JP2016029167A - Rubber composition and pneumatic tire using the same - Google Patents
Rubber composition and pneumatic tire using the same Download PDFInfo
- Publication number
- JP2016029167A JP2016029167A JP2015142569A JP2015142569A JP2016029167A JP 2016029167 A JP2016029167 A JP 2016029167A JP 2015142569 A JP2015142569 A JP 2015142569A JP 2015142569 A JP2015142569 A JP 2015142569A JP 2016029167 A JP2016029167 A JP 2016029167A
- Authority
- JP
- Japan
- Prior art keywords
- silica
- mass
- rubber composition
- acid ester
- rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 40
- 239000005060 rubber Substances 0.000 title claims abstract description 40
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 109
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 54
- 235000011187 glycerol Nutrition 0.000 claims abstract description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 29
- 239000011593 sulfur Substances 0.000 claims abstract description 29
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 15
- 239000000194 fatty acid Substances 0.000 claims abstract description 14
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 11
- 229930195729 fatty acid Natural products 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims description 31
- 150000002148 esters Chemical class 0.000 claims description 31
- 229920001577 copolymer Polymers 0.000 claims description 9
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 claims description 6
- 229920006164 aromatic vinyl copolymer Polymers 0.000 claims description 6
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 claims description 3
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 claims description 3
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 claims description 3
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 claims description 3
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 claims description 3
- 229930006722 beta-pinene Natural products 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 claims description 3
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 claims description 3
- -1 and (D) for example Chemical compound 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 3
- 230000002787 reinforcement Effects 0.000 abstract description 3
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 19
- 238000013329 compounding Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 241001441571 Hiodontidae Species 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000004073 vulcanization Methods 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
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N pentadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-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 group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 238000000034 method Methods 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
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-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
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004636 vulcanized rubber Substances 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
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- 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
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- IABJHLPWGMWHLX-UHFFFAOYSA-N 3-(1,3-benzothiazol-2-yl)propyl-trimethoxysilane Chemical compound C1=CC=C2SC(CCC[Si](OC)(OC)OC)=NC2=C1 IABJHLPWGMWHLX-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid 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
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 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
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004898 kneading Methods 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
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- JPPLPDOXWBVPCW-UHFFFAOYSA-N s-(3-triethoxysilylpropyl) octanethioate Chemical compound CCCCCCCC(=O)SCCC[Si](OCC)(OCC)OCC JPPLPDOXWBVPCW-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- 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
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Classifications
-
- 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
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ゴム組成物およびそれを用いた空気入りタイヤに関するものであり、詳しくは、シリカの分散性を高め、破断特性を向上させるとともに、硫黄のヤケの問題も防止可能なゴム組成物およびそれを用いた空気入りタイヤに関するものである。 The present invention relates to a rubber composition and a pneumatic tire using the rubber composition. Specifically, the rubber composition improves the dispersibility of silica, improves the fracture characteristics, and prevents the problem of sulfur burns, and The present invention relates to a pneumatic tire using the same.
近年益々厳しくなるタイヤ高性能化への要求に伴い、タイヤにシリカを配合する手法が知られている。しかしながらシリカは、その粒子表面に存在するシラノール基による水素結合の形成のために凝集する傾向を有し、混練時にゴム組成物のムーニー粘度が高くなり、加工性を悪化させるという問題点があった。
シリカの分散性を高めるためには、反応性の高い硫黄含有シランカップリング剤を添加するのが有利である。しかし、このような硫黄含有シランカップリング剤は、未加硫ゴムのヤケ等、加工上の問題があるため多量に配合することができず、シリカの十分な分散性が得られないという課題があった。
Along with the demand for higher tire performance that has become increasingly severe in recent years, a method of blending silica into a tire is known. However, silica has a tendency to agglomerate due to the formation of hydrogen bonds due to silanol groups present on the surface of the particles, and has a problem that the Mooney viscosity of the rubber composition increases during kneading and deteriorates workability. .
In order to increase the dispersibility of silica, it is advantageous to add a highly reactive sulfur-containing silane coupling agent. However, such a sulfur-containing silane coupling agent cannot be blended in large quantities due to processing problems such as unvulcanized rubber burns, and there is a problem that sufficient dispersibility of silica cannot be obtained. there were.
一方、下記特許文献１には、硫黄含有シランカップリング剤とアルキルトリエトキシシランとを併用し、シリカの分散性を高める技術が開示されている。この技術によれば、加工性を損なうことなくシリカの高い分散性が得られるが、アルキルトリエトキシシランは、シリカ−ポリマー間に結合を生成しないためゴムの補強性を低下させてしまい、これにより破断特性が低下し耐摩耗性を悪化させることが懸念されていた。この理由としては、シリカ表面のシラノール基に対する、硫黄含有シランカップリング剤とアルキルトリエトキシシランカップリング剤の反応速度が両者間であまり変わらず、硫黄含有シランカップリング剤の反応量が相対的に減少するためであると考えられる。 On the other hand, Patent Document 1 below discloses a technique for improving the dispersibility of silica by using a sulfur-containing silane coupling agent and an alkyltriethoxysilane in combination. According to this technology, high dispersibility of silica can be obtained without impairing processability, but alkyltriethoxysilane does not form a bond between silica and polymer, thereby reducing rubber reinforcement. There has been a concern that the fracture characteristics will deteriorate and the wear resistance will deteriorate. The reason for this is that the reaction rate of the sulfur-containing silane coupling agent and the alkyltriethoxysilane coupling agent with respect to silanol groups on the silica surface does not change much between the two, and the reaction amount of the sulfur-containing silane coupling agent is relatively This is thought to be due to a decrease.
したがって本発明の目的は、シリカの分散性を高め、破断特性を向上させるとともに、硫黄のヤケの問題も防止可能なゴム組成物およびそれを用いた空気入りタイヤを提供することにある。 Accordingly, an object of the present invention is to provide a rubber composition capable of improving the dispersibility of silica and improving fracture characteristics, and also preventing the problem of sulfur burn, and a pneumatic tire using the same.
本発明者らは鋭意研究を重ねた結果、ジエン系ゴムに対し、シリカ、硫黄含有シランカップリング剤、アルキルトリエトキシシランおよび特定のグリセリンモノ脂肪酸エステルを特定量でもって配合することにより、上記課題を解決できることを見出し、本発明を完成することができた。
すなわち本発明は以下の通りである。
As a result of intensive research, the present inventors have formulated the above-mentioned problem by blending silica, sulfur-containing silane coupling agent, alkyltriethoxysilane and specific glycerin monofatty acid ester with a specific amount with respect to diene rubber. The present invention has been completed.
That is, the present invention is as follows.
１．（Ａ）ジエン系ゴム１００質量部に対し、
（Ｂ）シリカを５〜２００質量部、
（Ｃ）硫黄含有シランカップリング剤を前記シリカに対し１〜２０質量％、
（Ｄ）下記式（１）で表されるアルキルトリエトキシシランを前記シリカに対し１〜２０質量％、および
（Ｅ）炭素数８〜２４の脂肪酸を由来とするグリセリンモノ脂肪酸エステルを前記（Ｂ）シリカの質量に対し１〜２０質量％配合してなることを特徴とするゴム組成物。
1. (A) For 100 parts by mass of diene rubber,
(B) 5 to 200 parts by mass of silica,
(C) 1-20% by mass of the sulfur-containing silane coupling agent with respect to the silica,
(D) 1 to 20% by mass of alkyltriethoxysilane represented by the following formula (1) with respect to the silica, and (E) glycerol monofatty acid ester derived from a fatty acid having 8 to 24 carbon atoms (B ) A rubber composition comprising 1 to 20% by mass based on the mass of silica.
（式（１）中、Ｒ１は炭素数１〜２０のアルキル基を表し、Ｅｔはエチル基を表す。） (In formula (1), R 1 represents an alkyl group having 1 to 20 carbon atoms, and Et represents an ethyl group.)
２．下記（１）〜（３）の共重合体および下記（４）の水素添加物のうち少なくとも１種をさらに配合してなることを特徴とする前記１に記載のゴム組成物。
（１） α−ピネン−芳香族ビニル共重合体
（２） β−ピネン−芳香族ビニル共重合体
（３） α−ピネン、β−ピネン、ジペンテンからなる群のうち少なくとも２種と芳香族ビニルとの共重合体
（４） 上記（１）〜（３）の共重合体の水素添加物。
2. 2. The rubber composition as described in 1 above, further comprising at least one of the following (1) to (3) copolymers and the following (4) hydrogenated product.
(1) α-pinene-aromatic vinyl copolymer (2) β-pinene-aromatic vinyl copolymer (3) At least two of the group consisting of α-pinene, β-pinene and dipentene and aromatic vinyl (4) A hydrogenated product of the copolymer of (1) to (3) above.
３．前記（Ｅ）グリセリンモノ脂肪酸エステルの配合量が、前記（Ｄ）式（１）で表されるアルキルトリエトキシシランに対して１０〜１０００質量％であることを特徴とする前記１に記載のゴム組成物。
４．前記（Ｅ）グリセリンモノ脂肪酸エステルが不飽和結合を含むことを特徴とする前記１〜３のいずれかに記載のゴム組成物。
５．前記１〜４のいずれかに記載のゴム組成物をトレッドに使用した空気入りタイヤ。
3. 2. The rubber according to 1 above, wherein the amount of the (E) glycerin monofatty acid ester is 10 to 1000% by mass with respect to the alkyltriethoxysilane represented by the formula (1) (D). Composition.
4). The rubber composition as described in any one of 1 to 3 above, wherein the (E) glycerin monofatty acid ester contains an unsaturated bond.
5. A pneumatic tire using the rubber composition according to any one of 1 to 4 as a tread.
本発明によれば、（Ａ）ジエン系ゴムに対し、（Ｂ）シリカ、（Ｃ）硫黄含有シランカップリング剤、（Ｄ）アルキルトリエトキシシランおよび特定の（Ｅ）グリセリンモノ脂肪酸エステルを特定量でもって配合したので、（Ｂ）シリカの分散性を高め、破断特性を向上させるとともに、硫黄のヤケの問題も防止可能なゴム組成物およびそれを用いた空気入りタイヤを提供することができる。
とくに、（Ｅ）グリセリンモノ脂肪酸エステルの持つ２つの−ＯＨ基が（Ｂ）シリカ表面のシラノール基に吸着し、脂肪酸の炭素鎖が疎水化部位として作用し分散性が向上し、シリカ凝集塊がより細かくなる。この作用によってシリカの表面積が増加するため、カップリング剤との反応点も増加する。一方で（Ｅ）グリセリンモノ脂肪酸エステルはシリカ表面には水素結合を介して吸着しているのみで脱離可能であり、シランカップリング剤の反応を阻害しない。そのため、（Ｄ）アルキルトリエトキシシラン存在下でも破断特性は悪化しない。
According to the present invention, (A) a specific amount of (B) silica, (C) a sulfur-containing silane coupling agent, (D) an alkyltriethoxysilane and a specific (E) glycerin monofatty acid ester with respect to (A) diene rubber. Therefore, (B) The rubber composition which can raise the dispersibility of a silica and can improve a fracture | rupture characteristic, and can also prevent the problem of a sulfur burn, and a pneumatic tire using the same can be provided.
In particular, (E) the two —OH groups of glycerin monofatty acid ester are adsorbed on (B) silanol groups on the silica surface, the carbon chain of the fatty acid acts as a hydrophobization site, and the dispersibility is improved. It becomes finer. Due to this action, the surface area of the silica increases, so that the reaction point with the coupling agent also increases. On the other hand, (E) glycerin monofatty acid ester can be detached only by being adsorbed on the silica surface through hydrogen bonds, and does not inhibit the reaction of the silane coupling agent. Therefore, the fracture characteristics do not deteriorate even in the presence of (D) alkyltriethoxysilane.
以下、本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail.
（Ａ）ジエン系ゴム
本発明で使用される（Ａ）ジエン系ゴムは、通常のゴム組成物に配合することができる任意のジエン系ゴムを用いることができ、例えば、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、アクリロニトリル−ブタジエン共重合体ゴム（ＮＢＲ）等が挙げられる。これらは、単独で用いてもよく、２種以上を併用してもよい。また、その分子量やミクロ構造はとくに制限されず、アミン、アミド、シリル、アルコキシシリル、カルボキシル、ヒドロキシル基等で末端変性されていても、エポキシ化されていてもよい。
これらのジエン系ゴムの中でも、本発明の効果の点からジエン系ゴムはＳＢＲ、ＢＲが好ましい。
(A) Diene Rubber The (A) diene rubber used in the present invention can be any diene rubber that can be blended in a normal rubber composition, such as natural rubber (NR), Examples include isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), and acrylonitrile-butadiene copolymer rubber (NBR). These may be used alone or in combination of two or more. The molecular weight and microstructure are not particularly limited, and may be terminally modified with an amine, amide, silyl, alkoxysilyl, carboxyl, hydroxyl group or the like, or may be epoxidized.
Among these diene rubbers, SBR and BR are preferable as the diene rubber from the viewpoint of the effect of the present invention.
（Ｂ）シリカ
本発明で使用されるシリカとしては、乾式シリカ、湿式シリカ、コロイダルシリカおよび沈降シリカなど、従来からゴム組成物において使用することが知られている任意のシリカを単独でまたは２種以上組み合わせて使用できる。
なお本発明では、本発明の効果がさらに向上するという観点から、シリカの窒素吸着比表面積（Ｎ２ＳＡ）は100〜400ｍ２／ｇであるのが好ましく、150〜300ｍ２／ｇであるのがさらに好ましい。窒素吸着比表面積（Ｎ２ＳＡ）はＪＩＳ Ｋ６２１７−２に準拠して求めた値である。
(B) Silica As the silica used in the present invention, any silica conventionally known to be used in rubber compositions such as dry silica, wet silica, colloidal silica and precipitated silica is used alone or in combination of two kinds. It can be used in combination.
In the present invention, from the viewpoint of the effect of the present invention is further improved, it is preferred the nitrogen adsorption specific surface area (N 2 SA) of silica is 100 to 400 m 2 / g, in the range of 150 to 300 m 2 / g Is more preferable. The nitrogen adsorption specific surface area (N 2 SA) is a value determined in accordance with JIS K6217-2.
（Ｃ）硫黄含有シランカップリング剤
本発明で使用される硫黄含有シランカップリング剤は、シリカ配合のゴム組成物に使用可能なものであればよく、例えばビス−（３−トリエトキシシリルプロピル）テトラスルフィド、ビス（３−トリエトキシシリルプロピル）ジスルフィド、３−トリメトキシシリルプロピルベンゾチアゾールテトラスルフィド、γ−メルカプトプロピルトリエトキシシラン、３−オクタノイルチオプロピルトリエトキシシラン等を例示することができる。
(C) Sulfur-containing silane coupling agent The sulfur-containing silane coupling agent used in the present invention only needs to be usable for a rubber composition containing silica, for example, bis- (3-triethoxysilylpropyl). Examples thereof include tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, γ-mercaptopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, and the like.
（Ｄ）アルキルトリエトキシシラン
本発明で使用されるアルキルトリエトキシシランは、下記式（１）で表される化合物である。
(D) Alkyltriethoxysilane The alkyltriethoxysilane used in the present invention is a compound represented by the following formula (1).
（式（１）中、Ｒ１は炭素数１〜２０のアルキル基を表し、Ｅｔはエチル基を表す。）
シラン化合物である。
(In formula (1), R1 represents an alkyl group having 1 to 20 carbon atoms, and Et represents an ethyl group.)
Silane compound.
ここで、Ｒ１の炭素数１〜２０のアルキル基としては、中でも、炭素数７〜２０のアルキル基が好ましく、具体的には、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基等が挙げられる。これらのうち、ジエン系ゴムとの相溶性の観点から、炭素数８〜１０のアルキル基がさらに好ましく、オクチル基、ノニル基であるのがとくに好ましい。
（Ｄ）アルキルトリエトキシシランを用いることにより、シリカの凝集や粘度上昇を抑制する効果を奏する。
Here, as a C1-C20 alkyl group of R1, a C7-C20 alkyl group is preferable especially, and a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, dodecyl is mentioned specifically, Groups and the like. Among these, from the viewpoint of compatibility with the diene rubber, an alkyl group having 8 to 10 carbon atoms is more preferable, and an octyl group and a nonyl group are particularly preferable.
(D) By using alkyltriethoxysilane, there is an effect of suppressing silica aggregation and viscosity increase.
（Ｅ）グリセリンモノ脂肪酸エステル
本発明で使用される（Ｅ）グリセリンモノ脂肪酸エステルは、炭素数８〜２４の脂肪酸を由来とするモノグリセリドである。
脂肪酸としては、具体的には、カプリル酸、ペラルゴン酸、カプリン酸、ラウリン酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、マルガリン酸、ステアリン酸、オレイン酸、アラキジン酸、ベヘン酸、リグノセリン酸等の直鎖脂肪酸類が挙げられる。
グリセリンモノ脂肪酸エステルは、１種類を使用してもよいし、２種以上を併用してもよい。
本発明の効果が向上するという観点から、前記脂肪酸は、ステアリン酸、オレイン酸、リノール酸、リノレン酸が好ましい。
特に、（Ｅ）グリセリンモノ脂肪酸エステルのアルキル鎖が不飽和である場合、不飽和結合が硫黄との反応点となり、ポリマーの架橋密度を相対的に低下させ、余分な架橋を抑制する事で破断強度・破断伸びを向上させることが可能である。
(E) Glycerol monofatty acid ester The (E) glycerin monofatty acid ester used in the present invention is a monoglyceride derived from a fatty acid having 8 to 24 carbon atoms.
Specific examples of fatty acids include caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, oleic acid, arachidic acid, behenic acid, lignoceric acid, etc. And chain fatty acids.
One type of glycerol mono fatty acid ester may be used, or two or more types may be used in combination.
From the viewpoint of improving the effect of the present invention, the fatty acid is preferably stearic acid, oleic acid, linoleic acid, or linolenic acid.
In particular, when the alkyl chain of (E) glycerin monofatty acid ester is unsaturated, the unsaturated bond becomes a reaction point with sulfur, the crosslink density of the polymer is relatively lowered, and the breakage is caused by suppressing excessive crosslinks. It is possible to improve strength and elongation at break.
（ゴム組成物の配合割合）
本発明のゴム組成物は、
（Ａ）ジエン系ゴム１００質量部に対し、
（Ｂ）シリカを５〜２００質量部、
（Ｃ）硫黄含有シランカップリング剤を前記シリカに対し１〜２０質量％、
（Ｄ）前記式（１）で表されるアルキルトリエトキシシランを前記シリカに対し１〜２０質量％、および
（Ｅ）炭素数８〜２４の脂肪酸を由来とするグリセリンモノ脂肪酸エステルを前記（Ｂ）シリカの質量に対し１〜２０質量％配合してなることを特徴とする。
(Rubber composition ratio)
The rubber composition of the present invention is
(A) For 100 parts by mass of diene rubber,
(B) 5 to 200 parts by mass of silica,
(C) 1-20% by mass of the sulfur-containing silane coupling agent with respect to the silica,
(D) 1 to 20% by mass of the alkyltriethoxysilane represented by the formula (1) with respect to the silica, and (E) a glycerin monofatty acid ester derived from a fatty acid having 8 to 24 carbon atoms (B ) 1 to 20% by mass based on the mass of silica.
（Ｂ）シリカの配合量が５質量部未満であると、補強性が悪化し、２００質量部を超えると加工性が悪化する。
（Ｃ）硫黄含有シランカップリング剤の配合量が（Ｂ）シリカに対し１質量％未満であると、配合量が少な過ぎて本発明の効果を奏することができない。逆に２０質量％を超えるとスコーチが悪化する。
（Ｄ）アルキルトリエトキシシランの配合量が（Ｂ）シリカに対し１質量％未満であると、配合量が少な過ぎて本発明の効果を奏することができない。逆に２０質量％を超えると破断強度・破断伸びが悪化する。
（Ｅ）グリセリンモノ脂肪酸エステルの配合量が（Ｂ）シリカに対し１質量％未満であると、配合量が少な過ぎて本発明の効果を奏することができない。逆に２０質量％を超えると破断強度・破断伸びが悪化する。
(B) Reinforcing property will deteriorate that the compounding quantity of silica is less than 5 mass parts, and workability will deteriorate when it exceeds 200 mass parts.
(C) When the compounding quantity of a sulfur containing silane coupling agent is less than 1 mass% with respect to (B) silica, there are too few compounding quantities and there exists no effect of this invention. Conversely, if it exceeds 20% by mass, the scorch will deteriorate.
When the blending amount of (D) alkyltriethoxysilane is less than 1% by mass based on (B) silica, the blending amount is too small to achieve the effects of the present invention. Conversely, if it exceeds 20% by mass, the breaking strength and breaking elongation deteriorate.
(E) When the compounding quantity of glycerol mono-fatty acid ester is less than 1 mass% with respect to (B) silica, there are too few compounding quantities and there exists no effect of this invention. Conversely, if it exceeds 20% by mass, the breaking strength and breaking elongation deteriorate.
（Ｂ）シリカのさらに好ましい配合量は、（Ａ）ジエン系ゴム１００質量部に対し、５０〜１５０質量部である。
（Ｃ）硫黄含有シランカップリング剤のさらに好ましい配合量は、（Ｂ）シリカに対し、２〜１５質量％である。
（Ｄ）アルキルトリエトキシシランのさらに好ましい配合量は、（Ｂ）シリカに対し、２〜１０質量％である。
（Ｅ）グリセリンモノ脂肪酸エステルのさらに好ましい配合量は、（Ｂ）シリカに対し、１〜１０質量％である。
(B) The more preferable compounding quantity of a silica is 50-150 mass parts with respect to 100 mass parts of (A) diene rubber.
(C) The more preferable compounding quantity of a sulfur containing silane coupling agent is 2-15 mass% with respect to (B) silica.
(D) The more preferable compounding quantity of alkyltriethoxysilane is 2-10 mass% with respect to (B) silica.
(E) The more preferable compounding quantity of glycerol mono-fatty acid ester is 1-10 mass% with respect to (B) silica.
ここで本発明では、（Ｅ）グリセリンモノ脂肪酸エステルの配合量が、（Ｄ）アルキルトリエトキシシランに対して１０〜１０００質量％であることが未加硫ゴムのヤケ防止、破断特性の向上の観点から好ましい。さらに好ましい上記割合は、20〜500質量％である。 Here, in the present invention, the blending amount of (E) glycerin monofatty acid ester is 10 to 1000% by mass with respect to (D) alkyltriethoxysilane, which prevents uncured rubber from being burned and improved in breaking properties. It is preferable from the viewpoint. A more preferable ratio is 20 to 500% by mass.
また本発明では、破断特性をさらに向上させることを目的として、下記（１）〜（３）の共重合体および下記（４）の水素添加物のうち少なくとも１種をさらに配合してなることが好ましい。
（１） α−ピネン−芳香族ビニル共重合体
（２） β−ピネン−芳香族ビニル共重合体
（３） α−ピネン、β−ピネン、ジペンテンからなる群のうち少なくとも２種と芳香族ビニルとの共重合体
（４） 上記（１）〜（３）の共重合体の水素添加物。
上記共重合体を構成する芳香族ビニルは、例えば、スチレン、α−メチルスチレンが挙げられ、スチレンを用いるのが好ましい。
上記共重合体の配合量は、（Ａ）ジエン系ゴム１００重量部に対し３〜３０重量部であるのが好ましい。
Further, in the present invention, for the purpose of further improving the breaking properties, at least one of the following (1) to (3) copolymers and the following (4) hydrogenated product may be further blended. preferable.
(1) α-pinene-aromatic vinyl copolymer (2) β-pinene-aromatic vinyl copolymer (3) At least two of the group consisting of α-pinene, β-pinene and dipentene and aromatic vinyl (4) A hydrogenated product of the copolymer of (1) to (3) above.
Examples of the aromatic vinyl constituting the copolymer include styrene and α-methylstyrene, and styrene is preferably used.
The blending amount of the copolymer is preferably 3 to 30 parts by weight with respect to 100 parts by weight of the (A) diene rubber.
（その他成分）
本発明におけるゴム組成物には、前記した成分に加えて、加硫又は架橋剤；加硫又は架橋促進剤；酸化亜鉛、カーボンブラック、クレー、タルク、炭酸カルシウムのような各種充填剤；老化防止剤；可塑剤などのゴム組成物に一般的に配合されている各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量も、本発明の目的に反しない限り、従来の一般的な配合量とすることができる。
(Other ingredients)
In the rubber composition of the present invention, in addition to the above-described components, a vulcanization or crosslinking agent; a vulcanization or crosslinking accelerator; various fillers such as zinc oxide, carbon black, clay, talc, calcium carbonate; Various additives generally blended in rubber compositions such as plasticizers can be blended, and these additives are kneaded by a general method to form a composition for vulcanization or crosslinking. Can be used. The blending amounts of these additives can be set to conventional general blending amounts as long as the object of the present invention is not violated.
また本発明のゴム組成物は従来の空気入りタイヤの製造方法に従って空気入りタイヤを製造するのに適しており、トレッドに適用するのがよい。 The rubber composition of the present invention is suitable for producing a pneumatic tire according to a conventional method for producing a pneumatic tire, and is preferably applied to a tread.
以下、本発明を実施例および比較例によりさらに説明するが、本発明は下記例に制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example further demonstrate this invention, this invention is not restrict | limited to the following example.
標準例１、実施例１〜２および比較例１〜７
サンプルの調製
表１に示す配合（質量部）において、加硫促進剤と硫黄を除く成分を１．７リットルの密閉式バンバリーミキサーで５分間混練した後、混練物をミキサー外に放出させて質量冷却させ、同バンバリーミキサーにて加硫促進剤および硫黄を加えてさらに混練し、ゴム組成物を得た。次に得られたゴム組成物を所定の金型中で１６０℃、２０分間プレス加硫して加硫ゴム試験片を得、以下に示す試験法で未加硫のゴム組成物および加硫ゴム試験片の物性を測定した。
Standard Example 1, Examples 1-2 and Comparative Examples 1-7
Preparation of Sample In the composition (parts by mass) shown in Table 1, the components excluding the vulcanization accelerator and sulfur were kneaded for 5 minutes with a 1.7 liter closed Banbury mixer, and then the kneaded product was discharged out of the mixer and massed. After cooling, a vulcanization accelerator and sulfur were added using the same Banbury mixer and further kneaded to obtain a rubber composition. Next, the obtained rubber composition was press vulcanized in a predetermined mold at 160 ° C. for 20 minutes to obtain a vulcanized rubber test piece, and an unvulcanized rubber composition and vulcanized rubber were tested by the following test method The physical properties of the test piece were measured.
ムーニービス：ＪＩＳ Ｋ６３００に従い、１００℃における未加硫ゴムの粘度を測定した。結果は標準例１の値を１００として指数表示した。この値が低いほど粘度が低く、加工性が良好であることを示す。
ムーニースコーチ：ＪＩＳ Ｋ６３００に従い、１２５℃で試験した。結果は標準例１の値を１００として指数表示した。この値が高いほど、ヤケ性に優れることを示す。
破断強度：ＪＩＳ Ｋ ６２５１に従い、室温で試験した。結果は標準例１の値を１００として指数表示した。この値が高いほど、補強性に優れることを示す。
破断伸び：ＪＩＳ Ｋ ６２５１に従い、室温で試験した。結果は標準例１の値を１００として指数表示した。この値が高いほど、耐摩耗性に優れることを示す。
結果を表１に併せて示す。
Mooney bis: The viscosity of unvulcanized rubber at 100 ° C. was measured according to JIS K6300. The results were expressed as an index with the value of standard example 1 being 100. The lower this value, the lower the viscosity and the better the workability.
Mooney scorch: Tested at 125 ° C. according to JIS K6300. The results were expressed as an index with the value of standard example 1 being 100. The higher this value, the better the discoloration.
Breaking strength: Tested at room temperature according to JIS K 6251. The results were expressed as an index with the value of standard example 1 being 100. It shows that it is excellent in reinforcement property, so that this value is high.
Elongation at break: tested at room temperature according to JIS K 6251. The results were expressed as an index with the value of standard example 1 being 100. It shows that it is excellent in abrasion resistance, so that this value is high.
The results are also shown in Table 1.
＊１：ＳＢＲ（旭化成（株）製タフデン３８３０、油展量＝ＳＢＲ１００質量部に対し３７．５質量部）
＊２：ＢＲ（日本ゼオン（株）製Ｎｉｐｏｌ ＢＲ１２２０）
＊３：シリカ（ローディア社製Zeosil 1165MP、窒素吸着比表面積（Ｎ２ＳＡ）＝１６５ｍ２／ｇ）
＊４：カーボンブラック（キャボットジャパン（株）製ショウブラックＮ３３９、窒素吸着比表面積（Ｎ２ＳＡ）＝９０ｍ２／ｇ））
＊５：シランカップリング剤（エボニックデグッサ社製Ｓｉ６９、ビス（３−トリエトキシシリルプロピル）テトラスルフィド）
＊６：アルキルトリエトキシシラン（信越化学（株）製ＫＢＥ−３０８３、ｎ−オクチルトリエトキシシラン）
＊７：酸化亜鉛（正同化学工業（株）製酸化亜鉛３種）
＊８：ステアリン酸（日油（株）製ステアリン酸ＹＲ）
＊９：老化防止剤（Solutia Europe社製Santoflex 6PPD）
＊１０：プロセスオイル（昭和シェル石油（株）製エキストラクト4号Ｓ）
＊１１：化合物−１（シグマアルドリッチ社製モノステアリン酸グリセロール）
＊１２：化合物−２（シグマアルドリッチ社製モノオレイン酸グリセロール）
＊１３：化合物−３（シグマアルドリッチ社製グリセリン）
＊１４：化合物−４（シグマアルドリッチ社製トリステアリン酸グリセリン）
＊１５：硫黄（軽井沢精錬所社製油処理イオウ）
＊１６：加硫促進剤−１（大内新興化学工業（株）製ノクセラーＣＺ−Ｇ）
＊１７：加硫促進剤−２（Flexsys社製Perkacit DPG）
* 1: SBR (Toughden 3830 manufactured by Asahi Kasei Co., Ltd., oil expansion amount = 37.5 parts by mass with respect to 100 parts by mass of SBR)
* 2: BR (Nipol BR1220 manufactured by Nippon Zeon Co., Ltd.)
* 3: Silica (Zeosil 1165MP, manufactured by Rhodia, nitrogen adsorption specific surface area (N 2 SA) = 165 m 2 / g)
* 4: Carbon black (show black N339 manufactured by Cabot Japan Co., Ltd., nitrogen adsorption specific surface area (N 2 SA) = 90 m 2 / g))
* 5: Silane coupling agent (Si69, bis (3-triethoxysilylpropyl) tetrasulfide manufactured by Evonik Degussa)
* 6: Alkyltriethoxysilane (KBE-3083, n-octyltriethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.)
* 7: Zinc oxide (3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd.)
* 8: Stearic acid (Stearic acid YR manufactured by NOF Corporation)
* 9: Anti-aging agent (Santoflex 6PPD manufactured by Solutia Europe)
* 10: Process oil (Extract No. 4 S manufactured by Showa Shell Sekiyu KK)
* 11: Compound-1 (glycerol monostearate manufactured by Sigma-Aldrich)
* 12: Compound-2 (glycerol monooleate manufactured by Sigma-Aldrich)
* 13: Compound-3 (glycerin manufactured by Sigma-Aldrich)
* 14: Compound-4 (Sigma Aldrich glyceryl tristearate)
* 15: Sulfur (Karuizawa Smelter Refinery sulfur)
* 16: Vulcanization accelerator-1 (Noxeller CZ-G manufactured by Ouchi Shinsei Chemical Co., Ltd.)
* 17: Vulcanization accelerator-2 (Perkacit DPG manufactured by Flexsys)
上記の表１の結果から明らかなように、実施例１および２で得られたゴム組成物は、（Ａ）ジエン系ゴムに対し、（Ｂ）シリカ、（Ｃ）硫黄含有シランカップリング剤、（Ｄ−１）アルキルトリエトキシシランおよび特定の（Ｅ）グリセリンモノ脂肪酸エステルを特定量でもって配合したので、前記（Ｄ）および（Ｅ）を配合していない標準例１に対し、（Ｂ）シリカの分散性が高まり、破断特性が向上し、硫黄のヤケの問題も防止されていることが分かる。
比較例１は、標準例１に記載のゴム組成物に、（Ｄ−１）アルキルトリエトキシシランを配合した例であるが、破断強度が悪化した。
比較例２は、標準例１に記載のゴム組成物に、（Ｅ）グリセリンモノ脂肪酸エステルを配合した例であるが、ムーニービスが悪化した。
比較例３は、標準例１に記載のゴム組成物における（Ｃ）硫黄含有シランカップリング剤を増量した例であるが、破断伸びおよびスコーチが悪化した。
比較例４は、（Ｃ）硫黄含有シランカップリング剤を配合していないので、破断強度およびムーニービスが悪化した。
比較例５は、（Ｃ）硫黄含有シランカップリング剤および（Ｄ−１）アルキルトリエトキシシランを配合せず、（Ｅ）グリセリンモノ脂肪酸エステルを増量した例であるので、破断強度およびムーニービスが悪化した。
比較例６は、（Ｅ）グリセリンモノ脂肪酸エステルを配合せず、その替わりにグリセリンを配合した例であるので、破断伸びおよびスコーチが悪化した。
比較例７は、（Ｅ）グリセリンモノ脂肪酸エステルを配合せず、その替わりにトリステアリン酸グリセリンを配合した例であるので、破断強度が悪化した。
As is clear from the results in Table 1 above, the rubber compositions obtained in Examples 1 and 2 were (B) silica, (C) sulfur-containing silane coupling agent, (A) diene rubber, (D-1) Since the alkyltriethoxysilane and the specific (E) glycerin monofatty acid ester were blended in a specific amount, the standard example 1 in which the (D) and (E) were not blended, (B) It can be seen that the dispersibility of silica is improved, the breaking properties are improved, and the problem of sulfur burn is prevented.
Comparative Example 1 is an example in which (D-1) alkyltriethoxysilane was blended with the rubber composition described in Standard Example 1, but the breaking strength deteriorated.
Comparative Example 2 is an example in which (E) glycerin monofatty acid ester was blended with the rubber composition described in Standard Example 1, but Mooney vis was deteriorated.
Comparative Example 3 is an example in which the amount of (C) sulfur-containing silane coupling agent in the rubber composition described in Standard Example 1 was increased, but the elongation at break and scorch deteriorated.
In Comparative Example 4, since (C) the sulfur-containing silane coupling agent was not blended, the breaking strength and Mooney vis were deteriorated.
Comparative Example 5 is an example in which (C) sulfur-containing silane coupling agent and (D-1) alkyltriethoxysilane were not blended, and (E) glycerin monofatty acid ester was increased, so that the breaking strength and Mooney vis were deteriorated. did.
Since Comparative Example 6 was an example in which (E) glycerin monofatty acid ester was not blended and glycerin was blended instead, break elongation and scorch deteriorated.
Since Comparative Example 7 was an example in which (E) glycerin monofatty acid ester was not blended and glyceryl tristearate was blended instead, the breaking strength deteriorated.
実施例３〜７および比較例８〜１１
（Ｂ）シリカに対する（Ｅ）グリセリンモノ脂肪酸エステルの配合量を種々変更する以外は、上記例を繰り返した。結果を表２に示す。なお、前掲の標準例１、実施例１、比較例１の結果も併せて表２に記載した。
Examples 3-7 and Comparative Examples 8-11
(B) The above example was repeated except that the blending amount of (E) glycerin monofatty acid ester with respect to silica was varied. The results are shown in Table 2. The results of the above-mentioned standard example 1, example 1, and comparative example 1 are also shown in Table 2.
実施例８〜９および比較例１２
樹脂を添加した系において、（Ｅ）グリセリンモノ脂肪酸エステルの配合の効果を調べた。それ以外は、上記例を繰り返した。結果を表２に併せて示す。
Examples 8 to 9 and Comparative Example 12
In the system to which the resin was added, the effect of blending (E) glycerin monofatty acid ester was examined. Otherwise, the above example was repeated. The results are also shown in Table 2.
樹脂：（ヤスハラケミカル（株）製テルペンスチレン樹脂ＴＯ−１２５） Resin: (Terpene styrene resin TO-125 manufactured by Yasuhara Chemical Co., Ltd.)
表２の結果から、比較例１、８、１０は、（Ｅ）グリセリンモノ脂肪酸エステルを配合していないか、配合量が本発明で規定する下限未満であるので、破断強度が悪化した。
これに対し、実施例３、５は、（Ｅ）グリセリンモノ脂肪酸エステルの配合量が本発明で規定する範囲内であるので、スコーチを悪化させずにムーニービスおよび破断伸びが向上している。実施例４、６、７は、（Ｅ）グリセリンモノ脂肪酸エステルの配合量を増加させた例であり、各物性がさらに向上している。
比較例９、１１は、（Ｅ）グリセリンモノ脂肪酸エステルの配合量が本発明で規定する上限を超えているので、破断強度が悪化した。
比較例１２は、（Ｅ）グリセリンモノ脂肪酸エステルを配合せずに、樹脂を配合した例であるが、破断伸びおよびムーニービスが悪化した。
これに対し、実施例８、９は、（Ｅ）グリセリンモノ脂肪酸エステルを本発明で規定する範囲内で配合したので、比較例１２の結果に比べ、すべての物性が向上した。
From the results of Table 2, Comparative Examples 1, 8, and 10 were not blended with (E) glycerin monofatty acid ester, or the blending amount was less than the lower limit defined in the present invention, so the breaking strength deteriorated.
On the other hand, in Examples 3 and 5, since the blending amount of (E) glycerin monofatty acid ester is within the range defined in the present invention, Mooney vis and elongation at break are improved without deteriorating scorch. Examples 4, 6, and 7 are examples in which the amount of (E) glycerin monofatty acid ester was increased, and each physical property was further improved.
In Comparative Examples 9 and 11, since the blending amount of (E) glycerin monofatty acid ester exceeded the upper limit defined in the present invention, the breaking strength was deteriorated.
Comparative Example 12 was an example in which resin was blended without blending (E) glycerin monofatty acid ester, but the elongation at break and Mooney vis were deteriorated.
On the other hand, in Examples 8 and 9, since (E) glycerin monofatty acid ester was blended within the range specified in the present invention, all physical properties were improved as compared with the results of Comparative Example 12.
実施例１０〜１５および比較例１３〜１６
（Ｄ−１）アルキルトリエトキシシランに対する（Ｅ）グリセリンモノ脂肪酸エステルの配合量を種々変更する以外は、上記例を繰り返した。結果を表３に示す。なお、前掲の標準例１の結果も併せて表３に記載した。
Examples 10-15 and Comparative Examples 13-16
(D-1) The above example was repeated except that the blending amount of (E) glycerin monofatty acid ester with respect to alkyltriethoxysilane was variously changed. The results are shown in Table 3. The results of Standard Example 1 described above are also shown in Table 3.
表３の結果から、実施例１０〜１５は、（Ｅ）グリセリンモノ脂肪酸エステルの配合量が、（Ｄ−１）アルキルトリエトキシシランに対して１０〜１０００質量％の範囲内であるので、各種物性が良化している。
比較例１３、１５は、（Ｄ−１）アルキルトリエトキシシランの配合量が本発明で規定する下限未満であるので、ムーニービスが悪化し、その他の物性も良化しなかった。
比較例１４、１６は、（Ｅ）グリセリンモノ脂肪酸エステルの配合量が本発明で規定する下限未満であり、（Ｅ）グリセリンモノ脂肪酸エステルの配合量が、（Ｄ−１）アルキルトリエトキシシランに対して約２質量％であるので、破断強度が悪化した。
From the result of Table 3, since Examples 10-15 have the compounding quantity of (E) glycerol mono fatty acid ester in the range of 10-1000 mass% with respect to (D-1) alkyltriethoxysilane, various The physical properties have improved.
In Comparative Examples 13 and 15, since the blending amount of (D-1) alkyltriethoxysilane was less than the lower limit specified in the present invention, Mooney vis was deteriorated and other physical properties were not improved.
In Comparative Examples 14 and 16, the blending amount of (E) glycerin monofatty acid ester is less than the lower limit specified in the present invention, and the blending amount of (E) glycerin monofatty acid ester is (D-1) alkyltriethoxysilane. On the other hand, the breaking strength deteriorated because it was about 2% by mass.
Claims (5)
（Ｂ）シリカを５〜２００質量部、
（Ｃ）硫黄含有シランカップリング剤を前記シリカに対し１〜２０質量％、
（Ｄ）下記式（１）で表されるアルキルトリエトキシシランを前記シリカに対し１〜２０質量％、および
（Ｅ）炭素数８〜２４の脂肪酸を由来とするグリセリンモノ脂肪酸エステルを前記（Ｂ）シリカの質量に対し１〜２０質量％配合してなることを特徴とするゴム組成物。
（式（１）中、Ｒ１は炭素数１〜２０のアルキル基を表し、Ｅｔはエチル基を表す。） (A) For 100 parts by mass of diene rubber,
(B) 5 to 200 parts by mass of silica,
(C) 1-20% by mass of the sulfur-containing silane coupling agent with respect to the silica,
(D) 1 to 20% by mass of alkyltriethoxysilane represented by the following formula (1) with respect to the silica, and (E) glycerol monofatty acid ester derived from a fatty acid having 8 to 24 carbon atoms (B ) A rubber composition comprising 1 to 20% by mass based on the mass of silica.
(In formula (1), R1 represents an alkyl group having 1 to 20 carbon atoms, and Et represents an ethyl group.)
（１） α−ピネン−芳香族ビニル共重合体
（２） β−ピネン−芳香族ビニル共重合体
（３） α−ピネン、β−ピネン、ジペンテンからなる群のうち少なくとも２種と芳香族ビニルとの共重合体
（４） 上記（１）〜（３）の共重合体の水素添加物。 The rubber composition according to claim 1, further comprising at least one of the following (1) to (3) copolymers and the following (4) hydrogenated product.
(1) α-pinene-aromatic vinyl copolymer (2) β-pinene-aromatic vinyl copolymer (3) At least two of the group consisting of α-pinene, β-pinene and dipentene and aromatic vinyl (4) A hydrogenated product of the copolymer of (1) to (3) above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015142569A JP6160661B2 (en) | 2014-07-18 | 2015-07-17 | Rubber composition and pneumatic tire using the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014147301 | 2014-07-18 | ||
| JP2014147301 | 2014-07-18 | ||
| JP2015142569A JP6160661B2 (en) | 2014-07-18 | 2015-07-17 | Rubber composition and pneumatic tire using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016029167A true JP2016029167A (en) | 2016-03-03 |
| JP6160661B2 JP6160661B2 (en) | 2017-07-12 |
Family
ID=55435189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015142569A Active JP6160661B2 (en) | 2014-07-18 | 2015-07-17 | Rubber composition and pneumatic tire using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6160661B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019026791A (en) * | 2017-08-02 | 2019-02-21 | 住友ゴム工業株式会社 | Pneumatic tire |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0827325A (en) * | 1994-07-12 | 1996-01-30 | Mitsui Petrochem Ind Ltd | Thermoplastic olefin elastomer |
| JPH09309978A (en) * | 1996-05-22 | 1997-12-02 | Yokohama Rubber Co Ltd:The | Rubber composition |
| JP2002212353A (en) * | 2001-01-19 | 2002-07-31 | Grand Polymer Co Ltd | Polypropylene resin composition |
| JP2011052090A (en) * | 2009-09-01 | 2011-03-17 | Yokohama Rubber Co Ltd:The | Rubber composition for tire and pneumatic tire using the same |
| WO2012035998A1 (en) * | 2010-09-13 | 2012-03-22 | 横浜ゴム株式会社 | Rubber composition for tires and pneumatic tire |
| WO2014098155A1 (en) * | 2012-12-19 | 2014-06-26 | 株式会社ブリヂストン | Rubber composition, and tire manufactured using same |
-
2015
- 2015-07-17 JP JP2015142569A patent/JP6160661B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0827325A (en) * | 1994-07-12 | 1996-01-30 | Mitsui Petrochem Ind Ltd | Thermoplastic olefin elastomer |
| JPH09309978A (en) * | 1996-05-22 | 1997-12-02 | Yokohama Rubber Co Ltd:The | Rubber composition |
| JP2002212353A (en) * | 2001-01-19 | 2002-07-31 | Grand Polymer Co Ltd | Polypropylene resin composition |
| JP2011052090A (en) * | 2009-09-01 | 2011-03-17 | Yokohama Rubber Co Ltd:The | Rubber composition for tire and pneumatic tire using the same |
| WO2012035998A1 (en) * | 2010-09-13 | 2012-03-22 | 横浜ゴム株式会社 | Rubber composition for tires and pneumatic tire |
| WO2014098155A1 (en) * | 2012-12-19 | 2014-06-26 | 株式会社ブリヂストン | Rubber composition, and tire manufactured using same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019026791A (en) * | 2017-08-02 | 2019-02-21 | 住友ゴム工業株式会社 | Pneumatic tire |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6160661B2 (en) | 2017-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106536610B (en) | Rubber composition and the pneumatic tire for having used the rubber composition | |
| JP6160663B2 (en) | Rubber composition and pneumatic tire using the same | |
| JP2016113515A (en) | Rubber composition and pneumatic tire for heavy load vehicle | |
| JP6281632B2 (en) | Rubber composition and pneumatic tire using the same | |
| JP6164260B2 (en) | Rubber composition and pneumatic tire using the same | |
| JP6160662B2 (en) | Rubber composition and pneumatic tire using the same | |
| JP2011246563A (en) | Rubber composition for tire and pneumatic tire using the same | |
| JP2014210829A (en) | Rubber composition and pneumatic tire using the same | |
| JP6245033B2 (en) | Rubber composition and pneumatic tire using the same | |
| WO2019163519A1 (en) | Rubber composition and pneumatic tire obtained using same | |
| JP7215104B2 (en) | Rubber composition and pneumatic tire using the same | |
| JP2006063209A (en) | Rubber composition for tire | |
| JP6443015B2 (en) | Rubber composition and pneumatic tire using the same | |
| JP6160661B2 (en) | Rubber composition and pneumatic tire using the same | |
| JP2016104833A (en) | Rubber composition and pneumatic tire using the same | |
| JP2016155980A (en) | Construction vehicle tire rubber composition and pneumatic tire using the same | |
| JP5998587B2 (en) | Rubber composition for tire and pneumatic tire using the same | |
| JP6458470B2 (en) | Rubber composition and pneumatic tire using the same | |
| JP2013177520A (en) | Rubber composition for tire and pneumatic tire using the composition | |
| JP2016113474A (en) | Rubber composition and pneumatic tire using the same | |
| JP6015308B2 (en) | Rubber composition and pneumatic tire using the same | |
| JP6164261B2 (en) | Rubber composition and pneumatic tire using the same | |
| JP6024268B2 (en) | Rubber composition for tire and pneumatic tire using the same | |
| JP6511791B2 (en) | Rubber composition and pneumatic tire using the same | |
| JP6597866B2 (en) | Rubber composition and pneumatic tire using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160706 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170222 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170307 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170501 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170516 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170529 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6160661 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |