3) 3), 58.4 (((-Si- (O- C H 2 -CH 3) 3) 3), 15.6 ((-S- CH 2 -CH 2 - C H 2 -Si- (O-CH 2 -CH 3 ) 3 ) 3 ), 16.8 ((-S-CH 2 - C H 2 -CH 2 -Si- (O-CH 2- CH 3 ) 3 ) 3 ), 36.7 ((-S- C H 2 -CH 2 -CH 2 -Si- (O-CH 2 -CH 3 ) 3 ) 3 ), 28.8 (CH 2 - C H 2 -S -), 40.7 ( C H 2 -CH 2 -S-), 19.9 (methyl- C H 3 ), 41.9 (CH- C H 2 -S-), 31.7 ( C H-CH 2 -S-), 15.5 (methyl- C H 3 ), 41.3 (CH- C H 2 -S-), 36.4 ( C H-CH 2 -S-), 14.9 (methyl- C H 3 ), 34.0 (cyclohexane C ), 40.4 (cyclohexane C H 2 ), 23.5 (cyclohexane C H 2 ), 39.9 (cyclohexane C H), 25.4 (cyclohexane C H 2 ), 53.3 (cyclohexane C H).
<ゴム組成物の評価>
バンバリーミキサーを使用し、下記表1に示す配合(質量部)に従って、まず、第一混合段階で、ジエン系ゴム成分に対し硫黄及び加硫促進剤を除く他の配合剤を添加し混練し(排出温度=160℃)、次いで、得られた混練物に、最終混合段階で、硫黄と加硫促進剤を添加し混練して(排出温度=90℃)、ゴム組成物を調製した。表1中の各成分の詳細は、以下の通りである。
<Evaluation of rubber composition>
Using a Banbury mixer, according to the formulation (parts by mass) shown in Table 1 below, first, in the first mixing stage, other compounding agents except for sulfur and vulcanization accelerator are added to the diene rubber component and kneaded ( (Discharge temperature = 160 ° C.) Then, sulfur and a vulcanization accelerator were added and kneaded to the obtained kneaded product in the final mixing stage (discharge temperature = 90 ° C.) to prepare a rubber composition. The details of each component in Table 1 are as follows.
・未変性SBR:ランクセス株式会社製「VSL5025−0HM」
・変性SBR:アミノ基及びアルコキシ基末端変性溶液重合スチレンブタジエンゴム、JSR株式会社製「HPR350」
・BR:宇部興産株式会社製「BR150B」
・シランカップリング剤:ビス(3−トリエトキシシリルプロピル)テトラスルフィド、エボニック・デグサ社製「Si69」
・有機シラン1〜5:合成例1〜5で合成したもの
・シリカ:東ソー・シリカ株式会社製「ニップシールAQ」(BET=205m2/g)
・カーボンブラック:三菱化学株式会社製「ダイアブラックN341」
・オイル:昭和シェル石油株式会社製「エキストラクト4号S」
・亜鉛華:三井金属鉱業株式会社製「亜鉛華1号」
・老化防止剤:住友化学株式会社製「アンチゲン6C」
・ステアリン酸:花王株式会社製「ルナックS−20」
・ワックス:日本精鑞株式会社製「OZOACE0355」
・硫黄:鶴見化学工業株式会社製「5%油入微粉末硫黄」
・加硫促進剤:住友化学株式会社製「ソクシノールCZ」
Unmodified SBR: “VSL5025-0HM” manufactured by LANXESS
-Modified SBR: amino group and alkoxy group terminal modified solution polymerized styrene butadiene rubber, "HPR350" manufactured by JSR Corporation
-BR: “BR150B” manufactured by Ube Industries, Ltd.
Silane coupling agent: bis (3-triethoxysilylpropyl) tetrasulfide, “Si69” manufactured by Evonik Degussa
・ Organic silane 1-5: synthesized in Synthesis Examples 1-5 ・ Silica: Tosoh ・ “Nip seal AQ” manufactured by Silica Co., Ltd. (BET = 205 m 2 / g)
Carbon black: “Dia Black N341” manufactured by Mitsubishi Chemical Corporation
-Oil: "Extract No. 4 S" manufactured by Showa Shell Sekiyu KK
・ Zinc flower: “Zinc flower No. 1” manufactured by Mitsui Mining & Smelting Co., Ltd.
Anti-aging agent: “Antigen 6C” manufactured by Sumitomo Chemical Co., Ltd.
・ Stearic acid: “Lunac S-20” manufactured by Kao Corporation
・ Wax: Nippon Seiki Co., Ltd. “OZOACE0355”
・ Sulfur: “5% oil-filled fine powder sulfur” manufactured by Tsurumi Chemical Co., Ltd.
・ Vulcanization accelerator: “Soxinol CZ” manufactured by Sumitomo Chemical Co., Ltd.
得られた各ゴム組成物について、160℃×20分で加硫して所定形状の試験片を作製し、低発熱性と耐摩耗性を評価した。各評価方法は以下の通りである。
・低発熱性:東洋精機株式会社製の粘弾性試験機を用いて、初期歪み10%、動的歪み1%、周波数10Hz、温度60℃の条件下で損失係数tanδを測定し、比較例2の値を100とした指数で示した。指数が小さいほどtanδが小さく、従って発熱しにくく、タイヤとしての低燃費性能に優れることを示す。
・耐摩耗性:JIS K6264に準拠し、岩本製作所(株)製のランボーン摩耗試験機を用いて、荷重40N、スリップ率30%の条件で摩耗減量を測定し、摩耗減量の逆数について比較例1の値を100とした指数で示した。指数が大きいほど、摩耗減量が少なく、耐摩耗性に優れることを示す。
About each obtained rubber composition, it vulcanized | cured at 160 degreeC * 20 minutes, the test piece of a predetermined shape was produced, and low heat build-up and abrasion resistance were evaluated. Each evaluation method is as follows.
Low exothermic property: Using a viscoelasticity tester manufactured by Toyo Seiki Co., Ltd., a loss factor tan δ was measured under conditions of initial strain 10%, dynamic strain 1%, frequency 10 Hz, and temperature 60 ° C. It was shown as an index with the value of 100 as 100. The smaller the index, the smaller the tan δ, and thus the less heat is generated, and the better the fuel efficiency of the tire.
-Abrasion resistance: In accordance with JIS K6264, a wear loss tester manufactured by Iwamoto Seisakusho Co., Ltd. was used to measure wear loss under the conditions of a load of 40 N and a slip rate of 30%. It was shown as an index with the value of 100 as 100. The larger the index, the less the weight loss and the better the wear resistance.
結果は、表1に示す通りである。実施例1〜5に示すように、シランカップリング剤として合成例1〜5に係る有機シラン1〜5を配合した場合、汎用のスルフィドシランカップリング剤を配合した比較例2に対して、低発熱性と耐摩耗性が顕著に改善された。また、実施例6に示すように、汎用のシランカップリング剤と有機シラン1を併用した場合にも、低発熱性と耐摩耗性が顕著に改善された。実施例10に示すように、シリカとカーボンブラックを同量で併用した場合でも、低発熱性と耐摩耗性に優れていた。 The results are as shown in Table 1. As shown in Examples 1 to 5, when the organic silanes 1 to 5 according to Synthesis Examples 1 to 5 are blended as silane coupling agents, they are low compared to Comparative Example 2 in which a general-purpose sulfide silane coupling agent is blended. The heat generation and wear resistance were remarkably improved. Further, as shown in Example 6, even when a general-purpose silane coupling agent and organosilane 1 were used in combination, the low heat buildup and wear resistance were remarkably improved. As shown in Example 10, even when silica and carbon black were used in the same amount, they were excellent in low heat buildup and wear resistance.
比較例3に示すように、汎用のシランカップリング剤において、ジエン系ゴムとして変性SBRを用いた場合、低発熱性は改善されたものの、耐摩耗性が低下していた。これに対し、実施例7〜9に示すように、実施形態に係る有機シランを用いた場合、変性SBRと組み合わせることにより、対応する実施例1,2,4に比べて低発熱性の更なる改善効果がみられ、また、比較例3に対して耐摩耗性の悪化を抑えることができた。 As shown in Comparative Example 3, when a modified SBR was used as a diene rubber in a general-purpose silane coupling agent, the low heat build-up was improved, but the wear resistance was reduced. On the other hand, as shown in Examples 7 to 9, when the organosilane according to the embodiment is used, by combining with the modified SBR, it is further less exothermic than the corresponding Examples 1, 2, and 4. The improvement effect was observed, and the deterioration of wear resistance was suppressed with respect to Comparative Example 3.
Claims (4)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014195069A JP6377476B2 (en) | 2014-09-25 | 2014-09-25 | Organosilane and rubber composition using the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014195069A JP6377476B2 (en) | 2014-09-25 | 2014-09-25 | Organosilane and rubber composition using the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2016065017A true JP2016065017A (en) | 2016-04-28 |
JP6377476B2 JP6377476B2 (en) | 2018-08-22 |
Family
ID=55804969
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2014195069A Active JP6377476B2 (en) | 2014-09-25 | 2014-09-25 | Organosilane and rubber composition using the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP6377476B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110719922A (en) * | 2017-06-07 | 2020-01-21 | 飞纳技术有限公司 | Silane-functionalized poly (farnesene) and rubber mixtures comprising the same |
WO2022215986A1 (en) * | 2021-04-06 | 2022-10-13 | 부산대학교 산학협력단 | Liquid butadiene compound with both ends modified, method for preparing same, and use of same |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102565386B1 (en) * | 2021-04-06 | 2023-08-09 | 부산대학교 산학협력단 | Rubber composition for manufacturing tires comprising terminally modified liquid polybutadienes |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004009695A1 (en) * | 2002-07-19 | 2004-01-29 | Societe De Technologie Michelin | Rubber composition for tyre comprising a coupling agent with cyclic polysulphide function |
JP2004514657A (en) * | 2000-09-08 | 2004-05-20 | クロムプトン コーポレイション | Hydrocarbon core polysulfide silane coupling agent for filled elastomer composition |
JP2007514033A (en) * | 2003-12-15 | 2007-05-31 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Coupling agent between filler and elastomer |
JP2010514765A (en) * | 2006-12-28 | 2010-05-06 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Silanized core polysulfides, their manufacture and use in filler-containing elastomer compositions |
WO2012050667A1 (en) * | 2010-10-13 | 2012-04-19 | Exxonmobil Chemical Patents Inc. | Silane-functionalized hydrocarbon polymer modifiers for elastomeric compositions |
JP2012111838A (en) * | 2010-11-24 | 2012-06-14 | Shikoku Chem Corp | Rubber composition |
JP2014177577A (en) * | 2013-03-15 | 2014-09-25 | Toyo Tire & Rubber Co Ltd | Rubber composition and pneumatic tire |
JP2014234378A (en) * | 2013-06-04 | 2014-12-15 | ダイソー株式会社 | Organosilicon compound, method for producing the same and rubber composition |
JP2015172018A (en) * | 2014-03-12 | 2015-10-01 | ダイソー株式会社 | Sulfur-containing organic silicon product, production method thereof, and rubber composition |
-
2014
- 2014-09-25 JP JP2014195069A patent/JP6377476B2/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004514657A (en) * | 2000-09-08 | 2004-05-20 | クロムプトン コーポレイション | Hydrocarbon core polysulfide silane coupling agent for filled elastomer composition |
WO2004009695A1 (en) * | 2002-07-19 | 2004-01-29 | Societe De Technologie Michelin | Rubber composition for tyre comprising a coupling agent with cyclic polysulphide function |
JP2007514033A (en) * | 2003-12-15 | 2007-05-31 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Coupling agent between filler and elastomer |
JP2010514765A (en) * | 2006-12-28 | 2010-05-06 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Silanized core polysulfides, their manufacture and use in filler-containing elastomer compositions |
WO2012050667A1 (en) * | 2010-10-13 | 2012-04-19 | Exxonmobil Chemical Patents Inc. | Silane-functionalized hydrocarbon polymer modifiers for elastomeric compositions |
JP2012111838A (en) * | 2010-11-24 | 2012-06-14 | Shikoku Chem Corp | Rubber composition |
JP2014177577A (en) * | 2013-03-15 | 2014-09-25 | Toyo Tire & Rubber Co Ltd | Rubber composition and pneumatic tire |
JP2014234378A (en) * | 2013-06-04 | 2014-12-15 | ダイソー株式会社 | Organosilicon compound, method for producing the same and rubber composition |
JP2015172018A (en) * | 2014-03-12 | 2015-10-01 | ダイソー株式会社 | Sulfur-containing organic silicon product, production method thereof, and rubber composition |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110719922A (en) * | 2017-06-07 | 2020-01-21 | 飞纳技术有限公司 | Silane-functionalized poly (farnesene) and rubber mixtures comprising the same |
CN110719922B (en) * | 2017-06-07 | 2022-07-05 | 飞纳技术有限公司 | Silane-functionalized poly (farnesene) and rubber mixtures comprising the same |
WO2022215986A1 (en) * | 2021-04-06 | 2022-10-13 | 부산대학교 산학협력단 | Liquid butadiene compound with both ends modified, method for preparing same, and use of same |
Also Published As
Publication number | Publication date |
---|---|
JP6377476B2 (en) | 2018-08-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6009381B2 (en) | Organosilane and method for producing the same | |
JP5903147B2 (en) | Free-flowing filler composition and rubber composition containing the same | |
JP5885504B2 (en) | Pneumatic tire | |
JP5835351B2 (en) | Rubber composition for tire tread | |
JP2014177432A (en) | Organosilane and its manufacturing method | |
JP6018001B2 (en) | Rubber composition and pneumatic tire | |
JP6047434B2 (en) | Organosilane and method for producing the same | |
JP2008163125A (en) | Rubber composition and pneumatic tire using the same | |
JP6377476B2 (en) | Organosilane and rubber composition using the same | |
JP6345562B2 (en) | Rubber composition and pneumatic tire using the same | |
JP6047435B2 (en) | Organosilane and method for producing the same | |
JP2014177580A (en) | Rubber composition and pneumatic tire | |
JP6058437B2 (en) | Rubber composition and pneumatic tire | |
JP2014133827A (en) | Rubber composition | |
JP5562798B2 (en) | Rubber composition for tire and pneumatic tire | |
JP2016008284A (en) | Rubber composition for tire | |
JP6359395B2 (en) | Silane compound and rubber composition using the same | |
JP2016030815A (en) | Rubber composition for tire | |
JP6451265B2 (en) | Rubber composition for tire | |
JP6067435B2 (en) | Rubber composition and pneumatic tire | |
JP6161506B2 (en) | Organosilane and rubber composition using the same | |
JP2017114975A (en) | Rubber composition and pneumatic tire | |
JP6719249B2 (en) | Rubber composition and pneumatic tire | |
JP6305796B2 (en) | Process for producing alkoxy-modified diene rubber and rubber composition using the same | |
JP5901993B2 (en) | Rubber compounding agent and method for producing rubber composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20170522 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180116 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180118 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180307 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20180717 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20180725 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6377476 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |