WO2021256295A1 - シランカップリング剤組成物およびそれを含むゴム組成物 - Google Patents
シランカップリング剤組成物およびそれを含むゴム組成物 Download PDFInfo
- Publication number
- WO2021256295A1 WO2021256295A1 PCT/JP2021/021318 JP2021021318W WO2021256295A1 WO 2021256295 A1 WO2021256295 A1 WO 2021256295A1 JP 2021021318 W JP2021021318 W JP 2021021318W WO 2021256295 A1 WO2021256295 A1 WO 2021256295A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- integer
- carbon atoms
- silane compound
- hydrogen atom
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 188
- 229920001971 elastomer Polymers 0.000 title claims abstract description 137
- 239000005060 rubber Substances 0.000 title claims abstract description 136
- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 85
- 229910000077 silane Inorganic materials 0.000 claims abstract description 174
- -1 silane compound Chemical class 0.000 claims abstract description 171
- 150000001875 compounds Chemical class 0.000 claims abstract description 112
- 125000000217 alkyl group Chemical group 0.000 claims description 129
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 127
- 125000004432 carbon atom Chemical group C* 0.000 claims description 125
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 104
- 229910052757 nitrogen Inorganic materials 0.000 claims description 69
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 58
- 229910052717 sulfur Chemical group 0.000 claims description 53
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 51
- 239000011593 sulfur Chemical group 0.000 claims description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 40
- 229910052760 oxygen Inorganic materials 0.000 claims description 35
- 239000001301 oxygen Chemical group 0.000 claims description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 31
- 239000000377 silicon dioxide Substances 0.000 claims description 31
- 125000005842 heteroatom Chemical group 0.000 claims description 29
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 28
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 24
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 22
- 125000003277 amino group Chemical group 0.000 claims description 21
- 125000003545 alkoxy group Chemical group 0.000 claims description 19
- 229920003244 diene elastomer Polymers 0.000 claims description 17
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000001993 dienes Chemical class 0.000 claims description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 7
- 239000000446 fuel Substances 0.000 abstract description 11
- 150000004756 silanes Chemical class 0.000 abstract description 11
- 150000002430 hydrocarbons Chemical group 0.000 description 53
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 46
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 26
- 229940125904 compound 1 Drugs 0.000 description 22
- 229940125782 compound 2 Drugs 0.000 description 19
- 244000043261 Hevea brasiliensis Species 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 18
- 238000004898 kneading Methods 0.000 description 18
- 229920003052 natural elastomer Polymers 0.000 description 18
- 229920001194 natural rubber Polymers 0.000 description 18
- 238000005259 measurement Methods 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 15
- 238000004073 vulcanization Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000011787 zinc oxide Substances 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 12
- 229920003049 isoprene rubber Polymers 0.000 description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 12
- 229920000620 organic polymer Polymers 0.000 description 12
- 239000002861 polymer material Substances 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 11
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 10
- 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 10
- 235000021355 Stearic acid Nutrition 0.000 description 10
- 230000003712 anti-aging effect Effects 0.000 description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 10
- 239000008117 stearic acid Substances 0.000 description 10
- 150000001721 carbon Chemical group 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 229910010272 inorganic material Inorganic materials 0.000 description 9
- 239000011147 inorganic material Substances 0.000 description 9
- 230000009257 reactivity Effects 0.000 description 9
- 239000006229 carbon black Substances 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 7
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 7
- 238000005698 Diels-Alder reaction Methods 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 6
- 238000007259 addition reaction Methods 0.000 description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 6
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 229920002857 polybutadiene Polymers 0.000 description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 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 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 5
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 5
- 239000006057 Non-nutritive feed additive Substances 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- 241001441571 Hiodontidae Species 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 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 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 150000008117 polysulfides Polymers 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 3
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910021385 hard carbon Inorganic materials 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 229920001021 polysulfide Polymers 0.000 description 3
- 239000005077 polysulfide Substances 0.000 description 3
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- 229960002447 thiram Drugs 0.000 description 3
- 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 2
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000007337 electrophilic addition reaction Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- AEOCXXJPGCBFJA-UHFFFAOYSA-N ethionamide Chemical compound CCC1=CC(C(N)=S)=CC=N1 AEOCXXJPGCBFJA-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000007149 pericyclic reaction Methods 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007342 radical addition reaction Methods 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- NYBWUHOMYZZKOR-UHFFFAOYSA-N tes-adt Chemical class C1=C2C(C#C[Si](CC)(CC)CC)=C(C=C3C(SC=C3)=C3)C3=C(C#C[Si](CC)(CC)CC)C2=CC2=C1SC=C2 NYBWUHOMYZZKOR-UHFFFAOYSA-N 0.000 description 2
- 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 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
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- FYFDQJRXFWGIBS-UHFFFAOYSA-N 1,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C([N+]([O-])=O)C=C1 FYFDQJRXFWGIBS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LOVYCUYJRWLTSU-UHFFFAOYSA-N 2-(3,4-dichlorophenoxy)-n,n-diethylethanamine Chemical compound CCN(CC)CCOC1=CC=C(Cl)C(Cl)=C1 LOVYCUYJRWLTSU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GKTKWAZAGKZHBW-UHFFFAOYSA-N 2-[diethoxy(methyl)silyl]ethanethiol Chemical compound CCO[Si](C)(CCS)OCC GKTKWAZAGKZHBW-UHFFFAOYSA-N 0.000 description 1
- RKBBVTOGABTTHK-UHFFFAOYSA-N 2-[dimethoxy(methyl)silyl]ethanethiol Chemical compound CO[Si](C)(OC)CCS RKBBVTOGABTTHK-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- LOSLJXKHQKRRFN-UHFFFAOYSA-N 2-trimethoxysilylethanethiol Chemical compound CO[Si](OC)(OC)CCS LOSLJXKHQKRRFN-UHFFFAOYSA-N 0.000 description 1
- UZEBPNPRXOYGRA-UHFFFAOYSA-N 2-tripropoxysilylethanethiol Chemical compound CCCO[Si](CCS)(OCCC)OCCC UZEBPNPRXOYGRA-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
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- DECHJJJXDGPZHY-UHFFFAOYSA-N 3-tripropoxysilylpropane-1-thiol Chemical compound CCCO[Si](CCCS)(OCCC)OCCC DECHJJJXDGPZHY-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- MAPRZJHECPREHW-UHFFFAOYSA-N 4-[diethoxy(methyl)silyl]butane-1-thiol Chemical compound CCO[Si](C)(OCC)CCCCS MAPRZJHECPREHW-UHFFFAOYSA-N 0.000 description 1
- ZDLNACVKVFFHBM-UHFFFAOYSA-N 4-[dimethoxy(methyl)silyl]butane-1-thiol Chemical compound CO[Si](C)(OC)CCCCS ZDLNACVKVFFHBM-UHFFFAOYSA-N 0.000 description 1
- TXLINXBIWJYFNR-UHFFFAOYSA-N 4-phenylpyridine-2-carbonitrile Chemical compound C1=NC(C#N)=CC(C=2C=CC=CC=2)=C1 TXLINXBIWJYFNR-UHFFFAOYSA-N 0.000 description 1
- RVAVYOJYNISEQK-UHFFFAOYSA-N 4-triethoxysilylbutane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCCS RVAVYOJYNISEQK-UHFFFAOYSA-N 0.000 description 1
- LMAFAQBMCIYHQS-UHFFFAOYSA-N 4-trimethoxysilylbutane-1-thiol Chemical compound CO[Si](OC)(OC)CCCCS LMAFAQBMCIYHQS-UHFFFAOYSA-N 0.000 description 1
- JRYUZCLLNMIMQM-UHFFFAOYSA-N 4-tripropoxysilylbutane-1-thiol Chemical compound CCCO[Si](OCCC)(OCCC)CCCCS JRYUZCLLNMIMQM-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 241001495453 Parthenium argentatum Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920005683 SIBR Polymers 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 241000341871 Taraxacum kok-saghyz Species 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- WMVSVUVZSYRWIY-UHFFFAOYSA-N [(4-benzoyloxyiminocyclohexa-2,5-dien-1-ylidene)amino] benzoate Chemical compound C=1C=CC=CC=1C(=O)ON=C(C=C1)C=CC1=NOC(=O)C1=CC=CC=C1 WMVSVUVZSYRWIY-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 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
- 125000006267 biphenyl group Chemical group 0.000 description 1
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 description 1
- MDBBOVGSTVJQCA-UHFFFAOYSA-N buta-1,3-diene;prop-1-en-2-ylbenzene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.CC(=C)C1=CC=CC=C1 MDBBOVGSTVJQCA-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 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
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007789 sealing Methods 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
- 239000007787 solid Substances 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- CEQGXFSRENZDFH-UHFFFAOYSA-N triethoxy(sulfanyl)silane Chemical compound CCO[Si](S)(OCC)OCC CEQGXFSRENZDFH-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- XSIGLRIVXRKQRA-UHFFFAOYSA-N triethoxysilylmethanethiol Chemical compound CCO[Si](CS)(OCC)OCC XSIGLRIVXRKQRA-UHFFFAOYSA-N 0.000 description 1
- ZFNFNJYRZOQPJF-UHFFFAOYSA-N trimethoxy(sulfanyl)silane Chemical compound CO[Si](S)(OC)OC ZFNFNJYRZOQPJF-UHFFFAOYSA-N 0.000 description 1
- QJOOZNCPHALTKK-UHFFFAOYSA-N trimethoxysilylmethanethiol Chemical compound CO[Si](CS)(OC)OC QJOOZNCPHALTKK-UHFFFAOYSA-N 0.000 description 1
- NDBGOFIMYAOZJI-UHFFFAOYSA-N tripropoxysilylmethanethiol Chemical compound CCCO[Si](CS)(OCCC)OCCC NDBGOFIMYAOZJI-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- WDHVIZKSFZNHJB-UHFFFAOYSA-L zinc;butanoate Chemical compound [Zn+2].CCCC([O-])=O.CCCC([O-])=O WDHVIZKSFZNHJB-UHFFFAOYSA-L 0.000 description 1
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 1
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/08—Isoprene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Definitions
- the present invention relates to a silane coupling agent composition and a rubber composition containing the same.
- the present invention also relates to a crosslinked product of the rubber composition and a tire using the rubber composition.
- a silane compound having a reactive functional group and a hydrolyzable group has been used as a silane coupling agent in order to improve the dispersibility between an organic polymer material such as rubber and an inorganic material such as silica in a rubber composition. Has been used as a constituent of.
- such a silane compound has a substituent such as a mercapto group, a polysulfide group, an amino group or an epoxy group as a reactive functional group having high reactivity with an organic polymer material such as rubber, and silica or the like.
- a hydrolyzable group having high reactivity with the inorganic material of it has a substituent such as an alkoxysilyl group.
- Patent Document 1 discloses a rubber composition containing a polysulfide-based silane coupling agent.
- Patent Document 2 proposes a silane compound having an amino group as a reactive functional group and a methoxy group as a hydrolyzable group.
- Patent Document 3 describes a rubber containing an organic silane compound having a monosulfide bond in order to improve the scorch resistance of the rubber composition and the exothermic property (viscoelastic property) of the crosslinked product of the rubber composition. Compositions have been proposed.
- Japanese Unexamined Patent Publication No. 8-259736 Japanese Unexamined Patent Publication No. 11-335381 Japanese Unexamined Patent Publication No. 2014-177432
- the reactive functional groups of the silane compounds proposed in Patent Documents 1 and 2 have high polarity, and when the organic polymer material to be mixed has a low polarity, the silane compound and the organic polymer material have an affinity. It was low and tended to cause poor dispersion and poor mixing. Therefore, when the silane coupling agent composition containing such a silane compound is contained in the rubber composition, the viscosity at the time of uncrosslinking (unvulcanized) tends to deteriorate. On the other hand, when a conventional silane compound having a low-polarity reactive functional group is added in order to enhance the affinity with a low-polarity organic polymer material, the reactivity with the organic polymer material is low and silane coupling is performed. The performance as an agent was insufficient.
- the present inventors have made an alicyclic hydrocarbon moiety having an olefin structure and having a silyl group, which has an affinity with an organic polymer material and an appropriate reactivity.
- silane compounds as a silane coupling agent, the coupling reaction is promoted, and as a result, when the compound is a rubber composition, the dispersibility of an inorganic material such as silica is improved and the scorch resistance is improved.
- the present invention is based on this finding.
- a silane coupling agent composition containing a silane compound has the following formula (1): [During the ceremony, R 1 , R 2 and R 3 independently represent a hydrocarbon group or a hydrogen atom which may contain an oxygen atom or a nitrogen atom. L is a hydrocarbon group which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. a is an integer of 0 or 1, b is an integer of 0 or 1 and is c is an integer of 0 or 1 independently of each other. d is an integer of 0 or 1 independently of each other.
- e is an integer from 0 to 5 and R 4 , R 5 , R 6 and R 7 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 4 or R 5 and R 6 or R 7 is-(CH).
- a crosslinked structure represented by f ⁇ may be formed. f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 8 or R 9 and R 10 or R 11 is-(CH). 2 )
- a crosslinked structure represented by g- may be formed.
- g is an integer from 1 to 5 and R 16 is a hydrogen atom, a methyl group or an alkyl group having 2 to 8 carbon atoms, and R 17 is a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, where R 12 and R 13 bonds to each other to form a double bond, and R 14 , R 15 and R 18 are hydrogen atoms, methyl groups or alkyl groups having 2 to 10 carbon atoms, or R 14 and R 15 Bond to each other to form a double bond, and R 12 , R 13 and R 18 are hydrogen atoms, methyl groups or alkyl groups having 2 to 10 carbon atoms.
- R 16 and R 17 may combine with each other to form a 4- to 9-membered alicyclic hydrocarbon, where R 14 and R 15 combine with each other to form a double bond.
- R 12 , R 13 and R 18 are hydrogen atoms, methyl groups or alkyl groups having 2 to 10 carbon atoms.
- a is an integer of 0 or 1
- b is an integer of 0 or 1
- is c is an integer of 0 or 1 independently of each other.
- d is an integer of 0 or 1 independently of each other.
- e is an integer from 0 to 5 and R 4 , R 5 , R 6 and R 7 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 4 or R 5 and R 6 or R 7 is-(CH). 2 )
- a crosslinked structure represented by f ⁇ may be formed.
- R 8 , R 9 , R 10 and R 11 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 8 or R 9 and R 10 or R 11 is-(CH).
- a crosslinked structure represented by g- may be formed.
- g is an integer from 1 to 5 and R 26 , R 27 and R 28 each independently represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms.
- a silane coupling agent composition comprising a second silane compound represented by.
- the first silane compound has the following formula (2): [During the ceremony, R 1 , R 2 and R 3 independently represent a hydrocarbon group or a hydrogen atom which may contain an oxygen atom or a nitrogen atom. h is an integer from 1 to 10 and a is an integer of 0 or 1, b is an integer of 0 or 1 and is c is an integer of 0 or 1 independently of each other. d is an integer of 0 or 1 independently of each other. e is an integer from 0 to 5 and R 4 , R 5 , R 6 and R 7 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 4 or R 5 and R 6 or R 7 is-(CH).
- a crosslinked structure represented by f ⁇ may be formed.
- f is an integer from 1 to 5
- R 8 , R 9 , R 10 and R 11 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 8 or R 9 and R 10 or R 11 is-(CH).
- a crosslinked structure represented by g- may be formed.
- g is an integer from 1 to 5 and R 16 is a hydrogen atom, a methyl group or an alkyl group having 2 to 8 carbon atoms, and R 17 is a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, where R 12 and R 13 bonds to each other to form a double bond, and R 14 , R 15 and R 18 are hydrogen atoms, methyl groups or alkyl groups having 2 to 10 carbon atoms, or R 14 and R 15 Bond to each other to form a double bond, and R 12 , R 13 and R 18 are hydrogen atoms, methyl groups or alkyl groups having 2 to 10 carbon atoms.
- R 16 and R 17 may combine with each other to form a 4- to 9-membered alicyclic hydrocarbon, where R 14 and R 15 combine with each other to form a double bond.
- R 12 , R 13 and R 18 are hydrogen atoms, methyl groups or alkyl groups having 2 to 10 carbon atoms.
- the second silane compound has the following formula (12): [During the ceremony, Each R 1 , R 2 and R 3 independently represent a hydrocarbon group or a hydrogen atom which may contain an oxygen atom or a nitrogen atom.
- h is an integer from 1 to 10 and m is an integer from 1 to 10 and a is an integer of 0 or 1
- b is an integer of 0 or 1 and is c is an integer of 0 or 1 independently of each other.
- d is an integer of 0 or 1 independently of each other.
- e is an integer from 0 to 5 and R 4 , R 5 , R 6 and R 7 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 4 or R 5 and R 6 or R 7 is-(CH). 2 )
- a crosslinked structure represented by f ⁇ may be formed.
- R 8 , R 9 , R 10 and R 11 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 8 or R 9 and R 10 or R 11 is-(CH).
- a crosslinked structure represented by g- may be formed.
- g is an integer from 1 to 5 and R 26 , R 27 and R 28 each independently represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms.
- the content of the second silane compound is 1 to 50% by mass with respect to the total content of the first silane compound and the second silane compound.
- the silane coupling agent composition according to any one. [5] The silane coupling agent composition according to any one of [1] to [4], wherein the silane compound further contains a first silane compound and another silane compound other than the second silane compound. .. [6]
- the other silane compound is the formula (13) :. [During the ceremony, t and v are independently integers from 0 to 10, respectively. u is an integer from 2 to 10 and q and r are independently integers of 1 to 3, respectively. w and z are independently integers of 0 or 1, respectively.
- L 2 and L 3 are hydrocarbon groups that may each independently contain at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur.
- R 21 and R 23 are independently amino groups substituted with an alkoxy group or one or more alkyl groups, respectively.
- R 22 and R 24 are independent hydrogen or alkyl groups, respectively.
- a silane coupling agent composition capable of obtaining a rubber composition having excellent scorch resistance and uncrosslinked compound viscosity while having appropriate reactivity with an organic polymer material such as rubber. be able to. Further, according to the present invention, a rubber composition having excellent scorch resistance and uncrosslinked compound viscosity is provided, and a crosslinked product of the rubber composition having excellent viscoelastic properties, and wet grip and fuel efficiency using these are provided. It is to provide tires with excellent balance.
- 1 H-NMR chart of the silane compound 1 synthesized in Preparation Example 1 is shown. It is a chromatogram which shows that the silane compound 1 synthesized in Preparation Example 1 was fractionated into (1A) fraction and (1B) fraction by gas chromatography, and each fraction was separated. It represents Preparation Example 1 Synthesis silane compound 1 (1A) 1 H-NMR chart of fractions. The peaks represented by a to g and the integers 1 to 7 surrounded by a circle indicate the peaks of the protons bonded to each carbon atom (shown in FIG. 3) of the compound represented by the formula (1A). The 13 C-NMR chart of the (1A) fraction of the silane compound 1 synthesized in Preparation Example 1 is shown.
- the peaks represented by a to g and the integers 1 to 7 surrounded by a circle indicate the peaks of each carbon atom (shown in FIG. 4) of the compound represented by the formula (1A).
- It represents Preparation Example 1 Synthesis silane compound 1 (1B) 1 H-NMR chart of fractions.
- the peaks shown by A to G and circles 1 to 7 indicate the peaks of protons bonded to each carbon atom (shown in FIG. 5) of the compound represented by the formula (1B).
- the 13 C-NMR chart of the (1B) fraction of the silane compound 1 synthesized in Preparation Example 1 is shown.
- the peaks shown by A to G and circles 1 to 7 indicate the peaks of protons bonded to each carbon atom (shown in FIG. 6) of the compound represented by the formula (1B).
- the silane coupling agent composition of the present invention comprises a silane compound, and the silane compound is characterized by containing a first silane compound and a second silane compound.
- the silane coupling agent composition of the present invention can obtain a rubber composition having excellent scorch resistance and uncrosslinked compound viscosity while having appropriate reactivity with an organic polymer material such as rubber.
- the total content of the first silane compound and the second silane compound in the silane coupling agent composition is preferably 20 to 100% by mass, more preferably 20 to 100% by mass, based on the total mass of the silane coupling agent composition. It is 50 to 100% by mass, and may be 60 to 99% by mass.
- the content of the second silane compound in the silane coupling agent composition is preferably 1 to 50% by mass, more preferably 2 with respect to the total content of the first silane compound and the second silane compound. It is about 40% by mass, more preferably 5 to 30% by mass.
- the ratio of the content of the second silane compound in the silane coupling agent composition is within the above numerical range, it has appropriate reactivity with an organic polymer material such as rubber, while having scorch resistance and non-scoelasticity. It is possible to provide a rubber composition having excellent crosslinked compound viscosity, a crosslinked product of a rubber composition having excellent viscoelastic properties, and a tire using these having an excellent balance between wet grip and fuel efficiency. It is easy to obtain a rubber composition having excellent scorch resistance and compound viscosity.
- the silane coupling agent composition may further contain carbon black.
- carbon black the carbon black described in the inorganic material described below can be used.
- each component of the silane coupling agent composition will be described in detail.
- the first silane compound contained in the silane coupling agent composition of the present invention has the following formula (1): [During the ceremony, R 1 , R 2 and R 3 independently represent a hydrocarbon group or a hydrogen atom which may contain an oxygen atom or a nitrogen atom. L is a hydrocarbon group which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. a is an integer of 0 or 1, b is an integer of 0 or 1 and is c is an integer of 0 or 1 independently of each other. d is an integer of 0 or 1 independently of each other.
- e is an integer from 0 to 5 and R 4 , R 5 , R 6 and R 7 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 4 or R 5 and R 6 or R 7 is-(CH).
- a crosslinked structure represented by f ⁇ may be formed. f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 8 or R 9 and R 10 or R 11 is-(CH). 2 )
- a crosslinked structure represented by g ⁇ may be formed.
- g is an integer from 1 to 5 and R 16 is a hydrogen atom, a methyl group or an alkyl group having 2 to 8 carbon atoms, and R 17 is a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, where R 12 and R 13 bonds to each other to form a double bond, and R 14 , R 15 and R 18 are hydrogen atoms, methyl groups or alkyl groups having 2 to 10 carbon atoms, or R 14 and R 15 Bond to each other to form a double bond, and R 12 , R 13 and R 18 are hydrogen atoms, methyl groups or alkyl groups having 2 to 10 carbon atoms.
- R 16 and R 17 may combine with each other to form a 4- to 9-membered alicyclic hydrocarbon, where R 14 and R 15 combine with each other to form a double bond.
- R 12 , R 13 and R 18 are hydrogen atoms, methyl groups or alkyl groups having 2 to 10 carbon atoms. ] It is a compound represented by.
- a is an integer of 0 or 1, preferably 1.
- b is an integer of 0 or 1, preferably 1.
- c is an integer of 0 or 1 independently of each other, and is preferably 1.
- d is an integer of 0 or 1 independently of each other, and is preferably 1.
- e is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably an integer of 0 or 1.
- R 4 , R 5 , R 6 and R 7 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 4 or R 5 and R 6 or R 7 is-.
- (CH 2 ) A crosslinked structure represented by f ⁇ may be formed. Further, f is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 1. Further, R 8 , R 9 , R 10 and R 11 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 8 or R 9 and R 10 or R 11 is-.
- (CH 2 ) A crosslinked structure represented by g ⁇ may be formed. Further, g is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 1.
- R 16 is a hydrogen atom, a methyl group or an alkyl group having 2 to 8 carbon atoms, preferably a hydrogen atom, a methyl group or an alkyl group having 2 or 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.
- R 17 is a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, and preferably a hydrogen atom, a methyl group or an alkyl having 2 to 5 carbon atoms.
- R 18 are hydrogen atoms, methyl groups or alkyl groups having 2 to 10 carbon atoms, or R 14 and R 15 bond with each other to form a double bond, and R 12 , R 13 and R Reference numeral 18 is a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms.
- R 16 and R 17 are bonded to each other to form a 4- to 9-membered alicyclic hydrocarbon, preferably a 4- to 7-membered alicyclic hydrocarbon, and more preferably a 5- or 6-membered alicyclic hydrocarbon. More preferably, a 5-membered alicyclic hydrocarbon may be formed, where R 14 and R 15 combine with each other to form a double bond, and R 12 , R 13 and R 18 are. It is a hydrogen atom, a methyl group, or an alkyl group having 2 to 10 carbon atoms.
- R 1 , R 2 and R 3 independently represent a hydrocarbon group or a hydrogen atom which may contain an oxygen atom or a nitrogen atom, respectively.
- the hydrocarbon group include an alkyl group, an aralkyl group, an aryl group and the like.
- the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclohexyl group and the like, and the alkyl group has 1 carbon atom.
- ⁇ 60 is preferable, 1 to 30 is more preferable, and a methyl group or an ethyl group is particularly preferable.
- the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like.
- the number of carbon atoms of the aralkyl group is preferably 7 to 60, more preferably 7 to 20, and even more preferably 7 to 14.
- the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xsilyl group and the like.
- the aryl group preferably has 6 to 60 carbon atoms, more preferably 6 to 24, and even more preferably 6 to 12.
- a hydrocarbon group containing an oxygen atom or a nitrogen atom is a group having a structure in which a carbon atom in the hydrocarbon group is replaced with an oxygen atom or a nitrogen atom.
- the hydrocarbon group may contain an oxygen atom or a nitrogen atom in R 1 , R 2 and R 3 is an alkoxy group, an amino group substituted with one or more alkyl groups, and the like. Or it is an alkyl group. More preferably, an alkoxy group having 1 to 30 carbon atoms, still more preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an amino group substituted with 1 or more alkyl groups having 1 to 30 carbon atoms, still more preferably 1 or more.
- alkyl group having 1 to 20 carbon atoms is an amino group substituted with an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 30 carbon atoms, and further preferably an alkyl group having 1 to 20 carbon atoms.
- alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group and an isobutoxy group, and among these, a methoxy group or an ethoxy group is preferable.
- Examples of the amino group substituted with one or more alkyl groups include an N-methylamino group, an N, N-dimethylamino group, an N-ethylamino group, an N, N-diethylamino group and an N-isopropylamino group. Among these, an N-methylamino group or an N-ethylamino group is preferable.
- alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group and the like.
- a methyl group and an ethyl group are preferable.
- L is a hydrocarbon group which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, preferably from nitrogen, oxygen and sulfur.
- a hydrocarbon group having 1 to 30 carbon atoms which may contain at least one heteroatom selected from the group consisting of, more preferably at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. It may contain a hydrocarbon group having 1 to 20 carbon atoms, more preferably at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, having 1 to 10 carbon atoms. It is a hydrocarbon group.
- L is particularly preferably a hydrocarbon group containing sulfur.
- the length of the linear moiety connecting the silyl group and the alicyclic hydrocarbon moiety in the hydrocarbon group is preferably 3 to 8, more preferably 4 to 7, as the total number of atoms of carbon, nitrogen, oxygen or sulfur. , More preferably 4 to 6.
- the first silane compound in the silane coupling agent composition of the present invention is preferably a sulfur-containing silane compound.
- the first silane compound contained in the silane coupling agent composition of the present invention is preferably the formula (2) :.
- R 1 , R 2 and R 3 independently represent a hydrocarbon group or a hydrogen atom which may contain an oxygen atom or a nitrogen atom.
- h is an integer from 1 to 10 and a is an integer of 0 or 1
- b is an integer of 0 or 1
- is c is an integer of 0 or 1 independently of each other.
- d is an integer of 0 or 1 independently of each other.
- e is an integer from 0 to 5 and R 4 , R 5 , R 6 and R 7 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 4 or R 5 and R 6 or R 7 is-(CH).
- a crosslinked structure represented by f ⁇ may be formed. f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 8 or R 9 and R 10 or R 11 is-(CH). 2 )
- a crosslinked structure represented by g- may be formed.
- g is an integer from 1 to 5 and R 16 is a hydrogen atom, a methyl group or an alkyl group having 2 to 8 carbon atoms, and R 17 is a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, where R 12 and R 13 bonds to each other to form a double bond, and R 14 , R 15 and R 18 are hydrogen atoms, methyl groups or alkyl groups having 2 to 10 carbon atoms, or R 14 and R 15 Bond to each other to form a double bond, and R 12 , R 13 and R 18 are hydrogen atoms, methyl groups or alkyl groups having 2 to 10 carbon atoms.
- R 16 and R 17 may combine with each other to form a 4- to 9-membered alicyclic hydrocarbon, where R 14 and R 15 combine with each other to form a double bond.
- R 12 , R 13 and R 18 are hydrogen atoms, methyl groups or alkyl groups having 2 to 10 carbon atoms. ] It is a compound represented by.
- H in the compound represented by the above formula (2) is an integer of 1 to 10, preferably 1 to 8, more preferably 2 to 7, still more preferably 3 to 6, and even more preferably 3 to 5. It is an integer, particularly preferably 3. Further, a to g and R 1 to R 18 are as described in the above formula (1).
- the first silane compound contained in the silane coupling agent composition of the present invention is more preferably the formula (3) :.
- R 1 , R 2 and R 3 independently represent a hydrocarbon group or a hydrogen atom which may contain an oxygen atom or a nitrogen atom.
- h is an integer from 1 to 10 and a is an integer of 0 or 1
- b is an integer of 0 or 1
- is c is an integer of 0 or 1 independently of each other.
- d is an integer of 0 or 1 independently of each other.
- e is an integer from 0 to 5 and R 4 , R 5 , R 6 and R 7 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 4 or R 5 and R 6 or R 7 is-(CH).
- a crosslinked structure represented by f ⁇ may be formed. f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 8 or R 9 and R 10 or R 11 is-(CH).
- a crosslinked structure represented by g- may be formed. g is an integer from 1 to 5 and R 31 is a hydrogen atom, a methyl group or an alkyl group having 2 to 8 carbon atoms. ] It is a compound represented by.
- R 31 in the formula (3) is a hydrogen atom, a methyl group or an alkyl group having 2 to 8 carbon atoms, preferably a hydrogen atom, a methyl group or an alkyl group having 2 to 5 carbon atoms, and more preferably a hydrogen atom.
- the first silane compound contained in the silane coupling agent composition of the present invention is more preferably the formula (4) :.
- R 1 , R 2 and R 3 independently represent a hydrocarbon group or a hydrogen atom which may contain an oxygen atom or a nitrogen atom.
- h is an integer from 1 to 10 and a is an integer of 0 or 1
- b is an integer of 0 or 1
- is c is an integer of 0 or 1 independently of each other.
- d is an integer of 0 or 1 independently of each other.
- e is an integer from 0 to 5 and R 4 , R 5 , R 6 and R 7 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 4 or R 5 and R 6 or R 7 is-(CH).
- a crosslinked structure represented by f ⁇ may be formed. f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 8 or R 9 and R 10 or R 11 is-(CH).
- a crosslinked structure represented by g- may be formed. g is an integer from 1 to 5 and R 32 is a hydrogen atom, a methyl group or an alkyl group having 2 to 9 carbon atoms. ] It is a compound represented by.
- R 32 in the formula (4) is a hydrogen atom, a methyl group or an alkyl group having 2 to 9 carbon atoms, preferably a methyl group or an alkyl group having 2 to 5 carbon atoms, and more preferably a methyl group or an alkyl group having 2 to 5 carbon atoms. It is an alkyl group of 1 or 2, more preferably a methyl group.
- the first silane compound contained in the silane coupling agent composition of the present invention is more preferably the formula (5) :.
- R 1 , R 2 and R 3 independently represent a hydrocarbon group or a hydrogen atom which may contain an oxygen atom or a nitrogen atom.
- h is an integer from 1 to 10 and a is an integer of 0 or 1
- b is an integer of 0 or 1
- is c is an integer of 0 or 1 independently of each other.
- d is an integer of 0 or 1 independently of each other.
- e is an integer from 0 to 5 and R 4 , R 5 , R 6 and R 7 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 4 or R 5 and R 6 or R 7 is-(CH).
- a crosslinked structure represented by f ⁇ may be formed. f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 8 or R 9 and R 10 or R 11 is-(CH).
- a crosslinked structure represented by g ⁇ may be formed. g is an integer from 1 to 5 and x is an integer from 0 to 5. ] It is a compound represented by.
- X in the formula (5) is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 1 or 2, and even more preferably 1.
- the first silane compound contained in the silane coupling agent composition of the present invention is more preferably the formula (6) :.
- R 1 , R 2 and R 3 each independently represent a hydrocarbon group or a hydrogen atom which may contain an oxygen atom or a nitrogen atom.
- formula (7) [In the formula, R 1 , R 2 and R 3 each independently represent a hydrocarbon group or a hydrogen atom which may contain an oxygen atom or a nitrogen atom. ]
- Equation (9) [In the formula, R 1 , R 2 and R 3 each independently represent a hydrocarbon group or a hydrogen atom which may contain an oxygen atom or a nitrogen atom. ] It is a compound represented by.
- Another further preferred embodiment of the first silane compound in the silane coupling agent composition of the present invention includes a compound represented by the following formula.
- R 1 to R 3 are as described in the above formula (1).
- R 1 , R 2 and R 3 independently represent a hydrocarbon group or a hydrogen atom which may contain an oxygen atom or a nitrogen atom, respectively.
- the R 1 R 2 R 3 Si group is represented by the formula (10).
- R 19 is an amino group independently substituted with an alkoxy group or one or more alkyl groups, respectively.
- R 20 are independently hydrogen atoms or alkyl groups, respectively.
- L 1 is a hydrocarbon group that may independently contain at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur.
- j is an integer of 0 or 1 independently of each other.
- k is an integer of 1 to 3 and
- An asterisk (*) indicates a site bonded to a portion other than the silyl group of the silane compound.
- Examples thereof include a silane compound having the above chemical structure.
- R 19 is an amino group independently substituted with an alkoxy group or one or more alkyl groups.
- R 19 is an independently hydrolyzable group, an alkoxy group, more preferably an alkoxy group having 1 to 30 carbon atoms, and even more preferably an alkoxy group having 1 to 20 carbon atoms.
- an amino group substituted with one or more alkyl groups more preferably an amino group substituted with one or more alkyl groups having 1 to 30 carbon atoms, and even more preferably an alkyl group having one or more carbon atoms 1 to 20. It is a substituted amino group.
- examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group and an isobutoxy group, and among these, a methoxy group or an ethoxy group is preferable.
- examples of the amino group substituted with one or more alkyl groups include an N-methylamino group, an N, N-dimethylamino group, an N-ethylamino group, an N, N-diethylamino group and an N-isopropylamino group. Among these, an N-methylamino group or an N-ethylamino group is preferable.
- R 20 is independently a hydrogen atom or an alkyl group, more preferably an alkyl group having 1 to 30 carbon atoms, still more preferably an alkyl group having 1 to 20 carbon atoms, and specifically, Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a cyclopentyl group, a hexyl group and a cyclohexyl group, and among these, a methyl group and an ethyl group. Groups are preferred.
- L 1 is a hydrocarbon group which may independently contain at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, preferably nitrogen.
- a hydrocarbon group having 1 to 30 carbon atoms which may contain at least one heteroatom selected from the group consisting of oxygen and sulfur, more preferably at least one selected from the group consisting of nitrogen, oxygen and sulfur. It may contain one heteroatom, a hydrocarbon group having 1 to 20 carbon atoms, more preferably at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. It is a hydrocarbon group of 1 to 10.
- k is an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.
- j is an integer of 0 or 1 independently of each other, and is preferably 0.
- the R 1 R 2 R 3 Si group is a triethoxysilyl group or a trimethoxysilyl group.
- a certain silane compound is more preferable, and a silane compound in which the R 1 R 2 R 3 Si group is a triethoxysilyl group is even more preferable.
- a particularly preferable embodiment of the first silane compound contained in the silane coupling agent composition of the present invention includes a compound represented by the following formula.
- the first silane compound of the present invention is preferably a stereoisomer thereof or any mixture thereof.
- the first silane compound is of formula (14) :.
- a is an integer of 0 or 1
- b is an integer of 0 or 1
- c is an integer of 0 or 1 independently of each other.
- d is an integer of 0 or 1 independently of each other.
- e is an integer from 0 to 5 and R 4 , R 5 , R 6 and R 7 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 4 or R 5 and R 6 or R 7 is-(CH).
- a crosslinked structure represented by f ⁇ may be formed. f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 8 or R 9 and R 10 or R 11 is-(CH). 2 )
- a crosslinked structure represented by g ⁇ may be formed.
- g is an integer from 1 to 5 and R 16 is a hydrogen atom, a methyl group or an alkyl group having 2 to 8 carbon atoms, and R 17 is a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, where R 12 and R 13 bonds to each other to form a double bond, and R 14 , R 15 and R 18 are hydrogen atoms, methyl groups or alkyl groups having 2 to 10 carbon atoms, or R 14 and R 15 Bond to each other to form a double bond, and R 12 , R 13 and R 18 are hydrogen atoms, methyl groups or alkyl groups having 2 to 10 carbon atoms.
- R 16 and R 17 may combine with each other to form a 4- to 9-membered alicyclic hydrocarbon, where R 14 and R 15 combine with each other to form a double bond.
- R 12 , R 13 and R 18 are hydrogen atoms, methyl groups or alkyl groups having 2 to 10 carbon atoms.
- R 1 ⁇ R 18 and a ⁇ g are as described in the first silane compound represented by the formula (1).
- Y is a hydrocarbon group which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, and is preferably nitrogen having 1 to 30 carbon atoms.
- a heteroatom may be contained, more preferably at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur having 1 to 10 carbon atoms.
- Y is particularly preferably a hydrocarbon group containing sulfur.
- the length of the linear portion connecting the silyl group and the portion bonded to the alicyclic hydrocarbon moiety in the hydrocarbon group is preferably 3 to 8 as the total number of atoms of carbon, nitrogen, oxygen or sulfur, more preferably 3 to 8. Is 4 to 7, more preferably 4 to 6.
- the compound represented by the formula (14) and the compound represented by the formula (15) are subjected to an addition reaction or condensation. It can be synthesized by subjecting it to a reaction.
- a radical addition reaction a conjugate addition reaction, a nucleophilic addition reaction, an electrophilic addition reaction, or the like can be used.
- a reaction similar to a pericyclic reaction, a hydrosilylation reaction, a hydroaminoization reaction, or the like can be used.
- the condensation reaction for example, an esterification reaction, an amidation reaction, a thioesterification reaction, a thioamide formation reaction, a Friedel-Crafts reaction and the like can be used.
- the compound represented by the above formula (14) is a Diels-Alder reaction between the same or different conjugated diene compounds, or a conjugated diene compound and an alkene compound, based on the knowledge already known to those skilled in the art. It can be synthesized by the Diels-Alder reaction with.
- the compound represented by the formula (14) can be prepared by heat-denaturing the compound synthesized by the Diels-Alder reaction as necessary and / or purifying it as necessary. can.
- the first silane compound represented by the formula (2) contained in the silane coupling agent composition of the present invention includes the compound represented by the above formula (14) and the formula (16) :.
- R 1 , R 2 and R 3 independently represent a hydrocarbon group or a hydrogen atom which may contain an oxygen atom or a nitrogen atom.
- h is an integer from 1 to 10. It can be produced by reacting the compound represented by.
- R 1 ⁇ R 18 and a ⁇ g are as described in the first silane compound represented by the formula (1). Further, h is as described in the compound represented by the formula (2).
- the compound represented by the above formula (2) is obtained by mixing the compound represented by the above formula (14) and the compound represented by the above formula (16) and heating the compound to obtain the above formula (1). It is considered that the compound is synthesized by reacting the mercapto group in the compound represented by 16) with the carbon-carbon unsaturated bond moiety in the compound represented by the above formula (14).
- the compound represented by the above formula (16) is preferably mixed so as to be 0.1 to 4 mol, and 0.2 to 3 mol, with respect to 1 mol of the compound represented by the above formula (14). It is more preferable to mix them so as to be.
- the heating temperature is preferably 40 to 300 ° C, more preferably 50 to 200 ° C.
- Examples of the compound represented by the above formula (16) include an alkoxysilane compound having a mercapto group.
- alkoxysilane compound having a mercapto group include mercaptotrimethoxysilane, mercaptotriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltripropoxysilane, 2-mercaptoethyltrimethoxysilane, and 2-mercaptoethyl.
- the compound represented by the above formula (2) can also be synthesized by mixing the compound represented by the above formula (14) and the compound represented by the formula (13) described later and heating them. Can be done. It is considered that the polysulfide bond in the compound represented by the formula (13) described later is cleaved and this is synthesized by reacting with the carbon-carbon unsaturated bond portion in the compound represented by the above formula (14).
- the compound represented by the formula (13) described later is preferably mixed so as to be 0.1 to 4 mol, and 0.3 to 3 mol, with respect to 1 mol of the compound represented by the above formula (14). It is more preferable to mix them so as to be.
- the heating temperature is preferably 40 to 300 ° C, more preferably 50 to 200 ° C.
- a radical initiator can be used in combination.
- the radical initiator include azobisisobutyronitrile (AIBN), azo compounds such as 1,1'-azobis (cyclohexanecarbonitrile) (ABCN), di-tert-butyl peroxide (t-BuOOBu-t), and the like.
- hydrogen peroxide and iron (II) salts such as persulfates and sodium hydrogen sulfite
- II salts such as persulfates and sodium hydrogen sulfite
- a redox initiator combination of oxidizing agent and reducing agent triethyl borane (Et 3 B) And diethyl zinc (Et 2 Zn) can also be used.
- bis [3- (triethoxysilyl) propyl] tetrasulfide may be used, for example, Si manufactured by Evonik Industries. -69 can be mentioned.
- bis [3- (triethoxysilyl) propyl] disulfide a commercially available one may be used, and examples thereof include Si-75 manufactured by Evonik Industries.
- the second silane compound contained in the silane coupling agent composition of the present invention has the following formula (11): [During the ceremony, Each R 1 , R 2 and R 3 independently represent a hydrocarbon group or hydrogen atom that may contain an oxygen or nitrogen atom. Each L is a hydrocarbon group that may independently contain at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. a is an integer of 0 or 1, b is an integer of 0 or 1 and is c is an integer of 0 or 1 independently of each other. d is an integer of 0 or 1 independently of each other.
- e is an integer from 0 to 5 and R 4 , R 5 , R 6 and R 7 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 4 or R 5 and R 6 or R 7 is-(CH).
- a crosslinked structure represented by f ⁇ may be formed. f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 8 or R 9 and R 10 or R 11 is-(CH).
- a crosslinked structure represented by g- may be formed. g is an integer from 1 to 5 and R 26 , R 27 and R 28 each independently represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms. ] It is a compound represented by.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 is the above formula (1).
- the preferred embodiment of each L is as described in the above formula (1).
- preferred embodiments of a, b, c, d, and e are as described in the above formula (1).
- R 26 , R 27 and R 28 each independently represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, and are preferably hydrogen atoms.
- the second silane compound in the silane coupling agent composition of the present invention is preferably a sulfur-containing silane compound.
- the first silane compound represented by the formula (11) contained in the silane coupling agent composition of the present invention is preferably the formula (12) :.
- Each R 1 , R 2 and R 3 independently represent a hydrocarbon group or hydrogen atom that may contain an oxygen or nitrogen atom.
- h is an integer from 1 to 10 and m is an integer from 1 to 10 and a is an integer of 0 or 1
- b is an integer of 0 or 1
- is c is an integer of 0 or 1 independently of each other.
- d is an integer of 0 or 1 independently of each other.
- e is an integer from 0 to 5 and R 4 , R 5 , R 6 and R 7 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 4 or R 5 and R 6 or R 7 is-(CH).
- a crosslinked structure represented by f ⁇ may be formed. f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 8 or R 9 and R 10 or R 11 is-(CH).
- a crosslinked structure represented by g ⁇ may be formed. g is an integer from 1 to 5 and R 26 , R 27 and R 28 each independently represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms. ] It is a compound represented by.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 26 , R 27 and R 28 respectively.
- a preferred embodiment is as described in the above formula (11).
- the preferred embodiment of each L is as described in the above formula (11).
- preferred embodiments of a, b, c, d, and e are as described in the above formula (11).
- the preferable embodiment of h is as described in the above formula (2).
- m is an integer of 1 to 10, preferably 1 to 8, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably an integer of 1 to 3. be.
- the second silane compound contained in the silane coupling agent composition of the present invention is more preferably of the formula (17) :.
- each R 1 , R 2 and R 3 independently represent a hydrocarbon group or a hydrogen atom which may contain an oxygen atom or a nitrogen atom.
- Or formula (18): [In the formula, each R 1 , R 2 and R 3 independently represent a hydrocarbon group or a hydrogen atom which may contain an oxygen atom or a nitrogen atom. ] It is a compound represented by.
- R 1 , R 2 and R 3 are as described in the above formula (11).
- Another further preferred embodiment of the first silane compound in the silane coupling agent composition of the present invention includes a compound represented by the following formula.
- R 1 to R 3 are as described in the above formula (1).
- the R 1 R 2 R 3 Si group has the above formula (10).
- examples thereof include silane compounds having a chemical structure.
- the second silane compound a silane compound in which the R 1 R 2 R 3 Si group is a triethoxysilyl group or a trimethoxysilyl group is more preferable, and the R 1 R 2 R 3 Si group is a triethoxysilyl group. Silane compounds are even more preferred.
- a particularly preferable embodiment of the second silane compound contained in the silane coupling agent composition of the present invention includes a compound represented by the following formula.
- the second silane compound of the present invention is preferably a stereoisomer thereof or any mixture thereof.
- the second silane compound has the following formula (14) :.
- a is an integer of 0 or 1
- b is an integer of 0 or 1
- c is an integer of 0 or 1 independently of each other.
- d is an integer of 0 or 1 independently of each other.
- e is an integer from 0 to 5 and R 4 , R 5 , R 6 and R 7 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 4 or R 5 and R 6 or R 7 is-(CH).
- a crosslinked structure represented by f ⁇ may be formed. f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or one of R 8 or R 9 and R 10 or R 11 is-(CH). 2 )
- a crosslinked structure represented by g ⁇ may be formed.
- R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, where R 12 and R 13 binds to each other to form a double bond, or R 14 and R 15 bind to each other to form a double bond, and R 16 and R 17 bind to each other to form a double bond 4-9.
- a member alicyclic hydrocarbon may be formed.
- It can be produced by reacting the compound represented by the above formula (15) with the compound represented by the above formula (15).
- the preferred embodiments of the above formulas (14) and (15) are as described in the first silane compound.
- the compound represented by the above formula (14) and the compound represented by the above formula (15) are synthesized by subjecting them to an addition reaction or a condensation reaction.
- an addition reaction here, a radical addition reaction, a conjugate addition reaction, a nucleophilic addition reaction, an electrophilic addition reaction, or the like can be used.
- a reaction similar to a pericyclic reaction, a hydrosilylation reaction, a hydroaminoization reaction, or the like can be used.
- the condensation reaction for example, an esterification reaction, an amidation reaction, a thioesterification reaction, a thioamide formation reaction, a Friedel-Crafts reaction and the like can be used.
- the compound represented by the above formula (14) is a Diels-Alder reaction between the same or different conjugated diene compounds, or a conjugated diene compound and an alkene compound, based on the knowledge already known to those skilled in the art. It can be synthesized by the Diels-Alder reaction with.
- the compound represented by the above formula (14) is prepared by heat-denaturing the compound synthesized by the Diels-Alder reaction as necessary and / or purifying it as necessary. Can be done.
- the second silane compound can be produced by reacting the compound represented by the above formula (14) with the compound represented by the above formula (16).
- the preferred embodiment of the above formula (16) is as described in the first silane compound.
- the second silane compound is represented by the above formula (16) by mixing the compound represented by the above formula (14) and the compound represented by the above formula (16) and heating the compound. It is considered that the compound is synthesized by reacting the mercapto group in the compound with two carbon-carbon unsaturated bond portions in the compound represented by the above formula (14).
- the compound represented by the above formula (16) is preferably mixed so as to be 0.1 to 4 mol with respect to 1 mol of the compound represented by the above formula (14), preferably 0.3 to 3 mol. It is more preferable to mix them so as to be.
- the heating temperature is preferably 40 to 300 ° C, more preferably 50 to 200 ° C.
- the second silane compound can also be synthesized by mixing the compound represented by the above formula (14) and the compound represented by the formula (13) described later and heating the compound.
- the polysulfide bond in the compound represented by the formula (13) described later is cleaved, and this is synthesized by reacting with two carbon-carbon unsaturated bond portions in the compound represented by the above formula (14). it is conceivable that.
- the compound represented by the formula (13) described later is preferably mixed so as to be 0.1 to 4 mol, and 0.3 to 3 mol, with respect to 1 mol of the compound represented by the above formula (14). It is more preferable to mix them so as to be.
- the heating temperature is preferably 40 to 300 ° C, more preferably 50 to 200 ° C.
- a radical initiator can be used in combination.
- the radical initiator include azobisisobutyronitrile (AIBN), azo compounds such as 1,1'-azobis (cyclohexanecarbonitrile) (ABCN), di-tert-butyl peroxide (t-BuOOBu-t), and the like.
- hydrogen peroxide and iron (II) salts such as persulfates and sodium hydrogen sulfite
- II salts such as persulfates and sodium hydrogen sulfite
- a redox initiator combination of oxidizing agent and reducing agent triethyl borane (Et 3 B) And diethyl zinc (Et 2 Zn) can also be used.
- bis [3- (triethoxysilyl) propyl] tetrasulfide may be used, for example, Si manufactured by Evonik Industries. -69 can be mentioned.
- bis [3- (triethoxysilyl) propyl] disulfide a commercially available one may be used, and examples thereof include Si-75 manufactured by Evonik Industries.
- the silane coupling agent composition of the present invention further comprises a silane compound other than the first silane compound and the second silane compound (sometimes referred to as "other silane compounds" in the present specification). May be good.
- a silane compound other than the first silane compound and the second silane compound sometimes referred to as "other silane compounds" in the present specification.
- other silane compounds are also incorporated into the sulfide reaction, so that the first silane compound and the second silane compound that function as the silane coupling agent are incorporated.
- the silane compound reacts with other silane compounds. It is thought that this reaction produces a synergistic effect of increasing the coupling efficiency.
- the other silane compound is preferably a sulfur-containing silane compound other than the first silane compound and the second silane compound.
- silane compound for example, the formula (13): [During the ceremony, t and v are independently integers from 0 to 10, respectively. u is an integer from 2 to 10 and q and r are independently integers of 1 to 3, respectively. w and z are independently integers of 0 or 1, respectively. L 2 and L 3 are each independently a hydrocarbon group which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. R 21 and R 23 are amino groups independently substituted with an alkoxy group or one or more alkyl groups, respectively. R 22 and R 24 are independent hydrogen atoms or alkyl groups, respectively. ] The compound represented by can be used.
- t and v are independently integers of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 1 to 3, and even more preferably 2.
- u is an integer of 2 to 10, and more preferably an integer of 2 to 8.
- q and r are independently integers of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.
- w and z are independently integers of 0 or 1, and are preferably 0.
- L 2 and L 3 are hydrocarbon groups which may independently contain at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, preferably nitrogen, oxygen and.
- a hydrocarbon group having 1 to 30 carbon atoms which may contain at least one heteroatom selected from the group consisting of sulfur, more preferably at least one hetero selected from the group consisting of nitrogen, oxygen and sulfur. It may contain an atom, a hydrocarbon group having 1 to 20 carbon atoms, more preferably at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, having 1 to 20 carbon atoms. There are 10 hydrocarbon groups.
- R 21 and R 23 are independently hydrolyzable groups, and each of them is an alkoxy group, more preferably an alkoxy group having 1 to 30 carbon atoms, and further preferably an alkoxy group having 1 to 20 carbon atoms, or 1 Amino group substituted with the above alkyl group, more preferably an amino group substituted with 1 or more alkyl groups having 1 to 30 carbon atoms, more preferably substituted with 1 or more alkyl groups having 1 to 20 carbon atoms. It is an amino group.
- examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group and an isobutoxy group, and among these, a methoxy group or an ethoxy group is preferable.
- examples of the amino group substituted with one or more alkyl groups include an N-methylamino group, an N, N-dimethylamino group, an N-ethylamino group, an N, N-diethylamino group and an N-isopropylamino group. Among these, an N-methylamino group or an N-ethylamino group is preferable.
- R 22 and R 24 are each independently a hydrogen atom or an alkyl group, more preferably an alkyl group having 1 to 30 carbon atoms, and further preferably an alkyl group having 1 to 20 carbon atoms. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group and the like. Groups and ethyl groups are preferred.
- silane compound in addition to the compound represented by the above formula (13), a compound represented by the above formula (16), particularly a silane compound having the following structure can be used.
- the content of the other silane compound in the silane coupling agent composition of the present invention is preferably 0 in terms of mass ratio with respect to the total content of the first silane compound, the second silane compound, and the other silane compound. It is .1 to 0.9, more preferably 0.2 to 0.8.
- the rubber composition of the present invention is characterized by containing the silane coupling agent composition of the present invention, a diene-based rubber, and silica.
- the rubber composition of the present invention is excellent in scorch resistance and uncrosslinked compound viscosity, is a crosslinked rubber composition having excellent viscoelastic properties, and is excellent in a balance between wet grip and fuel efficiency using these. Can provide tires. Such a rubber composition can be suitably used for tires.
- each component of the rubber composition will be described in detail.
- the silane coupling agent composition is as described in detail above.
- the total content of the first silane compound and the second silane compound in the rubber composition is preferably 0.5 to 30 parts by mass, and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of silica. Yes, more preferably 2 to 15 parts by mass.
- the rubber composition is excellent in scorch resistance and uncrosslinked compound viscosity, and is excellent in viscoelastic property. It is possible to provide a compound and a tire using these with an excellent balance between wet grip and low fuel consumption.
- the content of the other silane compound in the rubber composition is preferably 0.01 to 20 parts by mass, and more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of silica.
- the diene-based rubber contained in the rubber composition of the present invention is not particularly limited, and conventionally known diene-based rubbers can be used.
- the diene-based rubber include isoprene-based rubber and other diene-based rubbers.
- examples of the isoprene-based rubber include natural rubber (NR), deproteinized natural rubber, and synthetic isoprene rubber.
- examples of natural rubber include natural rubber latex, technically rated rubber (TSR), smoked sheet (RSS), backlash, natural rubber derived from Tochu, natural rubber derived from guayule, natural rubber derived from Russian dandelion, fermented plant component rubber and the like.
- the natural rubber also includes modified natural rubber such as epoxidized natural rubber, methacrylic acid-modified natural rubber, styrene-modified natural rubber, sulfonic acid-modified natural rubber, and zinc sulfonate-modified natural rubber, which are modified from these natural rubbers. ..
- modified natural rubber such as epoxidized natural rubber, methacrylic acid-modified natural rubber, styrene-modified natural rubber, sulfonic acid-modified natural rubber, and zinc sulfonate-modified natural rubber, which are modified from these natural rubbers. ..
- the ratio of cis / trans / vinyl in the double bond portion of the natural rubber is not particularly limited, and any ratio can be preferably used.
- Examples of the synthetic isoprene rubber include copolymers of cis-1,4 isoprene, trans-1,4 isoprene, and 3,4 isoprene (so-called isoprene rubber (IR)
- Examples of those having a part of the structure of synthetic isoprene rubber include isoprene-butadiene rubber and halogenated isoprene rubber.
- isoprene rubber IR
- isoprene rubber is preferably used as the diene rubber, and it is more preferable to use synthetic isoprene rubber containing 75% or more of the cis-1,4 isoprene structure.
- the number average molecular weight and the molecular weight distribution of the diene rubber are not particularly limited, but the number average molecular weight is preferably 500 to 3000000 and the molecular weight distribution is preferably 1.5 to 15.
- diene rubbers include butadiene rubber, styrene-butadiene rubber, styrene-isoprene-butadiene rubber, styrene-isoprene rubber, partially hydrogenated styrene-butadiene rubber, styrene- ⁇ -methylstyrene-butadiene rubber, and ethylene-propylene-.
- examples include butadiene rubber. Among these, it is preferable to use butadiene rubber and styrene-butadiene rubber.
- the method for producing the diene rubber is not particularly limited, and examples thereof include emulsion polymerization, solution polymerization, radical polymerization, anionic polymerization, and cationic polymerization. Further, the glass transition point is not particularly limited.
- the content of the diene-based rubber is preferably 20 to 80% by mass, more preferably 25 to 75% by mass, and further preferably 30 to 70% by mass with respect to the total solid content mass of the rubber composition. be.
- inorganic material examples of the inorganic material contained in the rubber composition of the present invention include silica, carbon black, calcium carbonate, titanium oxide, clay and talc, and these can be used alone or in combination. Among these, at least silica is used in the present invention because it can further improve mechanical properties and heat resistance.
- the amount of the inorganic material added is preferably 0.1 to 500 parts by mass, and more preferably 1 to 300 parts by mass with respect to 100 parts by mass of the diene rubber.
- the silica is not particularly limited, and examples thereof include dry silica, wet silica, colloidal silica, and precipitated silica. Among these, wet method silica containing hydrous silicic acid as a main component is preferable. Each of these silicas can be used alone or in combination of two or more.
- the specific surface area of these silicas is not particularly limited, but is usually in the range of 10 to 400 m 2 / g, preferably 20 to 300 m 2 / g, and more preferably 120 to 190 m 2 / g in terms of the nitrogen adsorption specific surface area (BET method). At some point, improvements in reinforcement, wear resistance, heat generation and the like are sufficiently achieved and suitable.
- the nitrogen adsorption specific surface area is a value measured by the BET method according to ASTM D3037-81.
- the amount of silica added is preferably 1 to 300 parts by mass, more preferably 5 to 200 parts by mass, and further preferably 10 to 150 parts by mass with respect to 100 parts by mass of the diene rubber.
- Carbon black is appropriately selected and used according to the application. Generally, carbon black is classified into hard carbon and soft carbon based on the particle size. Soft carbon has low reinforcing properties against rubber, and hard carbon has high reinforcing properties against rubber. In the rubber composition of the present invention, it is preferable to use hard carbon having particularly high reinforcing properties.
- the amount of carbon black added is preferably 1 to 300 parts by mass, more preferably 5 to 200 parts by mass, and further preferably 10 to 150 parts by mass with respect to 100 parts by mass of the diene rubber.
- the carbon black may be added to the rubber composition or may be added to the silane coupling agent composition.
- the rubber composition of the present invention is a vulcanizing agent such as sulfur, a vulcanization accelerator, a vulcanization accelerating aid, an antioxidant, a coloring agent, a softening agent, various oils, and oxidation within a range not deviating from the gist of the present invention.
- a vulcanizing agent such as sulfur, a vulcanization accelerator, a vulcanization accelerating aid, an antioxidant, a coloring agent, a softening agent, various oils, and oxidation within a range not deviating from the gist of the present invention.
- Other processing aids such as inhibitors, fillers and plastics may be included.
- the vulcanizing agent examples include sulfur-based vulcanizing agents such as powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholindisulfide, and alkylphenol disulfide, zinc oxide, magnesium oxide, litharge, and p. -Kinone dioxam, p-dibenzoylquinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrobenzene, methylenedianiline, phenolic resin, brominated alkylphenol resin, chlorinated alkylphenol resin and the like can be mentioned.
- the amount of the vulcanizing agent added is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the diene rubber.
- vulcanization accelerator examples include thiuram-based vulcanization accelerators such as tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), and tetramethylthiuram monosulfide (TMTM), aldehyde / ammonia-based agents such as hexamethylenetetramine, and guanidine such as diphenylguanidine.
- TMTD tetramethylthiuram disulfide
- TETD tetraethylthiuram disulfide
- TMTM tetramethylthiuram monosulfide
- aldehyde / ammonia-based agents such as hexamethylenetetramine
- guanidine such as diphenylguanidine.
- thiazole system such as 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (DM), N-cyclohexyl-2-benzothiadylsulfene amide (CBS), Nt-butyl-2-benzothia
- MBT 2-mercaptobenzothiazole
- DM dibenzothiazyl disulfide
- CBS N-cyclohexyl-2-benzothiadylsulfene amide
- Nt-butyl-2-benzothia examples thereof include a sulfenamide-based vulcanization accelerator such as disulfene amide (BBS) and a dithiocarbamate-based vulcanization accelerator such as zinc dimethyldithiocarbamate (ZnPDC).
- the amount of the vulcanization accelerator added is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the dien
- Fatty acids such as acetyl acid, propionic acid, butanoic acid, steaic acid, acrylic acid, and maleic acid, zinc acetylate, zinc propionate, zinc butanoate, zinc stearate, zinc acrylate, and maleine are examples of vulture-promoting aids.
- fatty acid zinc such as zinc acid acid and zinc oxide.
- the amount of the vulcanization accelerating aid added is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the diene rubber.
- anti-aging agent examples include hindered phenol-based compounds, aliphatic and aromatic hindered amine-based compounds.
- the amount of the antiaging agent added is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the diene rubber.
- antioxidants examples include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
- BHT butylhydroxytoluene
- BHA butylhydroxyanisole
- the amount of the antioxidant added is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the diene rubber.
- the colorant examples include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine, red iron oxide, rithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, azo pigments, and copper phthalocyanine pigments.
- the amount of the colorant added is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the diene rubber.
- processing aids can be kneaded with a known rubber kneader, for example, a roll, a Banbury mixer, a kneader, etc., and vulcanized under arbitrary conditions to be used as a rubber composition.
- the addition amount of these other processing aids can also be a conventional general addition amount as long as the gist of the present invention is not deviated.
- the method for producing the rubber composition of the present invention comprises a step of kneading the silane coupling agent, the diene-based rubber and the inorganic material.
- the method for producing the rubber composition of the present invention preferably comprises a step of kneading the silane coupling agent, the diene rubber, the inorganic material and the vulcanization accelerating aid.
- the method for producing the rubber composition of the present invention may preferably further include a step of kneading the vulcanizing agent. More preferably, it may further include a step of kneading the vulcanizing agent and the vulcanization accelerator.
- the rubber composition can appropriately contain the above-mentioned other processing aids as long as it does not deviate from the gist of the present invention.
- a conventionally known kneading device can be used for producing the rubber composition, and the kneading temperature, time, blending order, etc. can be appropriately selected.
- a crosslinked product of the rubber composition can be produced according to a conventionally known method and common general technical knowledge well known to those skilled in the art. For example, a crosslink is formed by extruding the rubber composition, then molding the rubber composition using a molding machine, and then heating and pressurizing the rubber composition using a vulcanizer to produce a crosslinked product.
- the tire of the present invention contains a crosslinked product of the rubber composition of the present invention.
- the tire of the present invention can be manufactured by using the above rubber composition by a conventionally known method and common general technical knowledge widely known to those skilled in the art.
- the rubber composition is extruded, then molded using a tire molding machine, and then heated and pressurized using a vulcanizer to form crosslinks, whereby a tire can be manufactured.
- wet grip and fuel efficiency in tire performance can be improved in a well-balanced manner.
- the use of the tire is not particularly limited, and examples thereof include passenger car tires, high load tires, motorcycle (motorcycle) tires, and studless tires.
- the shape, structure, size and material of the tire are not particularly limited and can be appropriately selected according to the purpose. Further, it can be applied to each part of the tire, and the applicable part of the tire is not particularly limited, and the tread, carcass, sidewall, inner liner, under tread, belt part, etc. of the tire are appropriately selected according to the purpose. be able to.
- a pneumatic tire using the rubber composition for the tire tread is preferable.
- silane compound 1 is represented by gas chromatography in a fraction containing a large amount of the compound represented by the above formula (1A) (“(1A) fraction”) and the above formula (1B). It was fractionated into a fraction containing a large amount of the compound (“(1B) fraction”) and fractionated (FIG. 2).
- (1A) The measurement result of 1 H-NMR of the fraction is shown in FIG. 3, and the measurement result of 13 C-NMR is shown in FIG. Further, the measurement result of 1 H-NMR of the (1B) fraction is shown in FIG. 5, and the measurement result of 13 C-NMR is shown in FIG.
- silane compound 1 is a mixture of eight types of stereoisomers represented by the following formula.
- the silane compound 2 is obtained by further reacting mercaptosilane with the vinyl groups of the eight stereoisomers (1 adduct) of the silane compound 1 synthesized in Preparation Example 1 to form a diadder. Inferred. At that time, it is presumed that the addition to the vinyl group causes only the reaction to the 1-position (outside) of the vinyl group with less steric hindrance, and the addition to the vinyl group retains the steric isomerism of the silane compound 1. .. From the above, it is presumed that the obtained silane compound 2 is a mixture of eight types of stereoisomers represented by the following formula.
- Example 1-1 (Preparation of silane coupling agent composition, rubber composition, and rubber sheet) First, the total amount of silane compound 1 (VNB-SSi) and the total amount of silane compound 2 (VNB-2SSi) were mixed to obtain a silane coupling agent composition. Subsequently, each of the following components was kneaded using a 100 mL kneader (Laboplast Mill manufactured by Toyo Seiki Co., Ltd.) to obtain a rubber composition. The details of the kneading operation performed are as follows (i) to (iii).
- Mixer kneading Natural rubber is put into a closed pressure kneader heated to 150 ° C., kneaded at 30 rpm for 1 minute, and then 1 of a mixture of silica, zinc oxide, stearic acid, and an antiaging agent. The measured amount of / 2 and the total amount of the silane coupling agent composition prepared above were added, and the number of revolutions was increased to 50 rpm for 1 minute and 30 seconds of kneading.
- the remaining 1/2 amount of the mixture of the silica, zinc oxide, stearic acid, and the antiaging agent was added, kneading was continued for 1 minute and 30 seconds, and then the ram (floating weight) was raised to attach the silica to the surroundings.
- Zinc oxide, stearic acid, and anti-aging agent mixture powder is poured into the kneaded product using a brush, and after further kneading is continued for 1 minute, the ram is raised again and the silica and zinc oxide attached to the surroundings.
- Stearic acid, and a mixture of antioxidants were added to the kneaded product using a brush, kneaded for a further 3 minutes, and released.
- the obtained unvulcanized rubber composition was placed in a mold (150 mm ⁇ 150 mm ⁇ 2 mm) and heated and pressed at 160 ° C. for 30 minutes to obtain a vulcanized rubber sheet having a thickness of 2 mm.
- -Styrene-butadiene rubber manufactured by ZS Elastomer, trade name: NS616
- 70 parts by mass-butadiene rubber manufactured by Ube Industries, Ltd., trade name: UBEPOL BR150
- silica AQ manufactured by Toso Co., Ltd., product name: Nipseal AQ 60 parts by mass, zinc oxide No.
- Example 1-2 Same as Example 1-1 except that the amount of silane compound 1 (VNB-SSi) added was changed to 4.32 parts by mass and the amount of silane compound 2 (VNB-2SSi) added was changed to 0.48 parts by mass.
- a silane coupling agent composition, a rubber composition, and a rubber sheet were obtained.
- Example 1-3 Same as Example 1-1 except that the amount of silane compound 1 (VNB-SSi) added was changed to 4.08 parts by mass and the amount of silane compound 2 (VNB-2SSi) added was changed to 0.72 parts by mass.
- a silane coupling agent composition, a rubber composition, and a rubber sheet were obtained.
- Example 1-4 Same as Example 1-1 except that the amount of silane compound 1 (VNB-SSi) added was changed to 3.60 parts by mass and the amount of silane compound 2 (VNB-2SSi) added was changed to 1.20 parts by mass.
- a silane coupling agent composition, a rubber composition, and a rubber sheet were obtained.
- Example 1-5 The amount of silane compound 1 (VNB-SSi) added was changed to 3.06 parts by mass, the amount of silane compound 2 (VNB-2SSi) added was changed to 0.54 parts by mass, and other silane compounds (Si69) were added.
- a silane coupling agent composition, a rubber composition, and a rubber sheet were obtained in the same manner as in Example 1-1 except that 1.20 parts by mass was added and the amount of sulfur added was changed to 1.86 parts by mass. ..
- Example 1-2 The silane coupling agent composition was the same as in Example 1-1 except that the silane compound 1 (VNB-SSi) was not added and the amount of the silane compound 2 (VNB-2SSi) added was changed to 4.80 parts by mass. A product, a rubber composition, and a rubber sheet were obtained.
- Example 2-1 Preparation of silane coupling agent composition, rubber composition, and rubber sheet
- VNB-SSi total amount of silane compound 1
- VNB-2SSi total amount of silane compound 2
- each of the following components was kneaded using a 100 mL kneader (Laboplast Mill manufactured by Toyo Seiki Co., Ltd.) to obtain a rubber composition.
- the details of the kneading operation performed are as follows (i) to (iii).
- Mixer kneading Natural rubber is put into a closed pressure kneader heated to 150 ° C., kneaded at 30 rpm for 1 minute, and then 1 of a mixture of silica, zinc oxide, stearic acid, and an antiaging agent. The measured amount of / 2 and the total amount of the silane coupling agent composition prepared above were added, and the number of revolutions was increased to 50 rpm for 1 minute and 30 seconds of kneading.
- the remaining 1/2 amount of the mixture of the silica, zinc oxide, stearic acid, and the antiaging agent was added, kneading was continued for 1 minute and 30 seconds, and then the ram (floating weight) was raised to attach the silica to the surroundings.
- Zinc oxide, stearic acid, and anti-aging agent mixture powder is poured into the kneaded product using a brush, and after further kneading is continued for 1 minute, the ram is raised again and the silica and zinc oxide attached to the surroundings.
- Stearic acid, and a mixture of antioxidants were added to the kneaded product using a brush, kneaded for a further 3 minutes, and released.
- the obtained unvulcanized rubber composition was placed in a mold (150 mm ⁇ 150 mm ⁇ 2 mm) and heated and pressed at 160 ° C. for 30 minutes to obtain a vulcanized rubber sheet having a thickness of 2 mm.
- -Synthetic isoprene rubber manufactured by Zeon Corporation, product name: IR-2200
- silica AQ manufactured by Toso Co., Ltd., product name: Nipseal AQ
- Example 2-1 The viscoelasticity of the rubber sheets obtained in Example 2-1 and Comparative Example 2-1 was evaluated, and the scorch resistance and the uncrosslinked compound viscosity of the rubber composition were evaluated by the above method in the same manner as in Example 1-1. did.
- Table 2 shows the above measurement results and calculation results (tan ⁇ balance). Each measured value and each calculated value are represented by an index in which each value in Comparative Example 2-1 is 100.
- Example 2-1 and Comparative Example 2-1 by using a silane coupling agent composition containing a silane compound 1 (VNB-SSi) and a silane compound 2 (VNB-SSi), a synthetic isoprene rubber is contained.
- the rubber composition had a reduced viscosity at the time of uncrosslinked compound, improved scorch resistance, and further improved viscoelastic properties of the rubber sheet. Therefore, it has been found that when the silane coupling agent composition and the rubber composition of the present invention are used, the workability of rubber is improved, and it is possible to manufacture a tire having an excellent balance between wet grip and fuel efficiency in practical use. did.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
[1] シラン化合物を含む、シランカップリング剤組成物であって、
前記シラン化合物が、下記式(1):
R1、R2およびR3は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
Lは、窒素、酸素および硫黄からなる群から選択される少なくとも1つのヘテロ原子を含んでいてもよい炭化水素基であり、
aは、0か1の整数であり、
bは、0か1の整数であり、
cは、それぞれ独立して、0か1の整数であり、
dは、それぞれ独立して、0か1の整数であり、
eは、0~5の整数であり、
R4、R5、R6およびR7は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R4若しくはR5およびR6若しくはR7の1つが、-(CH2)f-で表される架橋構造を形成してもよく、
fは、1~5の整数であり、
R8、R9、R10およびR11は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R8若しくはR9およびR10若しくはR11の1つが、-(CH2)g-で表される架橋構造を形成してもよく、
gは、1~5の整数であり、
R16は、水素原子、メチル基または炭素数2~8のアルキル基であり、かつ、R17は、水素原子、メチル基または炭素数2~10のアルキル基であり、ここで、R12およびR13は、互いに結合して二重結合を形成し、かつ、R14、R15およびR18は水素原子、メチル基または炭素数2~10のアルキル基であり、若しくは、R14およびR15は、互いに結合して二重結合を形成し、かつ、R12、R13およびR18は水素原子、メチル基または炭素数2~10のアルキル基であり、
または、
R16およびR17は、互いに結合して4~9員の脂環式炭化水素を形成してもよく、ここで、R14およびR15は、互いに結合して二重結合を形成し、かつ、R12、R13およびR18は水素原子、メチル基または炭素数2~10のアルキル基である。]
で表される第1のシラン化合物と、
下記式(11):
各R1、R2およびR3は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
各Lは、それぞれ独立して、窒素、酸素および硫黄からなる群から選択される少なくとも1つのヘテロ原子を含んでいてもよい炭化水素基であり、
aは、0か1の整数であり、
bは、0か1の整数であり、
cは、それぞれ独立して、0か1の整数であり、
dは、それぞれ独立して、0か1の整数であり、
eは、0~5の整数であり、
R4、R5、R6およびR7は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R4若しくはR5およびR6若しくはR7の1つが、-(CH2)f-で表される架橋構造を形成してもよく、
fは、1~5の整数であり、
R8、R9、R10およびR11は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R8若しくはR9およびR10若しくはR11の1つが、-(CH2)g-で表される架橋構造を形成してもよく、
gは、1~5の整数であり、
R26、R27およびR28は、それぞれ独立して、水素原子、メチル基または炭素数2~10のアルキル基を表す。]
で表される第2のシラン化合物を含む、シランカップリング剤組成物。
[2] 前記第1のシラン化合物が、下記式(2):
R1、R2およびR3は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
hは、1~10の整数であり、
aは、0か1の整数であり、
bは、0か1の整数であり、
cは、それぞれ独立して、0か1の整数であり、
dは、それぞれ独立して、0か1の整数であり、
eは、0~5の整数であり、
R4、R5、R6およびR7は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R4若しくはR5およびR6若しくはR7の1つが、-(CH2)f-で表される架橋構造を形成してもよく、
fは、1~5の整数であり、
R8、R9、R10およびR11は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R8若しくはR9およびR10若しくはR11の1つが、-(CH2)g-で表される架橋構造を形成してもよく、
gは、1~5の整数であり、
R16は、水素原子、メチル基または炭素数2~8のアルキル基であり、かつ、R17は、水素原子、メチル基または炭素数2~10のアルキル基であり、ここで、R12およびR13は、互いに結合して二重結合を形成し、かつ、R14、R15およびR18は水素原子、メチル基または炭素数2~10のアルキル基であり、若しくは、R14およびR15は、互いに結合して二重結合を形成し、かつ、R12、R13およびR18は水素原子、メチル基または炭素数2~10のアルキル基であり、
または、
R16およびR17は、互いに結合して4~9員の脂環式炭化水素を形成してもよく、ここで、R14およびR15は、互いに結合して二重結合を形成し、かつ、R12、R13およびR18は水素原子、メチル基または炭素数2~10のアルキル基である。]
で表される化合物である、[1]に記載のシランカップリング剤組成物。
[3] 前記第2のシラン化合物が、下記式(12):
各R1、R2およびR3は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
hは、1~10の整数であり、
mは、1~10の整数であり、
aは、0か1の整数であり、
bは、0か1の整数であり、
cは、それぞれ独立して、0か1の整数であり、
dは、それぞれ独立して、0か1の整数であり、
eは、0~5の整数であり、
R4、R5、R6およびR7は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R4若しくはR5およびR6若しくはR7の1つが、-(CH2)f-で表される架橋構造を形成してもよく、
fは、1~5の整数であり、
R8、R9、R10およびR11は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R8若しくはR9およびR10若しくはR11の1つが、-(CH2)g-で表される架橋構造を形成してもよく、
gは、1~5の整数であり、
R26、R27およびR28は、それぞれ独立して、水素原子、メチル基または炭素数2~10のアルキル基を表す。]
で表される化合物である、[1]または[2]に記載のシランカップリング剤組成物。
[4] 前記第2のシラン化合物の含有量が、前記第1のシラン化合物および第2のシラン化合物の合計含有量に対して、1~50質量%である、[1]~[3]のいずれかに記載のシランカップリング剤組成物。
[5] 前記シラン化合物が、第1のシラン化合物および第2のシラン化合物以外の他のシラン化合物をさらに含んでなる、[1]~[4]のいずれかに記載のシランカップリング剤組成物。
[6] 前記他のシラン化合物が、式(13):
tおよびvは、それぞれ独立して、0~10の整数であり、
uは、2~10の整数であり、
qおよびrは、それぞれ独立して、1~3の整数であり、
wおよびzは、それぞれ独立して、0か1の整数であり、
L2およびL3は、それぞれ独立して、窒素、酸素および硫黄からなる群から選択される少なくとも1つのヘテロ原子を含んでいてもよい炭化水素基であり、
R21およびR23は、それぞれ独立して、アルコキシ基または1以上のアルキル基で置換されたアミノ基であり、
R22およびR24は、それぞれ独立して、水素またはアルキル基である。]
で表されるシラン化合物である、[5]に記載のシランカップリング剤組成物。
[7] ジエン系ゴムに用いられる、[1]~[6]のいずれかに記載のシランカップリング剤組成物。
[8] [1]~[7]のいずれかに記載のシランカップリング剤組成物と、ジエン系ゴムと、シリカとを含むゴム組成物であって、
前記第1のシラン化合物および前記第2のシラン化合物の合計含有量が、前記シリカ100質量部に対して、0.5~30質量部である、ゴム組成物。
[9] 前記シリカの含有量が、前記ジエン系ゴム100質量部に対して、0.5~300質量部である、[8]に記載のゴム組成物。
[10] タイヤに用いられる、[8]または[9]に記載のゴム組成物。
[11] [8]~[10]のいずれかに記載のゴム組成物の架橋物。
[12] [11]に記載の架橋物をタイヤトレッドに用いた、空気入りタイヤ。
本明細書において、配合を示す「部」、「%」等は特に断らない限り質量基準である。
本発明のシランカップリング剤組成物は、シラン化合物を含み、シラン化合物は、第1のシラン化合物および第2のシラン化合物を含むことを特徴とする。本発明のシランカップリング剤組成物は、ゴム等の有機高分子材料に対して適度な反応性を有しながら、耐スコーチ性および未架橋コンパウンド粘度に優れるゴム組成物を得ることができる。
本発明のシランカップリング剤組成物に含まれる第1のシラン化合物は、下記の式(1):
R1、R2およびR3は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
Lは、窒素、酸素および硫黄からなる群から選択される少なくとも1つのヘテロ原子を含んでいてもよい炭化水素基であり、
aは、0か1の整数であり、
bは、0か1の整数であり、
cは、それぞれ独立して、0か1の整数であり、
dは、それぞれ独立して、0か1の整数であり、
eは、0~5の整数であり、
R4、R5、R6およびR7は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R4若しくはR5およびR6若しくはR7の1つが、-(CH2)f-で表される架橋構造を形成してもよく、
fは、1~5の整数であり、
R8、R9、R10およびR11は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R8若しくはR9およびR10若しくはR11の1つが、-(CH2)g-で表される架橋構造を形成してもよく、
gは、1~5の整数であり、
R16は、水素原子、メチル基または炭素数2~8のアルキル基であり、かつ、R17は、水素原子、メチル基または炭素数2~10のアルキル基であり、ここで、R12およびR13は、互いに結合して二重結合を形成し、かつ、R14、R15およびR18は水素原子、メチル基または炭素数2~10のアルキル基であり、若しくは、R14およびR15は、互いに結合して二重結合を形成し、かつ、R12、R13およびR18は水素原子、メチル基または炭素数2~10のアルキル基であり、
または、
R16およびR17は、互いに結合して4~9員の脂環式炭化水素を形成してもよく、ここで、R14およびR15は、互いに結合して二重結合を形成し、かつ、R12、R13およびR18は水素原子、メチル基または炭素数2~10のアルキル基である。]
で表される化合物である。
また、bは、0か1の整数であり、好ましくは1である。
また、cは、それぞれ独立して、0か1の整数であり、好ましくは1である。
また、dは、それぞれ独立して、0か1の整数であり、好ましくは1である。
また、eは、0~5の整数であり、好ましくは0~3の整数、より好ましくは0~2の整数、さらに好ましくは0または1の整数である。
また、R4、R5、R6およびR7は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R4若しくはR5およびR6若しくはR7の1つが、-(CH2)f-で表される架橋構造を形成してもよい。
また、fは、1~5の整数であり、好ましくは1~4の整数、より好ましくは1~3の整数、さらに好ましくは1である。
また、R8、R9、R10およびR11は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R8若しくはR9およびR10若しくはR11の1つが、-(CH2)g-で表される架橋構造を形成してもよい。
また、gは、1~5の整数であり、好ましくは1~4の整数、より好ましくは1~3の整数、さらに好ましくは1である。
また、R16は、水素原子、メチル基または炭素数2~8のアルキル基であり、好ましくは、水素原子、メチル基または炭素数2または3のアルキル基、より好ましくは、水素原子またはメチル基、さらにより好ましくは、水素原子であり、かつ、R17は、水素原子、メチル基または炭素数2~10のアルキル基であり、好ましくは、水素原子、メチル基または炭素数2~5のアルキル基、より好ましくは、水素原子またはメチル基、さらにより好ましくは、水素原子であり、ここで、R12およびR13は、互いに結合して二重結合を形成し、かつ、R14、R15およびR18は水素原子、メチル基または炭素数2~10のアルキル基であり、若しくは、R14およびR15は、互いに結合して二重結合を形成し、かつ、R12、R13およびR18は水素原子、メチル基または炭素数2~10のアルキル基であり、
または、
R16およびR17は、互いに結合して4~9員の脂環式炭化水素、好ましくは4~7員の脂環式炭化水素、より好ましくは5員または6員の脂環式炭化水素、さらに好ましくは5員の脂環式炭化水素を形成してもよく、ここで、R14およびR15は、互いに結合して二重結合を形成し、かつ、R12、R13およびR18は水素原子、メチル基または炭素数2~10のアルキル基である。
アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、tert-ブチル基、2-エチルヘキシル基、シクロペンチル基、シクロヘキシル基等が挙げられ、アルキル基の炭素原子数は1~60が好ましく、1~30がより好ましく、中でもメチル基またはエチル基であることが好ましい。
アラルキル基としては、例えば、ベンジル基、フェネチル基、ナフチルメチル基、ビフェニルメチル基等が挙げられる。アラルキル基の炭素原子数は7~60が好ましく、7~20がより好ましく、7~14がさらに好ましい。
アリール基としては、フェニル基、ビフェニル基、ナフチル基、トリル基、キシリル基等が挙げられる。アリール基の炭素原子数は6~60が好ましく、6~24がより好ましく、6~12がさらに好ましい。
酸素原子または窒素原子を含む炭化水素基とは、炭化水素基中の炭素原子が酸素原子または窒素原子で置き換えられた構造を有する基である。
R1、R2およびR3は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
hは、1~10の整数であり、
aは、0か1の整数であり、
bは、0か1の整数であり、
cは、それぞれ独立して、0か1の整数であり、
dは、それぞれ独立して、0か1の整数であり、
eは、0~5の整数であり、
R4、R5、R6およびR7は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R4若しくはR5およびR6若しくはR7の1つが、-(CH2)f-で表される架橋構造を形成してもよく、
fは、1~5の整数であり、
R8、R9、R10およびR11は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R8若しくはR9およびR10若しくはR11の1つが、-(CH2)g-で表される架橋構造を形成してもよく、
gは、1~5の整数であり、
R16は、水素原子、メチル基または炭素数2~8のアルキル基であり、かつ、R17は、水素原子、メチル基または炭素数2~10のアルキル基であり、ここで、R12およびR13は、互いに結合して二重結合を形成し、かつ、R14、R15およびR18は水素原子、メチル基または炭素数2~10のアルキル基であり、若しくは、R14およびR15は、互いに結合して二重結合を形成し、かつ、R12、R13およびR18は水素原子、メチル基または炭素数2~10のアルキル基であり、
または、
R16およびR17は、互いに結合して4~9員の脂環式炭化水素を形成してもよく、ここで、R14およびR15は、互いに結合して二重結合を形成し、かつ、R12、R13およびR18は水素原子、メチル基または炭素数2~10のアルキル基である。]
で表される化合物である。
R1、R2およびR3は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
hは、1~10の整数であり、
aは、0か1の整数であり、
bは、0か1の整数であり、
cは、それぞれ独立して、0か1の整数であり、
dは、それぞれ独立して、0か1の整数であり、
eは、0~5の整数であり、
R4、R5、R6およびR7は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R4若しくはR5およびR6若しくはR7の1つが、-(CH2)f-で表される架橋構造を形成してもよく、
fは、1~5の整数であり、
R8、R9、R10およびR11は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R8若しくはR9およびR10若しくはR11の1つが、-(CH2)g-で表される架橋構造を形成してもよく、
gは、1~5の整数であり、
R31は、水素原子、メチル基または炭素数2~8のアルキル基である。]
で表される化合物である。
R1、R2およびR3は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
hは、1~10の整数であり、
aは、0か1の整数であり、
bは、0か1の整数であり、
cは、それぞれ独立して、0か1の整数であり、
dは、それぞれ独立して、0か1の整数であり、
eは、0~5の整数であり、
R4、R5、R6およびR7は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R4若しくはR5およびR6若しくはR7の1つが、-(CH2)f-で表される架橋構造を形成してもよく、
fは、1~5の整数であり、
R8、R9、R10およびR11は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R8若しくはR9およびR10若しくはR11の1つが、-(CH2)g-で表される架橋構造を形成してもよく、
gは、1~5の整数であり、
R32は、水素原子、メチル基または炭素数2~9のアルキル基である。]
で表される化合物である。
R1、R2およびR3は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
hは、1~10の整数であり、
aは、0か1の整数であり、
bは、0か1の整数であり、
cは、それぞれ独立して、0か1の整数であり、
dは、それぞれ独立して、0か1の整数であり、
eは、0~5の整数であり、
R4、R5、R6およびR7は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R4若しくはR5およびR6若しくはR7の1つが、-(CH2)f-で表される架橋構造を形成してもよく、
fは、1~5の整数であり、
R8、R9、R10およびR11は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R8若しくはR9およびR10若しくはR11の1つが、-(CH2)g-で表される架橋構造を形成してもよく、
gは、1~5の整数であり、
xは、0~5の整数である。]
で表される化合物である。
式(7):
式(8):
式(9):
で表される化合物である。
R19は、それぞれ独立して、アルコキシ基または1以上のアルキル基で置換されたアミノ基であり、
R20は、それぞれ独立して、水素原子またはアルキル基であり、
L1は、それぞれ独立して、窒素、酸素および硫黄からなる群から選択される少なくとも1つのヘテロ原子を含んでいてもよい炭化水素基であり、
jは、それぞれ独立して、0か1の整数であり、
kは、1~3の整数であり、
アスタリスク(*)は、前記シラン化合物のシリル基以外の部分と結合している部位を示す。]
の化学構造を有するシラン化合物が挙げられる。
また、R20は、それぞれ独立して、水素原子またはアルキル基であり、より好ましくは炭素数1~30のアルキル基、さらに好ましくは炭素数1~20のアルキル基であり、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、tert-ブチル基、ペンチル基、シクロペンチル基、へキシル基およびシクロへキシル基等が挙げられ、これらの中でも、メチル基およびエチル基が好ましい。
また、jは、それぞれ独立して、0か1の整数であり、好ましくは0である。
本発明のシランカップリング剤組成物に含まれる式(1)で表される第1のシラン化合物の製造方法の一実施形態について説明するが、以下の製造方法に限定されるものではない。例えば、第1のシラン化合物は、式(14):
aは、0か1の整数であり、
bは、0か1の整数であり、
cは、それぞれ独立して、0か1の整数であり、
dは、それぞれ独立して、0か1の整数であり、
eは、0~5の整数であり、
R4、R5、R6およびR7は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R4若しくはR5およびR6若しくはR7の1つが、-(CH2)f-で表される架橋構造を形成してもよく、
fは、1~5の整数であり、
R8、R9、R10およびR11は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R8若しくはR9およびR10若しくはR11の1つが、-(CH2)g-で表される架橋構造を形成してもよく、
gは、1~5の整数であり、
R16は、水素原子、メチル基または炭素数2~8のアルキル基であり、かつ、R17は、水素原子、メチル基または炭素数2~10のアルキル基であり、ここで、R12およびR13は、互いに結合して二重結合を形成し、かつ、R14、R15およびR18は水素原子、メチル基または炭素数2~10のアルキル基であり、若しくは、R14およびR15は、互いに結合して二重結合を形成し、かつ、R12、R13およびR18は水素原子、メチル基または炭素数2~10のアルキル基であり、
または、
R16およびR17は、互いに結合して4~9員の脂環式炭化水素を形成してもよく、ここで、R14およびR15は、互いに結合して二重結合を形成し、かつ、R12、R13およびR18は水素原子、メチル基または炭素数2~10のアルキル基である。]
で表される化合物と、式(15):
R1、R2およびR3は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
Yは、窒素、酸素および硫黄からなる群から選択される少なくとも1つのヘテロ原子を含んでいてもよい炭化水素基である。]
で表される化合物を反応させることにより、製造することができる。
R1、R2およびR3は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
hは、1~10の整数である。]
で表される化合物を反応することにより、製造することができる。
本発明のシランカップリング剤組成物に含まれる第2のシラン化合物は、下記の式(11):
各R1、R2およびR3は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
各Lは、それぞれ独立して、窒素、酸素および硫黄からなる群から選択される少なくとも1つのヘテロ原子を含んでいてもよい炭化水素基であり、
aは、0か1の整数であり、
bは、0か1の整数であり、
cは、それぞれ独立して、0か1の整数であり、
dは、それぞれ独立して、0か1の整数であり、
eは、0~5の整数であり、
R4、R5、R6およびR7は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R4若しくはR5およびR6若しくはR7の1つが、-(CH2)f-で表される架橋構造を形成してもよく、
fは、1~5の整数であり、
R8、R9、R10およびR11は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R8若しくはR9およびR10若しくはR11の1つが、-(CH2)g-で表される架橋構造を形成してもよく、
gは、1~5の整数であり、
R26、R27およびR28は、それぞれ独立して、水素原子、メチル基または炭素数2~10のアルキル基を表す。]
で表される化合物である。
また、各Lの好ましい実施態様は、上記式(1)で説明した通りである。
また、a、b、c、d、eの好ましい態様は、上記式(1)で説明した通りである。
R26、R27およびR28は、それぞれ独立して、水素原子、メチル基または炭素数2~10のアルキル基を表し、好ましくは水素原子である。
各R1、R2およびR3は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
hは、1~10の整数であり、
mは、1~10の整数であり、
aは、0か1の整数であり、
bは、0か1の整数であり、
cは、それぞれ独立して、0か1の整数であり、
dは、それぞれ独立して、0か1の整数であり、
eは、0~5の整数であり、
R4、R5、R6およびR7は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R4若しくはR5およびR6若しくはR7の1つが、-(CH2)f-で表される架橋構造を形成してもよく、
fは、1~5の整数であり、
R8、R9、R10およびR11は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R8若しくはR9およびR10若しくはR11の1つが、-(CH2)g-で表される架橋構造を形成してもよく、
gは、1~5の整数であり、
R26、R27およびR28は、それぞれ独立して、水素原子、メチル基または炭素数2~10のアルキル基を表す。]
で表される化合物である。
また、各Lの好ましい実施態様は、上記式(11)で説明した通りである。
また、a、b、c、d、eの好ましい態様は、上記式(11)で説明した通りである。
また、hの好ましい実施態様は、上記式(2)で説明した通りである。
また、上記式(12)において、mは、1~10の整数であり、好ましくは1~8、より好ましくは1~6、さらに好ましくは1~4、さらにより好ましくは1~3の整数である。
式(18):
で表される化合物である。
本発明のシランカップリング剤組成物に含まれる式(11)で表される第2のシラン化合物の製造方法の一実施形態について説明するが、以下の製造方法に限定されるものではない。例えば、第2のシラン化合物は、下記式(14):
aは、0か1の整数であり、
bは、0か1の整数であり、
cは、それぞれ独立して、0か1の整数であり、
dは、それぞれ独立して、0か1の整数であり、
eは、0~5の整数であり、
R4、R5、R6およびR7は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R4若しくはR5およびR6若しくはR7の1つが、-(CH2)f-で表される架橋構造を形成してもよく、
fは、1~5の整数であり、
R8、R9、R10およびR11は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R8若しくはR9およびR10若しくはR11の1つが、-(CH2)g-で表される架橋構造を形成してもよく、
gは、1~5の整数であり、
R12、R13、R14、R15、R16、R17およびR18は、それぞれ独立して、水素原子、メチル基または炭素数2~10のアルキル基を表し、但し、R12およびR13は、互いに結合して二重結合を形成するか、あるいは、R14およびR15は互いに結合して二重結合を形成し、また、R16およびR17は、互いに結合して4~9員の脂環式炭化水素を形成してもよい。]
で表される化合物と、上記式(15)で表される化合物を反応させることにより、製造することができる。なお、上記式(14)および(15)の好ましい実施態様については、第1のシラン化合物において説明した通りである。
本発明のシランカップリング剤組成物は、第1のシラン化合物および第2のシラン化合物以外の他のシラン化合物(本明細書において「他のシラン化合物」と称することもある)をさらに含んでいてもよい。本発明のシランカップリング剤組成物を含むゴム組成物を加硫反応させると、他のシラン化合物も加硫反応に組み込まれるため、シランカップリング剤として機能する第1のシラン化合物および第2のシラン化合物と、他のシラン化合物が反応する。この反応によって、カップリング効率が高まるという相乗効果が生まれると考えられる。本発明のゴム組成物において、他のシラン化合物は、好ましくは、第1のシラン化合物および第2のシラン化合物以外の含硫黄シラン化合物である。
tおよびvは、それぞれ独立して、0~10の整数であり、
uは、2~10の整数であり、
qおよびrは、それぞれ独立して、1~3の整数であり、
wおよびzは、それぞれ独立して、0か1の整数であり、
L2およびL3は、それぞれ独立して、窒素、酸素および硫黄からなる群から選択される少なくとも1つのヘテロ原子を含んでいてもよい炭化水素基であり、
R21およびR23は、それぞれ独立して、アルコキシ基または1以上のアルキル基で置換されたアミノ基であり、
R22およびR24は、それぞれ独立して、水素原子またはアルキル基である。]
で表される化合物を使用することができる。
また、uは、2~10の整数であり、より好ましくは、2~8の整数である。
また、qおよびrは、それぞれ独立して、1~3の整数であり、好ましくは2~3の整数、より好ましくは3である。
また、wおよびzは、それぞれ独立して、0か1の整数であり、好ましくは0である。
また、L2およびL3は、それぞれ独立して、窒素、酸素および硫黄からなる群から選択される少なくとも1つのヘテロ原子を含んでいてもよい炭化水素基であり、好ましくは、窒素、酸素および硫黄からなる群から選択される少なくとも1つのヘテロ原子を含んでいてもよい、炭素数1~30の炭化水素基、より好ましくは、窒素、酸素および硫黄からなる群から選択される少なくとも1つのヘテロ原子を含んでいてもよい、炭素数1~20の炭化水素基、さらに好ましくは、窒素、酸素および硫黄からなる群から選択される少なくとも1つのヘテロ原子を含んでいてもよい、炭素数1~10の炭化水素基である。
また、R21およびR23は、それぞれ独立して、加水分解性基であり、アルコキシ基、より好ましくは炭素数1~30のアルコキシ基、さらに好ましくは炭素数1~20のアルコキシ基、または1以上のアルキル基で置換されたアミノ基、より好ましくは1以上の炭素数1~30のアルキル基で置換されたアミノ基、より好ましくは1以上の炭素数1~20のアルキル基で置換されたアミノ基である。具体的には、アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基およびイソブトキシ基等が挙げられ、これらの中でも、メトキシ基またはエトキシ基が好ましい。また、1以上のアルキル基で置換されたアミノ基としては、N-メチルアミノ基、N,N-ジメチルアミノ基、N-エチルアミノ基、N,N-ジエチルアミノ基およびN-イソプロピルアミノ基等が挙げられ、これらの中でも、N-メチルアミノ基またはN-エチルアミノ基が好ましい。なお、アルコキシ基およびアミノ基は、窒素、酸素および硫黄からなる群から選択される少なくとも1つのヘテロ原子を含んでいてもよい炭化水素基からなる連結基を介してケイ素(Si)と結合してもよい。
また、R22およびR24は、それぞれ独立して、水素原子またはアルキル基であり、より好ましくは炭素数1~30のアルキル基、さらに好ましくは炭素数1~20のアルキル基であり、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、tert-ブチル基、ペンチル基、シクロペンチル基、へキシル基およびシクロへキシル基等が挙げられ、これらの中でも、メチル基およびエチル基が好ましい。
本発明のゴム組成物は、本発明のシランカップリング剤組成物、ジエン系ゴムと、シリカとを含むことを特徴とする。本発明のゴム組成物は、耐スコーチ性および未架橋コンパウンド粘度に優れるものであり、粘弾性特性に優れるゴム組成物の架橋物、およびこれらを用いたウェットグリップ性と低燃費性のバランスに優れたタイヤを提供することができる。このようなゴム組成物は、タイヤ用として好適に用いることができる。以下、ゴム組成物の各成分について詳述する。なお、シランカップリング剤組成物については、上記で詳述した通りである。
本発明のゴム組成物に含まれるジエン系ゴムは、特に限定されず、従来公知のジエン系ゴムを用いることができる。ジエン系ゴムとしては、イソプレン系ゴムおよび他のジエン系ゴムが挙げられる。イソプレン系ゴムとしては、天然ゴム(NR)、脱タンパク質天然ゴム、および合成イソプレンゴム等が挙げられる。天然ゴムとしては、天然ゴムラテックス、技術的格付けゴム(TSR)、スモークドシート(RSS)、ガタパーチャ、杜仲由来天然ゴム、グアユール由来天然ゴム、ロシアンタンポポ由来天然ゴム、植物成分発酵ゴム等が挙げられ、さらにこれらの天然ゴムを変性した、エポキシ化天然ゴム、メタクリル酸変性天然ゴム、スチレン変性天然ゴム、スルホン酸変性天然ゴム、スルホン酸亜鉛変性天然ゴム等の変性天然ゴム等も、天然ゴムに含まれる。天然ゴムの二重結合部のシス/トランス/ビニルの比率は、特に制限はなく、いずれの比率においても好適に用いることができる。合成イソプレンゴムとしては、シス-1,4イソプレン、トランス-1,4イソプレン、および3,4イソプレンの共重合体(いわゆる、イソプレンゴム(IR))が挙げられる。また、合成イソプレンゴムの構造を一部有するものとして、イソプレン-ブタジエンゴム、およびハロゲン化イソプレンゴム等が挙げられる。本発明においては、ジエン系ゴムとしてイソプレンゴム(IR)を用いることが好ましく、シス―1,4イソプレン構造を75%以上含む合成イソプレンゴムを用いることがさらに好ましい。また、ジエン系ゴムの数平均分子量および分子量分布は、特に制限はないが、数平均分子量500~3000000、分子量分布1.5~15が好ましい。
本発明のゴム組成物に含まれる無機材料としては、例えば、シリカ、カーボンブラック、炭酸カルシウム、酸化チタン、クレイおよびタルク等が挙げられ、これらを単独または組み合わせて用いることができる。これらの中でも、機械的特性および耐熱性をより向上させることができることから、本発明においては、少なくともシリカを用いる。無機材料の添加量は、ジエン系ゴム100質量部に対して、好ましくは0.1~500質量部であり、より好ましくは1~300質量部である。
本発明のゴム組成物は、本発明の趣旨を逸脱しない範囲で、硫黄等の加硫剤、加硫促進剤、加硫促進助剤、老化防止剤、着色剤、軟化剤、各種オイル、酸化防止剤、充填剤および可塑材等のその他の加工助剤を含んでいてもよい。
本発明のゴム組成物を製造する方法は、上記シランカップリング剤、上記ジエン系ゴムおよび上記無機材料を混練する工程を含んでなるものである。本発明のゴム組成物を製造する方法は、好ましくは、上記シランカップリング剤、上記ジエン系ゴム、上記無機材料および上記加硫促進助剤を混練する工程を含んでなるものである。
本発明のゴム組成物を用いて、従来公知の方法および当業者に広く知られた技術常識に従い、ゴム組成物の架橋物を製造することができる。例えば、上記ゴム組成物を押し出し、次いで、成型機を用いて成形した後、加硫機を用いて加熱・加圧することにより架橋が形成され、架橋物を製造することができる。
本発明のタイヤは、本発明のゴム組成物の架橋物を含むものである。本発明のタイヤは、上記ゴム組成物を用いて、従来公知の方法および当業者に広く知られた技術常識によりタイヤを製造することができる。例えば、上記ゴム組成物を押し出し、次いで、タイヤ成型機を用いて成形した後、加硫機を用いて加熱・加圧することにより架橋が形成され、タイヤを製造することができる。本発明のゴム組成物を用いてタイヤを製造することにより、タイヤ性能におけるウエットグリップ性および低燃費性をバランス良く向上させることができる。
100mLの三口フラスコに玉栓、真空/ドライ窒素ラインを繋げた三方コック、セプタムを取り付けた後、スターラーバーを入れ、ドライヤーで加熱しながら、系内の脱気-窒素置換を10回繰り返し、常圧窒素雰囲気下とした。そのフラスコ内に、シリンジを用いて2-ビニルノルボルネン(VNB)27.5g(0.225mоl)を注入し、窒素雰囲気下でアゾビスイソブチロニトリル0.074g(0.45mmоl)を添加した後、窒素バブリングを20分行った。続いて、ガスタイトシリンジで10.7g(0.045mol)のメルカプトプロピルトリエトキシシランを吸引して定量ポンプに取り付け、3時間で全量が滴下されるよう設定した。最後に、シリコングリースで接続部を密閉し、ガスタイトシリンジの針先をセプタムを通じてフラスコに導入し、フラスコをオイルバスに浸漬し、バス温度を徐々に上昇させて、内温が50℃に到達した時点で定量ポンプを作動させ、メルカプトプロピルトリエトキシシランを滴下して反応させた。全量の滴下が完了してから2時間後にフラスコからオイルバスを外し、室温まで放置した。次に余剰のVNBを減圧留去した後、目的の無色澄明液体を37.4g得た。得られた化合物の1H-NMRの測定結果を図1に示す。1H-NMRの測定および13C-NMRの測定によりシランの導入率は100%であり、ノルボルネン環の二重結合が消失していることを確認した。
得られたシラン化合物1を、ガスクロマトグラフィーにより、上記の式(1A)で表される化合物が多く含まれる画分(「(1A)画分」)と、上記の式(1B)で表される化合物が多く含まれる画分(「(1B)画分」)とに分画し、分取した(図2)。(1A)画分の1H-NMRの測定結果を図3に、13C-NMRの測定結果を図4に示す。また、(1B)画分の1H-NMRの測定結果を図5に、13C-NMRの測定結果を図6に示す。式(1A)および(1B)で表される化学構造において、ビニル基の二重結合のノルボルネン環に直接結合している方の炭素原子(図3または図5において、円形で囲まれた整数2により表示された炭素原子)に結合するプロトンのピークが分裂していることが認められた。このデータより、ノルボルネン環に結合したビニル基がノルボルネン環の架橋構造と同様に紙面向かって前側に伸びている異性体(シン異性体)と、ノルボルネン環に結合したビニル基がノルボルネン環の架橋構造と反対に紙面向かって後側に伸びている異性体(アンチ異性体)の2種の立体異性体が存在していることが推察された。同様に、ノルボルネン環に結合した硫黄原子がノルボルネン環の架橋構造と同様に紙面向かって前側に伸びている異性体(シン異性体)と、ノルボルネン環に結合した硫黄原子がノルボルネン環の架橋構造と反対に紙面向かって後側に伸びている異性体(アンチ異性体)の2種の立体異性体が存在していると推察される。以上により、得られたシラン化合物1は、以下の式で表される8種の立体異性体の混合物であると推察される。
50mLの三口フラスコに玉栓、真空/ドライ窒素ラインを繋げた三方コック、セプタムを取り付けた後、スターラーバーを入れ、ドライヤーで加熱しながら、系内の脱気-窒素置換を10回繰り返し、常圧窒素雰囲気下とした。そのフラスコ内に、シリンジを用いて2-ビニルノルボルネン(VNB)5.2g(0.043mоl)、メルカプトプロピルトリエトキシシラン20.3g(0.085mol)を注入し、窒素雰囲気下でアゾビスイソブチロニトリル0.14g(0.85mmоl)を添加した後、窒素バブリングを20分行った。シリコングリースで接続部を密閉した後、フラスコをオイルバスに浸漬し、バス温度を50℃まで徐々に上昇させ、13時間反応させた後、さらに70℃に昇温して5時間反応させた。次にメルカプトプロピルトリエトキシシランについて、計2回の追加添加(1回目:0.10g(0.85 mmol)、2回目:0.26g(2.13 mmol))を行い、それぞれ70℃で5時間を反応させた後、室温まで放冷し、目的の無色~淡黄色澄明液体を25.0g得た。
得られた化合物の1H-NMRの測定結果を図7に示す。1H-NMRの測定によりシランの導入率は100%であり、ノルボルネン環およびビニル基の両方の二重結合が消失していることを確認した。
得られたシラン化合物2の1H-NMRの測定結果を図7に示す。1H-NMRの測定結果により、ビニル基の二重結合ビニル基が消失していることを確認した。ここで、シラン化合物2は、調製例1で合成したシラン化合物1の8種の立体異性体(1付加体)のビニル基にさらにメルカプトシランが反応し、2付加体が生成して得られると推察される。その際、ビニル基への付加は、立体障害の少ないビニル基の1位(外側)への反応のみが起こり、ビニル基への付加ではシラン化合物1の立体異性はそのまま保持されると推察される。以上により、得られたシラン化合物2は、以下の式で表される8種の立体異性体の混合物であると推察される。
(シランカップリング剤組成物、ゴム組成物、およびゴムシートの作製)
まず、シラン化合物1(VNB-SSi)の全量およびシラン化合物2(VNB-2SSi)の全量を混合し、シランカップリング剤組成物を得た。続いて、以下の各成分を、100mLニーダー(東洋精機社製ラボプラストミル)を用いて混練し、ゴム組成物を得た。実施した混練操作の詳細は以下の(i)~(iii)の通りである。
(i)ミキサー混練:150℃に加熱した密閉式加圧ニーダーへ天然ゴムを投入し、30rpmで1分間素練りを行った後、シリカ、酸化亜鉛、ステアリン酸、および老化防止剤の混合物の1/2量を測り取ったものと、上記で調製したシランカップリング剤組成物の全量を投入し、50rpmに回転数を上げて1分30秒間混練を行った。さらに残りの1/2量の前記シリカ、酸化亜鉛、ステアリン酸、および老化防止剤の混合物を加えて、混練を1分30秒間継続した後、ラム(フローティングウェイト)を上げて周りについた前記シリカ、酸化亜鉛、ステアリン酸、および老化防止剤の混合物の粉体を、はけを用いて混練物に投入し、さらに混練を1分間継続後、再度ラムを上げて周りについた前記シリカ、酸化亜鉛、ステアリン酸、および老化防止剤の混合物の粉体を、はけを用いて混練物に投入し、さらに3分間混練して、放出した。
(ii)リミル:シリカの分散をよくするために、120℃に加熱した密閉式加圧ニーダーへ放出して十分温度が下がった混練物を、さらに50rpmで2分間混練を行った後、放出した。
(iii)ロール混練(加硫系添加):放出して十分温度が下がった後、2本ロールで上述の混練物に硫黄、加硫促進剤等を加え、混練し、ゴム組成物を得た。
その後、得られた未加硫ゴム組成物を金型(150mm×150mm×2mm)に入れて、160℃で30分間、加熱加圧して、厚さ2mmの加硫ゴムシートを得た。
・スチレン-ブタジエンゴム(ZSエラストマー社製、商品名:NS616) 70質量部
・ブタジエンゴム(宇部興産社製、商品名:UBEPOL BR150)
30質量部
・シリカAQ(東ソー社製、商品名:ニップシールAQ) 60質量部
・酸化亜鉛3号(東邦亜鉛社製、商品名:銀嶺R) 3質量部
・ステアリン酸(新日本理化製、商品名:ステアリン酸300) 1質量部
・老化防止剤(大内新興化学社製、商品名:ノクラック6C) 1質量部
・シラン化合物1(VNB-SSi)(調製例1) 4.56質量部
・シラン化合物2(VNB-2SSi)(調製例2) 0.24質量部
・硫黄(細井化学社製、5%油処理硫黄) 2.14質量部
・加硫促進剤(大内新興化学社製、商品名:ノクセラーCZ)2.3質量部
・加硫促進剤(大内新興化学社製、商品名:ノクセラーD) 1.1質量部
シラン化合物1(VNB-SSi)の添加量を4.32質量部に変更し、シラン化合物2(VNB-2SSi)の添加量を0.48質量部に変更した以外は実施例1-1と同様にして、シランカップリング剤組成物、ゴム組成物、およびゴムシートを得た。
シラン化合物1(VNB-SSi)の添加量を4.08質量部に変更し、シラン化合物2(VNB-2SSi)の添加量を0.72質量部に変更した以外は実施例1-1と同様にして、シランカップリング剤組成物、ゴム組成物、およびゴムシートを得た。
シラン化合物1(VNB-SSi)の添加量を3.60質量部に変更し、シラン化合物2(VNB-2SSi)の添加量を1.20質量部に変更した以外は実施例1-1と同様にして、シランカップリング剤組成物、ゴム組成物、およびゴムシートを得た。
シラン化合物1(VNB-SSi)の添加量を3.06質量部に変更し、シラン化合物2(VNB-2SSi)の添加量を0.54質量部に変更し、その他のシラン化合物(Si69)を1.20質量部添加し、硫黄の添加量を1.86質量部に変更した以外は実施例1-1と同様にして、シランカップリング剤組成物、ゴム組成物、およびゴムシートを得た。
シラン化合物1(VNB-SSi)およびシラン化合物2(VNB-2SSi)を添加せず、その他のシラン化合物(Si69)を4.80質量部添加し、硫黄の添加量を1.00質量部に変更した以外は実施例1-1と同様にして、シランカップリング剤組成物、ゴム組成物、およびゴムシートを得た。
シラン化合物1(VNB-SSi)を添加せず、シラン化合物2(VNB-2SSi)の添加量を4.80質量部に変更した以外は実施例1-1と同様にして、シランカップリング剤組成物、ゴム組成物、およびゴムシートを得た。
上記実施例1-1~1-5および比較例1-1~1-2で得られたゴムシートの物性を下記の方法により評価した。
粘弾性測定装置(UBM社製REOGEL E-4000)を用い、JIS K 6394に準拠して、歪約0.1%、周波数10Hzの条件下において、実施例1-1~1-5および比較例1-1~1-2で得られたゴムシートの、測定温度0℃および60℃におけるtanδを求め、この値からtanδバランス(=tanδ(0℃)/tanδ(60℃))を算出した。tanδバランスが大きいほど、ゴムシートの粘弾性特性が優れ、タイヤとしてのウェットグリップ性と低燃費性のバランスに優れることを意味する。
実施例1-1~1-5および比較例1-1~1-2で得られたゴム組成物のムーニー粘度をJIS K6300に準拠して、ムーニー粘度計にてL型ロータ(38.1mm径、5.5mm厚)を使用し、予熱時間1分、ロータの回転時間4分、100℃、2rpmの条件で測定した。測定結果が小さいほど、ゴム組成物の粘度が小さく、加工性に優れることを意味する。
JIS K6300に準拠して東洋精機(株)製ロータレスムーニー測定機を用い、未加硫のゴム組成物を125℃で1分間予熱後、最低粘度Vmより5ムーニー単位上昇するのに要した時間t5を測定した。測定結果が大きいほど、スコーチタイムが長く、ゴム組成物の加工性に優れることを意味する。
(シランカップリング剤組成物、ゴム組成物、およびゴムシートの作製)
まず、シラン化合物1(VNB-SSi)の全量およびシラン化合物2(VNB-2SSi)の全量を混合し、シランカップリング剤組成物を得た。続いて、以下の各成分を、100mLニーダー(東洋精機社製ラボプラストミル)を用いて混練し、ゴム組成物を得た。実施した混練操作の詳細は以下の(i)~(iii)の通りである。
(i)ミキサー混練:150℃に加熱した密閉式加圧ニーダーへ天然ゴムを投入し、30rpmで1分間素練りを行った後、シリカ、酸化亜鉛、ステアリン酸、および老化防止剤の混合物の1/2量を測り取ったものと、上記で調製したシランカップリング剤組成物の全量を投入し、50rpmに回転数を上げて1分30秒間混練を行った。さらに残りの1/2量の前記シリカ、酸化亜鉛、ステアリン酸、および老化防止剤の混合物を加えて、混練を1分30秒間継続した後、ラム(フローティングウェイト)を上げて周りについた前記シリカ、酸化亜鉛、ステアリン酸、および老化防止剤の混合物の粉体を、はけを用いて混練物に投入し、さらに混練を1分間継続後、再度ラムを上げて周りについた前記シリカ、酸化亜鉛、ステアリン酸、および老化防止剤の混合物の粉体を、はけを用いて混練物に投入し、さらに3分間混練して、放出した。
(ii)リミル:シリカの分散をよくするために、120℃に加熱した密閉式加圧ニーダーへ放出して十分温度が下がった混練物を、さらに50rpmで2分間混練を行った後、放出した。
(iii)ロール混練(加硫系添加):放出して十分温度が下がった後、2本ロールで上述の混練物に硫黄、加硫促進剤等を加え、混練し、ゴム組成物を得た。
その後、得られた未加硫ゴム組成物を金型(150mm×150mm×2mm)に入れて、160℃で30分間、加熱加圧して、厚さ2mmの加硫ゴムシートを得た。
・合成イソプレンゴム(日本ゼオン社製、商品名:IR-2200)
100質量部
・シリカAQ(東ソー社製、商品名:ニップシールAQ) 60質量部
・酸化亜鉛3号(東邦亜鉛社製、商品名:銀嶺R) 3質量部
・ステアリン酸(新日本理化製、商品名:ステアリン酸300) 1質量部
・老化防止剤(大内新興化学社製、商品名:ノクラック6C) 1質量部
・シラン化合物1(VNB-SSi)(調製例1) 4.27質量部
・シラン化合物2(VNB-2SSi)(調製例2) 0.53質量部
・硫黄(細井化学社製、5%油処理硫黄) 3.14質量部
・加硫促進剤(大内新興化学社製、商品名:ノクセラーCZ)
1.00質量部
・加硫促進剤(大内新興化学社製、商品名:ノクセラーD) 0.5質量部
シラン化合物1(VNB-SSi)およびシラン化合物2(VNB-2SSi)を添加せず、他のシラン化合物(Si69)を4.80質量部添加し、硫黄の添加量を2.00質量部に変更した以外は実施例2-1と同様にして、シランカップリング剤組成物、ゴム組成物、およびゴムシートを得た。
上記実施例2-1および比較例2-1で得られたゴムシートについて粘弾性を、ゴム組成物について耐スコーチ性および未架橋コンパウンド粘度を実施例1-1と同様にして上記の方法により評価した。以上の測定結果および算出結果(tanδバランス)を表2に表す。なお、各測定値および各算出値は、比較例2-1における各値を100とする指数で表わした。
Claims (12)
- シラン化合物を含むシランカップリング剤組成物であって、
前記シラン化合物が、下記式(1):
R1、R2およびR3は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
Lは、窒素、酸素および硫黄からなる群から選択される少なくとも1つのヘテロ原子を含んでいてもよい炭化水素基であり、
aは、0か1の整数であり、
bは、0か1の整数であり、
cは、それぞれ独立して、0か1の整数であり、
dは、それぞれ独立して、0か1の整数であり、
eは、0~5の整数であり、
R4、R5、R6およびR7は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R4若しくはR5およびR6若しくはR7の1つが、-(CH2)f-で表される架橋構造を形成してもよく、
fは、1~5の整数であり、
R8、R9、R10およびR11は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R8若しくはR9およびR10若しくはR11の1つが、-(CH2)g-で表される架橋構造を形成してもよく、
gは、1~5の整数であり、
R16は、水素原子、メチル基または炭素数2~8のアルキル基であり、かつ、R17は、水素原子、メチル基または炭素数2~10のアルキル基であり、ここで、R12およびR13は、互いに結合して二重結合を形成し、かつ、R14、R15およびR18は水素原子、メチル基または炭素数2~10のアルキル基であり、若しくは、R14およびR15は、互いに結合して二重結合を形成し、かつ、R12、R13およびR18は水素原子、メチル基または炭素数2~10のアルキル基であり、
または、
R16およびR17は、互いに結合して4~9員の脂環式炭化水素を形成してもよく、ここで、R14およびR15は、互いに結合して二重結合を形成し、かつ、R12、R13およびR18は水素原子、メチル基または炭素数2~10のアルキル基である。]
で表される第1のシラン化合物と、
下記式(11):
各R1、R2およびR3は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
各Lは、それぞれ独立して、窒素、酸素および硫黄からなる群から選択される少なくとも1つのヘテロ原子を含んでいてもよい炭化水素基であり、
aは、0か1の整数であり、
bは、0か1の整数であり、
cは、それぞれ独立して、0か1の整数であり、
dは、それぞれ独立して、0か1の整数であり、
eは、0~5の整数であり、
R4、R5、R6およびR7は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R4若しくはR5およびR6若しくはR7の1つが、-(CH2)f-で表される架橋構造を形成してもよく、
fは、1~5の整数であり、
R8、R9、R10およびR11は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R8若しくはR9およびR10若しくはR11の1つが、-(CH2)g-で表される架橋構造を形成してもよく、
gは、1~5の整数であり、
R26、R27およびR28は、それぞれ独立して、水素原子、メチル基または炭素数2~10のアルキル基を表す。]
で表される第2のシラン化合物を含む、シランカップリング剤組成物。 - 前記第1のシラン化合物が、下記式(2):
R1、R2およびR3は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
hは、1~10の整数であり、
aは、0か1の整数であり、
bは、0か1の整数であり、
cは、それぞれ独立して、0か1の整数であり、
dは、それぞれ独立して、0か1の整数であり、
eは、0~5の整数であり、
R4、R5、R6およびR7は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R4若しくはR5およびR6若しくはR7の1つが、-(CH2)f-で表される架橋構造を形成してもよく、
fは、1~5の整数であり、
R8、R9、R10およびR11は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R8若しくはR9およびR10若しくはR11の1つが、-(CH2)g-で表される架橋構造を形成してもよく、
gは、1~5の整数であり、
R16は、水素原子、メチル基または炭素数2~8のアルキル基であり、かつ、R17は、水素原子、メチル基または炭素数2~10のアルキル基であり、ここで、R12およびR13は、互いに結合して二重結合を形成し、かつ、R14、R15およびR18は水素原子、メチル基または炭素数2~10のアルキル基であり、若しくは、R14およびR15は、互いに結合して二重結合を形成し、かつ、R12、R13およびR18は水素原子、メチル基または炭素数2~10のアルキル基であり、
または、
R16およびR17は、互いに結合して4~9員の脂環式炭化水素を形成してもよく、ここで、R14およびR15は、互いに結合して二重結合を形成し、かつ、R12、R13およびR18は水素原子、メチル基または炭素数2~10のアルキル基である。]
で表される化合物である、請求項1に記載のシランカップリング剤組成物。 - 前記第2のシラン化合物が、下記式(12):
各R1、R2およびR3は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
hは、1~10の整数であり、
mは、1~10の整数であり、
aは、0か1の整数であり、
bは、0か1の整数であり、
cは、それぞれ独立して、0か1の整数であり、
dは、それぞれ独立して、0か1の整数であり、
eは、0~5の整数であり、
R4、R5、R6およびR7は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R4若しくはR5およびR6若しくはR7の1つが、-(CH2)f-で表される架橋構造を形成してもよく、
fは、1~5の整数であり、
R8、R9、R10およびR11は、水素原子、メチル基または炭素数2~10のアルキル基を表し、または、R8若しくはR9およびR10若しくはR11の1つが、-(CH2)g-で表される架橋構造を形成してもよく、
gは、1~5の整数であり、
R26、R27およびR28は、それぞれ独立して、水素原子、メチル基または炭素数2~10のアルキル基を表す。]
で表される化合物である、請求項1または2に記載のシランカップリング剤組成物。 - 前記第2のシラン化合物の含有量が、前記第1のシラン化合物および第2のシラン化合物の合計含有量に対して、1~50質量%である、請求項1~3のいずれか一項に記載のシランカップリング剤組成物。
- 前記シラン化合物が、第1のシラン化合物および第2のシラン化合物以外の他のシラン化合物をさらに含んでなる、請求項1~4のいずれか一項に記載のシランカップリング剤組成物。
- 前記他のシラン化合物が、式(13):
tおよびvは、それぞれ独立して、0~10の整数であり、
uは、2~10の整数であり、
qおよびrは、それぞれ独立して、1~3の整数であり、
wおよびzは、それぞれ独立して、0か1の整数であり、
L2およびL3は、それぞれ独立して、窒素、酸素および硫黄からなる群から選択される少なくとも1つのヘテロ原子を含んでいてもよい炭化水素基であり、
R21およびR23は、それぞれ独立して、アルコキシ基または1以上のアルキル基で置換されたアミノ基であり、
R22およびR24は、それぞれ独立して、水素またはアルキル基である。]
で表されるシラン化合物である、請求項5に記載のシランカップリング剤組成物。 - ジエン系ゴムに用いられる、請求項1~6のいずれか一項に記載のシランカップリング剤組成物。
- 請求項1~7のいずれか一項に記載のシランカップリング剤組成物と、ジエン系ゴムと、シリカとを含むゴム組成物であって、
前記第1のシラン化合物および前記第2のシラン化合物の合計含有量が、前記シリカ100質量部に対して、0.5~30質量部である、ゴム組成物。 - 前記シリカの含有量が、前記ジエン系ゴム100質量部に対して、0.5~300質量部である、請求項8に記載のゴム組成物。
- タイヤに用いられる、請求項8または9に記載のゴム組成物。
- 請求項8~10のいずれか一項に記載のゴム組成物の架橋物。
- 請求項11に記載の架橋物をタイヤトレッドに用いた、空気入りタイヤ。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP21826161.8A EP4169735A4 (en) | 2020-06-18 | 2021-06-04 | SILANE COUPLING AGENT COMPOSITION AND RUBBER COMPOSITION CONTAINING THE SAME |
US18/002,265 US20230340231A1 (en) | 2020-06-18 | 2021-06-04 | Silane coupling agent composition and rubber composition comprising same |
CN202180043416.XA CN115698158B (zh) | 2020-06-18 | 2021-06-04 | 硅烷偶联剂组合物和包含该硅烷偶联剂组合物的橡胶组合物 |
JP2022531661A JPWO2021256295A1 (ja) | 2020-06-18 | 2021-06-04 | |
KR1020227044212A KR20230012581A (ko) | 2020-06-18 | 2021-06-04 | 실란 커플링제 조성물 및 그것을 포함하는 고무 조성물 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020105624 | 2020-06-18 | ||
JP2020-105624 | 2020-06-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2021256295A1 true WO2021256295A1 (ja) | 2021-12-23 |
Family
ID=79267855
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2021/021318 WO2021256295A1 (ja) | 2020-06-18 | 2021-06-04 | シランカップリング剤組成物およびそれを含むゴム組成物 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20230340231A1 (ja) |
EP (1) | EP4169735A4 (ja) |
JP (1) | JPWO2021256295A1 (ja) |
KR (1) | KR20230012581A (ja) |
CN (1) | CN115698158B (ja) |
TW (1) | TW202210571A (ja) |
WO (1) | WO2021256295A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024071407A1 (ja) * | 2022-09-29 | 2024-04-04 | Eneos株式会社 | シラン化合物およびそれを含む組成物 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08259736A (ja) | 1995-03-10 | 1996-10-08 | Goodyear Tire & Rubber Co:The | シリカ強化ゴム配合物及びそのトレッドを有するタイヤ |
JPH11335381A (ja) | 1998-05-22 | 1999-12-07 | Nitto Boseki Co Ltd | 耐熱耐水性向上シランカップリング剤 |
JP2010514908A (ja) * | 2006-12-28 | 2010-05-06 | コンチネンタル アクチェンゲゼルシャフト | ブロックト・メルカプトシランカップリング剤を含有するタイヤ組成物および部品 |
JP2014177578A (ja) * | 2013-03-15 | 2014-09-25 | Toyo Tire & Rubber Co Ltd | ゴム組成物及び空気入りタイヤ |
JP2014177432A (ja) | 2013-03-15 | 2014-09-25 | Toyo Tire & Rubber Co Ltd | 有機シラン及びその製造方法 |
JP2014177429A (ja) * | 2013-03-15 | 2014-09-25 | Toyo Tire & Rubber Co Ltd | 有機シラン及びその製造方法 |
JP2015078156A (ja) * | 2013-10-17 | 2015-04-23 | 東洋ゴム工業株式会社 | 有機シラン及びそれを用いたゴム組成物 |
WO2016181679A1 (ja) * | 2015-05-14 | 2016-11-17 | Jxエネルギー株式会社 | シラン化合物 |
WO2017188411A1 (ja) * | 2016-04-28 | 2017-11-02 | Jxtgエネルギー株式会社 | 含硫黄シラン化合物およびこの合成方法、ゴム組成物、タイヤ、接着剤組成物、ならびにシーリング剤組成物 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4190858B2 (ja) * | 2002-10-28 | 2008-12-03 | 三井化学株式会社 | オレフィン系重合体、オレフィン系重合体組成物、成型用材料、架橋体、架橋体の製造方法、成型用材料の用途および架橋体の用途 |
JP6047434B2 (ja) * | 2013-03-15 | 2016-12-21 | 東洋ゴム工業株式会社 | 有機シラン及びその製造方法 |
JP6625453B2 (ja) * | 2016-03-14 | 2019-12-25 | Jxtgエネルギー株式会社 | シラン化合物、ゴム組成物およびタイヤ |
-
2021
- 2021-06-04 EP EP21826161.8A patent/EP4169735A4/en active Pending
- 2021-06-04 KR KR1020227044212A patent/KR20230012581A/ko unknown
- 2021-06-04 WO PCT/JP2021/021318 patent/WO2021256295A1/ja unknown
- 2021-06-04 JP JP2022531661A patent/JPWO2021256295A1/ja active Pending
- 2021-06-04 US US18/002,265 patent/US20230340231A1/en active Pending
- 2021-06-04 CN CN202180043416.XA patent/CN115698158B/zh active Active
- 2021-06-04 TW TW110120404A patent/TW202210571A/zh unknown
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08259736A (ja) | 1995-03-10 | 1996-10-08 | Goodyear Tire & Rubber Co:The | シリカ強化ゴム配合物及びそのトレッドを有するタイヤ |
JPH11335381A (ja) | 1998-05-22 | 1999-12-07 | Nitto Boseki Co Ltd | 耐熱耐水性向上シランカップリング剤 |
JP2010514908A (ja) * | 2006-12-28 | 2010-05-06 | コンチネンタル アクチェンゲゼルシャフト | ブロックト・メルカプトシランカップリング剤を含有するタイヤ組成物および部品 |
JP2014177578A (ja) * | 2013-03-15 | 2014-09-25 | Toyo Tire & Rubber Co Ltd | ゴム組成物及び空気入りタイヤ |
JP2014177432A (ja) | 2013-03-15 | 2014-09-25 | Toyo Tire & Rubber Co Ltd | 有機シラン及びその製造方法 |
JP2014177429A (ja) * | 2013-03-15 | 2014-09-25 | Toyo Tire & Rubber Co Ltd | 有機シラン及びその製造方法 |
JP2015078156A (ja) * | 2013-10-17 | 2015-04-23 | 東洋ゴム工業株式会社 | 有機シラン及びそれを用いたゴム組成物 |
WO2016181679A1 (ja) * | 2015-05-14 | 2016-11-17 | Jxエネルギー株式会社 | シラン化合物 |
WO2017188411A1 (ja) * | 2016-04-28 | 2017-11-02 | Jxtgエネルギー株式会社 | 含硫黄シラン化合物およびこの合成方法、ゴム組成物、タイヤ、接着剤組成物、ならびにシーリング剤組成物 |
Non-Patent Citations (1)
Title |
---|
See also references of EP4169735A4 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024071407A1 (ja) * | 2022-09-29 | 2024-04-04 | Eneos株式会社 | シラン化合物およびそれを含む組成物 |
Also Published As
Publication number | Publication date |
---|---|
CN115698158B (zh) | 2024-04-05 |
TW202210571A (zh) | 2022-03-16 |
EP4169735A4 (en) | 2024-07-10 |
EP4169735A1 (en) | 2023-04-26 |
US20230340231A1 (en) | 2023-10-26 |
JPWO2021256295A1 (ja) | 2021-12-23 |
CN115698158A (zh) | 2023-02-03 |
KR20230012581A (ko) | 2023-01-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2020250824A1 (ja) | シラン化合物およびタンパク質変性剤を含んでなるシランカップリング剤組成物、ならびにそれを含むゴム組成物 | |
WO2020138056A1 (ja) | シラン化合物およびその組成物 | |
JP2014084410A (ja) | ドライマスターバッチ、それを用いたタイヤ用ゴム組成物及びその製造方法 | |
WO2021256295A1 (ja) | シランカップリング剤組成物およびそれを含むゴム組成物 | |
WO2021256292A1 (ja) | シランカップリング剤組成物およびそれを含むゴム組成物 | |
JP2011079978A (ja) | 変性ジエン系ゴムおよびゴム組成物 | |
JP2020132822A (ja) | シラン化合物および石油樹脂を含んでなるゴム組成物 | |
WO2021256294A1 (ja) | シランカップリング剤組成物およびそれを含むゴム組成物 | |
WO2014112654A1 (ja) | ゴム組成物 | |
JP2021054992A (ja) | タイヤ用ゴム組成物および空気入りタイヤ | |
WO2021256296A1 (ja) | シランカップリング剤組成物およびそれを含むゴム組成物 | |
JP2006008749A (ja) | ゴム組成物、架橋性ゴム組成物および架橋物 | |
JP2021055000A (ja) | タイヤ用ゴム組成物および空気入りタイヤ | |
WO2022255360A1 (ja) | シランカップリング剤組成物およびそれを含むゴム組成物 | |
JP2021054997A (ja) | タイヤ用ゴム組成物および空気入りタイヤ | |
JP2021054991A (ja) | タイヤ用ゴム組成物および空気入りタイヤ | |
JP2021054998A (ja) | タイヤ用ゴム組成物および空気入りタイヤ | |
JP4670132B2 (ja) | 共役ジエン系重合体及びその製法 | |
JP2012121980A (ja) | 変性単独重合体ジエン系ゴム及びその製造方法並びにそれを用いたゴム組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21826161 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20227044212 Country of ref document: KR Kind code of ref document: A Ref document number: 2022531661 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2021826161 Country of ref document: EP Effective date: 20230118 |