JP6279554B2 - 変性共役ジエン系重合体の連続製造方法、それから収得された重合体及びそれを含むゴム組成物 - Google Patents
変性共役ジエン系重合体の連続製造方法、それから収得された重合体及びそれを含むゴム組成物 Download PDFInfo
- Publication number
- JP6279554B2 JP6279554B2 JP2015513961A JP2015513961A JP6279554B2 JP 6279554 B2 JP6279554 B2 JP 6279554B2 JP 2015513961 A JP2015513961 A JP 2015513961A JP 2015513961 A JP2015513961 A JP 2015513961A JP 6279554 B2 JP6279554 B2 JP 6279554B2
- Authority
- JP
- Japan
- Prior art keywords
- conjugated diene
- diene polymer
- modified conjugated
- terminal
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000642 polymer Polymers 0.000 title claims description 120
- 150000001993 dienes Chemical class 0.000 title claims description 114
- 239000000203 mixture Substances 0.000 title claims description 36
- 229920001971 elastomer Polymers 0.000 title claims description 33
- 239000005060 rubber Substances 0.000 title claims description 33
- 238000000034 method Methods 0.000 title claims description 19
- 239000000178 monomer Substances 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 229920002554 vinyl polymer Polymers 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 150000002902 organometallic compounds Chemical class 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000011256 inorganic filler Substances 0.000 claims description 9
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000010924 continuous production Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- YMXRPHMIOQYZOO-UHFFFAOYSA-N 3-(diethoxymethylsilyl)-N-[3-(diethoxymethylsilyl)propyl]-N-methylpropan-1-amine Chemical compound C(C)OC(OCC)[SiH2]CCCN(C)CCC[SiH2]C(OCC)OCC YMXRPHMIOQYZOO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- KHEPTLRYFDPMLD-UHFFFAOYSA-N 3-dimethoxysilyl-N-(3-dimethoxysilylbutyl)-N-methylbutan-1-amine Chemical compound CC(CCN(C)CCC(C)[SiH](OC)OC)[SiH](OC)OC KHEPTLRYFDPMLD-UHFFFAOYSA-N 0.000 claims description 3
- 229920002959 polymer blend Polymers 0.000 claims description 3
- 229920005604 random copolymer Polymers 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims 1
- -1 diethylaminopropyl Chemical group 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 125000005103 alkyl silyl group Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- VDNSZPNSUQRUMS-UHFFFAOYSA-N 1-cyclohexyl-4-ethenylbenzene Chemical compound C1=CC(C=C)=CC=C1C1CCCCC1 VDNSZPNSUQRUMS-UHFFFAOYSA-N 0.000 description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 2
- VVTGQMLRTKFKAM-UHFFFAOYSA-N 1-ethenyl-4-propylbenzene Chemical compound CCCC1=CC=C(C=C)C=C1 VVTGQMLRTKFKAM-UHFFFAOYSA-N 0.000 description 2
- OIEANVCCDIRIDJ-UHFFFAOYSA-N 1-ethenyl-5-hexylnaphthalene Chemical compound C1=CC=C2C(CCCCCC)=CC=CC2=C1C=C OIEANVCCDIRIDJ-UHFFFAOYSA-N 0.000 description 2
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 2
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 2
- FZLHAQMQWDDWFI-UHFFFAOYSA-N 2-[2-(oxolan-2-yl)propan-2-yl]oxolane Chemical compound C1CCOC1C(C)(C)C1CCCO1 FZLHAQMQWDDWFI-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- UGWOAPBVIGCNOV-UHFFFAOYSA-N 5-ethenyldec-5-ene Chemical compound CCCCC=C(C=C)CCCC UGWOAPBVIGCNOV-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- WTXITWGJFPAEIU-UHFFFAOYSA-N n-methyl-3-trimethoxysilyl-n-(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCN(C)CCC[Si](OC)(OC)OC WTXITWGJFPAEIU-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KQSMCAVKSJWMSI-UHFFFAOYSA-N 2,4-dimethyl-1-n,1-n,3-n,3-n-tetrakis(oxiran-2-ylmethyl)benzene-1,3-diamine Chemical compound CC1=C(N(CC2OC2)CC2OC2)C(C)=CC=C1N(CC1OC1)CC1CO1 KQSMCAVKSJWMSI-UHFFFAOYSA-N 0.000 description 1
- NUNQKTCKURIZQX-UHFFFAOYSA-N 2-(2-ethoxyethoxy)-2-methylpropane Chemical compound CCOCCOC(C)(C)C NUNQKTCKURIZQX-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 description 1
- CSBDTEMAXHVRBB-UHFFFAOYSA-N 2-ethoxy-n,n-dimethylethanamine Chemical compound CCOCCN(C)C CSBDTEMAXHVRBB-UHFFFAOYSA-N 0.000 description 1
- UNVFWCQQWZUPLB-UHFFFAOYSA-N 3-[dimethoxy(pentan-3-yloxy)silyl]propan-1-amine Chemical compound CCC(CC)O[Si](OC)(OC)CCCN UNVFWCQQWZUPLB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 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
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- NTYDXFVCCCPXRG-UHFFFAOYSA-N [Li]C(C)(C)CC(C)(C)C Chemical compound [Li]C(C)(C)CC(C)(C)C NTYDXFVCCCPXRG-UHFFFAOYSA-N 0.000 description 1
- FYOQEFGAZKEPGG-UHFFFAOYSA-N [Li]C1=CC=C(C)C=C1 Chemical compound [Li]C1=CC=C(C)C=C1 FYOQEFGAZKEPGG-UHFFFAOYSA-N 0.000 description 1
- SEVZJBPKDJZGFW-UHFFFAOYSA-N [Li]C1=CC=C(CCCC)C=C1 Chemical compound [Li]C1=CC=C(CCCC)C=C1 SEVZJBPKDJZGFW-UHFFFAOYSA-N 0.000 description 1
- XAGXFZXSTCZIQR-UHFFFAOYSA-N [Li]C1CC(CCCCCCC)CC(CCCCCCC)C1 Chemical compound [Li]C1CC(CCCCCCC)CC(CCCCCCC)C1 XAGXFZXSTCZIQR-UHFFFAOYSA-N 0.000 description 1
- LFASRCHQAYIROH-UHFFFAOYSA-N [Li]C1CCCC1 Chemical compound [Li]C1CCCC1 LFASRCHQAYIROH-UHFFFAOYSA-N 0.000 description 1
- SHJXVDAAVHAKFB-UHFFFAOYSA-N [Li]CCCCCCCCCC Chemical compound [Li]CCCCCCCCCC SHJXVDAAVHAKFB-UHFFFAOYSA-N 0.000 description 1
- WZBHJENIKYQMHC-UHFFFAOYSA-N [Li]CCCCCCCCCCCCCCCCCCCC Chemical compound [Li]CCCCCCCCCCCCCCCCCCCC WZBHJENIKYQMHC-UHFFFAOYSA-N 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- LEKSIJZGSFETSJ-UHFFFAOYSA-N cyclohexane;lithium Chemical compound [Li]C1CCCCC1 LEKSIJZGSFETSJ-UHFFFAOYSA-N 0.000 description 1
- BOTLEXFFFSMRLQ-UHFFFAOYSA-N cyclopentyloxycyclopentane Chemical compound C1CCCC1OC1CCCC1 BOTLEXFFFSMRLQ-UHFFFAOYSA-N 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- 238000010551 living anionic polymerization reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 150000003298 rubidium compounds Chemical class 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
- C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Claims (15)
- (a)共役ジエン系単量体、または共役ジエン系単量体とスチレンとのみを、溶媒存在下で有機金属化合物を用いて重合させて、金属末端を有する活性重合体を形成する工程と、
(b)前記活性重合体に、下記化学式1で表される化合物を加えることにより以下の化学式2で表される末端変性共役ジエン系重合体を製造する工程と、からなる、末端変性共役ジエン系重合体の連続製造方法であって、
前記化学式1で表される化合物は、ビス(メチルジメトキシシリルプロピル)−N−メチルアミン、およびビス(ジエトキシメチルシリルプロピル)−N−メチルアミンから選択された1つ以上である製造方法。。
R2はアルキレン基であり、
R3及びR4はアルキル基であり、
aは2、
nは1、
kは1、
mは1であり、
l+k+mは3を満足し、
pは共役ジエン系ポリマー鎖であり、
bは2である。
3−nが2以上の場合、それに該当する基(groups)は互いに同一であってもよく、異なっていてもよい。) - 前記有機金属化合物は、前記単量体総100gを基準として0.01〜10mmol使用される、請求項1に記載の方法。
- 前記有機金属化合物と前記化学式1で表される化合物とのモル比は、1:0.1〜1:10である、請求項1または2に記載の方法。
- 前記(a)の重合は、極性添加剤を添加する工程をさらに含む、請求項1〜3のいずれか一項に記載の方法。
- 前記極性添加剤は、前記有機金属化合物総1mmolを基準として0.001〜50g添加される、請求項4に記載の方法。
- 前記共役ジエン系ポリマー鎖は、共役ジエン系単量体及びスチレンを含んでなるランダム共重合体鎖である、請求項6に記載の末端変性共役ジエン系重合体。
- 前記末端変性共役ジエン系重合体は、数平均分子量が1,000〜2,000,000g/molである、請求項6または7に記載の末端変性共役ジエン系重合体。
- 前記末端変性共役ジエン系重合体は、ビニル含量が18%以上である、請求項6〜8のいずれか一項に記載の末端変性共役ジエン系重合体。
- 前記末端変性共役ジエン系重合体は、前記共役ジエン系単量体と前記スチレンとの合計100重量%を基準として、スチレンを10〜50重量%含む、請求項6〜8のいずれか一項に記載の末端変性共役ジエン系重合体。
- 前記末端変性共役ジエン系重合体は、分子量分布(PDI)が1〜4である、請求項6〜10のいずれか一項に記載の末端変性共役ジエン系重合体。
- 請求項6乃至11のいずれか1項に記載の末端変性共役ジエン系重合体100重量部に対して無機充填剤0.1〜200重量部を含む、末端変性共役ジエン系重合体ゴム組成物。
- 前記末端変性共役ジエン系重合体10〜100重量%と、これと異なる共役ジエン系重合体0〜90重量%を含む重合体混合物100重量部、
カーボンブラック0〜100重量部、
シリカ5〜200重量部及び
シランカップリング剤2〜20重量部を含んでなる、請求項12に記載の末端変性共役ジエン系重合体ゴム組成物。 - 前記無機充填剤はシリカ系充填剤である、請求項12または13に記載の末端変性共役ジエン系重合体ゴム組成物。
- 請求項12〜14のいずれか一項に記載の末端変性共役ジエン系重合体ゴム組成物を含んでなるタイヤ。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20130045823 | 2013-04-25 | ||
KR10-2013-0045823 | 2013-04-25 | ||
KR1020130089221A KR101594217B1 (ko) | 2013-04-25 | 2013-07-29 | 변성 공액 디엔계 중합체의 연속 제조방법, 이로부터 수득된 중합체 및 이를 포함하는 고무 조성물 |
KR10-2013-0089221 | 2013-07-29 | ||
PCT/KR2014/002624 WO2014175562A1 (ko) | 2013-04-25 | 2014-03-27 | 변성 공액 디엔계 중합체의 연속 제조방법, 이로부터 수득된 중합체 및 이를 포함하는 고무 조성물 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2015520789A JP2015520789A (ja) | 2015-07-23 |
JP6279554B2 true JP6279554B2 (ja) | 2018-02-14 |
Family
ID=52451889
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2015513961A Active JP6279554B2 (ja) | 2013-04-25 | 2014-03-27 | 変性共役ジエン系重合体の連続製造方法、それから収得された重合体及びそれを含むゴム組成物 |
Country Status (3)
Country | Link |
---|---|
US (1) | US10253158B2 (ja) |
JP (1) | JP6279554B2 (ja) |
KR (1) | KR101594217B1 (ja) |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101745788B1 (ko) * | 2015-01-05 | 2017-06-09 | 주식회사 엘지화학 | 변성 공역디엔계 중합체, 이를 포함하는 변성 고무 조성물 및 변성 공역디엔계 중합체의 제조방법 |
EP3301120B1 (en) | 2015-12-18 | 2020-02-05 | LG Chem, Ltd. | Method for preparing modified conjugated diene-based polymer |
KR101880370B1 (ko) | 2015-12-24 | 2018-07-19 | 주식회사 엘지화학 | 고분자 화합물, 이를 이용한 변성 공액디엔계 중합체의 제조방법 및 변성 공액디엔계 중합체 |
WO2017111557A1 (ko) * | 2015-12-24 | 2017-06-29 | 주식회사 엘지화학 | 실릴기 함유 신규 화합물, 변성 공액디엔계 중합체 및 이의 제조방법 |
KR101874718B1 (ko) | 2015-12-24 | 2018-08-02 | 주식회사 엘지화학 | 실릴기 함유 신규 화합물, 변성 공액디엔계 중합체 및 이의 제조방법 |
KR102071590B1 (ko) * | 2016-05-03 | 2020-01-30 | 주식회사 엘지화학 | 신규 아미노실란계 화합물 및 이의 제조방법 |
JP6769780B2 (ja) * | 2016-08-19 | 2020-10-14 | 旭化成株式会社 | 変性共役ジエン系重合体及びそのゴム組成物、並びにタイヤ |
KR102036026B1 (ko) * | 2016-11-14 | 2019-10-24 | 주식회사 엘지화학 | 변성 단량체, 이를 포함하는 변성 공액디엔계 중합체 및 이의 제조방법 |
KR102039128B1 (ko) | 2016-11-21 | 2019-10-31 | 주식회사 엘지화학 | 변성제, 이의 제조방법 및 이를 포함하는 변성 공액디엔계 중합체 |
KR102072088B1 (ko) | 2016-11-28 | 2020-02-03 | 주식회사 엘지화학 | 변성 공액디엔계 중합체 및 이의 제조방법 |
KR101857392B1 (ko) * | 2017-01-03 | 2018-06-19 | 주식회사 엘지화학 | 변성 공액디엔계 중합체 제조방법 |
KR20190038344A (ko) * | 2017-09-29 | 2019-04-08 | 주식회사 엘지화학 | 고무 조성물 |
KR102167122B1 (ko) | 2017-12-05 | 2020-10-16 | 주식회사 엘지화학 | 변성 공액디엔계 중합체 및 이를 포함하는 고무 조성물 |
WO2019112261A1 (ko) * | 2017-12-05 | 2019-06-13 | 주식회사 엘지화학 | 변성 공액디엔계 중합체 및 이를 포함하는 고무 조성물 |
WO2019112263A1 (ko) * | 2017-12-05 | 2019-06-13 | 주식회사 엘지화학 | 변성 공액디엔계 중합체 및 이를 포함하는 고무 조성물 |
KR102323810B1 (ko) | 2017-12-05 | 2021-11-10 | 주식회사 엘지화학 | 변성 공액디엔계 중합체 및 이를 포함하는 고무 조성물 |
KR102122471B1 (ko) | 2017-12-05 | 2020-06-26 | 주식회사 엘지화학 | 변성 공액디엔계 중합체 및 이를 포함하는 고무 조성물 |
KR102179487B1 (ko) | 2017-12-05 | 2020-11-16 | 주식회사 엘지화학 | 변성 공액디엔계 중합체 및 이를 포함하는 고무 조성물 |
WO2019122750A1 (fr) * | 2017-12-22 | 2019-06-27 | Compagnie Generale Des Etablissements Michelin | Composé comprenant au moins deux groupements trialcoxysilyles, son utilisation à titre d'agent de fonctionnalisation d'élastomère diénique, élastomère diénique modifié et composition le contenant |
WO2019225824A1 (ko) * | 2018-05-25 | 2019-11-28 | 주식회사 엘지화학 | 변성 공액디엔계 중합체 및 이를 포함하는 고무 조성물 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4655706B2 (ja) * | 2005-03-17 | 2011-03-23 | 住友化学株式会社 | 変性ジエン系重合体ゴム及びその製造方法 |
JP2006257261A (ja) * | 2005-03-17 | 2006-09-28 | Sumitomo Chemical Co Ltd | 変性ジエン系重合体ゴムの製造方法 |
WO2007114203A1 (ja) | 2006-03-31 | 2007-10-11 | Zeon Corporation | 共役ジエン系ゴム、その製造方法、タイヤ用ゴム組成物、及びタイヤ |
JP2008285558A (ja) | 2007-05-16 | 2008-11-27 | Asahi Kasei Chemicals Corp | 油展共役ジエン系重合体組成物 |
JP5473360B2 (ja) | 2008-03-10 | 2014-04-16 | 株式会社ブリヂストン | ゴム組成物及びそれを用いたタイヤ |
JP5547058B2 (ja) * | 2008-03-10 | 2014-07-09 | 株式会社ブリヂストン | 変性共役ジエン(共)重合体の製造方法、変性共役ジエン(共)重合体、並びにそれを用いたゴム組成物及びタイヤ |
CN101724185B (zh) * | 2008-10-16 | 2013-10-23 | 住友橡胶工业株式会社 | 橡胶组合物及轮胎 |
CN101724127A (zh) * | 2008-10-16 | 2010-06-09 | 住友橡胶工业株式会社 | 聚合物、橡胶组合物及使用该橡胶组合物的轮胎 |
JP4881362B2 (ja) | 2008-11-05 | 2012-02-22 | 住友ゴム工業株式会社 | ゴム組成物及びタイヤ |
KR101413791B1 (ko) * | 2009-10-02 | 2014-06-30 | 아사히 가세이 케미칼즈 가부시키가이샤 | 변성 공액 디엔계 중합체의 제조 방법, 변성 공액 디엔계 중합체 및 변성 공액 디엔계 중합체 조성물 |
JP5563281B2 (ja) | 2009-12-01 | 2014-07-30 | 住友ゴム工業株式会社 | サイドウォール用ゴム組成物及び空気入りタイヤ |
JP2011132298A (ja) | 2009-12-22 | 2011-07-07 | Sumitomo Rubber Ind Ltd | 変性共重合体、それを用いたゴム組成物および空気入りタイヤ |
JP2011195802A (ja) | 2010-02-25 | 2011-10-06 | Sumitomo Chemical Co Ltd | 共役ジエン系重合体、共役ジエン系重合体組成物及び共役ジエン系重合体の製造方法 |
KR101791281B1 (ko) * | 2010-03-31 | 2017-10-27 | 제이에스알 가부시끼가이샤 | 변성 공액 디엔계 고무의 제조 방법, 변성 공액 디엔계 고무, 및 고무 조성물 |
JP2013043954A (ja) | 2011-08-25 | 2013-03-04 | Sumitomo Rubber Ind Ltd | ゴム組成物及び空気入りタイヤ |
JP6032880B2 (ja) * | 2011-10-12 | 2016-11-30 | 旭化成株式会社 | 変性共役ジエン系重合体組成物、トレッド用組成物、サイドウォール用組成物及びタイヤ |
JP5896323B2 (ja) * | 2013-08-01 | 2016-03-30 | エルジー・ケム・リミテッド | 変性共役ジエン系重合体及びその製造方法 |
-
2013
- 2013-07-29 KR KR1020130089221A patent/KR101594217B1/ko active IP Right Grant
-
2014
- 2014-03-27 US US14/391,303 patent/US10253158B2/en active Active
- 2014-03-27 JP JP2015513961A patent/JP6279554B2/ja active Active
Also Published As
Publication number | Publication date |
---|---|
KR20140127716A (ko) | 2014-11-04 |
US10253158B2 (en) | 2019-04-09 |
US20160053059A1 (en) | 2016-02-25 |
JP2015520789A (ja) | 2015-07-23 |
KR101594217B1 (ko) | 2016-02-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6279554B2 (ja) | 変性共役ジエン系重合体の連続製造方法、それから収得された重合体及びそれを含むゴム組成物 | |
JP6058013B2 (ja) | 変性共役ジエン重合体及びその製造方法 | |
JP6218258B2 (ja) | 変性共役ジエン系重合体、その製造方法、およびこれを含むゴム組成物 | |
JP6218259B2 (ja) | 変性共役ジエン系重合体、その製造方法、およびこれを含むゴム組成物 | |
JP6476179B2 (ja) | 変性共役ジエン系重合体、その製造方法、およびこれを含むゴム組成物 | |
JP5896323B2 (ja) | 変性共役ジエン系重合体及びその製造方法 | |
JP6552514B2 (ja) | 変性共役ジエン系重合体、これを含む変性ゴム組成物および変性共役ジエン系重合体の製造方法 | |
JP6300245B2 (ja) | 末端官能性共役ジエン系重合体およびその製造方法 | |
KR101668567B1 (ko) | 변성 공역디엔계 중합체, 이의 제조방법, 및 이를 포함하는 고무 조성물 | |
JP6273044B2 (ja) | アミン基を含む陰イオン末端を有する陰イオン重合開始剤、これを用いた変性共役ジエン系共重合体の製造方法、およびこれにより製造した変性共役ジエン系共重合体を含むゴム組成物 | |
JP6312173B2 (ja) | 末端機能性共役ジエン系重合体及びこの製造方法 | |
KR101674305B1 (ko) | 말단 기능성 공액 디엔계 중합체 및 이의 제조 방법 | |
JP5896324B2 (ja) | 変性共役ジエン系重合体、その製造方法及び該変性共役ジエン系重合体を含むゴム組成物 | |
JP6456517B2 (ja) | 官能基が導入されたアミノシラン系末端変性剤を利用するゴム組成物の製造方法、及びこれによって製造したゴム組成物 | |
JP6342009B2 (ja) | 変性共役ジエン系重合体、これを含む変性ゴム組成物および変性共役ジエン系重合体の製造方法 | |
KR20160076161A (ko) | 관능기가 도입된 아미노실란계 말단변성제를 이용하는 고무 조성물의 제조방법 및 이에 따라 제조한 고무 조성물 | |
KR20140098716A (ko) | 변성 공액 디엔계 중합체 및 이의 제조방법 | |
KR20170061895A (ko) | 변성 공액 디엔계 중합체의 제조 방법 및 이로부터 제조된 변성 공액 디엔계 중합체 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20151109 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20151117 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160216 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20160317 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160719 |
|
A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20160726 |
|
A912 | Re-examination (zenchi) completed and case transferred to appeal board |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20160902 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170831 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20180117 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6279554 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 |