JP6807653B2 - Rubber composition for tires - Google Patents
Rubber composition for tires Download PDFInfo
- Publication number
- JP6807653B2 JP6807653B2 JP2016075722A JP2016075722A JP6807653B2 JP 6807653 B2 JP6807653 B2 JP 6807653B2 JP 2016075722 A JP2016075722 A JP 2016075722A JP 2016075722 A JP2016075722 A JP 2016075722A JP 6807653 B2 JP6807653 B2 JP 6807653B2
- Authority
- JP
- Japan
- Prior art keywords
- fatty acid
- group
- rubber composition
- silica
- cationic surfactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 64
- 229920001971 elastomer Polymers 0.000 title claims description 56
- 239000005060 rubber Substances 0.000 title claims description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 120
- 239000000194 fatty acid Substances 0.000 claims description 80
- 229930195729 fatty acid Natural products 0.000 claims description 78
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 77
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 66
- 239000000377 silicon dioxide Substances 0.000 claims description 60
- 239000003093 cationic surfactant Substances 0.000 claims description 52
- 150000004665 fatty acids Chemical class 0.000 claims description 47
- -1 fatty acid ester Chemical class 0.000 claims description 42
- 229910052751 metal Inorganic materials 0.000 claims description 42
- 239000002184 metal Substances 0.000 claims description 42
- 150000003839 salts Chemical class 0.000 claims description 39
- 235000011187 glycerol Nutrition 0.000 claims description 33
- 229920003244 diene elastomer Polymers 0.000 claims description 21
- 238000001179 sorption measurement Methods 0.000 claims description 17
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000002252 acyl group Chemical group 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 150000002148 esters Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 description 20
- 230000000694 effects Effects 0.000 description 17
- 229920001577 copolymer Polymers 0.000 description 15
- 239000000446 fuel Substances 0.000 description 13
- 150000001993 dienes Chemical class 0.000 description 11
- 239000005062 Polybutadiene Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 229920002857 polybutadiene Polymers 0.000 description 10
- 238000005299 abrasion Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000011324 bead Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 238000004073 vulcanization Methods 0.000 description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000002280 amphoteric surfactant Substances 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 235000003441 saturated fatty acids Nutrition 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 229920005549 butyl rubber Polymers 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 4
- 230000005593 dissociations Effects 0.000 description 4
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 150000004671 saturated fatty acids Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000021357 Behenic acid Nutrition 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229940116226 behenic acid Drugs 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- HABLENUWIZGESP-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O.CCCCCCCCCC(O)=O HABLENUWIZGESP-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 235000019359 magnesium stearate Nutrition 0.000 description 2
- OBQVOBQZMOXRAL-UHFFFAOYSA-L magnesium;docosanoate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O OBQVOBQZMOXRAL-UHFFFAOYSA-L 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229940114930 potassium stearate Drugs 0.000 description 2
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- OUSXYCTXXLYBGJ-UHFFFAOYSA-N 1-ethenyl-2,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C=C)C(C(C)C)=C1 OUSXYCTXXLYBGJ-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- FXRQXYSJYZPGJZ-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethenylbenzene Chemical compound CC(C)(C)OC=CC1=CC=CC=C1 FXRQXYSJYZPGJZ-UHFFFAOYSA-N 0.000 description 1
- TYENDWOHUUAIJH-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCC1=CC=C(C=C)C=C1 TYENDWOHUUAIJH-UHFFFAOYSA-N 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KJQMOGOKAYDMOR-UHFFFAOYSA-N CC(=C)C=C.CC(=C)C=C Chemical compound CC(=C)C=C.CC(=C)C=C KJQMOGOKAYDMOR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 235000021353 Lignoceric acid Nutrition 0.000 description 1
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 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
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- KYYWBEYKBLQSFW-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCC(O)=O KYYWBEYKBLQSFW-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- NHXTZGXYQYMODD-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCCCC(O)=O NHXTZGXYQYMODD-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- VMPHSYLJUKZBJJ-UHFFFAOYSA-N lauric acid triglyceride Natural products CCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC)COC(=O)CCCCCCCCCCC VMPHSYLJUKZBJJ-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229940105112 magnesium myristate Drugs 0.000 description 1
- 229940063002 magnesium palmitate Drugs 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- OUCWKVJZEFNZQE-GRVYQHKQSA-L magnesium;(9z,12z)-octadeca-9,12-dienoate Chemical compound [Mg+2].CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O OUCWKVJZEFNZQE-GRVYQHKQSA-L 0.000 description 1
- BJZBHTNKDCBDNQ-UHFFFAOYSA-L magnesium;dodecanoate Chemical compound [Mg+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BJZBHTNKDCBDNQ-UHFFFAOYSA-L 0.000 description 1
- ABSWXCXMXIZDSN-UHFFFAOYSA-L magnesium;hexadecanoate Chemical compound [Mg+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O ABSWXCXMXIZDSN-UHFFFAOYSA-L 0.000 description 1
- DMRBHZWQMKSQGR-UHFFFAOYSA-L magnesium;tetradecanoate Chemical compound [Mg+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O DMRBHZWQMKSQGR-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- AXLHVTKGDPVANO-UHFFFAOYSA-N methyl 2-amino-3-[(2-methylpropan-2-yl)oxycarbonylamino]propanoate Chemical compound COC(=O)C(N)CNC(=O)OC(C)(C)C AXLHVTKGDPVANO-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- UBHHTPOLMACCDD-UHFFFAOYSA-N n,n-dimethyl-4-phenylbut-3-en-1-amine Chemical compound CN(C)CCC=CC1=CC=CC=C1 UBHHTPOLMACCDD-UHFFFAOYSA-N 0.000 description 1
- DZRKBPWATCKLKY-UHFFFAOYSA-N n-benzyl-n-methylprop-2-en-1-amine Chemical compound C=CCN(C)CC1=CC=CC=C1 DZRKBPWATCKLKY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RQFLGKYCYMMRMC-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O RQFLGKYCYMMRMC-UHFFFAOYSA-N 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- FWYOUDFYBVXIDS-UHFFFAOYSA-N propane-1,2,3-triol;2-(trimethylazaniumyl)acetate Chemical compound OCC(O)CO.C[N+](C)(C)CC([O-])=O FWYOUDFYBVXIDS-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- QZZGJDVWLFXDLK-UHFFFAOYSA-N tetracosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(O)=O QZZGJDVWLFXDLK-UHFFFAOYSA-N 0.000 description 1
- ZTUXEFFFLOVXQE-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCC(O)=O ZTUXEFFFLOVXQE-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 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 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、タイヤ用ゴム組成物に関する。 The present invention relates to a rubber composition for a tire.
近年、車両の燃費の面から、タイヤの転がり抵抗を低減することが求められている。これに対し、タイヤを構成するゴム成分にシリカを配合してヒステリシスロス（ｔａｎδ）を小さくすることにより、タイヤの転がり抵抗を低減し、タイヤの低燃費性能を向上させる方法が知られている。
しかし、シリカはゴム成分との親和性が低く、また、シリカ同士の凝集性が高いため、ゴム成分に単にシリカを配合してもシリカが分散せず、転がり抵抗を低減する効果が十分に得られないという問題があった。また、シリカ同士の凝集により加工性が悪化するという問題もあった。
In recent years, it has been required to reduce the rolling resistance of tires from the viewpoint of vehicle fuel efficiency. On the other hand, there is known a method of reducing the rolling resistance of a tire and improving the fuel efficiency of the tire by blending silica with a rubber component constituting the tire to reduce the hysteresis loss (tan δ).
However, since silica has a low affinity with the rubber component and has high cohesiveness between silicas, even if silica is simply mixed with the rubber component, the silica does not disperse, and the effect of reducing rolling resistance is sufficiently obtained. There was a problem that it could not be done. In addition, there is also a problem that workability deteriorates due to aggregation of silicas.
このようななか、例えば、特許文献１には、タイヤ用ゴム組成物に両性界面活性剤を配合することで加工性やタイヤにしたときの低転がり抵抗性を改良する技術が開示されている。 Under such circumstances, for example, Patent Document 1 discloses a technique for improving workability and low rolling resistance when a tire is formed by blending an amphoteric surfactant in a rubber composition for a tire.
一方、本発明者らが特許文献１をもとに両性界面活性剤を含有するタイヤ用ゴム組成物について検討したところ、その加工性やタイヤにしたときの低燃費性能は必ずしも十分ではないことが明らかになった。また、タイヤにしたときの耐摩耗性についてもさらなる向上が必要であることが明らかになった。 On the other hand, when the present inventors examined a rubber composition for a tire containing an amphoteric surfactant based on Patent Document 1, it was found that its workability and fuel efficiency performance when made into a tire were not always sufficient. It was revealed. It was also clarified that the wear resistance of tires needs to be further improved.
そこで、本発明は、上記実情を鑑みて、加工性、ならびに、タイヤにしたときの低燃費性能および耐摩耗性に優れたゴム組成物を提供することを目的とする。 Therefore, in view of the above circumstances, it is an object of the present invention to provide a rubber composition having excellent workability, low fuel consumption performance and wear resistance when made into a tire.
本発明者らは、上記課題について鋭意検討した結果、アミド結合を有する４級アンモニウム塩である特定のカチオン界面活性剤を配合することで上記課題が解決できることを見出し、本発明に至った。
すなわち、本発明者は、以下の構成により上記課題が解決できることを見出した。
As a result of diligent studies on the above problems, the present inventors have found that the above problems can be solved by blending a specific cationic surfactant which is a quaternary ammonium salt having an amide bond, and have reached the present invention.
That is, the present inventor has found that the above problem can be solved by the following configuration.
（１） ジエン系ゴムと、シリカと、カチオン界面活性剤とを含有し、
上記シリカのＣＴＡＢ吸着比表面積が、１１５〜３００ｍ２／ｇであり、
上記カチオン界面活性剤が、アミド結合を有する４級アンモニウム塩であり、
上記シリカの含有量が、上記ジエン系ゴム１００質量部に対して、５０〜２００質量部であり、
上記カチオン界面活性剤の含有量が、上記ジエン系ゴム１００質量部に対して、０．０５〜１０質量部である、タイヤ用ゴム組成物。
（２） 上記カチオン界面活性剤が、アミド結合を２個以上有する、上記（１）に記載のタイヤ用ゴム組成物。
（３） 上記カチオン界面活性剤が、後述する式（１）で表される化合物である、上記（１）または（２）に記載のタイヤ用ゴム組成物。
（４） さらに、グリセリン部分脂肪酸エステルを含有する、上記（１）〜（３）のいずれかに記載のタイヤ用ゴム組成物。
（５） 上記グリセリン部分脂肪酸エステルが、グリセリンと炭素数１４〜２４の脂肪酸とのエステルである、上記（４）に記載のタイヤ用ゴム組成物。
（６） 上記グリセリン部分脂肪酸エステルの含有量に対する、上記カチオン界面活性剤の含有量の割合が、質量比で、０．１〜１．０である、上記（４）または（５）に記載のタイヤ用ゴム組成物。
（７） さらに、脂肪酸金属塩を含有する、上記（１）〜（３）のいずれかに記載のタイヤ用ゴム組成物。
（８） 上記脂肪酸金属塩が、脂肪酸マグネシウム塩である、上記（７）に記載のタイヤ用ゴム組成物。
（９） 上記脂肪酸金属塩が、炭素数８〜２４の脂肪酸の金属塩である、上記（７）または（８）に記載のタイヤ用ゴム組成物。
（１０） 上記脂肪酸金属塩の含有量に対する、上記カチオン界面活性剤の含有量の割合が、質量比で、０．１〜１．０である、上記（７）〜（９）のいずれかに記載のタイヤ用ゴム組成物。
（１１） 上記シリカのＣＴＡＢ吸着比表面積が、１８０〜３００ｍ２／ｇである、上記（１）〜（１０）のいずれかに記載のタイヤ用ゴム組成物。
(1) Contains diene-based rubber, silica, and a cationic surfactant,
The CTAB adsorption specific surface area of the silica is 115-300 m 2 / g.
The above-mentioned cationic surfactant is a quaternary ammonium salt having an amide bond.
The content of the silica is 50 to 200 parts by mass with respect to 100 parts by mass of the diene rubber.
A rubber composition for a tire, wherein the content of the cationic surfactant is 0.05 to 10 parts by mass with respect to 100 parts by mass of the diene rubber.
(2) The rubber composition for a tire according to (1) above, wherein the cationic surfactant has two or more amide bonds.
(3) The rubber composition for a tire according to the above (1) or (2), wherein the cationic surfactant is a compound represented by the formula (1) described later.
(4) The rubber composition for a tire according to any one of (1) to (3) above, which further contains a glycerin partial fatty acid ester.
(5) The rubber composition for a tire according to (4) above, wherein the glycerin partial fatty acid ester is an ester of glycerin and a fatty acid having 14 to 24 carbon atoms.
(6) The above-mentioned (4) or (5), wherein the ratio of the content of the cationic surfactant to the content of the glycerin partial fatty acid ester is 0.1 to 1.0 by mass ratio. Rubber composition for tires.
(7) The rubber composition for a tire according to any one of (1) to (3) above, which further contains a fatty acid metal salt.
(8) The rubber composition for a tire according to (7) above, wherein the fatty acid metal salt is a fatty acid magnesium salt.
(9) The rubber composition for a tire according to (7) or (8) above, wherein the fatty acid metal salt is a metal salt of a fatty acid having 8 to 24 carbon atoms.
(10) Any of the above (7) to (9), wherein the ratio of the content of the cationic surfactant to the content of the fatty acid metal salt is 0.1 to 1.0 by mass ratio. The described rubber composition for tires.
(11) The rubber composition for a tire according to any one of (1) to (10) above, wherein the CTAB adsorption specific surface area of the silica is 180 to 300 m 2 / g.
以下に示すように、本発明によれば、加工性、ならびに、タイヤにしたときの低燃費性能および耐摩耗性に優れたゴム組成物を提供することができる。 As shown below, according to the present invention, it is possible to provide a rubber composition having excellent workability, low fuel consumption performance and wear resistance when made into a tire.
以下に、本発明のタイヤ用ゴム組成物、および、本発明のタイヤについて説明する。
なお、本明細書において「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
The rubber composition for a tire of the present invention and the tire of the present invention will be described below.
The numerical range represented by using "~" in the present specification means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
［タイヤ用ゴム組成物］
本発明のタイヤ用ゴム組成物（以下、「本発明の組成物」とも言う）は、ジエン系ゴムと、シリカと、カチオン界面活性剤とを含有する。
ここで、上記シリカのＣＴＡＢ吸着比表面積は、１１５〜３００ｍ２／ｇである。また、上記カチオン界面活性剤は、アミド結合を有する４級アンモニウム塩である。また、上記シリカの含有量は、上記ジエン系ゴム１００質量部に対して５０〜２００質量部であり、上記カチオン界面活性剤の含有量は、上記ジエン系ゴム１００質量部に対して０．０５〜１０質量部である。
本発明の組成物はこのような構成をとるため、上述した効果が得られるものと考えらえる。その理由は明らかではないが、およそ以下のとおりと考えられる。
[Rubber composition for tires]
The rubber composition for tires of the present invention (hereinafter, also referred to as "composition of the present invention") contains a diene-based rubber, silica, and a cationic surfactant.
Here, the CTAB adsorption specific surface area of the silica is 115 to 300 m 2 / g. The cationic surfactant is a quaternary ammonium salt having an amide bond. The content of the silica is 50 to 200 parts by mass with respect to 100 parts by mass of the diene rubber, and the content of the cationic surfactant is 0.05 with respect to 100 parts by mass of the diene rubber. It is 10 parts by mass.
Since the composition of the present invention has such a structure, it is considered that the above-mentioned effects can be obtained. The reason is not clear, but it is thought to be as follows.
本発明の組成物は、カチオン界面活性剤として、アミド結合を有する４級アンモニウム塩を含有する。ここで、カチオン界面活性剤中の４級アンモニウムイオンはシリカ表面の水酸基と相互作用することでシリカ同士の凝集を抑制し、さらに、カチオン界面活性剤中のアミド結合は界面活性剤同士の凝集を抑制するものと考えられる。その結果、本発明の組成物において、シリカの分散性は極めて高くなり、優れた加工性を示すものと考えられる。また、本発明の組成物から得られるタイヤにおいてもシリカの分散性は極めて高くなり、シリカによるヒステリシスロス低減の効果が十分に発現されるものと考えられる。さらには、シリカの凝集が少ないために、耐摩耗性にも優れるものと考えられる。
なお、カチオン界面活性剤の代わりに両性界面活性剤を使用した場合、両性界面活性剤同士の凝集により、上述した効果が十分に発現されなくなるものと考えられる。
もっとも、上記メカニズムは推定であり、当該メカニズム以外であっても、本発明の範囲である。
The composition of the present invention contains a quaternary ammonium salt having an amide bond as a cationic surfactant. Here, the quaternary ammonium ion in the cationic surfactant interacts with the hydroxyl group on the surface of the silica to suppress the aggregation of the silicas, and further, the amide bond in the cationic surfactant causes the aggregation of the surfactants. It is thought to suppress it. As a result, in the composition of the present invention, the dispersibility of silica is extremely high, and it is considered that the composition exhibits excellent processability. Further, it is considered that the dispersibility of silica is extremely high also in the tire obtained from the composition of the present invention, and the effect of reducing hysteresis loss by silica is sufficiently exhibited. Furthermore, it is considered that the abrasion resistance is also excellent because the aggregation of silica is small.
When an amphoteric surfactant is used instead of the cationic surfactant, it is considered that the above-mentioned effects are not sufficiently exhibited due to the aggregation of the amphoteric surfactants.
However, the above mechanism is an estimation, and even if it is other than the mechanism, it is within the scope of the present invention.
以下、本発明の組成物に含有される各成分について説明する。 Hereinafter, each component contained in the composition of the present invention will be described.
＜ジエン系ゴム＞
本発明の組成物に含有されるジエン系ゴムは特に限定されず、その具体例としては、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、芳香族ビニル−共役ジエン共重合体ゴム、アクリロニトリル−ブタジエン共重合ゴム（ＮＢＲ）、ブチルゴム（ＩＩＲ）、ハロゲン化ブチルゴム（Ｂｒ−ＩＩＲ、Ｃｌ−ＩＩＲ）、クロロプレンゴム（ＣＲ）などが挙げられる。上記ジエン系ゴムは、１種のジエン系ゴムを単独で用いても、２種以上のジエン系ゴムを併用してもよい。
<Diene rubber>
The diene-based rubber contained in the composition of the present invention is not particularly limited, and specific examples thereof include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), and aromatic vinyl-conjugated diene copolymer. Examples thereof include coalesced rubber, acrylonitrile-butadiene copolymer rubber (NBR), butyl rubber (IIR), halogenated butyl rubber (Br-IIR, Cl-IIR), and chloroprene rubber (CR). As the diene rubber, one kind of diene rubber may be used alone, or two or more kinds of diene rubber may be used in combination.
上記ジエン系ゴムとしては、得られるタイヤの剛性が優れる理由から、芳香族ビニル−共役ジエン共重合体ゴムを用いることが好ましく、芳香族ビニル−共役ジエン共重合体とともにブタジエンゴム（ＢＲ）を併用することがより好ましい。
また、上記芳香族ビニル−共役ジエン共重合体ゴムとしては、例えば、スチレンブタジエンゴム（ＳＢＲ）、スチレンイソプレン共重合体ゴムなどが挙げられる。なかでも、得られるタイヤの剛性が優れる理由から、スチレンブタジエンゴム（ＳＢＲ）であることが好ましい。
As the diene-based rubber, it is preferable to use an aromatic vinyl-conjugated diene copolymer rubber because the obtained tire has excellent rigidity, and a butadiene rubber (BR) is used in combination with the aromatic vinyl-conjugated diene copolymer. It is more preferable to do so.
Examples of the aromatic vinyl-conjugated diene copolymer rubber include styrene butadiene rubber (SBR) and styrene isoprene copolymer rubber. Of these, styrene-butadiene rubber (SBR) is preferable because the obtained tire has excellent rigidity.
上記芳香族ビニル−共役ジエン共重合体の芳香族ビニル含有量（例えば、スチレン含有量）は、本発明の効果がより優れる理由から、２０〜４５質量％であることが好ましく、２３〜４２質量％であることがより好ましい。
また、上記芳香族ビニル−共役ジエン共重合体の共役ジエン中のビニル結合量は、本発明の効果がより優れる理由から、１０〜５０％であることが好ましく、２５〜４８％であることがより好ましい。ここで、ビニル結合量とは、共役ジエンの結合様式であるシス−１，４−結合、トランス−１，４−結合および１，２−ビニル結合のうち、１，２−ビニル結合の割合をいう。
The aromatic vinyl content (for example, styrene content) of the aromatic vinyl-conjugated diene copolymer is preferably 20 to 45% by mass, preferably 23 to 42% by mass, for the reason that the effect of the present invention is more excellent. More preferably.
Further, the amount of vinyl bond in the conjugated diene of the aromatic vinyl-conjugated diene copolymer is preferably 10 to 50%, preferably 25 to 48%, for the reason that the effect of the present invention is more excellent. More preferred. Here, the amount of vinyl bond refers to the ratio of 1,2-vinyl bond among cis-1,4-bond, trans-1,4-bond and 1,2-vinyl bond, which are the bonding modes of conjugated diene. Say.
上記芳香族ビニル−共役ジエン共重合体は、その製造方法について特に限定されず、従来公知の方法で製造することができる。
また、上記芳香族ビニル−共役ジエン共重合体を製造する際に使用される単量体としての、芳香族ビニル、共役ジエンは特に限定されない。
ここで、上記共役ジエン単量体としては、例えば、１，３−ブタジエン、イソプレン（２−メチル−１，３−ブタジエン）、２，３−ジメチル−１，３−ブタジエン、２−クロロ−１，３−ブタジエン、１，３−ペンタジエンなどが挙げられる。
一方、上記芳香族ビニル単量体としては、例えば、スチレン、２−メチルスチレン、３−メチルスチレン、４−メチルスチレン、α−メチルスチレン、２，４−ジメチルスチレン、２，４−ジイソプロピルスチレン、４−ｔｅｒｔ−ブチルスチレン、ジビニルベンゼン、ｔｅｒｔ−ブトキシスチレン、ビニルベンジルジメチルアミン、（４−ビニルベンジル）ジメチルアミノエチルエーテル、Ｎ，Ｎ−ジメチルアミノエチルスチレン、ビニルピリジンなどが挙げられる。
The method for producing the aromatic vinyl-conjugated diene copolymer is not particularly limited, and the aromatic vinyl-conjugated diene copolymer can be produced by a conventionally known method.
Further, the aromatic vinyl and the conjugated diene as the monomer used in producing the aromatic vinyl-conjugated diene copolymer are not particularly limited.
Here, examples of the conjugated diene monomer include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, and 2-chloro-1. , 3-butadiene, 1,3-pentadiene and the like.
On the other hand, examples of the aromatic vinyl monomer include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, and 2,4-diisopropylstyrene. Examples thereof include 4-tert-butylstyrene, divinylbenzene, tert-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl) dimethylaminoethyl ether, N, N-dimethylaminoethylstyrene and vinylpyridine.
上記芳香族ビニル−共役ジエン共重合体を用いる場合の含有量は、得られるタイヤの剛性が優れる理由から、上記ジエン系ゴムの５０〜１００質量％であることが好ましく、５５〜９５質量％であることがより好ましく、６０〜９０質量％であることがさらに好ましい。
また、上記芳香族ビニル−共役ジエン共重合体とともに上記ブタジエンゴム（ＢＲ）を併用する場合、上記ブタジエンゴム（ＢＲ）の含有量は、本発明の効果がより優れる理由から、上記ジエン系ゴムの５〜５０質量％であることが好ましく、１０〜４５質量％であることがより好ましく、２０〜４０質量％であることがさらに好ましい。
When the aromatic vinyl-conjugated diene copolymer is used, the content is preferably 50 to 100% by mass and 55 to 95% by mass of the diene rubber because the obtained tire has excellent rigidity. More preferably, it is more preferably 60 to 90% by mass.
Further, when the butadiene rubber (BR) is used in combination with the aromatic vinyl-conjugated diene copolymer, the content of the butadiene rubber (BR) is higher than that of the diene rubber because the effect of the present invention is more excellent. It is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 20 to 40% by mass.
上記ジエン系ゴム（特に、上記芳香族ビニル−共役ジエン共重合体）の重量平均分子量は特に制限されないが、取り扱いの観点から、１００，０００〜１，５００，０００であることが好ましく、６００，０００〜１，３００，０００であることがより好ましい。なお、ジエン系ゴムの重量平均分子量（Ｍｗ）は、テトラヒドロフランを溶媒とするゲルパーミエーションクロマトグラフィー（ＧＰＣ）により標準ポリスチレン換算により測定するものとする。 The weight average molecular weight of the diene-based rubber (particularly, the aromatic vinyl-conjugated diene copolymer) is not particularly limited, but is preferably 100,000 to 1,500,000 from the viewpoint of handling, 600, More preferably, it is 000 to 1,300,000. The weight average molecular weight (Mw) of the diene-based rubber shall be measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent in terms of standard polystyrene.
上記ジエン系ゴム（特に、上記芳香族ビニル−共役ジエン共重合体）のＴｇ（ガラス転移温度）は特に制限されないが、本発明の効果がより優れる理由から、−７０〜−１０℃であることが好ましく、−４０〜−２０℃であることがより好ましい。 The Tg (glass transition temperature) of the diene-based rubber (particularly, the aromatic vinyl-conjugated diene copolymer) is not particularly limited, but it should be −70 to −10 ° C. for the reason that the effect of the present invention is more excellent. Is preferable, and the temperature is more preferably -40 to -20 ° C.
＜シリカ＞
本発明の組成物に含有されるシリカはＣＴＡＢ（セチルトリメチルアンモニウムブロマイド）吸着比表面積が１１５〜３００ｍ２／ｇのシリカであれば特に制限されず、タイヤ等の用途でゴム組成物に配合されている従来公知の任意のシリカを用いることができる。
上記シリカとしては、例えば、湿式シリカ、乾式シリカ、ヒュームドシリカ、珪藻土などが挙げられる。上記シリカは、１種のシリカを単独で用いても、２種以上のシリカを併用してもよい。
<Silica>
The silica contained in the composition of the present invention is not particularly limited as long as it is silica having a CTAB (cetyltrimethylammonium bromide) adsorption specific surface area of 115 to 300 m 2 / g, and is blended in a rubber composition for applications such as tires. Any conventionally known silica can be used.
Examples of the silica include wet silica, dry silica, fumed silica, and diatomaceous earth. As the silica, one kind of silica may be used alone, or two or more kinds of silica may be used in combination.
上記ＣＴＡＢ吸着比表面積は、本発明の効果がより優れる理由から、１８０〜３００ｍ２／ｇであることが好ましい。 The CTAB adsorption specific surface area is preferably 180 to 300 m 2 / g because the effect of the present invention is more excellent.
なお、本明細書において、ＣＴＡＢ吸着比表面積は、シリカ表面へのＣＴＡＢ吸着量をＪＩＳ Ｋ６２１７−３：２００１「第３部：比表面積の求め方−ＣＴＡＢ吸着法」にしたがって測定した値である。 In the present specification, the CTAB adsorption specific surface area is a value obtained by measuring the amount of CTAB adsorbed on the silica surface according to JIS K6217-3: 2001 "Part 3: How to obtain the specific surface area-CTAB adsorption method".
本発明の組成物において、シリカの含有量は、上記ジエン系ゴム１００質量部に対して、５０〜２００質量部である。なかでも、本発明の効果がより優れる理由から、７０〜１５０質量部であることが好ましい。 In the composition of the present invention, the content of silica is 50 to 200 parts by mass with respect to 100 parts by mass of the diene rubber. Among them, 70 to 150 parts by mass is preferable because the effect of the present invention is more excellent.
＜カチオン界面活性剤＞
本発明の組成物に含有されるカチオン界面活性剤（陽イオン界面活性剤）は、アミド結合（−ＮＲ−ＣＯ−：ここでＲは水素原子または置換基（好ましくは炭化水素基）を表す）を有する４級アンモニウム塩（以下、「特定カチオン界面活性剤」とも言う）である。４級アンモニウム塩は、４級アンモニウムイオンとハロゲン化物イオン（フッ化物イオン、塩化物イオン、臭化物イオン、ヨウ化物イオンなど）との塩であるのが好ましい。
なお、本明細書において、カチオン界面活性剤は、解離基としてカチオン性（陽イオン性）の解離基のみを有する界面活性剤であり、解離基としてカチオン性（陽イオン性）の解離基とアニオン性（陰イオン性）の解離基の両方を有するいわゆる両性界面活性剤は含まれない。
<Cationic surfactant>
The cationic surfactant (cationic surfactant) contained in the composition of the present invention has an amide bond (-NR-CO-: where R represents a hydrogen atom or a substituent (preferably a hydrocarbon group)). It is a quaternary ammonium salt having (hereinafter, also referred to as "specific cationic surfactant"). The quaternary ammonium salt is preferably a salt of a quaternary ammonium ion and a halide ion (fluoride ion, chloride ion, bromide ion, iodide ion, etc.).
In the present specification, the cationic surfactant is a surfactant having only a cationic (cationic) dissociation group as a dissociation group, and a cationic (cationic) dissociation group and an anion as a dissociation group. So-called amphoteric surfactants having both sex (anionic) dissociative groups are not included.
特定カチオン界面活性剤が有するアミド結合の数は、シリカの吸着及びシリカの分散性の点から、２個以上、４個以下であることが好ましい。 The number of amide bonds contained in the specific cationic surfactant is preferably 2 or more and 4 or less from the viewpoint of silica adsorption and silica dispersibility.
特定カチオン界面活性剤の好適な態様としては、例えば、下記式（１）で表される化合物が挙げられる。 Preferable embodiments of the specific cationic surfactant include, for example, a compound represented by the following formula (1).
式（１）中、Ｒ１は炭素数１〜８の炭化水素基又は下記式（２）で表される基を表し、Ｒ２はアルキレン基を表し、Ｒ３はアシル基を表し、Ｒ４はメチル基、エチル基又はベンジル基を表し、Ｘはハロゲン原子を表し、ｍは１〜３の数を表す。 In the formula (1), R 1 represents a hydrocarbon group having 1 to 8 carbon atoms or a group represented by the following formula (2), R 2 represents an alkylene group, R 3 represents an acyl group, and R 4 Represents a methyl group, an ethyl group or a benzyl group, X represents a halogen atom, and m represents a number 1 to 3.
式（２）中、Ｒ５は水素原子又はアシル基を表し、Ｒ６は水素原子又はメチル基を表し、ｎは１〜３の数を表す。 In formula (2), R 5 represents a hydrogen atom or an acyl group, R 6 represents a hydrogen atom or a methyl group, and n represents a number 1 to 3.
式（１）において、Ｒ１は、炭素数１〜８の炭化水素基又は上記式（２）で表される基を表す。炭素数１〜８の炭化水素基としては、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、２級ブチル基、ｔ−ブチル基、ペンチル基、イソペンチル基、２級ペンチル基、ｔ−ペンチル基、ヘキシル基、２級ヘキシル基、ヘプチル基、２級ヘプチル基、オクチル基、２級オクチル基、２−メチルペンチル基、２−エチルヘキシル基、ビニル基、アリル基、プロペニル基、ブテニル基、イソブテニル基、ペンテニル基、イソペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、シクロヘキシル基、フェニル基、メチルフェニル基、ベンジル基等が挙げられる。 In the formula (1), R 1 represents a hydrocarbon group having 1 to 8 carbon atoms or a group represented by the above formula (2). The hydrocarbon group having 1 to 8 carbon atoms includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a t-butyl group, a pentyl group, an isopentyl group, and a secondary pentyl group. , T-pentyl group, hexyl group, secondary hexyl group, heptyl group, secondary heptyl group, octyl group, secondary octyl group, 2-methylpentyl group, 2-ethylhexyl group, vinyl group, allyl group, propenyl group, Examples thereof include a butenyl group, an isobutenyl group, a pentanyl group, an isopentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a cyclohexyl group, a phenyl group, a methylphenyl group and a benzyl group.
式（２）において、Ｒ５は、水素原子又はアシル基を表す。本発明において、アシル基とは、一価カルボン酸からＯＨを除いた残基をいう。このようなカルボン酸としては、酢酸、プロピオン酸、ブタン酸、ペンタン酸、イソペンタン酸、カプロン酸（ヘキサン酸）、ヘプタン酸、カプリル酸（オクタン酸）、ノナン酸、カプリン酸（デカン酸）、ラウリン酸（ウンデカン酸）、ミリスチン酸（テトラデカン酸）、パルミチン酸（ヘキサデカン酸）、ステアリン酸（オクタデカン酸）、アラキジン酸（エイコサン酸）、ベヘン酸（ドコサン酸）、テトラコサン酸、ヘキサコサン酸等の飽和脂肪酸；オレイン酸、リノール酸、リノレン酸、エライジン酸、エルカ酸等の不飽和脂肪酸；リシノレイン酸、ヒドロキシステアリン酸のヒドロキシ脂肪酸等が挙げられる。 In formula (2), R 5 represents a hydrogen atom or an acyl group. In the present invention, the acyl group refers to a residue obtained by removing OH from a monovalent carboxylic acid. Examples of such carboxylic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, isopentanoic acid, caproic acid (hexanoic acid), heptanic acid, caproic acid (octanoic acid), nonanoic acid, capric acid (decanoic acid), and laurin. Saturated fatty acids such as acid (undecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), arachidic acid (eicosanoic acid), behenic acid (docosic acid), tetracosanoic acid, hexacosanoic acid, etc. Unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, ellaic acid, and erucic acid; hydroxy fatty acids such as ricinoleic acid and hydroxystearic acid can be mentioned.
式（２）において、Ｒ６は水素原子又はメチル基を表し、ｎは１〜３の数（好ましくは１〜３の整数）を表す。シリカへの吸着性により優れることから、Ｒ６は水素原子が好ましく、ｎは１が好ましい。 In formula (2), R 6 represents a hydrogen atom or a methyl group, and n represents a number 1-3 (preferably an integer 1-3). R 6 is preferably a hydrogen atom, and n is preferably 1 because it is more excellent in adsorptivity to silica.
式（１）において、Ｒ１は、シリカへの吸着性の点から、メチル基、エチル基が好ましく、メチル基がより好ましい。 In the formula (1), R 1 is preferably a methyl group or an ethyl group, and more preferably a methyl group, from the viewpoint of adsorptivity to silica.
式（１）において、Ｒ２はアルキレン基を表す。アルキレン基としてはメチレン基、エチレン基、プロピレン基、ヘキサメチレン基、オクタメチレン基等が挙げられ、シリカへの吸着性により優れ、原料の工業的な入手も容易であることから、Ｒ２はエチレン基、プロピレン基が好ましい。 In formula (1), R 2 represents an alkylene group. Examples of the alkylene group a methylene group, an ethylene group, a propylene group, a hexamethylene group, since octamethylene group and the like, excellent by adsorption onto silica, industrial availability of raw materials is easy, R 2 is ethylene A group and a propylene group are preferable.
式（１）において、Ｒ３はアシル基を表し、アシル基に対応するカルボン酸としては、式（２）のＲ５で例示したカルボン酸が挙げられる。シリカへの吸着性及びシリカの分散性の点から、炭素数８〜２２の脂肪酸が好ましく、炭素数１０〜１８の脂肪酸がより好ましい。Ｒ４はメチル基、エチル基又はベンジル基を表し、シリカへの吸着性の点からメチル基が好ましい。Ｘはハロゲン原子を表し、ハロゲン原子としては、塩素原子、臭素原子、ヨウ素原子等が挙げられる。Ｘとしては、シリカへの吸着性の点から塩素原子が好ましい。ｍは１〜３の数（好ましくは１〜３の整数）を表し、シリカへの吸着性及びシリカの分散性の点から、ｍは２が好ましい。なお、式（１）で表される化合物中に、複数のアシル基が存在する場合には、同一の基でもよいし異なる基でもよい。 In the formula (1), R 3 represents an acyl group, and examples of the carboxylic acid corresponding to the acyl group include the carboxylic acid exemplified by R 5 in the formula (2). From the viewpoint of adsorptivity to silica and dispersibility of silica, fatty acids having 8 to 22 carbon atoms are preferable, and fatty acids having 10 to 18 carbon atoms are more preferable. R 4 represents a methyl group, an ethyl group or a benzyl group, and a methyl group is preferable from the viewpoint of adsorptivity to silica. X represents a halogen atom, and examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom. As X, a chlorine atom is preferable from the viewpoint of adsorptivity to silica. m represents a number of 1 to 3 (preferably an integer of 1 to 3), and m is preferably 2 from the viewpoint of adsorptivity to silica and dispersibility of silica. When a plurality of acyl groups are present in the compound represented by the formula (1), they may be the same group or different groups.
本発明の組成物において、特定カチオン界面活性剤の含有量は、上述したジエン系ゴム１００質量部に対して、０．０５〜１０質量部である。特定カチオン界面活性剤の含有量が０．０５質量部より少ない場合には、シリカの分散性が不十分となり、１０質量部を超える場合は、ゴムの耐久性が低下する。ジエン系ゴム１００質量部に対する特定カチオン界面活性剤の含有量は、０．１〜５質量部であることが好ましく、１〜３質量部であることが更に好ましい。なお、特定カチオン界面活性剤は、１種を単独で用いてもよく、２種以上を併用してもよい。 In the composition of the present invention, the content of the specific cationic surfactant is 0.05 to 10 parts by mass with respect to 100 parts by mass of the above-mentioned diene rubber. If the content of the specific cationic surfactant is less than 0.05 parts by mass, the dispersibility of silica becomes insufficient, and if it exceeds 10 parts by mass, the durability of the rubber is lowered. The content of the specific cationic surfactant with respect to 100 parts by mass of the diene rubber is preferably 0.1 to 5 parts by mass, and more preferably 1 to 3 parts by mass. As the specific cationic surfactant, one type may be used alone, or two or more types may be used in combination.
＜任意成分＞
（グリセリン部分脂肪酸エステル）
本発明の組成物は、上述した特定カチオン界面活性剤とともに、グリセリン部分脂肪酸エステルを含有するのが好ましい。グリセリン部分脂肪酸エステルは特定カチオン界面活性剤の分散性を向上させるため、結果として、シリカの分散性がさらに高まり、上述した本発明の効果がより優れたものとなる。なお、本発明において、部分脂肪酸エステルとは、多価アルコールの一部の水酸基が脂肪酸でエステル化された化合物をいい、グリセリン部分脂肪酸エステルには、グリセリンモノ脂肪酸エステルとグリセリンジ脂肪酸エステルが含まれる。
<Arbitrary ingredient>
(Glycerin partial fatty acid ester)
The composition of the present invention preferably contains a glycerin partial fatty acid ester together with the above-mentioned specific cationic surfactant. Since the glycerin partial fatty acid ester improves the dispersibility of the specific cationic surfactant, as a result, the dispersibility of silica is further enhanced, and the above-mentioned effect of the present invention becomes more excellent. In the present invention, the partial fatty acid ester means a compound in which a part of the hydroxyl groups of the polyhydric alcohol is esterified with a fatty acid, and the glycerin partial fatty acid ester includes a glycerin monofatty acid ester and a glycerin difatty acid ester. ..
上記グリセリン部分脂肪酸エステルの脂肪酸としては、式（２）のＲ５で例示したカルボン酸が挙げられ、シリカの分散性の点から、炭素数１４〜２４の飽和脂肪酸が好ましく、１６〜２２の飽和脂肪酸が更に好ましく、ステアリン酸が最も好ましい。脂肪酸は１種を単独で用いてもよく、２種以上を併用してもよいが、脂肪酸が２種以上の場合は、そのうちの１種はステアリン酸であることが好ましい。 The fatty acid of the glycerin partial fatty acid esters, include carboxylic acids exemplified by R 5 of formula (2), from the viewpoint of dispersibility of the silica, preferably saturated fatty acids from 14 to 24 carbon atoms, saturated 16-22 Fatty acids are more preferred, and stearic acid is most preferred. One type of fatty acid may be used alone or two or more types may be used in combination, but when there are two or more types of fatty acids, one of them is preferably stearic acid.
グリセリン部分脂肪酸エステルは、シリカの分散性の点から、グリセリンモノ脂肪酸エステルが好ましく、グリセリンモノ脂肪酸エステルとグリセリンジ脂肪酸エステルとの混合物の場合には、グリセリンモノ脂肪酸エステルの含有量が少なくとも５０質量％であることが好ましい。 The glycerin partial fatty acid ester is preferably a glycerin monofatty acid ester from the viewpoint of silica dispersibility, and in the case of a mixture of the glycerin monofatty acid ester and the glycerin difatty acid ester, the content of the glycerin monofatty acid ester is at least 50% by mass. Is preferable.
本発明の組成物がグリセリン部分脂肪酸エステルを含有する場合において、グリセリン部分脂肪酸エステルの含有量が少なすぎる場合には、シリカの分散性の向上効果が得られず、多すぎる場合にはゴムの物性に悪影響がでることがある。このため、グリセリン部分脂肪酸エステルの含有量に対する、上述した特定カチオン界面活性剤の含有量の割合（特定カチオン界面活性剤／グリセリン部分脂肪酸エステル）が、質量比で、０．０１〜１０であることが好ましく、０．１〜１．０であることがより好ましく、０．２〜０．５であることがさらに好ましい。
また、グリセリン部分脂肪酸エステルの含有量は、上述したジエン系ゴム１００質量部に対して、０．１〜１０質量部であることが好ましく、１〜５質量部であることがより好ましい。また、上述した特定カチオン界面活性剤とグリセリン部分脂肪酸エステルの合計の含有量は、上述したジエン系ゴム１００質量部に対して、０．２〜１０質量部であることが好ましい。グリセリン部分脂肪酸エステルは、１種を単独で用いてもよく、２種以上を併用してもよい。
When the composition of the present invention contains a glycerin partial fatty acid ester, if the content of the glycerin partial fatty acid ester is too small, the effect of improving the dispersibility of silica cannot be obtained, and if it is too large, the physical properties of rubber. May have an adverse effect on. Therefore, the ratio of the content of the above-mentioned specific cationic surfactant to the content of the glycerin partial fatty acid ester (specific cationic surfactant / glycerin partial fatty acid ester) is 0.01 to 10 by mass ratio. Is preferable, 0.1 to 1.0 is more preferable, and 0.2 to 0.5 is further preferable.
The content of the glycerin partial fatty acid ester is preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the diene rubber described above. The total content of the above-mentioned specific cationic surfactant and the glycerin partial fatty acid ester is preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the above-mentioned diene rubber. One type of glycerin partial fatty acid ester may be used alone, or two or more types may be used in combination.
（脂肪酸金属塩）
本発明の組成物は、上述した特定カチオン界面活性剤とともに、脂肪酸金属塩を含有するのが好ましい。脂肪酸金属塩は特定カチオン界面活性剤の分散性を向上させるため、結果として、シリカの分散性がさらに高まり、上述した本発明の効果がより優れたものとなる。
(Fatty acid metal salt)
The composition of the present invention preferably contains a fatty acid metal salt together with the above-mentioned specific cationic surfactant. Since the fatty acid metal salt improves the dispersibility of the specific cationic surfactant, as a result, the dispersibility of silica is further enhanced, and the above-mentioned effect of the present invention becomes more excellent.
上記脂肪酸金属塩は、脂肪酸と金属との塩である。
上記脂肪酸金属塩の脂肪酸としては、式（２）のＲ５で例示したカルボン酸が挙げられ、シリカの分散性の点から、炭素数８〜２４の飽和脂肪酸が好ましく、炭素数１０〜２２の飽和脂肪酸がより好ましく、炭素数１６〜２２の飽和脂肪酸が更に好ましく、ベヘン酸が最も好ましい。脂肪酸は１種を単独で用いてもよく、２種以上を併用してもよい。
上記脂肪酸金属塩の金属としては、アルカリ金属、アルカリ土類金属、遷移金属（３〜１１族の金属）、アルミニウム、ゲルマニウム、スズ、アンチモンなどが挙げられ、なかでも、アルカリ金属（リチウム、カリウム、ナトリウムなど）、アルカリ土類金属（ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウムなど）等が挙げられ、シリカの分散性の点から、アルカリ金属、アルカリ土類金属がより好ましく、アルカリ土類金属が更に好ましく、マグネシウムが最も好ましい。
好ましい脂肪酸金属塩の具体例としては、ステアリン酸カリウム、ステアリン酸亜鉛、ステアリン酸マグネシウム、オレイン酸マグネシウム、パルミチン酸マグネシウム、ミリスチン酸マグネシウム、ラウリル酸マグネシウム、リノール酸マグネシウム、ベヘン酸マグネシウムなどが挙げられる。
The fatty acid metal salt is a salt of a fatty acid and a metal.
The fatty acid of the fatty acid metal salt, include carboxylic acids exemplified by R 5 of formula (2), from the viewpoint of the dispersibility of the silica, saturated fatty acids having 8 to 24 carbon atoms are preferred, 10 to 22 carbon atoms Saturated fatty acids are more preferred, saturated fatty acids with 16 to 22 carbon atoms are even more preferred, and behenic acid is most preferred. One type of fatty acid may be used alone, or two or more types may be used in combination.
Examples of the metal of the fatty acid metal salt include alkali metals, alkaline earth metals, transition metals (metals of groups 3 to 11), aluminum, germanium, tin, antimony, etc. Among them, alkali metals (lithium, potassium, (Sodium, etc.), alkaline earth metals (berylium, magnesium, calcium, strontium, barium, etc.), etc., and from the viewpoint of silica dispersibility, alkali metals and alkaline earth metals are more preferable, and alkaline earth metals are further preferable. Preferably, magnesium is most preferred.
Specific examples of preferable fatty acid metal salts include potassium stearate, zinc stearate, magnesium stearate, magnesium oleate, magnesium palmitate, magnesium myristate, magnesium laurate, magnesium linoleate, magnesium behenate and the like.
本発明の組成物が脂肪酸金属塩を含有する場合において、脂肪酸金属塩の含有量が少なすぎる場合には、シリカの分散性の向上効果が得られず、多すぎる場合にはゴムの物性に悪影響がでることがある。このため、脂肪酸金属塩の含有量に対する、上述した特定カチオン界面活性剤の含有量の割合（特定カチオン界面活性剤／脂肪酸金属塩）が、質量比で、０．０１〜１０であることが好ましく、０．１〜１．０であることがより好ましく、０．２〜０．５であることがさらに好ましい。また、脂肪酸金属塩の含有量は、上述したジエン系ゴム１００質量部に対して、０．１〜１０質量部であることが好ましく、１〜５質量部であることがより好ましい。また、上述した特定カチオン界面活性剤と脂肪酸金属塩の合計の含有量は、上述したジエン系ゴム１００質量部に対して、０．２〜１０質量部であることが好ましい。脂肪酸金属塩は、１種を単独で用いてもよく、２種以上を併用してもよい。 When the composition of the present invention contains a fatty acid metal salt, if the content of the fatty acid metal salt is too small, the effect of improving the dispersibility of silica cannot be obtained, and if it is too large, the physical properties of rubber are adversely affected. May appear. Therefore, the ratio of the content of the above-mentioned specific cationic surfactant to the content of the fatty acid metal salt (specific cationic surfactant / fatty acid metal salt) is preferably 0.01 to 10 in terms of mass ratio. , 0.1 to 1.0, more preferably 0.2 to 0.5. The content of the fatty acid metal salt is preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the above-mentioned diene rubber. The total content of the above-mentioned specific cationic surfactant and the fatty acid metal salt is preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the above-mentioned diene rubber. One type of fatty acid metal salt may be used alone, or two or more types may be used in combination.
本発明の組成物は、上述した本発明の効果がさらに優れる理由から、上述した特定カチオン界面活性剤とともに、グリセリン部分酸エステルと脂肪酸金属塩の両方を含有するのが好ましい。 The composition of the present invention preferably contains both a glycerin partial acid ester and a fatty acid metal salt together with the above-mentioned specific cationic surfactant, for the reason that the above-mentioned effect of the present invention is further excellent.
（その他の添加剤）
本発明の組成物には、必要に応じて、その効果や目的を損なわない範囲でさらに添加剤を含有することができる。
上記添加剤としては、例えば、シリカ以外の充填剤（例えば、カーボンブラック）、酸化亜鉛（亜鉛華）、ステアリン酸、老化防止剤、加工助剤、プロセスオイル、アロマオイル、液状ポリマー、テルペン樹脂、熱硬化性樹脂、加硫剤（例えば、硫黄）、加硫促進剤などのゴム組成物に一般的に使用される各種添加剤が挙げられる。
(Other additives)
If necessary, the composition of the present invention may further contain additives as long as the effects and purposes are not impaired.
Examples of the above-mentioned additives include fillers other than silica (for example, carbon black), zinc oxide (zinc oxide), stearic acid, antiaging agents, processing aids, process oils, aroma oils, liquid polymers, and terpene resins. Examples thereof include various additives generally used in rubber compositions such as thermosetting resins, vulcanizing agents (for example, sulfur), and vulcanization accelerators.
＜タイヤ用ゴム組成物の調製方法＞
本発明の組成物の調製方法は特に限定されず、その具体例としては、例えば、上述した各成分を、公知の方法、装置（例えば、バンバリーミキサー、ニーダー、ロールなど）を用いて、混練する方法などが挙げられる。本発明の組成物が硫黄または加硫促進剤を含有する場合は、硫黄および加硫促進剤以外の成分を先に高温（好ましくは１４０〜１６０℃）で混合し、冷却してから、硫黄または加硫促進剤を混合するのが好ましい。
また、本発明の組成物は、従来公知の加硫または架橋条件で加硫または架橋することができる。
<Method of preparing rubber composition for tires>
The method for preparing the composition of the present invention is not particularly limited, and as a specific example thereof, each of the above-mentioned components is kneaded using a known method or device (for example, Banbury mixer, kneader, roll, etc.). The method etc. can be mentioned. When the composition of the present invention contains sulfur or a vulcanization accelerator, components other than sulfur and the vulcanization accelerator are first mixed at a high temperature (preferably 140 to 160 ° C.), cooled, and then sulfur or It is preferable to mix the vulcanization accelerator.
In addition, the composition of the present invention can be vulcanized or crosslinked under conventionally known vulcanization or crosslinking conditions.
［タイヤ］
本発明のタイヤは、上述した本発明の組成物を用いて製造したタイヤである。なかでも、本発明の組成物をタイヤトレッドに用いたタイヤであることが好ましい。
図１に、本発明のタイヤの実施態様の一例を表すタイヤの部分断面概略図を示すが、本発明のタイヤは図１に示す態様に限定されるものではない。
[tire]
The tire of the present invention is a tire manufactured by using the composition of the present invention described above. Of these, a tire using the composition of the present invention for a tire tread is preferable.
FIG. 1 shows a schematic partial cross-sectional view of a tire showing an example of an embodiment of the tire of the present invention, but the tire of the present invention is not limited to the aspect shown in FIG.
図１において、符号１はビード部を表し、符号２はサイドウォール部を表し、符号３はタイヤトレッド部を表す。
また、左右一対のビード部１間においては、繊維コードが埋設されたカーカス層４が装架されており、このカーカス層４の端部はビードコア５およびビードフィラー６の廻りにタイヤ内側から外側に折り返されて巻き上げられている。
また、タイヤトレッド部３においては、カーカス層４の外側に、ベルト層７がタイヤ１周に亘って配置されている。
また、ビード部１においては、リムに接する部分にリムクッション８が配置されている。
なお、タイヤトレッド部３は上述した本発明の組成物により形成されている。
In FIG. 1, reference numeral 1 represents a bead portion, reference numeral 2 represents a sidewall portion, and reference numeral 3 represents a tire tread portion.
Further, a carcass layer 4 in which a fiber cord is embedded is mounted between the pair of left and right bead portions 1, and the end portion of the carcass layer 4 is placed around the bead core 5 and the bead filler 6 from the inside to the outside of the tire. It is folded back and rolled up.
Further, in the tire tread portion 3, a belt layer 7 is arranged on the outside of the carcass layer 4 over one circumference of the tire.
Further, in the bead portion 1, the rim cushion 8 is arranged at a portion in contact with the rim.
The tire tread portion 3 is formed by the composition of the present invention described above.
本発明のタイヤは、例えば、従来公知の方法に従って製造することができる。また、タイヤに充填する気体としては、通常のまたは酸素分圧を調整した空気の他、窒素、アルゴン、ヘリウムなどの不活性ガスを用いることができる。 The tire of the present invention can be manufactured, for example, according to a conventionally known method. Further, as the gas to be filled in the tire, an inert gas such as nitrogen, argon or helium can be used in addition to normal air or air having an adjusted oxygen partial pressure.
以下、実施例により、本発明についてさらに詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
＜タイヤ用ゴム組成物の調製＞
下記表１に示される成分を、同表に示される割合（質量部）で配合した。
具体的には、まず、同表に示す成分のうち硫黄および加硫促進剤を除く成分を、１．７リットルの密閉式バンバリーミキサーを用いて５分間混合を実施した。なお放出時の温度は１５２℃であり、室温まで冷却してマスターバッチを得た。さらに、上記バンバリーミキサーを用いて、得られたマスターバッチに硫黄および加硫促進剤を３分間混合し、１１０℃にて放出しタイヤ用ゴム組成物を得た。
<Preparation of rubber composition for tires>
The components shown in Table 1 below were blended in the proportions (parts by mass) shown in the same table.
Specifically, first, among the components shown in the same table, the components excluding sulfur and the vulcanization accelerator were mixed for 5 minutes using a 1.7 liter sealed Banbury mixer. The temperature at the time of release was 152 ° C., and the mixture was cooled to room temperature to obtain a masterbatch. Further, using the above-mentioned Bunbury mixer, sulfur and a vulcanization accelerator were mixed with the obtained masterbatch for 3 minutes and released at 110 ° C. to obtain a rubber composition for a tire.
＜評価＞
得られたタイヤ用ゴム組成物について、以下の評価を行った。
<Evaluation>
The obtained rubber composition for tires was evaluated as follows.
（加工性）
ＪＩＳ Ｋ６３００−１：２０１３に準じて、１００℃におけるムーニー粘度（ＭＬ１＋４）を測定した。ムーニー粘度の逆数を表１に示す。結果は比較例１のムーニー粘度の逆数を１００とする指数で表した。指数が大きいほど粘度が低く、加工性に優れる。
(Workability)
Mooney viscosity (ML 1 + 4 ) at 100 ° C. was measured according to JIS K6300-1: 2013. The reciprocal of Mooney viscosity is shown in Table 1. The results were expressed as an index with the reciprocal of the Mooney viscosity of Comparative Example 1 as 100. The larger the index, the lower the viscosity and the better the workability.
（低燃費性能）
得られたタイヤ用ゴム組成物（未加硫）を金型（１５ｃｍ×１５ｃｍ×０．２ｃｍ）中で、１６０℃で２０分間プレス加硫して加硫ゴムシートを作製した。
作製した加硫ゴムシートについて、ＪＩＳＫ６３９４：２００７に準じて、粘弾性スペクトロメーター（東洋精機製作所社製）を用いて、伸張変形歪率１０％±２％、振動数２０Ｈｚ、温度６０℃の条件で、ｔａｎδ（６０℃）を測定した。
ｔａｎδ（６０℃）の逆数を表１に示す。結果は比較例１のｔａｎδ（６０℃）の逆数を１００とする指数で表した。指数が大きいほどｔａｎδ（６０℃）が小さく、低燃費性能に優れる。
(Fuel efficiency performance)
The obtained rubber composition for tires (unvulcanized) was press-vulcanized in a mold (15 cm × 15 cm × 0.2 cm) at 160 ° C. for 20 minutes to prepare a vulcanized rubber sheet.
The produced vulcanized rubber sheet was subjected to a viscoelastic spectrometer (manufactured by Toyo Seiki Seisakusho Co., Ltd.) in accordance with JIS K6394: 2007 under the conditions of a stretch deformation strain rate of 10% ± 2%, a frequency of 20 Hz, and a temperature of 60 ° C. , Tan δ (60 ° C.) was measured.
The reciprocal of tan δ (60 ° C.) is shown in Table 1. The results were expressed as an index with the reciprocal of tan δ (60 ° C.) of Comparative Example 1 as 100. The larger the index, the smaller the tan δ (60 ° C.), and the better the fuel efficiency performance.
（耐摩耗性）
上述のとおり作製した加硫ゴムシートについて、ＪＩＳ Ｋ６２６４−１、２：２００５に準拠し、ランボーン摩耗試験機（岩本製作所製）を用いて、温度２０℃、スリップ率５０％の条件で摩耗減量を測定した。
結果を表１に示す。結果は比較例１の摩耗量を１００として、次式により指数化したものを示した。指数が大きいほど摩耗量が小さく、耐摩耗性に優れる。
耐摩耗性＝（比較例１の摩耗量／試料の摩耗量）×１００
(Abrasion resistance)
The vulcanized rubber sheet prepared as described above is subjected to wear reduction under the conditions of a temperature of 20 ° C. and a slip ratio of 50% using a Lambourn wear tester (manufactured by Iwamoto Seisakusho) in accordance with JIS K6264-1, 2: 2005. It was measured.
The results are shown in Table 1. The results are indexed by the following equation, with the wear amount of Comparative Example 1 as 100. The larger the index, the smaller the amount of wear and the better the wear resistance.
Abrasion resistance = (Abrasion amount of Comparative Example 1 / Abrasion amount of sample) × 100
表１中、各成分の詳細は以下のとおりである。
・ＳＢＲ：ＬＡＮＸＥＳＳ社製 Ｂｕｎａ ＶＳＬ ５０２５−２ ＨＭ、Ｔｇ（ガラス転移温度）：−２７℃、スチレン含有量：２５質量％
・ＢＲ：日本ゼオン社製 Ｎｉｐｏｌ ＢＲ １２２０
・カーボンブラック：東海カーボン社製 シースト７ＨＭ
・シリカ１：Ｓｏｌｖａｙ社製 Ｚｅｏｓｉｌ １１６５ＭＰ
・シリカ２：Ｓｏｌｖａｙ社製 Ｚｅｏｓｉｌ １２０５ＭＰ
・シランカップリング剤：信越化学社製 ＫＢＥ−８４６（ビス（３−（トリエトキシシリル）プロピル）テトラスルフィド）
・カチオン界面活性剤：下記構造（ここで、Ｒ３はデカン酸（カプリン酸）由来のアシル基を表す）
The details of each component in Table 1 are as follows.
-SBR: Buna VSL 5025-2 HM manufactured by LANXESS, Tg (glass transition temperature): -27 ° C., styrene content: 25% by mass
・ BR: Nipol BR 1220 manufactured by Zeon Corporation
・ Carbon Black: Tokai Carbon Co., Ltd. Seest 7HM
-Silica 1: Solvay Zeosil 1165MP
-Silica 2: Zeosil 1205MP manufactured by Solvay
-Silane coupling agent: KBE-846 (bis (3- (triethoxysilyl) propyl) tetrasulfide) manufactured by Shin-Etsu Chemical Co., Ltd.
Cationic surfactants: following structure (where, R 3 represents an acyl group derived from decanoic acid (capric acid))
・両性界面活性剤：花王社製 アンヒトール２０ＡＢ、コカミドプロピルベタイン
・グリセリン部分脂肪酸エステル：グリセリンモノステアリン酸エステル／グリセリンジステアリン酸エステル＝２／１（質量比）
・脂肪酸金属塩１：ステアリン酸カリウム（カリウム含量１２．５質量％）
・脂肪酸金属塩２：ステアリン酸マグネシウム（マグネシウム含量４．５質量％）
・脂肪酸金属塩３：ベヘン酸マグネシウム（マグネシウム含量３．４質量％）
・アロマオイル：Ｈ＆Ｒ社製 アロマオイル
・亜鉛華：正同化学社製 酸化亜鉛３種
・ステアリン酸：千葉脂肪酸社製 工業ステアリン酸Ｎ
・加硫促進剤：大内新興社製 ノクセラＣＺ−Ｇ
・硫黄：細井化学社製 油処理硫黄
-Amphoteric tenside: Anhitor 20AB manufactured by Kao Co., Ltd., cocamidopropyl betaine-glycerin partial fatty acid ester: glycerin monostearic acid ester / glycerin distearate ester = 2/1 (mass ratio)
-Fatty acid metal salt 1: potassium stearate (potassium content 12.5% by mass)
-Fatty acid metal salt 2: Magnesium stearate (magnesium content 4.5% by mass)
-Fatty acid metal salt 3: Magnesium behenate (magnesium content 3.4% by mass)
・ Aroma oil: H & R aroma oil ・ Zinc flower: Zinc oxide 3 types manufactured by Shodo Chemical Co., Ltd. ・ Stearic acid: Industrial stearic acid N manufactured by Chiba Fatty Acid Co., Ltd.
・ Vulcanization accelerator: Noxera CZ-G manufactured by Ouchi Shinko Co., Ltd.
・ Sulfur: Oil-treated sulfur manufactured by Hosoi Chemical Co., Ltd.
特定カチオン界面活性剤を含有する実施例１〜１０は、優れた加工性、低燃費性能および耐摩耗性を示した。
実施例１と３〜４と６〜９との対比（シリカのＣＴＡＢ吸着比表面積が１６０ｍ２／ｇである態様の対比）、および、実施例２と５と１０との対比（シリカのＣＴＡＢ吸着比表面積が２００ｍ２／ｇである態様の対比）から、さらにグリセリン部分脂肪酸エステルまたは脂肪酸金属塩を含有する実施例３〜４および６〜９、ならびに、実施例５および１０は、より優れた加工性、低燃費性能および耐摩耗性を示した。なかでも、脂肪酸金属塩を含有する実施例６〜９および１０は、さらに優れた加工性および低燃費性能を示した。
また、実施例１〜２の対比（グリセリン部分脂肪酸エステルと脂肪酸金属塩のいずれも含有しない態様の対比）、実施例３〜５の対比（グリセリン部分脂肪酸エステルを含有する態様の対比）、および、実施例６〜１０の対比（脂肪酸金属塩を含有する態様の対比）から、シリカのＣＴＡＢ吸着比表面積が１８０〜３００ｍ２／ｇである実施例２、５および１０は、より優れた耐摩耗性を示した。
また、実施例３と４との対比（シリカのＣＴＡＢ吸着比表面積が１６０ｍ２／ｇであり、かつ、グリセリン部分脂肪酸エステルを含有する態様の対比）から、グリセリン部分脂肪酸エステルの含有量に対するカチオン界面活性剤の含有量の割合が、質量比で、０．１〜１．０である実施例４は、より優れた加工性、低燃費性能および耐摩耗性を示した。
また、実施例６〜９の対比（シリカのＣＴＡＢ吸着比表面積が１６０ｍ２／ｇであり、かつ、脂肪酸金属塩を含有する態様の対比）から、脂肪酸金属塩の含有量に対するカチオン界面活性剤の含有量の割合が、質量比で、０．１〜１．０である実施例７〜９は、より優れた加工性および耐摩耗性を示した。
また、実施例７と８との対比（ステアリン酸金属塩を含有し、かつ、ステアリン酸金属塩の含有量に対するカチオン界面活性剤の含有量の割合が０．２５である態様の対比）から、含有される脂肪酸金属塩が脂肪酸のマグネシウム塩である実施例８は、より優れた加工性を示した。
また、実施例８と９との対比（シリカのＣＴＡＢ吸着比表面積が１６０ｍ２／ｇであり、かつ、脂肪酸マグネシウ塩を含有する態様の対比）から、含有される脂肪酸金属塩が炭素数２０以上の脂肪酸の金属塩である実施例９は、より優れた加工性、低燃費性能および耐摩耗性を示した。
Examples 1 to 10 containing the specific cationic surfactant showed excellent processability, fuel efficiency and abrasion resistance.
Comparison of Examples 1 and 3 to 4 and 6 to 9 (contrast of the embodiment in which the CTAB adsorption specific surface area of silica is 160 m 2 / g) and comparison of Examples 2 and 5 and 10 (CTAB adsorption of silica). Examples 3 to 4 and 6 to 9 and Examples 5 and 10 further containing a glycerin partial fatty acid ester or a fatty acid metal salt from the aspect of the specific surface area of 200 m 2 / g) are more excellent processed. It showed good properties, low fuel consumption performance and wear resistance. Among them, Examples 6 to 9 and 10 containing a fatty acid metal salt showed further excellent processability and fuel efficiency.
In addition, the contrast of Examples 1 and 2 (contrast of the embodiment containing neither the glycerin partial fatty acid ester nor the fatty acid metal salt), the contrast of Examples 3 to 5 (contrast of the embodiment containing the glycerin partial fatty acid ester), and From the comparison of Examples 6 to 10 (contrast of the aspect containing the fatty acid metal salt), Examples 2, 5 and 10 in which the CTAB adsorption specific surface area of silica is 180 to 300 m 2 / g have better wear resistance. showed that.
Further, from the comparison between Examples 3 and 4 (contrast of the embodiment in which the CTAB adsorption specific surface area of silica is 160 m 2 / g and the glycerin partial fatty acid ester is contained), the cationic interface with respect to the content of the glycerin partial fatty acid ester. Example 4 in which the ratio of the content of the activator was 0.1 to 1.0 by mass showed better processability, low fuel consumption performance and abrasion resistance.
Further, from the comparison of Examples 6 to 9 (contrast of the embodiment in which the CTAB adsorption specific surface area of silica is 160 m 2 / g and the fatty acid metal salt is contained), the cationic surfactant with respect to the content of the fatty acid metal salt Examples 7 to 9 in which the content ratio was 0.1 to 1.0 by mass showed better workability and abrasion resistance.
Further, from the comparison between Examples 7 and 8 (contrast in the embodiment in which the metal stearic acid salt is contained and the ratio of the content of the cationic surfactant to the content of the metal stearic acid salt is 0.25). Example 8 in which the fatty acid metal salt contained was a magnesium salt of a fatty acid showed better processability.
Further, from the comparison between Examples 8 and 9 (contrast of the aspect in which the CTAB adsorption specific surface area of silica is 160 m 2 / g and the fatty acid magnesium salt is contained), the fatty acid metal salt contained has 20 or more carbon atoms. Example 9, which is a metal salt of the fatty acid of the above, showed better processability, low fuel consumption performance and abrasion resistance.
一方、特定カチオン界面活性剤を含有しない比較例１および２は、加工性が不十分であった。比較例１は、低燃費性能も不十分であった。
また、特定カチオン界面活性剤を含有するがその含有量がジエン系ゴム１００質量部に対して１０質量部を超える比較例３も、加工性が不十分であった。
また、特定カチオン界面活性剤の代わりに、アミド結合を有する４級アンモニウム塩である両性界面活性剤を含有する比較例４は、耐摩耗性が不十分であった。
On the other hand, Comparative Examples 1 and 2 containing no specific cationic surfactant had insufficient processability. In Comparative Example 1, the fuel efficiency performance was also insufficient.
Further, Comparative Example 3 in which the specific cationic surfactant was contained but the content of the specific cationic surfactant exceeded 10 parts by mass with respect to 100 parts by mass of the diene rubber was also insufficient in processability.
Further, Comparative Example 4 containing an amphoteric surfactant which is a quaternary ammonium salt having an amide bond instead of the specific cationic surfactant had insufficient wear resistance.
１ ビード部
２ サイドウォール部
３ タイヤトレッド部
４ カーカス層
５ ビードコア
６ ビードフィラー
７ ベルト層
８ リムクッション
1 bead part 2 sidewall part 3 tire tread part 4 carcass layer 5 bead core 6 bead filler 7 belt layer 8 rim cushion
Claims (11)
前記シリカのＣＴＡＢ吸着比表面積が、１１５〜３００ｍ２／ｇであり、
前記カチオン界面活性剤が、アミド結合を有する４級アンモニウム塩であり、
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、５０〜２００質量部であり、
前記カチオン界面活性剤の含有量が、前記ジエン系ゴム１００質量部に対して、０．０５〜１０質量部である、タイヤ用ゴム組成物。 Contains diene rubber, silica, and cationic surfactant,
The CTAB adsorption specific surface area of the silica is 115-300 m 2 / g.
The cationic surfactant is a quaternary ammonium salt having an amide bond.
The content of the silica is 50 to 200 parts by mass with respect to 100 parts by mass of the diene rubber.
A rubber composition for a tire, wherein the content of the cationic surfactant is 0.05 to 10 parts by mass with respect to 100 parts by mass of the diene rubber.
式（２）中、Ｒ５は水素原子又はアシル基を表し、Ｒ６は水素原子又はメチル基を表し、ｎは１〜３の数を表す。 The rubber composition for a tire according to claim 1 or 2, wherein the cationic surfactant is a compound represented by the following formula (1).
In formula (2), R 5 represents a hydrogen atom or an acyl group, R 6 represents a hydrogen atom or a methyl group, and n represents a number 1 to 3.
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