JP2020152763A - Polymer particle, rubber modifier, rubber composition and molding thereof - Google Patents
Polymer particle, rubber modifier, rubber composition and molding thereof Download PDFInfo
- Publication number
- JP2020152763A JP2020152763A JP2019050190A JP2019050190A JP2020152763A JP 2020152763 A JP2020152763 A JP 2020152763A JP 2019050190 A JP2019050190 A JP 2019050190A JP 2019050190 A JP2019050190 A JP 2019050190A JP 2020152763 A JP2020152763 A JP 2020152763A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- rubber
- parts
- polymer particles
- less
- 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.)
- Pending
Links
- 239000002245 particle Substances 0.000 title claims abstract description 130
- 229920000642 polymer Polymers 0.000 title claims abstract description 106
- 229920001971 elastomer Polymers 0.000 title claims abstract description 90
- 239000005060 rubber Substances 0.000 title claims abstract description 90
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 239000003607 modifier Substances 0.000 title claims abstract description 12
- 238000000465 moulding Methods 0.000 title abstract description 3
- 239000000178 monomer Substances 0.000 claims abstract description 69
- 150000001993 dienes Chemical class 0.000 claims abstract description 40
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 51
- 239000000843 powder Substances 0.000 claims description 30
- 229920003244 diene elastomer Polymers 0.000 claims description 27
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 10
- 239000005062 Polybutadiene Substances 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- 229920002857 polybutadiene Polymers 0.000 claims description 9
- 244000043261 Hevea brasiliensis Species 0.000 claims description 5
- 229920003049 isoprene rubber Polymers 0.000 claims description 5
- 229920003052 natural elastomer Polymers 0.000 claims description 5
- 229920001194 natural rubber Polymers 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 9
- 238000004073 vulcanization Methods 0.000 description 24
- -1 vinyl aromatic compound Chemical class 0.000 description 21
- 239000003795 chemical substances by application Substances 0.000 description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000002156 mixing Methods 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000004132 cross linking Methods 0.000 description 13
- 239000004816 latex Substances 0.000 description 12
- 229920000126 latex Polymers 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000011164 primary particle Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 150000004665 fatty acids Chemical class 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 6
- 239000010734 process oil Substances 0.000 description 6
- 239000012779 reinforcing material Substances 0.000 description 6
- 239000003760 tallow Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000012936 vulcanization activator Substances 0.000 description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- 235000015278 beef Nutrition 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 239000011790 ferrous sulphate Substances 0.000 description 5
- 235000003891 ferrous sulphate Nutrition 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 5
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 3
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 3
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-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
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- YKFLAYDHMOASIY-UHFFFAOYSA-N γ-terpinene Chemical compound CC(C)C1=CCC(C)=CC1 YKFLAYDHMOASIY-UHFFFAOYSA-N 0.000 description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-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
- HIACAHMKXQESOV-UHFFFAOYSA-N 1,2-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC=C1C(C)=C HIACAHMKXQESOV-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
- IZAAQLHXFIKGLS-UHFFFAOYSA-N 1,5-dichloro-2-ethenyl-3-methylbenzene Chemical compound CC1=CC(Cl)=CC(Cl)=C1C=C IZAAQLHXFIKGLS-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- UJPKMTDFFUTLGM-UHFFFAOYSA-N 1-aminoethanol Chemical compound CC(N)O UJPKMTDFFUTLGM-UHFFFAOYSA-N 0.000 description 1
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-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
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-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
- XHUZSRRCICJJCN-UHFFFAOYSA-N 1-ethenyl-3-ethylbenzene Chemical compound CCC1=CC=CC(C=C)=C1 XHUZSRRCICJJCN-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
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- XSQHUYDRSDBCHN-UHFFFAOYSA-N 2,3-dimethyl-2-propan-2-ylbutanenitrile Chemical compound CC(C)C(C)(C#N)C(C)C XSQHUYDRSDBCHN-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- NTHFKMZKTASAMH-UHFFFAOYSA-N 2,4-dibromo-1-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C(Br)=C1 NTHFKMZKTASAMH-UHFFFAOYSA-N 0.000 description 1
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- YAQDPWONDFRAHF-UHFFFAOYSA-N 2-methyl-2-(2-methylpentan-2-ylperoxy)pentane Chemical compound CCCC(C)(C)OOC(C)(C)CCC YAQDPWONDFRAHF-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-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
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 101150096839 Fcmr gene Proteins 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- WMVSVUVZSYRWIY-UHFFFAOYSA-N [(4-benzoyloxyiminocyclohexa-2,5-dien-1-ylidene)amino] benzoate Chemical compound C=1C=CC=CC=1C(=O)ON=C(C=C1)C=CC1=NOC(=O)C1=CC=CC=C1 WMVSVUVZSYRWIY-UHFFFAOYSA-N 0.000 description 1
- ZXZSYHLGFSXNNU-UHFFFAOYSA-N [[methyl(4-trimethoxysilylbutyl)carbamothioyl]trisulfanyl] N-methyl-N-(4-trimethoxysilylbutyl)carbamodithioate Chemical compound CO[Si](CCCCN(C(=S)SSSSC(N(C)CCCC[Si](OC)(OC)OC)=S)C)(OC)OC ZXZSYHLGFSXNNU-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- SWXJERQXXBPMHI-UHFFFAOYSA-N carbamothioyl n-methylcarbamodithioate Chemical compound CNC(=S)SC(N)=S SWXJERQXXBPMHI-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 229940100539 dibutyl adipate Drugs 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 1
- 229930004069 diterpene Natural products 0.000 description 1
- 125000000567 diterpene group Chemical group 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- FFYWKOUKJFCBAM-UHFFFAOYSA-N ethenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC=C FFYWKOUKJFCBAM-UHFFFAOYSA-N 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- QJQZEJFUIOWFMS-UHFFFAOYSA-N formaldehyde;sulfanediol Chemical compound O=C.OSO QJQZEJFUIOWFMS-UHFFFAOYSA-N 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229960004198 guanidine Drugs 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- QUPCNWFFTANZPX-UHFFFAOYSA-M paramenthane hydroperoxide Chemical compound [O-]O.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-M 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- IRZFQKXEKAODTJ-UHFFFAOYSA-M sodium;propan-2-yloxymethanedithioate Chemical compound [Na+].CC(C)OC([S-])=S IRZFQKXEKAODTJ-UHFFFAOYSA-M 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 229940052367 sulfur,colloidal Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 1
- PGNWIWKMXVDXHP-UHFFFAOYSA-L zinc;1,3-benzothiazole-2-thiolate Chemical compound [Zn+2].C1=CC=C2SC([S-])=NC2=C1.C1=CC=C2SC([S-])=NC2=C1 PGNWIWKMXVDXHP-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、重合体粒子、それを用いたゴム用改質剤、ゴム組成物及びその成形体に関する。 The present invention relates to polymer particles, a rubber modifier using the polymer particles, a rubber composition, and a molded product thereof.
環境負荷の低減や安全性の向上を目的に自動車分野の技術開発が進んでおり、タイヤに関しても、低燃費を達成するために転がり抵抗の低減や、耐摩耗性の向上が望まれている。 Technological development in the automobile field is progressing for the purpose of reducing environmental load and improving safety, and it is desired to reduce rolling resistance and improve wear resistance of tires in order to achieve low fuel consumption.
タイヤのトレッドを構成するゴム材料としては、現在、合成ゴムであるスチレン・ブタジエンゴム（ＳＢＲ）に補強材としてカーボンブラックを配合したゴム組成物が主流である。これに対し、低燃費性を有するエコタイヤにおいては、カーボンブラックに代わる補強材としてシリカを配合したゴム組成物が使用されている。しかし、シリカは親水性無機材料であるために、ゴム材料との親和性が低く、ゴム中での分散性が低いという問題がある。シリカの分散性を向上させるために、シリカをシランカップリング剤と併用することが行なわれている。 As the rubber material constituting the tread of a tire, a rubber composition in which carbon black is blended as a reinforcing material with styrene-butadiene rubber (SBR), which is a synthetic rubber, is currently the mainstream. On the other hand, in eco-tires having low fuel consumption, a rubber composition containing silica is used as a reinforcing material in place of carbon black. However, since silica is a hydrophilic inorganic material, it has a problem that it has a low affinity with a rubber material and has a low dispersibility in rubber. In order to improve the dispersibility of silica, silica is used in combination with a silane coupling agent.
一方で、架橋型ポリマーに対する補強材として有機系の材料を用いる試みも行なわれている。特許文献１では、機械的特性を損なわずに、耐摩耗性および低発熱性に優れるゴム組成物を提供することを目的に、共役ジエン単量体単位８３〜９８．９重量％、芳香族ビニル単量体単位１６．９〜１重量％、および架橋性単量体単位０．１〜１．５重量％からなる共役ジエン系ゴムゲルと、硫黄で架橋し得るゴムとを含有するゴム組成物が開示されている。 On the other hand, attempts have been made to use an organic material as a reinforcing material for the crosslinked polymer. In Patent Document 1, for the purpose of providing a rubber composition having excellent wear resistance and low heat generation without impairing mechanical properties, a conjugated diene monomer unit of 83 to 98.9% by weight and an aromatic vinyl are used. A rubber composition containing a conjugated diene rubber gel composed of 16.9 to 1% by weight of a monomer unit and 0.1 to 1.5% by weight of a crosslinkable monomer unit and a rubber that can be crosslinked with sulfur. It is disclosed.
また、特許文献２では、共役ジエン単位３９．８９〜７９．８９重量％、芳香族ビニル単位２０〜６０重量％、２個以上の重合性不飽和性基を有する単量体単位０．０１〜１０重量％、及び重合性不飽和基とアミノ基とを有する単量体単位０．１〜３０重量％を含む架橋ゴム粒子、並びに、共役ジエン／芳香族ビニル共重合ゴムを含有するゴム組成物が開示されている。この構成により、補強材としてシリカを用いた場合であっても、混練時の加工性に優れ、シートの平滑性が良好なゴム組成物が得られると記載されており、実施例では、架橋ゴム粒子の製造において１〜２重量％のジビニルベンゼンが使用されている（表１）。特許文献３でも同様の発明が記載されている。 Further, in Patent Document 2, the conjugated diene unit is 39.89 to 79.89% by weight, the aromatic vinyl unit is 20 to 60% by weight, and the monomer unit having two or more polymerizable unsaturated groups is 0.01 to. A rubber composition containing 10% by weight, crosslinked rubber particles containing 0.1 to 30% by weight of a monomer unit having a polymerizable unsaturated group and an amino group, and a conjugated diene / aromatic vinyl copolymerized rubber. Is disclosed. It is described that this configuration provides a rubber composition having excellent workability during kneading and good sheet smoothness even when silica is used as a reinforcing material. In the examples, the crosslinked rubber is described. 1-2% by weight of divinylbenzene is used in the production of particles (Table 1). A similar invention is described in Patent Document 3.
本発明は、以上に鑑み、ゴム材料と混合したときに転がり抵抗の低減と耐摩耗性の向上を達成すると共に、分散性にも優れている重合体粒子、ゴム用改質剤、ゴム組成物及びその成形体を提供することを目的とする。 In view of the above, the present invention achieves reduction of rolling resistance and improvement of wear resistance when mixed with a rubber material, and is also excellent in dispersibility of polymer particles, a modifier for rubber, and a rubber composition. And the molded product thereof.
本発明者らは、ジエン系ゴム材料に配合する重合体粒子が特定の単量体単位から構成されるようにすることで、ジエン系ゴム材料の架橋反応に関与できる架橋点を重合体粒子に導入して、重合体粒子がゴム材料と共有結合を介して一体化できるようにすることで転がり抵抗を低減させると同時に、重合体粒子自体の架橋度を向上させることで、耐摩耗性を向上させ、かつ、粒子同士の凝集を制御し分散性も向上させ得ることを見出し、本発明を完成した。 By making the polymer particles to be blended in the diene-based rubber material composed of specific monomer units, the present inventors make the cross-linking points that can participate in the cross-linking reaction of the diene-based rubber material into the polymer particles. Introduced to reduce rolling resistance by allowing the polymer particles to integrate with the rubber material via covalent bonds, while improving wear resistance by improving the degree of cross-linking of the polymer particles themselves. The present invention has been completed by finding that it is possible to control the aggregation of particles and improve the dispersibility.
すなわち、本発明は、共役ジエン単量体単位２０重量％以上９５重量％以下、ラジカル重合性反応基を２以上有する単量体（ただし、前記共役ジエン単量体は除く）単位５重量％以上４０重量％以下、及び、芳香族モノアルケニル単量体単位０重量％以上７０重量％以下から構成される重合体粒子に関する。 That is, in the present invention, the conjugated diene monomer unit is 20% by weight or more and 95% by weight or less, and the monomer having 2 or more radically polymerizable reactive groups (however, excluding the conjugated diene monomer) is 5% by weight or more. The present invention relates to polymer particles composed of 40% by weight or less and 0% by weight or more and 70% by weight or less of an aromatic monoalkenyl monomer unit.
好ましくは、単層から構成される。好ましくは、最表面に二重結合を有する。好ましくは、前記重合体粒子の体積平均粒子径が１０ｎｍ以上５００ｎｍ以下である。好ましくは、前記重合体粒子が凝集して粉体の形態を有する。好ましくは、前記粉体の体積平均粒子径が１０μｍ以上１０００μｍ以下である。 It is preferably composed of a single layer. Preferably, it has a double bond on the outermost surface. Preferably, the volume average particle diameter of the polymer particles is 10 nm or more and 500 nm or less. Preferably, the polymer particles aggregate to have a powder form. Preferably, the volume average particle size of the powder is 10 μm or more and 1000 μm or less.
また本発明は、前記重合体粒子からなるゴム用改質剤にも関する。さらに本発明は、ジエン系ゴムと、前記ゴム用改質剤を含む、ゴム組成物、又は、該ゴム組成物から成形された成形体にも関する。好ましくは、前記ジエン系ゴムは、天然ゴム、イソプレンゴム、ブタジエンゴム、及びスチレン−ブタジエン共重合ゴムより選択される少なくとも１種である。好ましくは、前記ゴム組成物は、さらに、シリカ、及び、シランカップリング剤を含む。好ましくは、前記ゴム組成物は、さらに、カーボンブラックを含む。 The present invention also relates to a rubber modifier composed of the polymer particles. Furthermore, the present invention also relates to a rubber composition containing a diene-based rubber and the modifier for rubber, or a molded product molded from the rubber composition. Preferably, the diene-based rubber is at least one selected from natural rubber, isoprene rubber, butadiene rubber, and styrene-butadiene copolymer rubber. Preferably, the rubber composition further comprises silica and a silane coupling agent. Preferably, the rubber composition further comprises carbon black.
本発明によれば、ゴム材料と混合したときに転がり抵抗の低減と耐摩耗性の向上を達成すると共に、分散性にも優れている重合体粒子、ゴム用改質剤、ゴム組成物及びその成形体を提供することができる。 According to the present invention, a polymer particle, a rubber modifier, a rubber composition, and a rubber composition thereof, which achieve a reduction in rolling resistance and an improvement in wear resistance when mixed with a rubber material and are also excellent in dispersibility. A molded body can be provided.
以下、本発明の実施形態を詳細に説明するが、本発明はこれらの実施形態に限定されない。 Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these embodiments.
本発明の重合体粒子は、共役ジエン単量体単位２０重量％以上９５重量％以下、ラジカル重合性反応基を２以上有する単量体（ただし、前記共役ジエン単量体は除く）単位５重量％以上４０重量％以下、及び、任意成分である芳香族モノアルケニル単量体単位０重量％以上７０重量％以下からなるものであり、これらの単量体を共重合した共重合体から構成される。 The polymer particles of the present invention have a conjugated diene monomer unit of 20% by weight or more and 95% by weight or less, and a monomer having 2 or more radically polymerizable reactive groups (however, excluding the conjugated diene monomer) by 5% by weight. It is composed of% or more and 40% by weight or less, and an aromatic monoalkenyl monomer unit which is an optional component, 0% by weight or more and 70% by weight or less, and is composed of a copolymer obtained by copolymerizing these monomers. To.
共役ジエン単量体単位とは、共役ジエン単量体を重合して得られる単量体単位のことをいい、架橋点となる二重結合を含む単量体単位である。共役ジエン単量体は、炭素−炭素二重結合を２つ有し、それら二重結合が１つの単結合によって隔てられ、共役したジエンを指す。共役ジエン単量体の具体例としては、イソプレン、１，３−ブタジエン、２−メチル−１，３−ブタジエン、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエン等が挙げられる。共役ジエン単量体は１種類のみを使用してもよいし、２種以上を併用してもよい。このうち、１，３−ブタジエンが好ましい。重合体粒子が共役ジエン単量体単位を含むことで、重合体粒子が、後述するジエン系ゴムの架橋反応に関与できる架橋点を有することになる。これにより、ジエン系ゴムを架橋反応させた時に、ジエン系ゴムと重合体粒子が共有結合により一体化することで、ゴム組成物中の架橋度を向上させ、ジエン系ゴムの反発弾性が改良され、転がり抵抗を低減することが可能になる。また、重合体粒子が共役ジエン単量体単位を含むことで、ジエン系ゴムと構成単位が類似し、重合体粒子とジエン系ゴムとの親和性（相溶性）を高めることができ、ジエン系ゴム内での重合体粒子の分散性が向上する利点もある。 The conjugated diene monomer unit refers to a monomer unit obtained by polymerizing a conjugated diene monomer, and is a monomer unit containing a double bond serving as a cross-linking point. A conjugated diene monomer refers to a conjugated diene having two carbon-carbon double bonds, the double bonds separated by one single bond. Specific examples of the conjugated diene monomer include isoprene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and the like. .. Only one type of conjugated diene monomer may be used, or two or more types may be used in combination. Of these, 1,3-butadiene is preferable. When the polymer particles contain the conjugated diene monomer unit, the polymer particles have a cross-linking point that can participate in the cross-linking reaction of the diene-based rubber described later. As a result, when the diene-based rubber is crosslinked, the diene-based rubber and the polymer particles are integrated by a covalent bond to improve the degree of cross-linking in the rubber composition and improve the repulsive elasticity of the diene-based rubber. , It becomes possible to reduce the rolling resistance. Further, since the polymer particles contain a conjugated diene monomer unit, the constituent unit is similar to that of the diene rubber, and the affinity (compatibility) between the polymer particles and the diene rubber can be enhanced, and the diene rubber can be enhanced. There is also an advantage that the dispersibility of the polymer particles in the rubber is improved.
共役ジエン単量体を用いた場合、一般的にラジカル重合は１，４−付加を経て、重合反応が進行する。そのため、生成する重合体粒子に二重結合が残存し、それにより、重合体粒子の最表面には二重結合を有することができる。この二重結合により、共役ジエン系ゴムと加硫反応によって共有結合を形成することができ、転がり抵抗の効果を向上させることができる。 When a conjugated diene monomer is used, the radical polymerization generally proceeds through 1,4-addition and the polymerization reaction. Therefore, a double bond remains in the produced polymer particles, so that the outermost surface of the polymer particles can have a double bond. With this double bond, a covalent bond can be formed by a vulcanization reaction with the conjugated diene rubber, and the effect of rolling resistance can be improved.
本発明の重合体粒子における共役ジエン単量体単位の含有量は、重合体粒子を構成する重合体の単量体単位の総量１００重量％に対して、２０重量％以上９５重量％以下である。２０重量％以上であると、転がり抵抗の低減効果を充分に達成することができ、９５重量％以下であると、後述する多官能性単量体単位を用いる利点が得られやすくなる。共役ジエン単量体単位の含有量の上限値は、９４重量％以下が好ましく、９３重量％以下がより好ましく、９２重量％以下がさらに好ましく、９１重量％以下がよりさらに好ましく、９０重量％以下が特に好ましく、８９重量％以下が最も好ましい。共役ジエン単量体単位の含有量の下限値は、２５重量％以上が好ましく、３０重量％以上がより好ましく、３５重量％以上がさらに好ましく、４０重量％以上がよりさらに好ましく、４５重量％以上が特に好ましい。 The content of the conjugated diene monomer unit in the polymer particles of the present invention is 20% by weight or more and 95% by weight or less with respect to 100% by weight of the total amount of the monomer units of the polymer constituting the polymer particles. .. When it is 20% by weight or more, the effect of reducing rolling resistance can be sufficiently achieved, and when it is 95% by weight or less, the advantage of using the polyfunctional monomer unit described later can be easily obtained. The upper limit of the content of the conjugated diene monomer unit is preferably 94% by weight or less, more preferably 93% by weight or less, further preferably 92% by weight or less, further preferably 91% by weight or less, and 90% by weight or less. Is particularly preferable, and 89% by weight or less is most preferable. The lower limit of the content of the conjugated diene monomer unit is preferably 25% by weight or more, more preferably 30% by weight or more, further preferably 35% by weight or more, further preferably 40% by weight or more, and 45% by weight or more. Is particularly preferable.
本発明の重合体粒子は、ラジカル重合性反応基を２以上有する単量体（本願では多官能性単量体ともいう）単位を含む。ただし、本願における多官能性単量体とは、上述した共役ジエン単量体以外のものを指す。多官能性単量体は重合反応に関与する反応基を２以上有するので、これを共役ジエン単量体と共重合することで、本発明の重合体粒子中のポリマー鎖同士を架橋させることができる。これにより重合体粒子の架橋度を向上させることで、ジエン系ゴムに配合したときの耐摩耗性を向上させることができる。さらには、架橋度の向上に伴い、重合体粒子の硬度も向上するため、重合体粒子の凝集を制御しやすくなり、重合体を粉体として取得することも容易になる。ラジカル重合性反応基とは、好ましくは、炭素−炭素二重結合である。 The polymer particles of the present invention contain a monomer (also referred to as a polyfunctional monomer in the present application) unit having two or more radically polymerizable reactive groups. However, the polyfunctional monomer in the present application refers to a monomer other than the above-mentioned conjugated diene monomer. Since the polyfunctional monomer has two or more reactive groups involved in the polymerization reaction, it is possible to crosslink the polymer chains in the polymer particles of the present invention by copolymerizing this with the conjugated diene monomer. it can. As a result, by improving the degree of cross-linking of the polymer particles, it is possible to improve the abrasion resistance when blended with the diene rubber. Furthermore, as the degree of cross-linking is improved, the hardness of the polymer particles is also improved, so that it becomes easier to control the aggregation of the polymer particles, and it becomes easier to obtain the polymer as a powder. The radically polymerizable reactive group is preferably a carbon-carbon double bond.
このようなラジカル重合性反応基を２以上有する単量体としては特に限定されないが、例えば、ジイソプロペニルベンゼン、ジビニルベンゼン等の多価ビニル芳香族化合物；アクリル酸ビニル、メタクリル酸ビニル、メタクリル酸アリル等のα,β−エチレン性不飽和カルボン酸の不飽和エステル化合物；フタル酸ジアリル、トリメリット酸トリアリル等の多価カルボン酸の不飽和エステル化合物；エチレングリコールジアクリレート、エチレングリコールジメタクリレート、プロピレングリコールジメタクリレート等の多価アルコールの不飽和エステル化合物；シアヌル酸トリアリル等のシアヌル酸の不飽和エステル化合物；イソシアヌル酸トリアリル等のイソシアヌル酸の不飽和エステル化合物；１，２−ブタジエン、ジビニルエーテル、ジビニルスルフォン、Ｎ，Ｎ´−ｍ−フェニレンマレイミド等が挙げられる。このような多官能性単量体は１種類のみを使用してもよいし、２種以上を併用してもよい。このうち、ラジカル重合における反応性の観点から、多価ビニル芳香族化合物、多価アルコールの不飽和エステル化合物、シアヌル酸の不飽和エステル化合物、及びイソシアヌル酸の不飽和エステル化合物が好ましく、共役ジエン単量体との共重合性の観点から、ジビニルベンゼン及びイソシアヌル酸トリアリルがより好ましい。 The monomer having two or more such radically polymerizable reactive groups is not particularly limited, but for example, a polyvalent vinyl aromatic compound such as diisopropenylbenzene or divinylbenzene; vinyl acrylate, vinyl methacrylate, methacrylic acid, etc. Unsaturated ester compounds of α, β-ethylenic unsaturated carboxylic acids such as allyl; unsaturated ester compounds of polyvalent carboxylic acids such as diallyl phthalate and triallyl trimellitic acid; ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene Unsaturated ester compounds of polyvalent alcohols such as glycol dimethacrylate; Unsaturated ester compounds of cyanulic acid such as triallyl cyanurate; Unsaturated ester compounds of isocyanuric acid such as triaryl isocyanurate; 1,2-butadiene, divinyl ether, divinyl Examples thereof include sulfone, N, N'-m-phenylene maleimide and the like. Only one kind of such a polyfunctional monomer may be used, or two or more kinds may be used in combination. Of these, from the viewpoint of reactivity in radical polymerization, polyvalent vinyl aromatic compounds, unsaturated ester compounds of polyhydric alcohols, unsaturated ester compounds of cyanuric acid, and unsaturated ester compounds of isocyanuric acid are preferable, and conjugated diene mono is preferable. From the viewpoint of copolymerizability with the compound, divinylbenzene and triaryl isocyanurate are more preferable.
本発明の重合体粒子における多官能性単量体単位の含有量は、重合体粒子を構成する重合体の単量体単位の総量１００重量％に対して、５重量％以上４０重量％以下である。５重量％以上では、重合体粒子における架橋度が高くなるため、耐摩耗性の向上効果を得ることができ、また、重合体粒子が比較的硬質になるため、重合体粒子間の凝集が起こりにくく、粉体として容易に取得できる。一方、４０重量％以下では、加工性に優れ、重合体粒子の製造において不都合が生じにくい。多官能性単量体単位の含有量の下限値は、６重量％以上が好ましく、７重量％以上がより好ましく、８重量％以上がさらに好ましく、９重量％以上がよりさらに好ましく、１０重量％以上が特に好ましく、１１重量％以上が最も好ましい。多官能性単量体単位の含有量の上限値は、３５重量％以下が好ましく、３０重量％以下がより好ましく、２５重量％以下がさらに好ましく、２０重量％以下がよりさらに好ましく、１５重量％以下が特に好ましい。 The content of the polyfunctional monomer unit in the polymer particles of the present invention is 5% by weight or more and 40% by weight or less with respect to 100% by weight of the total amount of the monomer units of the polymer constituting the polymer particles. is there. If it is 5% by weight or more, the degree of cross-linking in the polymer particles is high, so that an effect of improving wear resistance can be obtained, and since the polymer particles are relatively hard, aggregation between the polymer particles occurs. It is difficult and can be easily obtained as a powder. On the other hand, when it is 40% by weight or less, the processability is excellent and inconvenience is unlikely to occur in the production of polymer particles. The lower limit of the content of the polyfunctional monomer unit is preferably 6% by weight or more, more preferably 7% by weight or more, further preferably 8% by weight or more, still more preferably 9% by weight or more, and 10% by weight. The above is particularly preferable, and 11% by weight or more is most preferable. The upper limit of the content of the polyfunctional monomer unit is preferably 35% by weight or less, more preferably 30% by weight or less, further preferably 25% by weight or less, still more preferably 20% by weight or less, and 15% by weight. The following are particularly preferred.
本発明の重合体粒子を構成する重合体は、共役ジエン単量体単位と多官能性単量体単位のみから形成される重合体であってもよいが、任意の単量体単位として、芳香族モノアルケニル単量体単位を含むものであってもよい。芳香族モノアルケニル単量体単位を用いることで、重合体粒子をジエン系ゴムに配合したときの両者の親和性を高めることができる。特にジエン系ゴムがスチレン−ブタジエン共重合ゴムを含有する場合には、当該ゴム中のスチレンの含有量を考慮して、重合体粒子における芳香族モノアルケニル単量体単位の含有量を調節して、両成分の親和性を高めることができる。 The polymer constituting the polymer particles of the present invention may be a polymer formed only from a conjugated diene monomer unit and a polyfunctional monomer unit, but an aromatic monomer unit may be used as an arbitrary monomer unit. It may contain a group monoalkenyl monomer unit. By using the aromatic monoalkenyl monomer unit, it is possible to enhance the affinity between the polymer particles when they are blended with the diene rubber. In particular, when the diene rubber contains a styrene-butadiene copolymer rubber, the content of the aromatic monoalkenyl monomer unit in the polymer particles is adjusted in consideration of the content of styrene in the rubber. , The affinity between both components can be enhanced.
芳香族モノアルケニル単量体としては、例えば、スチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、２，４−ジメチルスチレン、ｏ−エチルスチレン、ｍ−エチルスチレン、ｐ−エチルスチレン、ｐ−ｔ−ブチルスチレン、α−メチルスチレン、α−メチル−ｐ−メチルスチレン、ｏ−クロロスチレン、ｍ−クロロスチレン、ｐ−クロロスチレン、ｐ−ブロモスチレン、２−メチル−４，６−ジクロロスチレン、ｐ−ブロモスチレン、２−メチル−４，６−ジクロロスチレン、２，４−ジブロモスチレン、ビニルナフタレン等が挙げられる。芳香族モノアルケニル単量体は１種類のみを使用してもよいし、２種以上を併用してもよい。このうち、ラジカル重合における反応性およびコストの観点から、スチレンが好ましい。 Examples of the aromatic monoalkenyl monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene. , Pt-butyl styrene, α-methyl styrene, α-methyl-p-methyl styrene, o-chloro styrene, m-chloro styrene, p-chloro styrene, p-bromo styrene, 2-methyl-4,6- Examples thereof include dichlorostyrene, p-bromostyrene, 2-methyl-4,6-dichlorostyrene, 2,4-dibromostyrene, vinylnaphthalene and the like. Only one type of aromatic monoalkenyl monomer may be used, or two or more types may be used in combination. Of these, styrene is preferable from the viewpoint of reactivity and cost in radical polymerization.
本発明の重合体粒子における芳香族モノアルケニル単量体単位の含有量は、重合体粒子を構成する重合体の単量体単位の総量１００重量％に対して、０重量％以上７０重量％以下である。ジエン系ゴムとの親和性の観点から、上限値は、好ましくは５０重量％以下であり、より好ましくは４０重量％以下であり、さらに好ましくは３０重量％以下である。 The content of the aromatic monoalkenyl monomer unit in the polymer particles of the present invention is 0% by weight or more and 70% by weight or less with respect to 100% by weight of the total amount of the monomer units of the polymer constituting the polymer particles. Is. From the viewpoint of affinity with the diene rubber, the upper limit value is preferably 50% by weight or less, more preferably 40% by weight or less, and further preferably 30% by weight or less.
本発明の重合体粒子は、単層から構成される重合体粒子であってもよいし、互いに単量体組成が異なる２層以上から構成される重合体粒子であってもよい。２層以上から構成される重合体粒子である場合、重合体粒子全体として、前述した各単量体の含有量の要件を満足すればよい。しかし、本発明では、製造の容易さ等の観点から、単層から構成される重合体粒子が好ましい。 The polymer particles of the present invention may be polymer particles composed of a single layer, or may be polymer particles composed of two or more layers having different monomer compositions from each other. In the case of polymer particles composed of two or more layers, the polymer particles as a whole may satisfy the above-mentioned requirements for the content of each monomer. However, in the present invention, polymer particles composed of a single layer are preferable from the viewpoint of ease of production and the like.
本発明の重合体粒子は、体積平均粒子径が１０ｎｍ以上５００ｎｍ以下である一次粒子から構成されることが好ましい。一次粒子の平均粒子径が１０ｎｍ以上では、重合体粒子製造時の重合による発熱が少なく、また、ジエン系ゴムへの重合体粒子の分散性が良好になる。また、一次粒子の平均粒子径が５００ｎｍ以下では、重合体粒子製造時の重合が比較的短時間で完了し、生産性が良好である。一次粒子の平均粒子径の下限値は、例えば、２０ｎｍ以上、３０ｎｍ以上、４０ｎｍ以上、５０ｎｍ以上、６０ｎｍ以上、７０ｎｍ以上、８０ｎｍ以上、９０ｎｍ以上、１００ｎｍ以上、１１０ｎｍ以上、１２０ｎｍ以上、１３０ｎｍ以上、１４０ｎｍ以上、又は、１５０ｎｍ以上が好ましい。一次粒子の平均粒子径の上限値は、３００ｎｍ以下がより好ましく、２００ｎｍ以下がよりさらに好ましい。なお、重合体粒子における一次粒子の体積平均粒子径は、重合体粒子が水中に分散してなるラテックスの状態で、日機装株式会社製のＮａｎｏｔｒａｃ Ｗａｖｅを用いて測定することができる。 The polymer particles of the present invention are preferably composed of primary particles having a volume average particle diameter of 10 nm or more and 500 nm or less. When the average particle size of the primary particles is 10 nm or more, the heat generated by the polymerization during the production of the polymer particles is small, and the dispersibility of the polymer particles in the diene rubber is good. Further, when the average particle size of the primary particles is 500 nm or less, the polymerization at the time of producing the polymer particles is completed in a relatively short time, and the productivity is good. The lower limit of the average particle size of the primary particles is, for example, 20 nm or more, 30 nm or more, 40 nm or more, 50 nm or more, 60 nm or more, 70 nm or more, 80 nm or more, 90 nm or more, 100 nm or more, 110 nm or more, 120 nm or more, 130 nm or more, 140 nm. The above, or 150 nm or more is preferable. The upper limit of the average particle size of the primary particles is more preferably 300 nm or less, and even more preferably 200 nm or less. The volume average particle size of the primary particles in the polymer particles can be measured by using Nanotrac Wave manufactured by Nikkiso Co., Ltd. in the state of latex in which the polymer particles are dispersed in water.
本発明の重合体粒子は、常法により、乳化重合または懸濁重合により製造することができる。粒子の大きさや粒子径の均一性の観点から、乳化重合が好ましい。具体的には、攪拌機を備えた反応容器に、各単量体、ラジカル重合開始剤、乳化剤、水、さらに必要に応じて連鎖移動剤を加え、加熱攪拌することで乳化重合を実施することができる。 The polymer particles of the present invention can be produced by emulsion polymerization or suspension polymerization by a conventional method. Emulsion polymerization is preferable from the viewpoint of particle size and particle size uniformity. Specifically, emulsion polymerization can be carried out by adding each monomer, a radical polymerization initiator, an emulsifier, water, and if necessary, a chain transfer agent to a reaction vessel equipped with a stirrer and stirring by heating. it can.
ラジカル重合開始剤としては特に限定されず、公知のものを使用することができるが、例えば、２，２’−アゾビスイソブチロニトリル、過酸化水素、過硫酸カリウム、過硫酸アンモニウム等の熱分解型重合開始剤を用いることができる。また、ｔ−ブチルパーオキシイソプロピルカーボネート、パラメンタンハイドロパーオキサイド、クメンハイドロパーオキサイド、ジクミルパーオキサイド、ｔ−ブチルハイドロパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ｔ−ヘキシルパーオキサイド等の有機過酸化物や、過酸化水素、過硫酸カリウム、過硫酸アンモニウム等の無機過酸化物といった過酸化物と、必要に応じてナトリウムホルムアルデヒドスルホキシレート、グルコース等の還元剤、及び必要に応じて硫酸鉄（ＩＩ）等の遷移金属塩、更に必要に応じてエチレンジアミン四酢酸二ナトリウム、ピロリン酸ナトリウム等のキレート剤を併用したレドックス系触媒等を用いることもできる。ラジカル重合開始剤は、１種類のみを用いてもよいし、２種以上を併用してもよい。 The radical polymerization initiator is not particularly limited, and known ones can be used. For example, thermal decomposition of 2,2'-azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, ammonium persulfate and the like can be used. A type polymerization initiator can be used. In addition, organic substances such as t-butylperoxyisopropyl carbonate, paramentan hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, and t-hexyl peroxide are used. Oxides and peroxides such as hydrogen peroxide, potassium persulfate, and inorganic peroxides such as ammonium persulfate, and if necessary, sodium formaldehyde sulfoxylate, reducing agents such as glucose, and iron sulfate (if necessary). A redox-based catalyst or the like in which a transition metal salt such as II) and a chelating agent such as disodium ethylenediamine tetraacetate and sodium pyrophosphate are used in combination can also be used, if necessary. Only one type of radical polymerization initiator may be used, or two or more types may be used in combination.
また、ｔｅｒｔ−ドデシルメルカプタン、ｎ−ドデシルメルカプタン等のメルカプタン類、四塩化炭素、チオグリコール類、ジテルペン、タ−ピノーレン及びγ−テルピネン類等の連鎖移動剤を併用することもできる。 In addition, mercaptans such as tert-dodecyl mercaptan and n-dodecyl mercaptan, and chain transfer agents such as carbon tetrachloride, thioglycols, diterpenes, tarpinene and γ-terpinene can also be used in combination.
乳化重合において用いられる乳化剤としては、アニオン系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、両性界面活性剤等が挙げられる。また、ふっ素系の界面活性剤を使用することもできる。 Examples of the emulsifier used in emulsion polymerization include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. In addition, a fluorine-based surfactant can also be used.
懸濁重合では懸濁安定剤を用いることができる。懸濁安定剤としては、ポリビニルアルコール、ポリアクリル酸ナトリウム及びヒドロキシエチルセルロース等が挙げられるが、これらに限定されない。 Suspension stabilizers can be used in suspension polymerization. Examples of the suspension stabilizer include, but are not limited to, polyvinyl alcohol, sodium polyacrylate, hydroxyethyl cellulose and the like.
乳化重合又は懸濁重合において、各々の単量体及びラジカル重合開始剤等は、反応容器に全量を投入してから重合を開始してもよいし、反応中に連続的または間欠的に添加しながら重合を行なってもよい。重合は酸素を除去した反応器を用いて０℃以上８０℃以下で行うことができ、反応途中で温度または攪拌等の操作条件などを適宜調節することができる。 In emulsion polymerization or suspension polymerization, each monomer, radical polymerization initiator, etc. may be added in the reaction vessel in its entirety before the polymerization is started, or may be added continuously or intermittently during the reaction. However, polymerization may be carried out. The polymerization can be carried out at 0 ° C. or higher and 80 ° C. or lower using a reactor from which oxygen has been removed, and operating conditions such as temperature and stirring can be appropriately adjusted during the reaction.
乳化重合または懸濁重合により得られた重合体粒子ラテックスに対し、塩化カルシウム、塩化マグネシウム、硫酸マグネシウム、塩化アルミニウム、酢酸カルシウムなどの二価以上の金属塩を添加して粒子を凝固させた後、脱水、洗浄、乾燥させることで、重合体粒子を水から分離することができる。また、前記ラテックスを噴霧凝固（スプレードライ）することによっても重合体粒子を水から分離することができる。 After adding a divalent or higher metal salt such as calcium chloride, magnesium chloride, magnesium sulfate, aluminum chloride, or calcium acetate to the polymer particle latex obtained by emulsion polymerization or suspension polymerization to coagulate the particles, Polymer particles can be separated from water by dehydration, washing and drying. The polymer particles can also be separated from water by spray-coagulating (spray-drying) the latex.
本発明の重合体粒子の形態は特に制限されず、水から分離した重合体粒子の形態を有するものであってもよいし、１０ｎｍ以上５００ｎｍ以下の体積平均粒子径を有する一次粒子が水などの液体に分散してなるラテックス又は分散体の形態を有するものであってもよい。また、重合体粒子のラテックスなどから液体を除去、乾燥する過程において一次粒子が凝集することで得られる二次粒子や凝集塊の形態を有するものであってもよい。二次粒子または凝集塊の形状は、粉体、顆粒、ペレット状、クラム状、ベールなどの何れでもよく、中でも取り扱い易さの観点から粉体が好ましい。 The form of the polymer particles of the present invention is not particularly limited, and may have the form of polymer particles separated from water, and the primary particles having a volume average particle diameter of 10 nm or more and 500 nm or less are water or the like. It may have the form of a latex or a dispersion dispersed in a liquid. Further, it may have the form of secondary particles or agglomerates obtained by agglutinating the primary particles in the process of removing the liquid from the latex of the polymer particles and drying. The shape of the secondary particles or agglomerates may be any of powder, granules, pellets, crumbs, veils and the like, and powder is particularly preferable from the viewpoint of ease of handling.
本発明の重合体粒子が凝集して粉体の形態を有する場合、該粉体の体積平均粒子径は、取り扱い易さや分散請性の観点から、１０μｍ以上１０００μｍ以下であることが好ましい。粉体の体積平均粒子径の下限値は、例えば、２０μｍ以上、３０μｍ以上、４０μｍ以上、５０μｍ以上、６０μｍ以上、７０μｍ以上、８０μｍ以上、９０μｍ以上、１００μｍ以上、１１０μｍ以上、１２０μｍ以上、１３０μｍ以上、１４０μｍ以上、又は、１５０μｍ以上が好ましい。粉体の体積平均粒子径の上限値は８００μｍ以下がより好ましく、７００μｍ以下がさらに好ましく、６００μｍ以下がよりさらに好ましい。さらに、前記粉体全体に占める粒子径が７００μｍ以上の粉体の割合（体積％）は、２０％以下であることが好ましく、１０％以下であることより好ましく、５％以下であることがさらに好ましい。また、前記粉体全体に占める粒子径が１０００μｍ以上の粉体の割合（体積％）は、２０％以下であることが好ましく、１０％以下であることより好ましく、５％以下であることがさらに好ましい。これら粉体の粒子径は、日機装株式会社製のマイクロトラックＭＴ３０００ＩＩを使用して光散乱法に基づき測定することができる。 When the polymer particles of the present invention are aggregated and have a powder form, the volume average particle size of the powder is preferably 10 μm or more and 1000 μm or less from the viewpoint of ease of handling and dispersion contractability. The lower limit of the volume average particle size of the powder is, for example, 20 μm or more, 30 μm or more, 40 μm or more, 50 μm or more, 60 μm or more, 70 μm or more, 80 μm or more, 90 μm or more, 100 μm or more, 110 μm or more, 120 μm or more, 130 μm or more, It is preferably 140 μm or more, or 150 μm or more. The upper limit of the volume average particle size of the powder is more preferably 800 μm or less, further preferably 700 μm or less, still more preferably 600 μm or less. Further, the proportion (volume%) of the powder having a particle size of 700 μm or more in the entire powder is preferably 20% or less, more preferably 10% or less, and further preferably 5% or less. preferable. The proportion (volume%) of the powder having a particle size of 1000 μm or more in the entire powder is preferably 20% or less, more preferably 10% or less, and further preferably 5% or less. preferable. The particle size of these powders can be measured based on the light scattering method using Microtrac MT3000II manufactured by Nikkiso Co., Ltd.
本発明の重合体粒子は、ジエン系ゴムに配合してその物性を改善するゴム用改質剤として使用することができる。 The polymer particles of the present invention can be blended with a diene-based rubber and used as a rubber modifier for improving its physical properties.
（ゴム組成物）
本発明のゴム組成物は、前記重合体粒子からなるゴム用改質剤と、ジエン系ゴムとを含有するものである。
(Rubber composition)
The rubber composition of the present invention contains a rubber modifier composed of the polymer particles and a diene-based rubber.
本発明で使用できるジエン系ゴムとは、原料モノマーとして共役ジエン単量体が使用され、主鎖に架橋点となる二重結合が導入されているゴム成分である。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−ブタジエン共重合ゴム（ＳＢＲ）、クロロプレンゴム（ＣＲ）、アクリロニトリル−ブタジエン共重合ゴム（ＮＢＲ）、エチレン−プロピレン−ジエン共重合ゴム（ＥＰＤＭ）、ブチルゴム等が挙げられるが、これらに限定されない。これらのうち１種のみを使用してもよいし、２種以上を併用してもよい。これらのゴム成分は末端に官能基を有するゴム成分であってもよい。好ましくは、天然ゴム、イソプレンゴム、ブタジエンゴム、スチレン−ブタジエン共重合ゴムであり、より好ましくは、ブタジエンゴム、スチレン−ブタジエン共重合ゴムである。シリカを配合した時の転がり抵抗性低減および分散性向上の観点から、末端に官能基を有するブタジエンゴム、末端に官能基を有するスチレン−ブタジエン共重合ゴムがさらに好ましい。 The diene-based rubber that can be used in the present invention is a rubber component in which a conjugated diene monomer is used as a raw material monomer and a double bond serving as a cross-linking point is introduced into the main chain. For example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), chloroprene rubber (CR), acrylonitrile-butadiene copolymer rubber (NBR), ethylene-propylene- Examples thereof include diene copolymer rubber (EPDM) and butyl rubber, but the present invention is not limited thereto. Only one of these may be used, or two or more thereof may be used in combination. These rubber components may be rubber components having a functional group at the end. Natural rubber, isoprene rubber, butadiene rubber, and styrene-butadiene copolymer rubber are preferable, and butadiene rubber and styrene-butadiene copolymer rubber are more preferable. From the viewpoint of reducing rolling resistance and improving dispersibility when silica is blended, butadiene rubber having a functional group at the end and styrene-butadiene copolymer rubber having a functional group at the end are more preferable.
本発明の重合体粒子をジエン系ゴムに配合するときの配合量は、ジエン系ゴム１００重量部に対して、２重量部以上５０重量部以下であることが好ましい。このような量で本発明の重合体粒子を配合することで、ジエン系ゴムの反発弾性を改良して、転がり抵抗を低減し、また、ジエン系ゴムの耐摩耗性を向上させることができる。さらに、優れた分散性も達成することができる。配合量が２重量部以上で、転がり抵抗の低減効果及び耐摩耗性の改善効果が良好になり、５０重量部以下で、優れた分散性を達成できる。配合量の下限値は３重量部以上がより好ましく、４重量部以上がさらに好ましく、５重量部以上がよりさらに好ましい。配合量の上限値は４０重量部以下がより好ましく、３０重量部以下がさらに好ましく、２０重量部以下がよりさらに好ましい。 When the polymer particles of the present invention are blended with the diene rubber, the blending amount is preferably 2 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the diene rubber. By blending the polymer particles of the present invention in such an amount, the impact resilience of the diene rubber can be improved, the rolling resistance can be reduced, and the wear resistance of the diene rubber can be improved. In addition, excellent dispersibility can be achieved. When the blending amount is 2 parts by weight or more, the effect of reducing rolling resistance and the effect of improving wear resistance are good, and when the amount is 50 parts by weight or less, excellent dispersibility can be achieved. The lower limit of the blending amount is more preferably 3 parts by weight or more, further preferably 4 parts by weight or more, and further preferably 5 parts by weight or more. The upper limit of the blending amount is more preferably 40 parts by weight or less, further preferably 30 parts by weight or less, and further preferably 20 parts by weight or less.
本発明のゴム組成物は、補強材であるシリカと、シランカップリング剤をさらに含有することが好ましい。シリカを配合することにより、転がり抵抗をさらに低減する効果が得られ、さらにシランカップリング剤を併用することにより、親水性のシリカ表面と疎水性のゴム成分が結合して界面の安定性が向上することで、ゴム成分中でのシリカの分散性を向上させて、シリカによる転がり抵抗の低減効果を高めることができる。 The rubber composition of the present invention preferably further contains silica as a reinforcing material and a silane coupling agent. By blending silica, the effect of further reducing rolling resistance can be obtained, and by using a silane coupling agent in combination, the hydrophilic silica surface and the hydrophobic rubber component are combined to improve the stability of the interface. By doing so, the dispersibility of silica in the rubber component can be improved, and the effect of reducing the rolling resistance of silica can be enhanced.
シリカとしては特に限定されないが、例えば、乾式シリカ、湿式シリカ、コロイダルシリカ、沈降シリカ等が挙げられる。なかでも、耐摩耗性に優れ、経済性にも優れている点で、湿式シリカが好ましい。 The silica is not particularly limited, and examples thereof include dry silica, wet silica, colloidal silica, and precipitated silica. Of these, wet silica is preferable because it has excellent wear resistance and is also excellent in economy.
シリカの配合量は、シリカによる補強効果の観点から適宜決定することができ、特に限定されないが、好ましくは、ジエン系ゴム１００重量部に対して０重量部以上１００重量部以下である。下限値は１０重量部以上がより好ましく、上限値は８０重量部以下がより好ましい。 The blending amount of silica can be appropriately determined from the viewpoint of the reinforcing effect of silica, and is not particularly limited, but is preferably 0 parts by weight or more and 100 parts by weight or less with respect to 100 parts by weight of the diene rubber. The lower limit is more preferably 10 parts by weight or more, and the upper limit is more preferably 80 parts by weight or less.
シランカップリング剤としては特に限定されず、例えば、ビニルトリエトキシシラン、β−（３,４−エポキシシクロヘキシル）エチルトリメトキシシラン、Ｎ−（β−アミノエチル）−γ−アミノプロピルトリメトキシシラン；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、特開平６−２４８１１６号公報に記載されるγ−トリメトキシシリルプロピルジメチルチオカルバミルテトラスルフィド、γ−トリメトキシシリルプロピルベンゾチアジルテトラスルフィドなどのテトラスルフィド類などが挙げられる。 The silane coupling agent is not particularly limited, and for example, vinyl triethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane; Bis (3- (triethoxysilyl) propyl) tetrasulfide, bis (3- (triethoxysilyl) propyl) disulfide, γ-trimethoxysilylpropyldimethylthiocarbamyltetrasulfide described in JP-A-6-248116. , Γ-Trimethoxysilylpropyl benzothiazil tetrasulfide and other tetrasulfides and the like.
シランカップリング剤は、シリカの分散性向上の観点から適宜決定することができ、特に限定されないが、好ましくは、ジエン系ゴム１００重量部に対して０重量部以上２０重量部以下である。下限値は１重量部以上がより好ましく、上限値は１０重量部以下がより好ましい。 The silane coupling agent can be appropriately determined from the viewpoint of improving the dispersibility of silica, and is not particularly limited, but is preferably 0 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the diene rubber. The lower limit is more preferably 1 part by weight or more, and the upper limit is more preferably 10 parts by weight or less.
本発明のゴム組成物は、補強材又は着色剤として、カーボンブラックをさらに含有することもできる。カーボンブラックは、シリカ及びシランカップリング剤と併用してもよいし、併用しなくてもよい。カーボンブラックとしては特に限定されず、例えば、ファーネスブラック、アセチレンブラック、サーマルブラック、チャンネルブラック、グラファイト等が挙げられる。カーボンブラックの配合量は、その配合目的に応じて適宜決定することができるが、例えば、ジエン系ゴム１００重量部に対して０重量部以上６０重量部以下が好ましい。下限値は２重量部以上がより好ましく、上限値は５０重量部以下がより好ましい。 The rubber composition of the present invention may further contain carbon black as a reinforcing material or a colorant. Carbon black may or may not be used in combination with silica and a silane coupling agent. The carbon black is not particularly limited, and examples thereof include furnace black, acetylene black, thermal black, channel black, and graphite. The blending amount of carbon black can be appropriately determined according to the blending purpose, but for example, it is preferably 0 parts by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the diene rubber. The lower limit is more preferably 2 parts by weight or more, and the upper limit is more preferably 50 parts by weight or less.
本発明のゴム組成物には、ゴム分野で一般的に使用されている、加硫剤、加硫促進剤、加硫活性化剤、充填剤、可塑剤、老化防止剤など他の配合剤を適宜配合することができる。 The rubber composition of the present invention contains other compounding agents generally used in the rubber field, such as vulcanizing agents, vulcanization accelerators, vulcanization activators, fillers, plasticizers, and antiaging agents. It can be appropriately blended.
加硫剤としては特に限定されないが、例えば、粉末硫黄、沈降硫黄、コロイド硫黄、不溶性硫黄、高分散性硫黄などの硫黄；一塩化硫黄、二塩化硫黄などのハロゲン化硫黄；ジクミルパーオキシド、ジターシャリブチルパーオキシドなどの有機過酸化物；ｐ−キノンジオキシム、ｐ,ｐ’−ジベンゾイルキノンジオキシムなどのキノンジオキシム；トリエチレンテトラミン、ヘキサメチレンジアミンカルバメート、４,４’−メチレンビス−ｏ−クロロアニリンなどの有機多価アミン化合物；メチロール基をもったアルキルフェノール樹脂などが挙げられる。これらの中でも、硫黄が好ましく、粉末硫黄が特に好ましい。加硫剤は１種のみを使用してもよいし、２種以上を併用してもよい。加硫剤の配合量は適宜決定することができるが、好ましくは、ジエン系ゴム１００重量部に対し０．１重量部以上１５重量部以下である。下限値は０．３重量部以上がより好ましく、上限値は１０重量部以下がより好ましい。 The sulfide is not particularly limited, but for example, sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur; sulfur halide such as sulfur monochloride and sulfur dichloride; dicumylperoxide, Organic peroxides such as ditershalibutylperoxide; quinonedioximes such as p-quinonedioxime, p, p'-dibenzoylquinonedioxime; triethylenetetramine, hexamethylenediaminecarbamate, 4,4'-methylenebis- Organic polyvalent amine compounds such as o-chloroaniline; alkylphenol resins having a methylol group and the like can be mentioned. Among these, sulfur is preferable, and powdered sulfur is particularly preferable. Only one type of vulcanizing agent may be used, or two or more types may be used in combination. The blending amount of the vulcanizing agent can be appropriately determined, but is preferably 0.1 part by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the diene rubber. The lower limit is more preferably 0.3 parts by weight or more, and the upper limit is more preferably 10 parts by weight or less.
加硫促進剤としては特に限定されないが、例えば、Ｎ−シクロヘキシル−２−ベンゾチアゾールスルフェンアミド、Ｎ−ｔ−ブチル−２−ベンゾチアゾールスルフェンアミド、Ｎ−オキシエチレン−２−ベンゾチアゾールスルフェンアミド、Ｎ−オキシエチレン−２−ベンゾチアゾールスルフェンアミド、Ｎ，Ｎ’−ジイソプロピル−２−ベンゾチアゾールスルフェンアミドなどのスルフェンアミド系加硫促進剤；ジフェニルグアニジン、ジオルトトリルグアニジン、オルトトリルビグアニジンなどのグアニジン系加硫促進剤；ジエチルチオウレアなどのチオウレア系加硫促進剤；２−メルカプトベンゾチアゾール、ジベンゾチアジルジスルフィド、２−メルカプトベンゾチアゾール亜鉛塩などのチアゾール系加硫促進剤；テトラメチルチウラムモノスルフィド、テトラメチルチウラムジスルフィドなどのチウラム系加硫促進剤；ジメチルジチオカルバミン酸ナトリウム、ジエチルジチオカルバミン酸亜鉛などのジチオカルバミン酸系加硫促進剤；イソプロピルキサントゲン酸ナトリウム、イソプロピルキサントゲン酸亜鉛、ブチルキサントゲン酸亜鉛などのキサントゲン酸系加硫促進剤；ヘキサメチレンテトラミン（Ｈ）等のアミン系加硫促進剤；ブチルアルデヒドアニリン（Ｂ）、ブチルアルデヒドモノブチルアミン（８３３）等のアルデヒドアンモニア系加硫促進剤等が挙げられる。加硫促進剤は１種のみを使用してもよいし、２種以上を併用してもよい。加硫促進剤の配合量は適宜決定することができるが、好ましくは、ジエン系ゴム１００重量部に対し０．１重量部以上１５重量部以下である。下限値は０．３重量部以上がより好ましく、上限値は１０重量部以下がより好ましい。 The vulcanization accelerator is not particularly limited, but for example, N-cyclohexyl-2-benzothiazolesulfenamide, Nt-butyl-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide. Sulfenamide-based vulcanization accelerators such as amides, N-oxyethylene-2-benzothiazolesulfenamides, N, N'-diisopropyl-2-benzothiazolesulfenamides; diphenylguanidine, dioltotrilguanidine, orthotri Guanidin-based vulcanization accelerators such as rubiguanidine; thiourea-based vulcanization accelerators such as diethylthiourea; thiazole-based vulcanization accelerators such as 2-mercaptobenzothiazole, dibenzothiadyldisulfide, 2-mercaptobenzothiazole zinc salt; tetra Thiuram-based vulcanization accelerators such as methylthiuram monosulfide and tetramethylthiuram disulfide; dithiocarbamic acid-based vulcanization accelerators such as sodium dimethyldithiocarbamate and zinc diethyldithiocarbamate; sodium isopropylxanthogenate, zinc isopropylxanthogenate, butylxanthogenic acid Xanthogenic acid-based vulcanization accelerator such as zinc; amine-based vulcanization accelerator such as hexamethylenetetramine (H); aldehyde ammonia-based vulcanization accelerator such as sulfenamide aniline (B) and butulfenamide monobutylamine (833), etc. Can be mentioned. Only one type of vulcanization accelerator may be used, or two or more types may be used in combination. The blending amount of the vulcanization accelerator can be appropriately determined, but is preferably 0.1 part by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the diene rubber. The lower limit is more preferably 0.3 parts by weight or more, and the upper limit is more preferably 10 parts by weight or less.
加硫活性化剤としては特に限定されないが、例えば、ステアリン酸などの高級脂肪酸、酸化亜鉛などが挙げられる。酸化亜鉛としては、表面活性の高い粒度５μｍ以下のものが好ましく、粒度が０.０５μｍ以上０.２μｍ以下の活性亜鉛華および０.３μｍ以上１μｍ以下の亜鉛華がより好ましい。また、酸化亜鉛としては、アミン系の分散剤または湿潤剤で表面処理したものを用いることができる。加硫活性化剤は１種のみを使用してもよいし、２種以上を併用してもよい。加硫活性化剤の配合量は適宜決定することができるが、加硫活性化剤が高級脂肪酸である場合、その配合量は、好ましくは、ジエン系ゴム１００重量部に対し０．０５重量部以上１５重量部以下である。下限値は０．１重量部以上がより好ましく、上限値は１０重量部以下がより好ましい。加硫活性化剤が酸化亜鉛である場合、その配合量は、好ましくは、ジエン系ゴム１００重量部に対し０．０５重量部以上１０重量部以下である。下限値は０．１重量部以上がより好ましく、上限値は５重量部以下がより好ましい。 The vulcanization activator is not particularly limited, and examples thereof include higher fatty acids such as stearic acid and zinc oxide. The zinc oxide preferably has a particle size of 5 μm or less and has a high surface activity, and more preferably active zinc oxide having a particle size of 0.05 μm or more and 0.2 μm or less and zinc oxide having a particle size of 0.3 μm or more and 1 μm or less. Further, as zinc oxide, those surface-treated with an amine-based dispersant or a wetting agent can be used. Only one type of vulcanization activator may be used, or two or more types may be used in combination. The blending amount of the vulcanization activator can be appropriately determined, but when the vulcanization activator is a higher fatty acid, the blending amount is preferably 0.05 parts by weight with respect to 100 parts by weight of the diene rubber. It is 15 parts by weight or less. The lower limit is more preferably 0.1 parts by weight or more, and the upper limit is more preferably 10 parts by weight or less. When the vulcanization activator is zinc oxide, the blending amount thereof is preferably 0.05 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the diene rubber. The lower limit is more preferably 0.1 parts by weight or more, and the upper limit is more preferably 5 parts by weight or less.
充填剤としては、前記シリカとカーボンブラック以外の充填剤が挙げられ、具体的には、クレー、タルク、マイカなどのケイ酸塩鉱物；シラス；炭酸カルシウム（例えば、膠質炭酸カルシウム、極微細炭酸カルシウム、軽微性炭酸カルシウム、重質炭酸カルシウム）、炭酸マグネシウム、炭酸カリウムなどの炭酸塩類；水酸化アルミニウム；硫酸バリウム；酸化アルミニウム、有機短繊維、（メタ）アクリル系樹脂微粒子、エポキシ樹脂微粒子、ガラス微粒子、ガラス繊維、フレークグラファイト等が挙げられる。充填剤は１種のみを使用してもよいし、２種以上を併用してもよい。 Examples of the filler include fillers other than the silica and carbon black, and specifically, silicate minerals such as clay, talc, and mica; silas; calcium carbonate (for example, glue calcium carbonate, ultrafine calcium carbonate). , Light calcium carbonate, heavy calcium carbonate), magnesium carbonate, potassium carbonate and other carbonates; aluminum hydroxide; barium sulfate; aluminum oxide, organic short fibers, (meth) acrylic resin fine particles, epoxy resin fine particles, glass fine particles , Glass fiber, flake graphite and the like. Only one type of filler may be used, or two or more types may be used in combination.
可塑剤としては、パラフィン系プロセスオイル、ナフテン系プロセスオイル、芳香族系プロセスオイルなどの石油系プロセスオイル、フタル酸ジエチル、フタル酸ジオクチル、アジピン酸ジブチルなどの二塩基酸ジアルキル、液状ポリブテン、液状ポリイソプレンなどの低分子量液状ポリマー、オレンジオイル等の天然オイルが例示され、なかでも、ジエン系ゴムとの相溶性から、液状ポリブテン、液状ポリイソプレン、芳香族系プロセスオイルが好ましい。可塑剤は１種のみを使用してもよいし、２種以上を併用してもよい。 Plasticizers include petroleum-based process oils such as paraffin-based process oils, naphthen-based process oils, and aromatic process oils, dialkyl dibasic acids such as diethyl phthalate, dioctyl phthalate, and dibutyl adipate, liquid polybutene, and liquid poly. Low molecular weight liquid polymers such as isoprene and natural oils such as orange oil are exemplified. Among them, liquid polybutene, liquid polyisoprene, and aromatic process oils are preferable because of their compatibility with diene rubber. Only one type of plasticizer may be used, or two or more types may be used in combination.
本発明のゴム組成物は、ジエン系ゴム以外のゴム成分（例えば、アクリルゴム、フッ素ゴム、シリコンゴム、エチレン−プロピレンゴム、ウレタンゴムなど）や、エピクロロヒドリン、エチレンオキサイド、プロピレンオキサイドおよびアリルグリシジルエーテルからなる群より選ばれる少なくとも１つの単量体の単独重合体または共重合体などをさらに含有するものであってもよい。 The rubber composition of the present invention contains rubber components other than diene rubber (for example, acrylic rubber, fluororubber, silicon rubber, ethylene-propylene rubber, urethane rubber, etc.), epichlorohydrin, ethylene oxide, propylene oxide and allyl. It may further contain a homopolymer or a copolymer of at least one monomer selected from the group consisting of glycidyl ether.
本発明のゴム組成物は、常法に従って各成分を混練することにより得ることができ、特に限定されないが、例えば、まず、加硫剤と加硫促進剤を除く配合剤、ジエン系ゴム、および本発明の重合体粒子を、タンブラー、タンブラー、ヘンシェルミキサー、リボブレンダー等で混合した後、押出機、バンパリー、ロール等で混練する方法を採用することができる。この混練時の温度は通常５０℃以上２００℃以下である。下限値は８０℃以上が好ましく、上限値は１９０℃以下が好ましい。混練に要する時間は通常３０秒以上３０分以下である。下限値は１分以上が好ましい。 The rubber composition of the present invention can be obtained by kneading each component according to a conventional method, and is not particularly limited. For example, first, a compounding agent excluding a vulcanizing agent and a vulcanization accelerator, a diene rubber, and A method can be adopted in which the polymer particles of the present invention are mixed with a tumbler, a tumbler, a henschel mixer, a rib blender or the like, and then kneaded with an extruder, a bumper, a roll or the like. The temperature at the time of kneading is usually 50 ° C. or higher and 200 ° C. or lower. The lower limit is preferably 80 ° C. or higher, and the upper limit is preferably 190 ° C. or lower. The time required for kneading is usually 30 seconds or more and 30 minutes or less. The lower limit is preferably 1 minute or more.
次いで、加硫剤と加硫促進剤を加えて、さらに、上記の装置を用いて混練する。この時の混練温度は加硫剤の反応を抑制する目的で８０℃以上１２０℃以下で行なうことが好ましい。これにより、加硫剤と加硫促進剤を含有する架橋性のゴム組成物が得られる。 Then, the vulcanizing agent and the vulcanization accelerator are added, and further kneaded using the above-mentioned apparatus. The kneading temperature at this time is preferably 80 ° C. or higher and 120 ° C. or lower for the purpose of suppressing the reaction of the vulcanizing agent. As a result, a crosslinkable rubber composition containing a vulcanizing agent and a vulcanization accelerator can be obtained.
得られた架橋性のゴム組成物を架橋反応させることで、架橋した成形体を得ることができる。架橋方法は、成形体の形状や大きさなどを考慮して適宜選択することができるが、一般にはプレス機や射出成型機を使用すればよい。架橋反応時の温度や時間は特に限定されないが、温度は、好ましくは１２０℃以上２００℃以下であり、より好ましい下限値は１４０℃以上、より好ましい上限値は１８０℃以下であり、時間は通常１分以上１２０分以下程度である。 By subjecting the obtained crosslinkable rubber composition to a crosslink reaction, a crosslinked molded product can be obtained. The cross-linking method can be appropriately selected in consideration of the shape and size of the molded body, but generally a press machine or an injection molding machine may be used. The temperature and time during the crosslinking reaction are not particularly limited, but the temperature is preferably 120 ° C. or higher and 200 ° C. or lower, the more preferable lower limit value is 140 ° C. or higher, the more preferable upper limit value is 180 ° C. or lower, and the time is usually It is about 1 minute or more and 120 minutes or less.
本発明の成形体は、例えば、タイヤ、ケーブル被覆剤、ホース、トランスミッションベルト、コンベアベルト、ロールカバー、靴本体または靴底、シール用リング、防振ゴムなどとして使用することができる。特に本発明の成形体は、タイヤトレッドとして好適に使用することができる。タイヤトレッドが多層構造を有する場合、その最外層を、本発明の成形体により構成することが好ましい。 The molded body of the present invention can be used as, for example, a tire, a cable coating agent, a hose, a transmission belt, a conveyor belt, a roll cover, a shoe body or a sole, a sealing ring, an anti-vibration rubber, or the like. In particular, the molded product of the present invention can be suitably used as a tire tread. When the tire tread has a multi-layer structure, it is preferable that the outermost layer thereof is composed of the molded product of the present invention.
タイヤトレッドが本発明の成形体により構成される場合、空気入りタイヤの製造方法は常法に従うことができる。例えば、未架橋の本発明のゴム組成物を、タイヤトレッドの形状にあわせて押出加工し、タイヤ成形機上にて成形したうえ、他のタイヤ部材に貼り合わせて、未架橋タイヤを形成する。この未架橋タイヤを加硫機中で加熱加圧することで、空気入りタイヤを製造することができる。この空気入りタイヤは、乗用車用タイヤ、または、トラック・バス用タイヤ（重荷重用タイヤ）として好適に用いることができる。 When the tire tread is composed of the molded product of the present invention, the method for manufacturing a pneumatic tire can follow a conventional method. For example, the uncrosslinked rubber composition of the present invention is extruded according to the shape of a tire tread, molded on a tire molding machine, and then bonded to another tire member to form an uncrosslinked tire. By heating and pressurizing this uncrosslinked tire in a vulcanizer, a pneumatic tire can be manufactured. This pneumatic tire can be suitably used as a passenger car tire or a truck / bus tire (heavy load tire).
以下、本発明を実施例にて具体的に説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
（製造例１）重合体粒子（Ｂ１）の製造
水２２０重量部、リン酸三カリウム０．５重量部、硫酸第一鉄（ＦｅＳＯ４・７Ｈ２Ｏ）０．００２１重量部、エチレンジアミン４酢酸・２Ｎａ塩０．００３５重量部を撹拌翼付き耐圧重合器に仕込み、撹拌しながら４５℃に昇温し、内部を窒素置換し、さらにアスピレータを用いて脱酸措置を施した。その後、ロジン酸カリウム１．９９重量部、ジビニルベンゼン１１．４重量部、スチレン８．６重量部、ブタジエン８０重量部を添加し、さらにパラメンタンハイドロパーオキサイド０．０５７４重量部、ホルムアルデヒドスルフォキシル酸ナトリウム０．０７５重量部を添加し、重合反応を開始した。さらに２時間後、半硬化牛脂脂肪酸カリウム０．１９重量部、パラメンタンハイドロパーオキサイド０．０２重量部、硫酸第一鉄（ＦｅＳＯ４・７Ｈ２Ｏ）０．０００３３重量部、エチレンジアミン４酢酸・２Ｎａ塩０．０００５４重量部、ホルムアルデヒドスルフォキシル酸ナトリウム０．０２重量部、さらに１．５時間後、半硬化牛脂脂肪酸カリウム０．４０重量部、パラメンタンハイドロパーオキサイド０．０２重量部、硫酸第一鉄（ＦｅＳＯ４・７Ｈ２Ｏ）０．０００３３重量部、エチレンジアミン４酢酸・２Ｎａ塩０．０００５４重量部、さらに１時間後、半硬化牛脂脂肪酸カリウム０．４０重量部を添加し、５０℃に昇温した。１．５時間後、パラメンタンハイドロパーオキサイド０．０２重量部、さらに０．５時間後、パラメンタンハイドロパーオキサイド０．０６重量部、硫酸第一鉄（ＦｅＳＯ４・７Ｈ２Ｏ）０．００１１重量部、エチレンジアミン４酢酸・２Ｎａ塩０．００１８重量部、ホルムアルデヒドスルフォキシル酸ナトリウム０．０７５重量部、さらに２時間おきにパラメンタンハイドロパーオキサイド０．０５８重量部を添加し、重合反応開始から１３時間後、重合転化率９７％、体積平均粒子径７８ｎｍの重合体粒子ラテックスを得た。
(Production Example 1) 220 parts by weight produced water of the polymer particles (B1), tripotassium 0.5 part by weight of phosphoric acid, (2 O FeSO 4 · 7H) 0.0021 parts by weight of ferrous sulfate, ethylenediaminetetraacetic acid, 0.0035 parts by weight of 2Na salt was charged into a pressure resistant polymer with a stirring blade, the temperature was raised to 45 ° C. while stirring, the inside was replaced with nitrogen, and deoxidization measures were taken using an aspirator. Then, 1.99 parts by weight of potassium loginate, 11.4 parts by weight of divinylbenzene, 8.6 parts by weight of styrene, and 80 parts by weight of butadiene were added, and further, 0.0574 parts by weight of paramentan hydroperoxide and 0.0574 parts by weight of formaldehyde sulfoxyl were added. 0.075 parts by weight of sodium acetate was added to initiate the polymerization reaction. After a further 2 hours, 0.19 parts by weight of potassium partially hydrogenated tallow fatty acid, 0.02 parts by weight p-menthane hydroperoxide, (2 O FeSO 4 · 7H ) 0.00033 parts of ferrous sulfate, ethylenediaminetetraacetic acid · 2Na 0.00054 parts by weight of salt, 0.02 parts by weight of sodium formaldehyde sulfoxylate, and after 1.5 hours, 0.40 parts by weight of semi-cured beef fatty acid potassium, 0.02 parts by weight of paramentan hydroperoxide, sulfate. monoferric (FeSO 4 · 7H 2 O) 0.00033 parts by weight of ethylenediamine tetraacetic acid · 2Na salt 0.00054 parts by weight, further 1 hour after, the addition of 0.40 parts by weight of potassium partially hydrogenated tallow fatty acid, in 50 ° C. The temperature was raised. After 1.5 hours, 0.02 parts by weight p-menthane hydroperoxide, further after 0.5 hours, 0.06 parts by weight p-menthane hydroperoxide, ferrous sulfate (FeSO 4 · 7H 2 O) 0.0011 From the start of the polymerization reaction, 0.0018 parts by weight of ethylenediamine tetraacetic acid / 2Na salt, 0.075 parts by weight of sodium formaldehyde sulfoxylate, and 0.058 parts by weight of paramentane hydroperoxide were added every 2 hours. After 13 hours, a polymer particle latex having a polymerization conversion rate of 97% and a volume average particle diameter of 78 nm was obtained.
水３．５重量部、ジラウリルチオジプロピオネート１．５重量部、トリエチレングリコール−ビス［３ー（３−ｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート］１．５重量部、半硬化牛脂脂肪酸カリウム０．４７重量部からなる混合物をホモジナイザーにより乳化した後、重合体粒子ラテックスに添加した。さらに塩化カルシウムの２５％水溶液５．０重量部を添加し、重合体粒子を凝固させ、ペーパーフィルターを用いて凝固物を分取、水により洗浄した後、５０℃で２日間乾燥させ、重合体粒子（Ｂ１）の凝集した粉体を得た。 3.5 parts by weight of water, 1.5 parts by weight of dilaurylthiodipropionate, 1.5 parts by weight of triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] , Semi-cured beef tallow fatty acid potassium 0.47 parts by weight was emulsified with a homogenizer and then added to the polymer particle latex. Further, 5.0 parts by weight of a 25% aqueous solution of calcium chloride was added to coagulate the polymer particles, the coagulated product was separated using a paper filter, washed with water, and then dried at 50 ° C. for 2 days to obtain the polymer. An agglomerated powder of particles (B1) was obtained.
（比較製造例１）重合体粒子（Ｂ２）の製造
水１２５重量部、リン酸三カリウム０．３８重量部、硫酸第一鉄（ＦｅＳＯ４・７Ｈ２Ｏ）０．０００８８重量部、エチレンジアミン４酢酸・２Ｎａ塩０．０１５重量部を撹拌翼付き耐圧重合器に仕込み、撹拌しながら４５℃に昇温し、内部を窒素置換し、さらにアスピレータを用いて脱酸措置を施した。その後、半硬化牛脂脂肪酸カリウム１．９８重量部、スチレン２０重量部、ブタジエン５０重量部、パラメンタンハイドロパーオキサイド０．０４９重量部を添加し、ホルムアルデヒドスルフォキシル酸ナトリウム０．００６重量部を添加して重合反応を開始した。重合反応開始から２時間後、パラメンタンハイドロパーオキサイド０．０１８重量部、ホルムアルデヒドスルフォキシル酸ナトリウム０．０３８重量部を添加し、さらに１時間後、５５℃に昇温した。さらに２時間後、ブタジエンを３０重量部、さらに１時間後、パラメンタンハイドロパーオキサイド０．０１８重量部、硫酸第一鉄（ＦｅＳＯ４・７Ｈ２Ｏ）０．００１３重量部、エチレンジアミン４酢酸・２Ｎａ塩０．００２２重量部を添加し、さらに１時間後、６０℃に昇温した。昇温から１時間後、パラメンタンハイドロパーオキサイド０．０１９重量部を添加し、さらに２時間撹拌を続け、転化率９８％、体積平均粒子径８１ｎｍの重合体粒子ラテックスを得た。
(Comparative Production Example 1) Production water 125 parts by weight of the polymer particles (B2), tripotassium 0.38 parts by weight of phosphoric acid, (2 O FeSO 4 · 7H ) 0.00088 parts of ferrous sulfate, ethylenediaminetetraacetic acid -0.015 parts by weight of 2Na salt was charged into a pressure resistant polymer with a stirring blade, the temperature was raised to 45 ° C. while stirring, the inside was replaced with nitrogen, and deoxidization measures were taken using an aspirator. Then, 1.98 parts by weight of potassium semi-cured beef tallow, 20 parts by weight of styrene, 50 parts by weight of butadiene, 0.049 parts by weight of paramentan hydroperoxide were added, and 0.006 parts by weight of sodium formaldehyde sulfoxylate was added. Then, the polymerization reaction was started. Two hours after the start of the polymerization reaction, 0.018 parts by weight of paramenthane hydroperoxide and 0.038 parts by weight of sodium formaldehyde sulfoxylate were added, and one hour later, the temperature was raised to 55 ° C. After a further 2 hours, 30 parts by weight of butadiene, after a further hour, 0.018 parts by weight p-menthane hydroperoxide, (2 O FeSO 4 · 7H ) 0.0013 parts by weight of ferrous sulfate, ethylenediaminetetraacetic acid · 2Na 0.0022 parts by weight of salt was added, and after 1 hour, the temperature was raised to 60 ° C. After 1 hour from the temperature rise, 0.019 parts by weight of paramentan hydroperoxide was added, and stirring was continued for another 2 hours to obtain a polymer particle latex having a conversion rate of 98% and a volume average particle diameter of 81 nm.
水３．５重量部、ジラウリルチオジプロピオネート１．５重量部、トリエチレングリコール−ビス［３ー（３−ｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート］１．５重量部、半硬化牛脂脂肪酸カリウム０．４７重量部からなる混合物をホモジナイザーにより乳化した後、重合体粒子ラテックスに添加した。さらに塩化カルシウムの２５％水溶液５．０重量部を添加し、重合体粒子を凝固させ、ペーパーフィルターを用いて凝固物を分取、水により洗浄した後、５０℃で２日間乾燥させ、重合体粒子（Ｂ２）の凝集した粉体を得た。 3.5 parts by weight of water, 1.5 parts by weight of dilaurylthiodipropionate, 1.5 parts by weight of triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] , Semi-cured beef tallow fatty acid potassium 0.47 parts by weight was emulsified with a homogenizer and then added to the polymer particle latex. Further, 5.0 parts by weight of a 25% aqueous solution of calcium chloride was added to coagulate the polymer particles, the coagulated product was separated using a paper filter, washed with water, and then dried at 50 ° C. for 2 days to obtain the polymer. An agglomerated powder of particles (B2) was obtained.
（比較製造例２）重合体粒子（Ｂ３）の製造
水２００重量部、硫酸第一鉄（ＦｅＳＯ４・７Ｈ２Ｏ）０．００１２重量部、エチレンジアミン４酢酸・２Ｎａ塩０．００２０重量部を撹拌翼付き耐圧重合器に仕込み、撹拌しながら４５℃に昇温し、内部を窒素置換し、さらにアスピレータを用いて脱酸措置を施した。その後、ポリオキシエチレンラウリルエーテルリン酸ナトリウム塩０．０７重量部、スチレン２０．０重量部、ブタジエン８０．０重量部を添加し、パラメンタンハイドロパーオキサイド０．０２８重量部、ホルムアルデヒドスルフォキシル酸ナトリウム０．０５重量部を添加し、重合反応を開始した。さらに２．５時間後、ポリオキシエチレンラウリルエーテルリン酸ナトリウム塩０．３７重量部、さらに２時間後、ポリオキシエチレンラウリルエーテルリン酸ナトリウム塩０．３７重量部、さらに１．５時間後、パラメンタンハイドロパーオキサイド０．０１４重量部、ポリオキシエチレンラウリルエーテルリン酸ナトリウム塩０．３７重量部、さらに４時間後、パラメンタンハイドロパーオキサイド０．０１４重量部を添加し、５５℃に昇温した。さらに３時間後、パラメンタンハイドロパーオキサイド０．０１４重量部、さらに３時間後、パラメンタンハイドロパーオキサイド０．０１４重量部を添加し、６５℃に昇温した。さらに３時間後パラメンタンハイドロパーオキサイド０．０１４重量部を添加し、重合反応開始から２１時間後、転化率９６％、体積平均粒子径１３４ｎｍの重合体粒子ラテックスを得た。
(Comparative Production Example 2) 200 parts by weight produced water of the polymer particles (B3), stirred ferrous (FeSO 4 · 7H 2 O) 0.0012 parts by weight of ethylenediamine tetraacetic acid · 2Na salt 0.0020 parts by weight of sulfuric acid It was charged in a pressure-resistant polymerizer with wings, heated to 45 ° C. with stirring, the inside was replaced with nitrogen, and deoxidized measures were taken using an aspirator. Then, 0.07 parts by weight of polyoxyethylene lauryl ether sodium phosphate, 20.0 parts by weight of styrene, and 80.0 parts by weight of butadiene were added, and 0.028 parts by weight of paramentan hydroperoxide and formaldehyde sulfoxylic acid were added. 0.05 parts by weight of sodium was added to initiate the polymerization reaction. After another 2.5 hours, 0.37 parts by weight of polyoxyethylene lauryl ether sodium phosphate salt, after another 2 hours, 0.37 parts by weight of polyoxyethylene lauryl ether sodium phosphate, and after another 1.5 hours, para 0.014 parts by weight of mentan hydroperoxide, 0.37 parts by weight of polyoxyethylene lauryl ether sodium phosphate salt, and after 4 hours, 0.014 parts by weight of paramentan hydroperoxide were added and the temperature was raised to 55 ° C. .. After 3 hours, 0.014 parts by weight of paramentan hydroperoxide was added, and after 3 hours, 0.014 parts by weight of paramentan hydroperoxide was added, and the temperature was raised to 65 ° C. After 3 hours, 0.014 parts by weight of paramentan hydroperoxide was added, and 21 hours after the start of the polymerization reaction, a polymer particle latex having a conversion rate of 96% and a volume average particle diameter of 134 nm was obtained.
水３．５重量部、ジラウリルチオジプロピオネート１．５重量部、トリエチレングリコール−ビス［３−（３−ｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート］１．５重量部、半硬化牛脂脂肪酸カリウム０．４７重量部からなる混合物をホモジナイザーにより乳化した後、重合体粒子ラテックスに添加した。さらに塩化カルシウムの２５％水溶液５．０重量部を添加し、重合体粒子を凝固させ、ペーパーフィルターを用いて凝固物を分取、水により洗浄した後、５０℃で２日間乾燥させ、重合体粒子（Ｂ３）の凝集した粉体を得た。 3.5 parts by weight of water, 1.5 parts by weight of dilaurylthiodipropionate, 1.5 parts by weight of triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] , Semi-cured beef tallow fatty acid potassium 0.47 parts by weight was emulsified with a homogenizer and then added to the polymer particle latex. Further, 5.0 parts by weight of a 25% aqueous solution of calcium chloride was added to coagulate the polymer particles, the coagulated product was separated using a paper filter, washed with water, and then dried at 50 ° C. for 2 days to obtain the polymer. An agglomerated powder of particles (B3) was obtained.
（重合体粒子である一次粒子の平均粒子径の測定方法）
一次粒子の体積平均粒子径は、各製造例及び比較製造例で塩化カルシウム水溶液を添加して凝固させる前のラテックスの状態で、日機装株式会社製のＮａｎｏｔｒａｃ Ｗａｖｅを用いて測定した。
(Method of measuring the average particle size of primary particles, which are polymer particles)
The volume average particle size of the primary particles was measured using Nanotrac Wave manufactured by Nikkiso Co., Ltd. in the state of latex before adding an aqueous solution of calcium chloride to solidify in each production example and comparative production example.
（重合体粒子が凝集した粉体の平均粒子径の測定方法）
粉体の平均粒子径は、各製造例及び比較製造例で得た乾燥後の、重合体粒子の凝集した粉体について、日機装株式会社製のマイクロトラックＭＴ３０００ＩＩを使用して光散乱法に基づき測定した。あわせて、粉体全体に占める粒子径が７００μｍ以上の粉体の割合（体積％）、及び、粉体全体に占める粒子径が１０００μｍ以上の粉体の割合（体積％）を測定した。
(Method of measuring the average particle size of powder in which polymer particles are aggregated)
The average particle size of the powder is measured based on the light scattering method using the Microtrac MT3000II manufactured by Nikkiso Co., Ltd. for the agglomerated powder of the polymer particles after drying obtained in each production example and the comparative production example. did. In addition, the proportion of the powder having a particle diameter of 700 μm or more in the entire powder (volume%) and the proportion of the powder having a particle diameter of 1000 μm or more in the entire powder (volume%) were measured.
（実施例１及び比較例１〜３）配合物の混練から加硫シート作製まで
実施例１及び比較例１〜３では以下の材料を使用した。
ジエン系ゴム：
スチレン−ブタジエン共重合体ゴム：ＪＳＲ ＳＬ５５２、ＪＳＲ社製（以下ＳＢＲと略す。）８０重量部
ブタジエンゴム：ＪＳＲ ＢＲ０１、ＪＳＲ社製（以下ＢＲと略す。）２０重量部
(Example 1 and Comparative Examples 1 to 3) From kneading of the compound to preparation of a vulcanized sheet In Example 1 and Comparative Examples 1 to 3, the following materials were used.
Diene rubber:
Styrene-butadiene copolymer rubber: JSR SL552, manufactured by JSR (hereinafter abbreviated as SBR) 80 parts by weight butadiene rubber: JSR BR01, manufactured by JSR (hereinafter abbreviated as BR) 20 parts by weight
ゴム用改質剤：
製造例又は比較製造例で製造した重合体粒子の凝集した粉体１０重量部（比較例３では使用せず）
Rubber modifier:
10 parts by weight of agglomerated powder of polymer particles produced in Production Example or Comparative Production Example (not used in Comparative Example 3)
各種添加剤：
シリカ：Ｓｉｌｉｃａ ＡＱ（東ソーシリカ社製）６０重量部
可塑剤（プロセスオイル）：ＶｉｖａＴｅｃ５００（Ｈ＆Ｒ社製）２５重量部
シランカップリング剤：ＫＢＥ−８４６（信越シリコーン社製）４．８重量部
カーボンブラック：旭＃７８（旭カーボン社製）５重量部
酸化亜鉛：酸化亜鉛２種（堺化学社製）３重量部
ステアリン酸：ステアリン酸（日本精化社製）１重量部
老化防止剤：ノクラック６Ｃ（大内新興化学工業社製）２重量部
加硫剤：３２５メッシュ粉末硫黄（細井化学工業社製）１．４重量部
加硫促進剤（１）：ノクセラーＮＳ（大内新興化学工業社製）１．２重量部
加硫促進剤（２）：ノクセラーＤ（大内新興化学工業社製）１．２重量部
Various additives:
Silica: Silica AQ (manufactured by Toso Silica) 60 parts by weight Plastic agent (process oil): VivaTec500 (manufactured by H & R) 25 parts by weight silane coupling agent: KBE-846 (manufactured by Shin-Etsu Silicone) 4.8 parts by weight Carbon black : Asahi # 78 (manufactured by Asahi Carbon Co., Ltd.) 5 parts by weight Zinc oxide: Zinc oxide 2 types (manufactured by Sakai Chemical Co., Ltd.) 3 parts by weight Stericic acid: Steric acid (manufactured by Nippon Seika Co., Ltd.) 1 part by weight Anti-aging agent: Nocrack 6C (Manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) 2 parts by weight vulcanizing agent: 325 mesh powder sulfur (manufactured by Hosoi Chemical Industry Co., Ltd.) 1.4 parts by weight vulcanization accelerator (1): Noxeller NS (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) ) 1.2 parts by weight Vulcanization accelerator (2): Noxeller D (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) 1.2 parts by weight
まず、ラボプラストミル（東洋精機社製）を用いて、加硫剤および加硫促進剤である３２５メッシュ粉末硫黄、ノクセラーＮＳ、及びノクセラーＤ以外の配合剤を、１００℃設定、１００ｒｐｍで混練し、剪断発熱による温度上昇が１４０℃に到達してから更に混練を５分間継続して行った後に回転を止めて排出した。 First, using a lab plast mill (manufactured by Toyo Seiki Co., Ltd.), a compounding agent other than the vulcanizing agent and the vulcanization accelerator 325 mesh powdered sulfur, Noxeller NS, and Noxeller D is kneaded at 100 ° C. and 100 rpm. After the temperature rise due to the heat generated by shearing reached 140 ° C., kneading was continued for 5 minutes, and then the rotation was stopped and the mixture was discharged.
次に、加硫剤および加硫促進剤を追加し、３０℃設定、８０ｒｐｍで混練し、剪断発熱による温度上昇が９０℃になったところで排出した。このようにして得られたゴム組成物を１６０℃で３０分間圧縮成形して、ゴム組成物を架橋して、２ｍ／ｍ厚のシートを作製した。得られたシートを用いて、動的粘弾性、および耐摩耗性を評価した。また、加硫剤および加硫促進剤を追加する前の配合物を使用して加工性も評価した。結果を表１に示す。 Next, a vulcanizing agent and a vulcanization accelerator were added, kneaded at 30 ° C. and 80 rpm, and discharged when the temperature rise due to shear heat generation reached 90 ° C. The rubber composition thus obtained was compression molded at 160 ° C. for 30 minutes, and the rubber composition was crosslinked to prepare a sheet having a thickness of 2 m / m. The obtained sheet was used to evaluate dynamic viscoelasticity and abrasion resistance. The processability was also evaluated using the formulation before the addition of the vulcanizing agent and the vulcanization accelerator. The results are shown in Table 1.
（動的粘弾性）
各実施例及び比較例で得られたシートから切り出した１５ｍｍ×１５ｍｍ×２ｍｍの試験片について、動的粘弾性測定装置ＡＲＥＳ（ＴＡインスツルメント社製）を用いて、ＪＩＳ Ｋ−６３９４（加硫ゴム及び熱可塑性ゴムの動的性質試験方法）に準じて、８ｍｍφの平行円板形治具を用いて、周波数１６Ｈｚ、歪み０．１％、温度６０℃、昇温速度５℃／ｍｉｎの条件で６０℃ｔａｎδを測定した。
(Dynamic viscoelasticity)
JIS K-6394 (vulcanization) was used for a 15 mm × 15 mm × 2 mm test piece cut out from the sheets obtained in each Example and Comparative Example using a dynamic viscoelasticity measuring device ARES (manufactured by TA Instruments). Condition of frequency 16Hz, strain 0.1%, temperature 60 ° C., temperature rise rate 5 ° C./min using a parallel disk jig of 8 mmφ according to the dynamic property test method of rubber and thermoplastic rubber). 60 ° C. tan δ was measured.
６０℃ｔａｎδは転がり抵抗の指標となる測定値であり、この数値が小さいほど転がり抵抗が小さく、低燃費を達成できることを示す。表１では、比較例３で得られた６０℃ｔａｎδの数値を指標の１００とし、実施例１及び他の比較例で得られた６０℃ｔａｎδの数値を指数に換算して示した。 60 ° C. tan δ is a measured value that is an index of rolling resistance, and the smaller this value is, the smaller the rolling resistance is, and it is shown that low fuel consumption can be achieved. In Table 1, the numerical value of 60 ° C. tan δ obtained in Comparative Example 3 was set as an index of 100, and the numerical value of 60 ° C. tan δ obtained in Example 1 and other Comparative Examples was converted into an index and shown.
（耐摩耗性）
各実施例及び比較例で得られたシートについて、アクロン摩耗試験機ＡＢ２０３（株式会社上島製作所製）を用いて、ＪＩＳ Ｋ−６２６４ Ｂ法に準拠して、回転数７５ｒｐｍ（試験片）、負荷荷重２７．０Ｎ、角度１５度、予備試験５００回、本試験５００回で摩耗試験を実施した。摩耗試験前後でシートの重量を測定して、摩耗量を算出した。
(Abrasion resistance)
For the sheets obtained in each Example and Comparative Example, the Akron wear tester AB203 (manufactured by Ueshima Seisakusho Co., Ltd.) was used, and the rotation speed was 75 rpm (test piece) and the load was applied in accordance with the JIS K-6264 B method. A wear test was carried out at 27.0 N, an angle of 15 degrees, a preliminary test of 500 times, and a main test of 500 times. The amount of wear was calculated by measuring the weight of the sheet before and after the wear test.
得られた結果を、比較例３で得られた数値を指標の１００とし、実施例１及び他の比較例で得られた数値を指数に換算して表１に示した。この指数が小さいほど耐摩耗性に優れていることを示す。 The obtained results are shown in Table 1 by converting the numerical values obtained in Comparative Example 3 into an index of 100 and converting the numerical values obtained in Example 1 and other Comparative Examples into indexes. The smaller this index is, the better the wear resistance is.
（加工性）
各実施例及び比較例でラボプラストミルから排出した、加硫剤および加硫促進剤を追加する前の配合物を塊状化して、常温で３分間圧縮成形して、未加硫状態の３ｍ／ｍシートを得た。得られたシート表面を目視にて観察して以下の基準に従って４段階で加工性を評価した。この加工性が良好であることは、ジエン系ゴム中での重合体粉体の分散性が良好であることを示す。
◎シート表面にブツや荒れが無く表面性が極めて良好である。
○シート表面にブツや荒れが殆ど無く表面性が良好である。
△シート表面にブツや荒れが多数点在して表面性が悪い。
×シート表面にブツや荒れを伴い表面性が悪く、かつ厚みが不均一である。
(Workability)
The formulation discharged from the lab plast mill in each Example and Comparative Example before the addition of the vulcanizing agent and the vulcanization accelerator was agglomerated, compression-molded at room temperature for 3 minutes, and 3 m / in an unvulcanized state. I got an m sheet. The surface of the obtained sheet was visually observed and the workability was evaluated in 4 steps according to the following criteria. Good processability indicates that the dispersibility of the polymer powder in the diene rubber is good.
◎ The surface of the sheet is extremely good with no bumps or roughness.
○ The surface of the sheet has good surface properties with almost no bumps or roughness.
△ The surface of the sheet is poor in surface quality with many bumps and roughness.
× The surface of the sheet is rough and rough, and the surface quality is poor and the thickness is uneven.
表１より、実施例１は、転がり抵抗が小さく、また、耐摩耗性にも優れており、さらに、加工性（分散性）も良好であることが分かる。
From Table 1, it can be seen that Example 1 has low rolling resistance, excellent wear resistance, and good workability (dispersibility).
Claims (12)
ラジカル重合性反応基を２以上有する単量体（ただし、前記共役ジエン単量体は除く）単位５重量％以上４０重量％以下、及び
芳香族モノアルケニル単量体単位０重量％以上７０重量％以下から構成される重合体粒子。 Conjugated diene monomer unit 20% by weight or more and 95% by weight or less,
Monomer having 2 or more radically polymerizable reactive groups (excluding the conjugated diene monomer) Unit 5% by weight or more and 40% by weight or less, and aromatic monoalkenyl monomer unit 0% by weight or more and 70% by weight Polymer particles composed of the following.
A molded product molded from the rubber composition according to any one of claims 8 to 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019050190A JP2020152763A (en) | 2019-03-18 | 2019-03-18 | Polymer particle, rubber modifier, rubber composition and molding thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019050190A JP2020152763A (en) | 2019-03-18 | 2019-03-18 | Polymer particle, rubber modifier, rubber composition and molding thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2020152763A true JP2020152763A (en) | 2020-09-24 |
Family
ID=72557750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019050190A Pending JP2020152763A (en) | 2019-03-18 | 2019-03-18 | Polymer particle, rubber modifier, rubber composition and molding thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2020152763A (en) |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002000779A1 (en) * | 2000-06-29 | 2002-01-03 | Jsr Corporation | Rubber composition |
| JP2002012703A (en) * | 2000-04-27 | 2002-01-15 | Jsr Corp | Rubber composition |
| JP2002012633A (en) * | 2000-04-27 | 2002-01-15 | Jsr Corp | Crosslinked rubber particles and rubber composition |
| WO2002010273A1 (en) * | 2000-08-01 | 2002-02-07 | The Yokohama Rubber Co., Ltd. | Rubber composition and crosslinked rubber |
| JP2002047305A (en) * | 2000-07-31 | 2002-02-12 | Nippon Zeon Co Ltd | Method for producing conjugated diene-aromatic vinyl copolymer rubber |
| JP2002309107A (en) * | 2001-04-13 | 2002-10-23 | Jsr Corp | Conductive rubber composition and electromagnetic wave shielding material using the same |
| JP2005146053A (en) * | 2003-11-12 | 2005-06-09 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread |
| WO2005082995A1 (en) * | 2004-02-27 | 2005-09-09 | The Yokohama Rubber Co., Ltd. | Rubber composition and pneumatic tire using the same |
| JP2006257160A (en) * | 2005-03-15 | 2006-09-28 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread |
| JP2006282837A (en) * | 2005-03-31 | 2006-10-19 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread |
| WO2012111640A1 (en) * | 2011-02-14 | 2012-08-23 | Jsr株式会社 | Rubber composition, method for producing same, and tire |
| JP2016533406A (en) * | 2014-06-03 | 2016-10-27 | エルジー・ケム・リミテッド | Polymer particle having core-shell structure and rubber composition containing the same |
| JP2018525484A (en) * | 2015-07-27 | 2018-09-06 | アランセオ・ドイチュランド・ゲーエムベーハー | Sealing gel, process for its production and its use in sealing compounds for self-sealing tires |
| JP2020507640A (en) * | 2017-01-26 | 2020-03-12 | アランセオ・ドイチュランド・ゲーエムベーハー | Foam sealing compound |
| JP2020508361A (en) * | 2017-01-26 | 2020-03-19 | アランセオ・ドイチュランド・ゲーエムベーハー | Filler-filled sealing gel, method for producing it and its use in sealing compounds for self-sealing tires |
-
2019
- 2019-03-18 JP JP2019050190A patent/JP2020152763A/en active Pending
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002012703A (en) * | 2000-04-27 | 2002-01-15 | Jsr Corp | Rubber composition |
| JP2002012633A (en) * | 2000-04-27 | 2002-01-15 | Jsr Corp | Crosslinked rubber particles and rubber composition |
| WO2002000779A1 (en) * | 2000-06-29 | 2002-01-03 | Jsr Corporation | Rubber composition |
| JP2002047305A (en) * | 2000-07-31 | 2002-02-12 | Nippon Zeon Co Ltd | Method for producing conjugated diene-aromatic vinyl copolymer rubber |
| WO2002010273A1 (en) * | 2000-08-01 | 2002-02-07 | The Yokohama Rubber Co., Ltd. | Rubber composition and crosslinked rubber |
| JP2002309107A (en) * | 2001-04-13 | 2002-10-23 | Jsr Corp | Conductive rubber composition and electromagnetic wave shielding material using the same |
| JP2005146053A (en) * | 2003-11-12 | 2005-06-09 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread |
| WO2005082995A1 (en) * | 2004-02-27 | 2005-09-09 | The Yokohama Rubber Co., Ltd. | Rubber composition and pneumatic tire using the same |
| JP2006257160A (en) * | 2005-03-15 | 2006-09-28 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread |
| JP2006282837A (en) * | 2005-03-31 | 2006-10-19 | Yokohama Rubber Co Ltd:The | Rubber composition for tire tread |
| WO2012111640A1 (en) * | 2011-02-14 | 2012-08-23 | Jsr株式会社 | Rubber composition, method for producing same, and tire |
| JP2016533406A (en) * | 2014-06-03 | 2016-10-27 | エルジー・ケム・リミテッド | Polymer particle having core-shell structure and rubber composition containing the same |
| JP2018525484A (en) * | 2015-07-27 | 2018-09-06 | アランセオ・ドイチュランド・ゲーエムベーハー | Sealing gel, process for its production and its use in sealing compounds for self-sealing tires |
| JP2020507640A (en) * | 2017-01-26 | 2020-03-12 | アランセオ・ドイチュランド・ゲーエムベーハー | Foam sealing compound |
| JP2020508361A (en) * | 2017-01-26 | 2020-03-19 | アランセオ・ドイチュランド・ゲーエムベーハー | Filler-filled sealing gel, method for producing it and its use in sealing compounds for self-sealing tires |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0849321B1 (en) | Diene rubber composition | |
| JP3736577B2 (en) | Rubber composition and method for producing the same | |
| US8662125B2 (en) | Modified gel particles and rubber composition | |
| JP5739094B2 (en) | Rubber mixtures containing functionalized diene rubbers and microgels, methods for making these mixtures, and uses | |
| US6114432A (en) | Diene rubber composition | |
| US20010053813A1 (en) | Rubber compositions | |
| EP0806452A1 (en) | Rubber composition and process for preparing the same | |
| JPH10204217A (en) | Rubber mixture containing sbr rubber gel | |
| JP6831923B2 (en) | A method for producing a conjugated diene-based copolymer, a conjugated diene-based copolymer produced from the method, and a rubber composition containing the same. | |
| EP1748056B1 (en) | Tire tread containing core-shell particles | |
| EP1081162A1 (en) | Conjugated diene rubber, process for producing the same, and rubber composition | |
| JP2002012703A (en) | Rubber composition | |
| JP2020152763A (en) | Polymer particle, rubber modifier, rubber composition and molding thereof | |
| JP7299908B2 (en) | Rubber composition for tire, tire and molding | |
| JP5319041B2 (en) | Rubber composition | |
| JP2002012633A (en) | Crosslinked rubber particles and rubber composition | |
| JP4774654B2 (en) | Oil-extended rubber and rubber composition | |
| JP7160473B2 (en) | Conjugated diene-based copolymer composition, method for producing the same, and rubber composition containing the same | |
| JP6753035B2 (en) | Rubber composition | |
| JP3216267B2 (en) | Vulcanizable rubber composition | |
| JP4670132B2 (en) | Conjugated diene polymer and process for producing the same | |
| JP3970631B2 (en) | Rubber composition and pneumatic tire using the same | |
| JP2001226529A (en) | Rubber-like polymer composition | |
| Wang | Enhancing performance, durability and service life of industrial rubber products by silica and silane fillers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220113 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20221125 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20221227 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20230620 |