JP2007297416A - Manufacturing method of rubber composition - Google Patents
Manufacturing method of rubber composition Download PDFInfo
- Publication number
- JP2007297416A JP2007297416A JP2006123775A JP2006123775A JP2007297416A JP 2007297416 A JP2007297416 A JP 2007297416A JP 2006123775 A JP2006123775 A JP 2006123775A JP 2006123775 A JP2006123775 A JP 2006123775A JP 2007297416 A JP2007297416 A JP 2007297416A
- Authority
- JP
- Japan
- Prior art keywords
- silica
- rubber
- weight
- parts
- oil emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 137
- 239000005060 rubber Substances 0.000 title claims abstract description 137
- 239000000203 mixture Substances 0.000 title claims abstract description 84
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 382
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 188
- 239000000839 emulsion Substances 0.000 claims abstract description 75
- 229920000126 latex Polymers 0.000 claims abstract description 69
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000004606 Fillers/Extenders Substances 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 239000004816 latex Substances 0.000 claims abstract description 28
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 26
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 21
- 239000003995 emulsifying agent Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000005299 abrasion Methods 0.000 abstract description 6
- 239000003921 oil Substances 0.000 description 105
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 46
- 238000004132 cross linking Methods 0.000 description 28
- 239000007787 solid Substances 0.000 description 23
- 239000007900 aqueous suspension Substances 0.000 description 21
- 238000005345 coagulation Methods 0.000 description 20
- 239000002245 particle Substances 0.000 description 18
- 230000000704 physical effect Effects 0.000 description 18
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000000725 suspension Substances 0.000 description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- -1 long-chain fatty acid salt Chemical class 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 125000000129 anionic group Chemical group 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 238000004898 kneading Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 description 8
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 239000012190 activator Substances 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 7
- 235000019241 carbon black Nutrition 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 235000014692 zinc oxide Nutrition 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229920006317 cationic polymer Polymers 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 241001441571 Hiodontidae Species 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000008117 stearic acid Substances 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
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000003568 Sodium, potassium and calcium salts of fatty acids Substances 0.000 description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 210000002966 serum Anatomy 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-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
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-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
- 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 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-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
- 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
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 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
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000004664 distearyldimethylammonium chloride (DHTDMAC) Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
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- 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
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、シリカ及び伸展油を含有したゴム組成物の新規な製造方法に関する。詳しくは、スチレンブタジエン共重合ゴムなどのジエン系ゴム中に伸展油、シリカを高度に分散させた加工性が良好で引張強度や耐摩耗性などの物性に優れたゴム組成物の製造方法に関する。 The present invention relates to a novel method for producing a rubber composition containing silica and an extending oil. More specifically, the present invention relates to a method for producing a rubber composition excellent in processability and excellent in physical properties such as tensile strength and wear resistance, in which extender oil and silica are highly dispersed in a diene rubber such as styrene-butadiene copolymer rubber.
近年の自動車に対する低燃費化の要求に伴い、ウェットグリップ性や耐摩耗性に優れるだけでなく、転がり抵抗の小さい自動車用タイヤが要望されている。通常、自動車用タイヤは、天然ゴム、ブタジエンゴム、スチレンブタジエン共重合ゴムなどのジエン系ゴムに充填材としてカーボンブラックを配合したゴム組成物が使用されているが、上記転がり抵抗を低減させるため、カーボンブラックの代わりにシリカが用いられるようになってきた。特に、地面と接するタイヤトレッド部には伸展油を含有させたゴム、いわゆる油展ゴムに充填材としてシリカを配合したゴム組成物が広く用いられている。
しかしながら、シリカはその表面がシラノール基に覆われ、強い自己凝集性を持っているために、ゴム中へ良好に分散させることは困難であり、ゴム混練時間を長くしても均一に分散せず、その結果、耐摩耗性が悪化するという欠点を有していた。
With the recent demand for fuel efficiency reduction for automobiles, there is a demand for automobile tires that not only have excellent wet grip and wear resistance, but also have low rolling resistance. Usually, a rubber composition in which carbon black is blended as a filler to a diene rubber such as natural rubber, butadiene rubber, and styrene butadiene copolymer rubber is used for an automobile tire, but in order to reduce the rolling resistance, Silica has been used instead of carbon black. In particular, a rubber composition in which silica is added to a rubber containing an extension oil, that is, a so-called oil-extended rubber, is widely used in a tire tread portion that is in contact with the ground.
However, since silica is covered with silanol groups and has a strong self-aggregation property, it is difficult to disperse it well in rubber. As a result, there was a drawback that the wear resistance deteriorated.
そこで、ゴム中のシリカの分散性を改善する方法として、ゴムラテックスとシリカとを適当な割合で混合した後、ゴムラテックス中のゴムを酸や塩などの凝固剤などを用いて凝固させることによって、該凝固したゴム中にシリカを均一に取り込ませる、いわゆる「共凝固」により、シリカを含有したゴム組成物を得る方法が検討されている。例えば、アルキルトリメチルアンモニウム塩でシリカを処理した後にゴムラテックスと混合し、塩化ナトリウムなどの塩と硫酸などの無機酸を用いて共凝固させる方法（特許文献１）、カチオン性高分子を含有するシリカの水性懸濁液とゴムラテックスを混合すると同時に、或いは混合した後に共凝固させる方法（特許文献２）が提案されている。 Therefore, as a method of improving the dispersibility of silica in rubber, after mixing rubber latex and silica in an appropriate ratio, the rubber in rubber latex is coagulated using a coagulant such as acid or salt. A method for obtaining a rubber composition containing silica by so-called “co-coagulation” in which silica is uniformly taken into the coagulated rubber has been studied. For example, a method in which silica is treated with an alkyltrimethylammonium salt and then mixed with rubber latex and co-coagulated with a salt such as sodium chloride and an inorganic acid such as sulfuric acid (Patent Document 1), silica containing a cationic polymer There has been proposed a method of co-coagulation (Patent Document 2) at the same time as or after mixing an aqueous suspension of the above and a rubber latex.
上記『共凝固』によるゴム組成物の製造方法においては、金属石鹸などのアニオン性界面活性剤を用いてモノマーを水中に乳化させラジカル重合させる、いわゆる乳化重合で製造するジエン系ゴムが、重合後のゴムラテックスをそのまま用いることができることから好適に採用される。さらに、上記ゴムラテックスにアニオン性界面活性剤で水中に乳化させた伸展油エマルジョンを加えた油展ゴムラテックスとカチオン性高分子を含有したシリカの水性懸濁液を混合し、共凝固させる方法（特許文献３）も開示されている。
油展ゴムラテックスを用いることにより、優れた物性を有するゴム組成物は得られるものの、伸展油エマルジョンとゴムラテックスの混合液は不安定であるため、油展ゴムラテックスをシリカの水性懸濁液と混合するまで、伸展油が分離しないように温度や攪拌条件などを適切に設定しておく必要がある。
In the above method for producing a rubber composition by “co-coagulation”, a diene rubber produced by so-called emulsion polymerization, in which a monomer is emulsified in water using an anionic surfactant such as a metal soap, is radically polymerized. This rubber latex is preferably employed because it can be used as it is. Further, a method of mixing and co-coagulating an oil-extended rubber latex obtained by adding an extending oil emulsion emulsified in water with an anionic surfactant to the rubber latex and an aqueous suspension of silica containing a cationic polymer ( Patent document 3) is also disclosed.
Although a rubber composition having excellent physical properties can be obtained by using an oil-extended rubber latex, the mixture of the extended oil emulsion and the rubber latex is unstable. Until mixing, it is necessary to set the temperature and stirring conditions appropriately so that the extending oil does not separate.
また、上記カチオン性高分子を含有したシリカの水性懸濁液を使用した方法で得られる共凝固物は、伸展油及びシリカの分散性に優れているが、それに架橋剤を配合したゴム組成物において、加工条件によっては、ゴムが部分的に架橋を起こし、後の成形ができなくなる現象、所謂、「スコーチ」を起こしやすいことが指摘されている。
そこで、スコーチ防止剤を配合する方法（特許文献４）や特定の加硫促進剤を配合する方法（特許文献５）が提案されているが、共凝固により得られるゴム組成物自体の改良も望まれていた。
Therefore, a method of blending a scorch inhibitor (Patent Document 4) and a method of blending a specific vulcanization accelerator (Patent Document 5) have been proposed, but improvement of the rubber composition itself obtained by co-coagulation is also desired. It was rare.
従って、本発明の目的は、スチレンブタジエン共重合ゴムなどのジエン系ゴム中に伸展油、シリカを高度に分散させた、耐スコーチ性が良好で、優れた引張強度や耐摩耗性などの物性を付与できるゴム組成物を、容易に効率よく製造する方法を提供することにある。 Accordingly, the object of the present invention is to provide a highly dispersed scorch resistance and excellent physical properties such as excellent tensile strength and wear resistance, in which extender oil and silica are highly dispersed in a diene rubber such as styrene-butadiene copolymer rubber. An object of the present invention is to provide a method for easily and efficiently producing a rubber composition that can be applied.
本発明者等は、上記技術課題を解決すべく鋭意研究を行なってきた。その結果、ジエン系ゴムラテックス、伸展油エマルジョン、シリカを混合し、ジエン系ゴムラテックス中のジエン系ゴム、伸展油エマルジョン中の伸展油、シリカを共凝固させて得られるゴム組成物において、伸展油エマルジョンに使用する界面活性剤を、従来から使用されているアニオン性の界面活性剤に代えて、カチオン性界面活性剤を用いることにより、安定性に課題であったゴムラテックスと伸展油エマルジョンの混合工程を経なくても、容易に効率よく凝固が進行し、また、これによりシリカ及び伸展油の分散性が良好なゴム組成物を得ることができ、さらには、それを用いたゴム組成物は耐スコーチ性が良好であることを見出し、本発明を完成した。 The present inventors have conducted intensive research to solve the above technical problems. As a result, diene rubber latex, extender oil emulsion, silica are mixed, diene rubber in diene rubber latex, extender oil in extender oil emulsion, rubber composition obtained by co-coagulation of silica, extender oil By using a cationic surfactant instead of the anionic surfactant used in the past for the surfactant used in the emulsion, mixing the rubber latex and the extender oil emulsion, which was a problem in stability Even without passing through the process, coagulation easily proceeds efficiently, and a rubber composition with good dispersibility of silica and extender oil can be obtained thereby. The present invention was completed by finding that the scorch resistance was good.
即ち、本発明は、アニオン性界面活性剤を乳化剤とするジエン系ゴムラテックス、伸展油エマルジョン、シリカを混合し、ジエン系ゴムラテックス中のジエン系ゴム、伸展油エマルジョン中の伸展油、シリカを共凝固させて伸展油及びシリカを含有したゴム組成物を製造する方法であって、伸展油エマルジョンとしてカチオン性界面活性剤を乳化剤とする伸展油エマルジョンを使用することを特徴とするゴム組成物の製造方法である。 That is, the present invention mixes a diene rubber latex containing an anionic surfactant as an emulsifier, an extension oil emulsion, and silica, and mixes the diene rubber in the diene rubber latex, the extension oil in the extension oil emulsion, and silica. A method for producing a rubber composition containing an extender oil and silica by coagulation, wherein an extender oil emulsion using a cationic surfactant as an emulsifier is used as the extender oil emulsion. Is the method.
また、本発明は、上記方法の一態様として、アニオン性界面活性剤を乳化剤とするジエン系ゴムラテックス、カチオン性界面活性剤を乳化剤とする伸展油エマルジョン及びシリカを同時に混合した後、該混合液のｐＨを７以下に調整し、ジエン系ゴムラテックス中のジエン系ゴム、伸展油エマルジョン中の伸展油、シリカを共凝固させることを特徴とするゴム組成物の製造方法；
カチオン性界面活性剤を乳化剤とする伸展油エマルジョン及びシリカを予め混合し、次いでアニオン性界面活性剤を乳化剤とするジエン系ゴムラテックスと混合した後にｐＨを７以下に調整し、ジエン系ゴムラテックス中のジエン系ゴム、伸展油エマルジョン中の伸展油、シリカを共凝固させることを特徴とするゴム組成物の製造方法；及び、
アニオン性界面活性剤を乳化剤とするジエン系ゴムラテックス及びシリカ予め混合し、次いでカチオン性界面活性剤を乳化剤とする伸展油エマルジョンを混合した後にｐＨを７以下に調整し、ジエン系ゴムラテックス中のジエン系ゴム、伸展油エマルジョン中の伸展油、シリカを共凝固させることを特徴とするゴム組成物の製造方法を提供する。
The present invention also provides a diene rubber latex having an anionic surfactant as an emulsifier, an extending oil emulsion having a cationic surfactant as an emulsifier, and silica at the same time. Adjusting the pH to 7 or less, and co-coagulating the diene rubber in the diene rubber latex, the extend oil in the extend oil emulsion, and silica;
In the diene rubber latex, the extender oil emulsion using a cationic surfactant as an emulsifier and silica are mixed in advance, and then mixed with a diene rubber latex using an anionic surfactant as an emulsifier, and then the pH is adjusted to 7 or less. A process for producing a rubber composition comprising co-coagulating a diene rubber, an extension oil in an extension oil emulsion, and silica; and
A diene rubber latex and an silica having an anionic surfactant as an emulsifier are mixed in advance, and then an extending oil emulsion having a cationic surfactant as an emulsifier is mixed, and then the pH is adjusted to 7 or less. Provided is a method for producing a rubber composition comprising co-coagulating a diene rubber, an extending oil in an extending oil emulsion, and silica.
さらに、本発明は、上記方法の一態様において、中間混合物として存在し、それのみで流通可能で、且つ、アニオン性界面活性剤を乳化剤とするジエン系ゴムラテックスと混合することによって本発明の目的とする共凝固物を得ることが可能な組成物として、水、伸展油、シリカ及びカチオン性界面活性剤を含有してなるシリカ含有伸展油エマルジョンをも提供する。 Furthermore, the present invention provides an object of the present invention by mixing with a diene rubber latex that exists as an intermediate mixture, can be distributed by itself, and has an anionic surfactant as an emulsifier in one embodiment of the above method. As a composition capable of obtaining the co-coagulated product, a silica-containing stretch oil emulsion comprising water, stretch oil, silica and a cationic surfactant is also provided.
本発明によれば、スチレンブタジエン共重合ゴムなどのジエン系ゴム中に伸展油、シリカを高度に分散させた耐スコーチ性に優れたゴム組成物を容易に効率よく製造でき、優れた引張強度や耐摩耗性などの物性を付与できる。
したがって、本発明のゴム組成物およびそれを架橋してなるゴム組成物は、その特性を生かす各種用途、例えば、トレッド、アンダートレッド、カーカス、サイドウオール、ビード部などのタイヤ用部材；ホース、窓枠、ベルト、靴底、防振ゴム、自動車部品、免震ゴムなどのゴム部材；耐衝撃性ポリスチレン、ＡＢＳ樹脂等の樹脂強化ゴム部材；などに利用できる。なかでも、タイヤ用部材として好適であり、低燃費タイヤのタイヤトレッドとして特に好適である。
According to the present invention, it is possible to easily and efficiently produce a rubber composition excellent in scorch resistance in which an extension oil and silica are highly dispersed in a diene rubber such as a styrene-butadiene copolymer rubber, and an excellent tensile strength and Physical properties such as wear resistance can be imparted.
Therefore, the rubber composition of the present invention and the rubber composition formed by crosslinking the rubber composition are used for various applications utilizing the characteristics, for example, tire members such as a tread, an under tread, a carcass, a side wall, and a bead part; a hose, a window It can be used for rubber members such as frames, belts, shoe soles, anti-vibration rubber, automobile parts, and seismic isolation rubber; resin-reinforced rubber members such as impact-resistant polystyrene and ABS resin; Especially, it is suitable as a member for tires, and is particularly suitable as a tire tread of a low fuel consumption tire.
（ジエン系ゴム）
本発明において用いられるジエン系ゴムラテックスは、アニオン性界面活性剤で乳化されたジエン系ゴムラテックス（以下、アニオン性ゴムラテックスともいう）が特に制限無く使用される。具体的には、乳化剤としてアニオン性界面活性剤を用い、乳化重合により製造されるジエン系の合成ゴムラテックスなどの公知のアニオン性ゴムラテックスが挙げられる。
上記乳化剤に用いられるアニオン性界面活性剤としては、例えば、炭素数１０以上の長鎖脂肪酸塩および／またはロジン酸塩が好ましい。具体例としては、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、オレイン酸、ステアリン酸などの脂肪酸のカリウム塩またはナトリウム塩が例示される。
(Diene rubber)
As the diene rubber latex used in the present invention, a diene rubber latex emulsified with an anionic surfactant (hereinafter also referred to as an anionic rubber latex) is used without particular limitation. Specific examples include known anionic rubber latexes such as diene-based synthetic rubber latex produced by emulsion polymerization using an anionic surfactant as an emulsifier.
As the anionic surfactant used for the emulsifier, for example, a long-chain fatty acid salt and / or a rosinate having 10 or more carbon atoms is preferable. Specific examples include potassium salts or sodium salts of fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid.
上記アニオン性ゴムラテックスは、必要に応じて、老化防止剤を含有してもよい。かかる老化防止剤としては、例えば、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール、オクタデシル−３−（３‘，３’−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネートやスチレン化フェノールなどのフェノール系安定剤、２，４−ビス（オクチルチオメチル）−６−メチルフェノールなどのイオウ系安定剤、Ｎ−（１，３−ジメチルブチル）−Ｎ‘−フェニル−ｐ−フェニレンジアミンなどのアミン系安定剤、２，２，４−トリメチル−１，２−ジヒドロキノリンなどのキノリン系安定剤、ヒドロキノン系安定剤、リン系安定剤などが挙げられる。 The anionic rubber latex may contain an anti-aging agent as necessary. Examples of such an antioxidant include 2,6-di-tert-butyl-4-methylphenol, octadecyl-3- (3 ′, 3′-di-tert-butyl-4-hydroxyphenyl) propionate, and styrenation. Phenol stabilizers such as phenol, sulfur stabilizers such as 2,4-bis (octylthiomethyl) -6-methylphenol, N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine Amine stabilizers such as quinoline stabilizers such as 2,2,4-trimethyl-1,2-dihydroquinoline, hydroquinone stabilizers and phosphorus stabilizers.
前記アニオン性ゴムラテックス中のジエン系ゴムを具体的に例示すると、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、クロロプレンゴム、ブチルゴム、アクリルニトリルブタジエン共重合ゴム、スチレンブタジエンイソプレン共重合ゴム、ブタジエンイソプレン共重合ゴム、アクリロニトリルスチレンブタジエン共重合ゴム、アクリルゴムなどがあげられる。
これらのうち、長鎖脂肪酸塩および／またはロジン酸塩を乳化剤として、乳化重合により得られたジエン系の合成ゴムが好ましく、中でもスチレンブタジエン共重合ゴムが最も好ましい。
また、ヒドロキシル基、カルボキシル基、アルコキシシリル基、アミノ基、エポキシ基等の官能基を導入した変性ゴムラテックスを用いることができる。
前記ジエン系ゴムラテックスに含有されるジエン系ゴムのムーニー粘度（ＭＬ１＋４，１００℃）は、１０〜２００、好ましくは３０〜１５０の範囲である。
Specific examples of the diene rubber in the anionic rubber latex include isoprene rubber, butadiene rubber, styrene butadiene copolymer rubber, chloroprene rubber, butyl rubber, acrylonitrile butadiene copolymer rubber, styrene butadiene isoprene copolymer rubber, butadiene isoprene. Examples thereof include copolymer rubber, acrylonitrile styrene butadiene copolymer rubber, and acrylic rubber.
Of these, a diene-based synthetic rubber obtained by emulsion polymerization using a long-chain fatty acid salt and / or a rosinate as an emulsifier is preferable, and a styrene-butadiene copolymer rubber is most preferable.
Further, a modified rubber latex into which a functional group such as a hydroxyl group, a carboxyl group, an alkoxysilyl group, an amino group, or an epoxy group is introduced can be used.
The Mooney viscosity (ML1 + 4, 100 ° C.) of the diene rubber contained in the diene rubber latex is in the range of 10 to 200, preferably 30 to 150.
スチレンブタジエン共重合ゴム、スチレンブタジエンイソプレン共重合ゴム、アクリロニトリルスチレンブタジエン共重合ゴム等のラテックスに含有されるスチレン共重合ジエン系ゴムのスチレン量は６０重量％以下、好ましくは５０重量％以下である。アクリロニトリル共重合ジエン系ゴムのアクリロニトリル量は６０重量％以下、好ましくは５５重量％以下である。スチレン量やアクリロニトリル量が多すぎると多過ぎると発熱性やスキッド性や低温脆化が劣る。
これらのアニオン性ゴムラテックスは、単独で、あるいは２種類以上を組み合わせて使用することができる。
上記アニオン性ゴムラテックス中のゴムの濃度は、特に限定されず、目的、用途に応じて適宜設定すれば良い。通常は５〜８０重量％の範囲が好適である。
The styrene content of the styrene copolymer diene rubber contained in the latex such as styrene butadiene copolymer rubber, styrene butadiene isoprene copolymer rubber, and acrylonitrile styrene butadiene copolymer rubber is 60% by weight or less, preferably 50% by weight or less. The amount of acrylonitrile in the acrylonitrile copolymerized diene rubber is 60% by weight or less, preferably 55% by weight or less. When the amount of styrene or the amount of acrylonitrile is too large, if it is too large, exothermic property, skid property and low temperature embrittlement are inferior.
These anionic rubber latexes can be used alone or in combination of two or more.
The concentration of the rubber in the anionic rubber latex is not particularly limited, and may be set as appropriate according to the purpose and application. Usually, the range of 5 to 80% by weight is preferable.
（伸展油）
本発明で用いる伸展油は、ゴム工業において通常使用されるものが使用でき、パラフィン系、芳香族系、ナフテン系の石油系軟化剤、植物系軟化剤、脂肪酸等が挙げられる。石油系軟化剤の場合には、多環芳香族の含有量が３％未満であることが好ましい。この含有量は、ＩＰ３４６の方法（英国のＴＨＥ ＩＮＳＴＩＴＵＴＥ ＰＥＴＲＯＬＥＵＭの検査方法）により測定される。また、上記伸展油の流動点は、好ましくは−５０℃〜＋７０℃、より好ましくは−３０℃〜＋５０℃である。流動点が低すぎると耐摩耗性が劣る傾向にあり、高すぎると伸展油の輸送が困難となる。
(Extension oil)
As the extender oil used in the present invention, those usually used in the rubber industry can be used, and examples thereof include paraffinic, aromatic and naphthenic petroleum softeners, plant softeners, fatty acids and the like. In the case of petroleum softeners, the polycyclic aromatic content is preferably less than 3%. This content is measured by the method of IP346 (the testing method of THE INSTITUTE PETROLEUM, UK). The pour point of the extending oil is preferably −50 ° C. to + 70 ° C., more preferably −30 ° C. to + 50 ° C. If the pour point is too low, the wear resistance tends to be inferior, and if it is too high, it becomes difficult to transport the extension oil.
本発明において伸展油は、カチオン性界面活性剤を乳化剤とする伸展油エマルジョンの形態で使用される。上記カチオン性界面活性剤は、水に溶かした際にイオンに解離して親油基の部分が正に解離するものであれば、何等制限無く使用できる。
カチオン性界面活性剤を更に具体的に例示すれば、ステアリルアミンアセテートなどのアルキルアミンアセテート類、セチルアミン塩酸塩、ステアリルアミン塩酸塩などのアルキルアミン塩酸塩類、ラウリルトリメチルアンモニウムクロライド、ステアリルトリメチルアンモニウムクロライド、セチルトリメチルアンモニウムクロライド、ジステアリルジメチルアンモニウムクロライド、ジデシルジメチルアンモニウムクロライドなどのアルキルアンモニウムハライド類、ラウリルジメチルアミンオキサイドなどのアルキルアミンオキサイド類、アルキルベンジルジメチルアンモニウムクロライドなどのアルキルアリールアンモニウムハライド類、ラウリルベタイン、ステアリルベタインなどのアルキルベタイン類などが挙げられる。これらのうち、アルキルトリメチルアンモニウムハライドが好ましく、中でも、ラウリルトリメチルアンモニウムクロライド、ステアリルトリメチルアンモニウムクロライド、セチルトリメチルアンモニウムクロライドが好ましい。
上記伸展油エマルジョンを調整する方法としては、何等制限はされないが、４０〜７０℃に加温した伸展油及び水、さらに上記カチオン性界面活性剤を混合し、ホモジナイザー、ホモミキサー、ウルトラミキサー等の、高速回転せん断型撹拌機を用いて分散させる方法が好適である。上記伸展油エマルジョン中の伸展油の濃度は、４０〜８０重量％が一般的である。
In the present invention, the extending oil is used in the form of an extending oil emulsion using a cationic surfactant as an emulsifier. The cationic surfactant can be used without any limitation as long as it is dissociated into ions when dissolved in water and the lipophilic group part is dissociated positively.
More specific examples of the cationic surfactant include alkylamine acetates such as stearylamine acetate, alkylamine hydrochlorides such as cetylamine hydrochloride and stearylamine hydrochloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyl Alkyl ammonium halides such as trimethylammonium chloride, distearyldimethylammonium chloride, didecyldimethylammonium chloride, alkylamine oxides such as lauryldimethylamine oxide, alkylarylammonium halides such as alkylbenzyldimethylammonium chloride, lauryl betaine, stearyl Examples include alkylbetaines such as betaine. Of these, alkyltrimethylammonium halides are preferable, and lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride are particularly preferable.
The method for preparing the extender oil emulsion is not limited in any way, but the extender oil and water heated to 40 to 70 ° C. and the cationic surfactant are mixed, and the homogenizer, homomixer, ultramixer, etc. A method of dispersing using a high-speed rotary shear type stirrer is preferable. The concentration of the extending oil in the extending oil emulsion is generally 40 to 80% by weight.
（シリカ）
本発明において、シリカは、ゴムに充填剤として添加されるシリカが特に制限なく使用される。例えば、珪酸アルカリと鉱酸との中和反応による、所謂、湿式法により製造される沈降シリカ、四塩化珪素を酸水素炎中で燃焼させて得られる乾式シリカ、テトラエメキシシランやテトラエトキシシラン等の珪素のアルコキシドを酸性あるいはアルカリ性の含水有機溶媒中で加水分解することによって得られるゾル−ゲル法シリカなどが挙げられる。また、沈降シリカにおいては、湿式法で、鉱酸の一部もしくは代わりに硫酸アルミニウムを用いて中和反応させた金属塩を多く含有した沈降シリカも用いることもできる。本発明においては、ゴムの補強性、生産性に優れる沈降シリカが好ましい。
上記沈降シリカについて、さらに詳細に説明すれば、窒素の吸着法により測定した比表面積（ＳBET ）は、７０〜３００ｍ2 ／ｇであるのが好ましく、８０〜２８０ｍ2 ／ｇであるのがより好ましく、９０〜２６０ｍ2 ／ｇであるのが最も好ましい。
上記シリカのセチルトリメチルアンモニウムブロマイド（ＣＴＡＢ）の吸着により測定した比表面積（ＳCTAB）は、６０〜３００ｍ2 ／ｇであるのが好ましく、７０〜２８０ｍ2 ／ｇであるのがより好ましく、８０〜２６０ｍ2 ／ｇであるのが最も好ましい。
(silica)
In the present invention, silica added as a filler to rubber is used without particular limitation. For example, the so-called wet silica produced by neutralization reaction between alkali silicate and mineral acid, dry silica obtained by burning silicon tetrachloride in an oxyhydrogen flame, tetraemexylsilane and tetraethoxysilane Examples thereof include sol-gel silica obtained by hydrolyzing silicon alkoxide such as in an acidic or alkaline water-containing organic solvent. In addition, in the precipitated silica, a precipitated silica containing a large amount of a metal salt neutralized with a part of a mineral acid or using aluminum sulfate in place of the mineral acid by a wet method can also be used. In the present invention, precipitated silica that is excellent in rubber reinforcement and productivity is preferred.
For the above precipitated silica, In detail, the measured specific surface area by the adsorption method of nitrogen (S BET) is preferably from 70~300m 2 / g, more that a 80~280m 2 / g Preferably, it is 90-260 m < 2 > / g.
Measured specific surface area by adsorption of cetyltrimethylammonium bromide of the silica (CTAB) (S CTAB) is preferably from 60~300m 2 / g, more preferably from 70~280m 2 / g, 80~ Most preferably, it is 260 m 2 / g.
さらに、上記シリカのジブチルフタレート吸油量（以下、単に吸油量ともいう）は１００〜４００ｍｌ／１００ｇのものが好ましく、１１０〜３５０ｍｌ／１００ｇのものがより好ましく、１２０〜３００ｍｌ／１００ｇであるものが最も好ましい。
本発明においては、シリカは粉状の状態でそのまま用いて良いが、シリカの水性懸濁液として用いるほうが、アニオン性ゴムラテックス、伸展油エマルジョンとの分散に優れるので好ましい。
上記シリカの水性懸濁液は、前述したシリカを水中に分散・懸濁させることにより調整できるが、本発明においては、これらのうち、珪酸アルカリと酸との中和反応によって得られたシリカを乾燥することなく、スラリー状あるいは湿ケーク状の形態で水に分散せしめて調整された水性懸濁液が好ましい。すなわち、乾燥工程を経ないで水に分散させることにより、シリカの物性設計の自由度が増し、乾燥時の熱収縮による自己凝集のデメリットを避けることができる。なお、上記水性懸濁液中のシリカの濃度は、通常は、１〜４０重量％のものが好適に使用される。
Furthermore, the silica dibutyl phthalate oil absorption (hereinafter also referred to simply as oil absorption) is preferably 100 to 400 ml / 100 g, more preferably 110 to 350 ml / 100 g, and most preferably 120 to 300 ml / 100 g. preferable.
In the present invention, silica may be used as it is in a powder state, but it is preferable to use it as an aqueous suspension of silica because it is excellent in dispersion with an anionic rubber latex and an extending oil emulsion.
The aqueous suspension of silica can be prepared by dispersing and suspending the above-described silica in water. In the present invention, silica obtained by neutralization reaction between an alkali silicate and an acid is used. An aqueous suspension prepared by dispersing in water in a slurry or wet cake form without drying is preferred. That is, by dispersing in water without passing through a drying step, the degree of freedom in designing the physical properties of silica is increased, and the disadvantage of self-aggregation due to heat shrinkage during drying can be avoided. In addition, as for the density | concentration of the silica in the said aqueous suspension, the thing of 1 to 40 weight% is normally used suitably.
本発明において、シリカの水性懸濁液中のシリカの平均粒子径は、特に限定されず、目的とする用途を勘案して適宜決定されればよい。一般的には、０．１〜５０μｍの範囲が好適に使用される。
上記平均粒子径を０．１μｍ以上にすることにより、シリカの自己凝集性による分散不良を防ぐことができ、得られるゴム組成物を用いて得られる加硫ゴムの硬度が良好になる。一方、平均粒子径を５０μｍ以下とすることにより、ゴム中でのシリカの分散が良好となり、十分な補強性が得られる。
その中でも、タイヤに用いられる場合は、シリカの平均粒子径を１μｍ以上、３０μｍ以下とするのが好ましい。
In the present invention, the average particle diameter of the silica in the aqueous silica suspension is not particularly limited, and may be appropriately determined in consideration of the intended use. In general, a range of 0.1 to 50 μm is preferably used.
By setting the average particle size to 0.1 μm or more, poor dispersion due to the self-aggregation of silica can be prevented, and the hardness of the vulcanized rubber obtained using the resulting rubber composition is improved. On the other hand, when the average particle size is 50 μm or less, the silica is well dispersed in the rubber, and sufficient reinforcement is obtained.
Among these, when used for a tire, the average particle diameter of silica is preferably 1 μm or more and 30 μm or less.
上記シリカの水性懸濁液の製造方法は、特に制限無く、目的とする水性懸濁液中のシリカの平均粒子径を勘案して、適宜分散方法を選択すればよい。シリカの平均粒子径が２０μｍ以上の水性懸濁液を製造する場合、せん断力の弱いプロペラ羽根、タービン羽根、パドル翼を有する一般撹拌機などを、シリカの平均粒子径が１〜２０μｍの水性懸濁液を製造する場合、ディスパーミキサー等の高速回転遠心放射型撹拌機、ホモジナイザー、ホモミキサー、ウルトラミキサー等の、高速回転せん断型撹拌機、コロイドミル、プラネタリミキサーなどを、シリカの平均粒子径が１μｍ以下の水性懸濁液を製造する場合、高圧ホモジナイザーなどを用いればよい。各分散機を用いる条件についても何等制限はなく、目的とする粒子径が得られるように適宜調整すればよい。 The method for producing the aqueous silica suspension is not particularly limited, and an appropriate dispersion method may be selected in consideration of the average particle diameter of silica in the target aqueous suspension. When an aqueous suspension having an average particle diameter of silica of 20 μm or more is produced, a general agitator having a propeller blade, a turbine blade, a paddle blade, etc., having a low shearing force is connected to an aqueous suspension having an average particle diameter of 1-20 μm. When producing suspensions, use a high-speed rotating centrifugal stirrer such as a disperser mixer, homogenizer, homomixer, or ultra mixer, a high-speed rotating shear stirrer, a colloid mill, or a planetary mixer. When producing an aqueous suspension of 1 μm or less, a high-pressure homogenizer or the like may be used. There are no restrictions on the conditions for using each disperser, and the conditions may be appropriately adjusted so as to obtain the desired particle size.
（各成分の混合方法）
本発明においては、上記アニオン性界面活性剤を乳化剤とするジエン系ゴムラテックス、カチオン性界面活性剤を乳化剤とする伸展油エマルジョン、シリカを混合し、ジエン系ゴムラテックス中のジエン系ゴム、伸展油エマルジョン中の伸展油、シリカを共凝固させることにより、伸展油及びシリカを含有したゴム組成物を得ることができる。
本発明のゴム組成物の製造方法において、アニオン性ゴムラテックス、伸展油エマルジョン、シリカの混合方法は、伸展油エマルジョンとゴムラテックスを優先的に混合する方法以外であれば良く、以下の方法が挙げられる。
(Mixing method of each component)
In the present invention, the diene rubber latex using the above anionic surfactant as an emulsifier, the extension oil emulsion using a cationic surfactant as an emulsifier, silica is mixed, and the diene rubber in the diene rubber latex and the extension oil are mixed. By co-coagulating the extending oil and silica in the emulsion, a rubber composition containing the extending oil and silica can be obtained.
In the method for producing a rubber composition of the present invention, the mixing method of the anionic rubber latex, the extending oil emulsion, and the silica may be any method other than the method of preferentially mixing the extending oil emulsion and the rubber latex, and examples thereof include the following methods. It is done.
（１）アニオン性界面活性剤を乳化剤とするジエン系ゴムラテックス、カチオン性界面活性剤を乳化剤とする伸展油エマルジョン及びシリカを同時に混合する方法。
（２）カチオン性界面活性剤を乳化剤とする伸展油エマルジョン及びシリカを予め混合し、次いでアニオン性界面活性剤を乳化剤とするジエン系ゴムラテックスと混合する方法。
（３）アニオン性界面活性剤を乳化剤とするジエン系ゴムラテックス及びシリカ予め混合し、次いでカチオン性界面活性剤を乳化剤とする伸展油エマルジョンを混合する方法。
(1) A method of simultaneously mixing a diene rubber latex using an anionic surfactant as an emulsifier, an extending oil emulsion using a cationic surfactant as an emulsifier, and silica.
(2) A method in which an extending oil emulsion using a cationic surfactant as an emulsifier and silica are mixed in advance, and then mixed with a diene rubber latex using an anionic surfactant as an emulsifier.
(3) A method in which a diene rubber latex and silica having an anionic surfactant as an emulsifier are mixed in advance, and then an extending oil emulsion having a cationic surfactant as an emulsifier is mixed.
これらのうち伸展油エマルジョンとシリカを優先的に混合する方法（２）が好ましく、特に、水１００重量部に対して、伸展油及びシリカの合計量が３〜３０重量部、好ましくは２〜２０重量部であり、伸展油に対するシリカの重量比が０．２〜１０、好ましくは０．５〜５であり、さらに、シリカ１００重量部に対してカチオン性界面活性剤を１〜４．５重量部、好ましくは１．５〜４重量部含有してなるシリカ含有伸展油エマルジョンとすると、シリカが沈降することのない安定なエマルジョンが得られ、さらに、アニオン性界面活性剤を乳化剤とするジエン系ゴムラテックスと混合した際の共凝固も速やかに進行する点で好ましい。
また、シリカの沈降をさらに長期間抑制したい場合には、上記範囲のシリカ含有伸展油エマルジョンの粘度を５０〜５０００ｍＰａ・ｓ、好ましくは１００〜３０００ｍＰａ・ｓに調整ことが望ましい。
Among these, the method (2) of preferentially mixing the extending oil emulsion and silica is preferred, and the total amount of the extending oil and silica is preferably 3 to 30 parts by weight, preferably 2 to 20 parts per 100 parts by weight of water. Parts by weight, the weight ratio of silica to extending oil is 0.2 to 10, preferably 0.5 to 5, and 1 to 4.5 parts by weight of cationic surfactant per 100 parts by weight of silica. Part, preferably 1.5 to 4 parts by weight of a silica-containing extender oil emulsion, a stable emulsion in which silica does not settle is obtained, and a diene system using an anionic surfactant as an emulsifier Co-coagulation when mixed with rubber latex is preferred in that it proceeds rapidly.
Moreover, when it is desired to further suppress the sedimentation of silica for a long period of time, it is desirable to adjust the viscosity of the silica-containing extending oil emulsion in the above range to 50 to 5000 mPa · s, preferably 100 to 3000 mPa · s.
本発明者らは、アニオン性ゴムラテックスとカチオン性界面活性剤を乳化剤とする伸展油エマルジョン、シリカを混合した場合の共凝固反応の機構については明らかではないが、カチオン性界面活性剤を用いることにより、親水性であり水中では負に帯電しているシリカと伸展油との親和性が向上し、その結果、疎水性であるゴムとの共凝固が容易に進行すると推定している。
なお、前記ジエン系ゴムと伸展油、シリカとの共凝固は、硫酸、燐酸、塩酸などの無機酸；蟻酸、酢酸、酪酸などの有機酸；硫酸アルミニウムなどのルイス酸；などの酸、塩化ナトリウム、塩化カルシウムなどの塩を用いて、凝固を完結させる。塩を用いると洗浄工程を長くする必要があるので、硫酸などの無機酸を用いてｐＨ７以下とするのが好ましい。通常は、ｐＨ４〜７の間で凝固させる。
The present inventors are not clear about the mechanism of co-coagulation reaction in the case of mixing an extended oil emulsion using an anionic rubber latex and a cationic surfactant as an emulsifier, and silica, but use a cationic surfactant. Thus, it is estimated that the affinity between the hydrophilic and negatively charged silica in the water and the extending oil is improved, and as a result, the co-coagulation with the hydrophobic rubber easily proceeds.
The co-coagulation of the diene rubber with the extender oil and silica is carried out by using inorganic acids such as sulfuric acid, phosphoric acid and hydrochloric acid; organic acids such as formic acid, acetic acid and butyric acid; Lewis acids such as aluminum sulfate; Complete the coagulation with a salt such as calcium chloride. When salt is used, it is necessary to lengthen the washing step. Therefore, it is preferable to adjust the pH to 7 or less using an inorganic acid such as sulfuric acid. Usually, it is solidified between pH 4-7.
本発明において、前記反応系における温度は、特に制限されないが、２０〜８０℃が好ましい。また、反応系の混合は、一般的に、プロペラ羽根、ディスパーミキサー、ホモジナイザー等の一般的な分散装置を用いて行う方法が好適に採用される。
本発明において、アニオン性ゴムラテックスと伸展油エマルジョン、シリカとの混合割合は特に制限されず、最終的に得られるゴム組成物の目的とする組成に応じて適宜決定すればよい。一般には、ゴム１００重量部に対して伸展油の配合量は、ジエン系ゴム１００重量部に対して、好ましく〜１００重量部、さらに好ましくは１０〜８０重量部、最も好ましくは１５〜６０重量部である。シリカが２０〜２００重量部、好ましくは２５〜１８０重量部、最も好ましくは３０〜１５０重量部となるように決定すればよい。
In the present invention, the temperature in the reaction system is not particularly limited, but is preferably 20 to 80 ° C. In general, the reaction system is preferably mixed by using a general dispersing apparatus such as a propeller blade, a disper mixer, or a homogenizer.
In the present invention, the mixing ratio of the anionic rubber latex, the extending oil emulsion, and silica is not particularly limited, and may be appropriately determined according to the intended composition of the finally obtained rubber composition. In general, the blending amount of the extender oil with respect to 100 parts by weight of rubber is preferably -100 parts by weight, more preferably 10-80 parts by weight, and most preferably 15-60 parts by weight with respect to 100 parts by weight of the diene rubber. It is. What is necessary is just to determine so that a silica may be 20-200 weight part, Preferably it is 25-180 weight part, Most preferably, it is 30-150 weight part.
（後処理）
本発明において、共凝固により得られる伸展油を含有したジエン系ゴムとシリカの固形分（以下、クラムという）のろ過、水洗、脱水、乾燥等、各々の工程についても特に制限されることはなく、一般的に用いられる方法を適宜使用すれば良い。クラムと液体成分（以下、セラムという）を分離し、得られたクラムを水洗し、ろ過後、スクイザ遠心脱水やフィルタープレス等で水分を絞って脱水し、粒状に粉砕した後に押出乾燥機、熱風式乾燥機や攪拌翼を有する間接加熱乾燥機などで乾燥し、ペレット状、あるいはブロック状に成形する方法が採用される。また、クラムとセラムを分離することなく、噴霧乾燥することにより、クラムを粉状に成形することができる。
(Post-processing)
In the present invention, there is no particular limitation on each step such as filtration, water washing, dehydration, and drying of the solids (hereinafter referred to as crumb) of diene rubber and silica containing the extender oil obtained by co-coagulation. A generally used method may be appropriately used. The crumb and liquid components (hereinafter referred to as serum) are separated, and the resulting crumb is washed with water, filtered, dewatered by squeezing the water with a squeezer centrifugal dewatering or filter press, etc. A method of drying by a type dryer or an indirect heating dryer having a stirring blade, and forming into a pellet shape or a block shape is employed. Further, the crumb can be formed into a powder by spray drying without separating the crumb and the serum.
本発明の方法によって得られるゴム組成物は、通常、ゴムに対して配合される公知の添加剤を必要に応じて配合することができ、また、必要に応じて架橋して実用に供される。 かかる添加剤としては、例えば、ゴム、追加のシリカ、カーボンブラック、カーボンブラック表面にシリカを担持させたカーボン−シリカデュアル・フェイズ・フィラー、タルク、クレー、炭酸カルシウムや水酸化アルミニウムなどの充填剤；追加の伸展油、シランカップリング剤、架橋剤、架橋促進剤、架橋活性化剤、老化防止剤、活性剤、可塑剤、滑剤などの配合剤が挙げられる。
追加のシリカ、伸展油としては、上記したゴム組成物中のシリカ、伸展油と同様の比表面積、吸油量を有したものが使用できる。
The rubber composition obtained by the method of the present invention can be blended with known additives that are usually blended with rubber as necessary, and is also put into practical use by crosslinking as necessary. . Examples of such additives include rubber, additional silica, carbon black, carbon-silica dual phase filler having silica supported on the surface of carbon black, talc, clay, fillers such as calcium carbonate and aluminum hydroxide; Additional extender oils, silane coupling agents, cross-linking agents, cross-linking accelerators, cross-linking activators, anti-aging agents, activators, plasticizers, lubricants and the like are included.
As the additional silica and extender oil, those having the same specific surface area and oil absorption as the silica and extender oil in the rubber composition described above can be used.
カーボンブラックとしては、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、グラファイトなどを用いることができる。これらの中でも、特にファーネスブラックが好ましく、その具体例としては、ＳＡＦ、ＩＳＡＦ、ＩＳＡＦ−ＨＳ、ＩＳＡＦ−ＬＳ、ＩＩＳＡＦ−ＨＳ、ＨＡＦ、ＨＡＦ−ＨＳ、ＨＡＦ−ＬＳ、ＦＥＦなどのグレードのものが挙げられる。これらのカーボンブラックは、それぞれ単独で、あるいは２種以上を組み合わせて用いることができる。 As carbon black, furnace black, acetylene black, thermal black, channel black, graphite, etc. can be used, for example. Among these, furnace black is particularly preferable, and specific examples thereof include SAF, ISAF, ISAF-HS, ISAF-LS, IISAF-HS, HAF, HAF-HS, HAF-LS, and FEF grades. It is done. These carbon blacks can be used alone or in combination of two or more.
本発明のゴム組成物にシランカップリング剤を添加すると、得られるゴム組成物において、引張特性および低発熱性がさらに改善されるため好ましい。
かかるシランカップリング剤としては、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、３−オクタチオ−１−プロピルトリエトキシシラン、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）ジスルフィドなどや、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を挙げることができる。また、シランカップリング剤は、一分子中に含有される硫黄が４個以下のものが、混練時のスコーチを避けられるために好ましい。これらのシランカップリング剤は、それぞれ単独で、あるいは２種以上を組み合わせて使用することができる。
It is preferable to add a silane coupling agent to the rubber composition of the present invention because the resulting rubber composition can further improve tensile properties and low exothermic properties.
Examples of the silane coupling agent include vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, 3-octathione. -1-propyltriethoxysilane, bis (3- (triethoxysilyl) propyl) tetrasulfide, bis (3- (triethoxysilyl) propyl) disulfide, and the like described in JP-A-6-248116. Examples thereof include tetrasulfides such as trimethoxysilylpropyldimethylthiocarbamyl tetrasulfide and γ-trimethoxysilylpropylbenzothiazyl tetrasulfide. In addition, the silane coupling agent is preferably one having 4 or less sulfur contained in one molecule because scorch during kneading can be avoided. These silane coupling agents can be used alone or in combination of two or more.
シランカップリング剤の配合量は、シリカ１００重量部に対して、好ましくは０．１〜３０重量部、より好ましくは１〜２０重量部、特に好ましくは２〜１０重量部である。
架橋剤としては、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、硫黄が好ましい。これらの架橋剤は、それぞれ単独で、あるいは２種以上を組み合わせて用いられる。架橋剤の配合量は、ゴム成分１００重量部に対して、好ましくは０．３〜１０重量部、より好ましくは０．５〜５重量部である。
The amount of the silane coupling agent is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, and particularly preferably 2 to 10 parts by weight with respect to 100 parts by weight of silica.
Examples of the crosslinking agent include sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur; sulfur halides such as sulfur monochloride and sulfur dichloride; dicumyl peroxide and ditertiary butyl peroxide. Organic peroxides such as p-quinone dioxime, quinone dioximes such as p, p'-dibenzoylquinone dioxime, triethylenetetramine, hexamethylenediamine carbamate, 4,4'-methylenebis-o-chloroaniline, etc. An organic polyvalent amine compound; an alkylphenol resin having a methylol group; and the like. Among these, sulfur is preferable. These crosslinking agents are used alone or in combination of two or more. The compounding amount of the crosslinking agent is preferably 0.3 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the rubber component.
架橋促進剤としては、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架橋促進剤；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架橋促進剤；ジエチルチオウレアなどのチオウレア系架橋促進剤；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架橋促進剤；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架橋促進剤；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架橋促進剤；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架橋促進剤；などの架橋促進剤が挙げられる。 Examples of the crosslinking accelerator include N-cyclohexyl-2-benzothiazole sulfenamide, Nt-butyl-2-benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, N-oxyethylene- Sulfenamide-based crosslinking accelerators such as 2-benzothiazole sulfenamide and N, N′-diisopropyl-2-benzothiazole sulfenamide; Agents: Thiourea crosslinking accelerators such as diethylthiourea; Thiazole crosslinking accelerators such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercaptobenzothiazole zinc salt; Tetramethylthiuram monosulfide, tetra Thiuram-based cross-linking accelerators such as tilthiuram disulfide; Dithiocarbamic acid-based cross-linking accelerators such as sodium dimethyldithiocarbamate and zinc diethyldithiocarbamate; And the like.
これらの架橋促進剤は、それぞれ単独で、あるいは２種以上を組み合わせて用いられるが、スルフェンアミド系架橋促進剤を含むものが好ましい。架橋促進剤の配合量は、ゴム成分１００重量部に対して、好ましくは０．３〜１０重量部、より好ましくは０．５〜５重量部である。
架橋活性化剤としては、例えば、ステアリン酸などの高級脂肪酸や酸化亜鉛などを用いることができる。酸化亜鉛としては、表面活性の高い粒度５μｍ以下のものを用いるのが好ましく、粒度が０．０５〜０．２μｍの活性亜鉛華や０．３〜１μｍの亜鉛華などを挙げることができる。また、酸化亜鉛は、アミン系の分散剤や湿潤剤で表面処理してあってもよい。これらの架橋活性化剤は、それぞれ単独で、あるいは２種以上を併用して用いることができる。架橋活性化剤の配合割合は、架橋活性化剤の種類により適宜選択される。高級脂肪酸の配合量は、ゴム成分１００重量部に対して、好ましくは０．３〜１０重量部、より好ましくは０．５〜５重量部である。酸化亜鉛の配合量は、ゴム成分１００重量部に対して、好ましくは０．１〜５重量部、より好ましくは０．５〜２重量部である。
さらに、配合剤としては、ジエチレングリコール、ポリエチレングリコール、シリコーンオイルなどの活性剤；充填剤；ワックスなどが挙げられる。
These crosslinking accelerators may be used alone or in combination of two or more, and those containing a sulfenamide-based crosslinking accelerator are preferred. The blending amount of the crosslinking accelerator is preferably 0.3 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the rubber component.
As the crosslinking activator, for example, higher fatty acids such as stearic acid, zinc oxide and the like can be used. As zinc oxide, those having a high surface activity particle size of 5 μm or less are preferably used, and examples thereof include activated zinc white having a particle size of 0.05 to 0.2 μm and zinc white having a particle size of 0.3 to 1 μm. Zinc oxide may be surface-treated with an amine-based dispersant or wetting agent. These crosslinking activators can be used alone or in combination of two or more. The blending ratio of the crosslinking activator is appropriately selected depending on the type of the crosslinking activator. The compounding amount of the higher fatty acid is preferably 0.3 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the rubber component. The compounding amount of zinc oxide is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight with respect to 100 parts by weight of the rubber component.
Further, examples of the compounding agent include activators such as diethylene glycol, polyethylene glycol, and silicone oil; fillers; waxes and the like.
本発明のゴム組成物を架橋してなるゴム組成物は、常法に従って本発明で得られるゴム組成物に各成分を混練後、架橋することにより得ることができる。例えば、ゴム組成物や他のゴム、架橋剤と架橋促進剤を除く配合剤、補強剤とを混練後、その混練物に架橋剤と架橋促進剤を混練してゴム組成物を得ることができる。ゴム組成物や他のゴム、架橋剤と架橋促進剤と除く配合剤、補強剤との混練温度は、好ましくは８０〜２００℃、より好ましくは１００〜１９０℃、特に好ましくは１４０〜１８０℃の範囲とする。次いで、得られた混練物を、好ましくは１００℃以下、より好ましくは８０℃以下まで冷却した後、それと架橋剤および架橋促進剤とを混練する。
架橋方法は、特に限定されず、架橋物の形状、大きさなどに応じて選択すればよい。金型中に架橋性ゴム組成物を充填して加熱することにより成形と同時に架橋してもよく、予め成形しておいた架橋性ゴム組成物を加熱して架橋してもよい。架橋温度や架橋時間も特に限定されず、架橋物の形状、大きさなどに応じて選択すればよい。架橋温度は、好ましくは１２０〜２００℃、より好ましくは１４０〜１８０℃である。
The rubber composition obtained by crosslinking the rubber composition of the present invention can be obtained by kneading each component with the rubber composition obtained by the present invention according to a conventional method and then crosslinking. For example, a rubber composition can be obtained by kneading a rubber composition, other rubber, a compounding agent excluding a crosslinking agent and a crosslinking accelerator, and a reinforcing agent and then kneading the kneaded material with a crosslinking agent and a crosslinking accelerator. . The kneading temperature of the rubber composition and other rubber, the compounding agent excluding the crosslinking agent and the crosslinking accelerator, and the reinforcing agent is preferably 80 to 200 ° C, more preferably 100 to 190 ° C, and particularly preferably 140 to 180 ° C. Range. Next, the obtained kneaded product is preferably cooled to 100 ° C. or lower, more preferably 80 ° C. or lower, and then kneaded with a crosslinking agent and a crosslinking accelerator.
The crosslinking method is not particularly limited, and may be selected according to the shape, size, etc. of the crosslinked product. The mold may be cross-linked simultaneously with molding by filling the mold with a cross-linkable rubber composition and heating, or the pre-molded cross-linkable rubber composition may be heated and cross-linked. The crosslinking temperature and the crosslinking time are not particularly limited, and may be selected according to the shape and size of the crosslinked product. The crosslinking temperature is preferably 120 to 200 ° C, more preferably 140 to 180 ° C.
本発明をさらに具体的に説明するために、以下に実施例および比較例を挙げて説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例および比較例における各種物性は、下記の方法により測定した。 In order to describe the present invention more specifically, examples and comparative examples will be described below, but the present invention is not limited to these examples. Various physical properties in Examples and Comparative Examples were measured by the following methods.
（１）シリカの比表面積
・窒素吸着法による比表面積（ＳBET ）の測定
シリカ湿ケークを乾燥器（１２０℃）に入れて乾燥した後、マイクロメリティクス社製のアサップ２０１０を使用して、窒素吸着量を測定し、相対圧０．２における１点法の値を採用した。
・セチルトリメチルアンモニウムブロマイド（ＣＴＡＢ）の吸着による比表面積（ＳCTA B ）の測定
シリカ湿ケークを乾燥器（１２０℃）に入れて乾燥した後、ＡＳＴＭ Ｄ３７６５−９２記載の方法に準じて実施した。ただし、ＡＳＴＭ Ｄ３７６５−９２記載の方法は、カーボンブラックのＳCTABを測定する方法なので、若干改良を加えた方法とした。すなわち、カーボンブラックの標品であるＩＴＲＢ（８３．０ｍ2 ／ｇ）を使用せず、別途にＣＴＡＢ標準液を調整し、これによってエアロゾルＯＴ溶液の標定を行い、シリカ表面に対するＣＴＡＢ１分子あたりの吸着断面積を３５平方オングストロームとしてＣＴＡＢの吸着量から比表面積を算出した。
（２）吸油量
ＪＩＳ Ｋ６２２０に準拠して求めた。
（３）シリカの平均粒子径
光散乱回折式の粒度分布測定装置（コールター社製、コールターＬＳ−２３０）を用いて体積基準中位径を測定し、この値を平均粒子径として採用した。
（４）粘度の測定
シリカ含有伸展油エマルジョン３００ｇを５００ｃｃ容器に採取し、Ｂ型粘度計（トキメック製、ＢＬ）を用いて６０ｒｐｍの条件で測定した。
（５）共重合体中のスチレン単位量：ＪＩＳ Ｋ６３８３（屈折率法）に準じて測定した。
（６）ムーニースコーチ時間
ＪＩＳ Ｋ６３００に準じて、Ｌ型ローターにて１３０℃で測定した。
ムーニースコーチ時間ｔ５（分）は、比較例３をインデクス１００とし、比較例１よりも大きい方がスコーチ安定性に優れることを示す。
（７）ムーニー粘度
ムーニー粘度計（上島製作所製、ＶＲ−１０３ＳＴ）を使用して、１３０℃で測定した。比較例３をインデックス１００とし、小さい方が混練や押出し加工性に優れていることを示す。
（８）シリカ含有率
熱分析装置ＴＧ／ＤＴＡ（セイコー電子工業製ＴＧ／ＤＴＡ３２０）を用いて、乾燥試料の空気中での熱分解後の残分率及び１５０℃までの重量減少率を測定し、下記式を用いて算出した。実施例では、ゴム１００重量部に対する量（重量部）に換算して記載した。測定条件は、空気中で昇温速度２０℃／ｍｉｎ、到達温度６００℃、６００℃での保持時間２０分で行った。実施例では、ゴム１００重量部に対する重量部に換算して記載した。 シリカ含有率（重量％）＝燃焼残分率／［１００−（１５０℃までの重量減少率）］
（９）引張強度
ＪＩＳ Ｋ６２５３の引張応力試験法に準拠して測定し、指数で表示した。この指数が大きいほど、引張強度特性に優れる。
（１０）耐摩耗性
アクロン式摩耗試験機を用い、予備擦り１０００回後の重量と本擦り１０００回後の重量の減量から、耐摩耗指数を算出した。この耐摩耗指数の値が大きいほど、摩耗性に優れることを示す。
（１１）ウェットグリップ性（０℃におけるｔａｎδ）
レオメトリックス社製動的粘弾性測定装置ＡＲＥＳを用い、歪み０．２％、周波数１５Ｈｚの条件で６０℃におけるｔａｎδを測定した。この特性は、指数で表示した。このｔａｎδ（０℃）の値が大きいとウェットグリップ性に優れることを示す。
（１２）低燃費性（６０℃におけるｔａｎδ）
レオメトリックス社製動的粘弾性測定装置ＡＲＥＳを用い、歪み０．２％、周波数１５Ｈｚの条件で６０℃におけるｔａｎδを測定した。この特性は、指数で表示した。このｔａｎδ（６０℃）値が小さいと低燃費性に優れることを示す。
(1) Specific surface area of silica / Measurement of specific surface area (S BET ) by nitrogen adsorption method After placing a silica wet cake in a drier (120 ° C.) and drying, use Asap 2010 made by Micromeritics, The nitrogen adsorption amount was measured, and the value of the one-point method at a relative pressure of 0.2 was adopted.
Measurement of specific surface area (S CTA B ) by adsorption of cetyltrimethylammonium bromide (CTAB) A silica wet cake was placed in a drier (120 ° C.) and dried, followed by the method described in ASTM D3765-92. However, the method described in ASTM D3765-92 is a method for measuring S CTAB of carbon black, and therefore, a method with a slight improvement added thereto. That is, the carbon black standard ITRB (83.0 m 2 / g) was not used, but a CTAB standard solution was prepared separately, whereby the aerosol OT solution was standardized, and the adsorption per CTAB molecule on the silica surface. The specific surface area was calculated from the amount of CTAB adsorbed with a cross-sectional area of 35 square angstroms.
(2) Oil absorption amount Determined according to JIS K6220.
(3) Average particle diameter of silica The volume-based median diameter was measured using a light scattering diffraction type particle size distribution measuring apparatus (Coulter LS-230, manufactured by Coulter, Inc.), and this value was adopted as the average particle diameter.
(4) Measurement of Viscosity 300 g of a silica-containing extending oil emulsion was collected in a 500 cc container, and measured using a B-type viscometer (manufactured by Tokimec, BL) at 60 rpm.
(5) Amount of styrene unit in copolymer: measured in accordance with JIS K6383 (refractive index method).
(6) Mooney scorch time It measured at 130 degreeC with the L-shaped rotor according to JISK6300.
As for Mooney scorch time t5 (minutes), comparative example 3 is indexed 100, and the larger one than comparative example 1 indicates that the scorch stability is superior.
(7) Mooney viscosity It measured at 130 degreeC using the Mooney viscometer (the Ueshima Seisakusho make, VR-103ST). Comparative example 3 is index 100, and the smaller one indicates better kneading and extruding workability.
(8) Silica content rate Using a thermal analyzer TG / DTA (TG / DTA320 manufactured by Seiko Denshi Kogyo Co., Ltd.), the residual rate after thermal decomposition of the dried sample in air and the weight loss rate up to 150 ° C were measured. It was calculated using the following formula. In the examples, it is described in terms of the amount (parts by weight) relative to 100 parts by weight of rubber. The measurement conditions were as follows: a temperature rising rate of 20 ° C./min in air, a final temperature of 600 ° C., and a holding time of 20 minutes at 600 ° C. In the examples, it is described in terms of parts by weight relative to 100 parts by weight of rubber. Silica content (% by weight) = combustion residue rate / [100- (weight reduction rate up to 150 ° C.)]
(9) Tensile strength Measured according to the tensile stress test method of JIS K6253 and displayed as an index. The larger the index, the better the tensile strength characteristics.
(10) Abrasion resistance Using an Akron-type abrasion tester, an abrasion resistance index was calculated from the weight reduction after 1000 times of preliminary rubbing and the weight after 1000 times of main rubbing. It shows that it is excellent in abrasion property, so that the value of this abrasion resistance index is large.
(11) Wet grip (tan δ at 0 ° C)
Using a dynamic viscoelasticity measuring device ARES manufactured by Rheometrics, tan δ at 60 ° C. was measured under the conditions of strain 0.2% and frequency 15 Hz. This characteristic is expressed as an index. A large value of tan δ (0 ° C.) indicates excellent wet grip properties.
(12) Low fuel consumption (tan δ at 60 ° C)
Using a dynamic viscoelasticity measuring device ARES manufactured by Rheometrics, tan δ at 60 ° C. was measured under the conditions of strain 0.2% and frequency 15 Hz. This characteristic is expressed as an index. A small tan δ (60 ° C.) value indicates excellent fuel efficiency.
（ゴムラテックスの製造例）
攪拌機付き耐圧反応器に脱イオン水２００部、ロジン酸石鹸１．５部、脂肪酸石鹸２．１部、単量体として１，３−ブタジエン５７．５部、スチレン４２．５部、およびｔ−ドデシルメルカプタン０．１２部を仕込んだ。反応器温度を１０℃とし、重合開始剤として、ジイソプロピルベンゼンハイドロパーオキサイド０．１部、ソディウム・ホルムアルデヒド・スルホキシレート０．０６部を、および、エチレンジアミン四酢酸ナトリウム０．０１４部と硫酸第二鉄０．０２部とを反応器に添加して重合を開始した。重合転化率が４５％に達した時点で、ｔ−ドデシルメルカプタン０．０５部を添加して反応を継続させた。重合転化率が７０％に達した時点で、ジエチルヒドロキシルアミンを０．０５部添加して反応を停止させた。
(Production example of rubber latex)
200 parts deionized water, 1.5 parts rosin acid soap, 2.1 parts fatty acid soap, 57.5 parts 1,3-butadiene, 42.5 parts styrene, and t- 0.12 part of dodecyl mercaptan was charged. The reactor temperature was 10 ° C., and 0.1 parts of diisopropylbenzene hydroperoxide, 0.06 part of sodium formaldehyde sulfoxylate, 0.014 part of sodium ethylenediaminetetraacetate and second sulfuric acid were used as polymerization initiators. Polymerization was initiated by adding 0.02 part of iron to the reactor. When the polymerization conversion reached 45%, 0.05 part of t-dodecyl mercaptan was added to continue the reaction. When the polymerization conversion reached 70%, 0.05 part of diethylhydroxylamine was added to stop the reaction.
未反応単量体を水蒸気蒸留により除去した後、重合体１００部に対して、老化防止剤として、スチレン化フェノール０．４５部および２，４−ビス（ｎ−オクチルチオメチル）
−６−メチルフェノール０．１５部と２，２，４−トリメチル−１，２−ジハイドロクイノリン０．１４部を添加し、固形分濃度が２０％のゴムラテックス（Ｌｘ１）を得た。その一部を取り出し、硫酸でｐＨ３〜５になるように調製しながら、塩化ナトリウムにより、５０℃でゴムラテックスを凝固し、クラム状のゴムを得た。このクラムを８０℃の熱風乾燥機で乾燥し、固形ゴムを得た。得られたゴムのスチレン量は３５．０重量％でムーニー粘度は１５０であった。
上記ゴムラテックス（Ｌｘ１）の一部を取り出し、ゴムラテックス中のゴム１００部に対して、伸展油としてＥｎｅｒｔｈｅｎｅ１８４９Ａ（ブリティッシュペトロリアム社製）を脂肪酸石鹸により６６重量％乳化水溶液として３７．５部を添加した。その後、硫酸でｐＨ３〜５になるように調製しながら、塩化ナトリウムにより、伸展油を含むゴムラテックスを６０℃で凝固し、クラム状のゴムを得た。このクラムを８０℃の熱風乾燥機で乾燥して 固形ゴム（ＳＢＲ１）を得た。得られたゴムのムーニー粘度は７０であった。得られた固形ゴム（ＳＢＲ１）は比較例３に用いた。
After removing the unreacted monomer by steam distillation, 0.45 parts of styrenated phenol and 2,4-bis (n-octylthiomethyl) are used as an anti-aging agent for 100 parts of the polymer.
0.15 part of -6-methylphenol and 0.14 part of 2,2,4-trimethyl-1,2-dihydroquinoline were added to obtain a rubber latex (Lx1) having a solid content concentration of 20%. A part thereof was taken out and adjusted to pH 3 to 5 with sulfuric acid, and the rubber latex was coagulated with sodium chloride at 50 ° C. to obtain a crumb-like rubber. This crumb was dried with a hot air dryer at 80 ° C. to obtain a solid rubber. The resulting rubber had a styrene content of 35.0% by weight and a Mooney viscosity of 150.
A part of the rubber latex (Lx1) was taken out, and 37.5 parts of an emulsion 1849A (manufactured by British Petroleum Co., Ltd.) as an extension oil was added as a 66 wt% emulsified aqueous solution with fatty acid soap to 100 parts of rubber in the rubber latex. . Thereafter, a rubber latex containing an extending oil was coagulated with sodium chloride at 60 ° C. while adjusting the pH to 3 to 5 with sulfuric acid to obtain a crumb-like rubber. This crumb was dried with a hot air dryer at 80 ° C. to obtain a solid rubber (SBR1). The resulting rubber had a Mooney viscosity of 70. The obtained solid rubber (SBR1) was used in Comparative Example 3.
（シリカの製造例１）
温度調節機付きのステンレス製反応容器に珪酸ナトリウム水溶液（ＳｉＯ2 濃度：１０ｇ／Ｌ、モル比：ＳｉＯ2 ／Ｎａ2 Ｏ＝３．４１）２３０重量部を投入し、８５℃に昇温した。次に、２２％硫酸７３重量部と珪酸ナトリウム水溶液（ＳｉＯ2 濃度：９０ｇ／Ｌ、モル比：ＳｉＯ2 ／Ｎａ2 Ｏ＝３．４１）４４０重量部を同時に１２０分かけて投入した。１０分間熟成後、２２％硫酸１６部を１５分かけて投入した。上記反応は反応液温度を８５℃に保持し、反応液を常時撹拌しながら行い、最終的に反応液のｐＨが３．２のシリカスラリーを得た。得られたシリカスラリーをフィルタープレスで水洗、ろ過し、シリカ固形分が２３％のシリカ湿ケークを得た。ここで、得られたシリカ湿ケークの一部を乾燥し、シリカ粉末を得た。このシリカ粉末（Ａ）のＢＥＴ比表面積（ＳBET ）は２０１ｍ2 ／ｇ、ＣＴＡＢ比表面積（ＳCTAB）は１９０ｍ2 ／ｇ、吸油量は２１０ｍｌ／１００ｇであった。
(Silica Production Example 1)
Into a stainless steel reaction vessel equipped with a temperature controller, 230 parts by weight of an aqueous sodium silicate solution (SiO 2 concentration: 10 g / L, molar ratio: SiO 2 / Na 2 O = 3.41) was added, and the temperature was raised to 85 ° C. Next, 73 parts by weight of 22% sulfuric acid and 440 parts by weight of an aqueous sodium silicate solution (SiO 2 concentration: 90 g / L, molar ratio: SiO 2 / Na 2 O = 3.41) were added simultaneously over 120 minutes. After aging for 10 minutes, 16 parts of 22% sulfuric acid was added over 15 minutes. The above reaction was performed while maintaining the reaction liquid temperature at 85 ° C. and constantly stirring the reaction liquid, and finally, a silica slurry having a reaction liquid pH of 3.2 was obtained. The obtained silica slurry was washed with a filter press and filtered to obtain a silica wet cake having a silica solid content of 23%. Here, a part of the obtained silica wet cake was dried to obtain silica powder. The silica powder (A) had a BET specific surface area (S BET ) of 201 m 2 / g, a CTAB specific surface area (S CTAB ) of 190 m 2 / g, and an oil absorption of 210 ml / 100 g.
（シリカの水性懸濁液（Ｓ１）の調整）
シリカの製造例１で得られたシリカ湿ケーク及び純水を、水性懸濁液中のシリカ固形分濃度が１５％になるように、ホモジナイザーを用いてシリカ湿ケークを粉砕しながら混合し、シリカ水性懸濁液（Ｓ１）を得た。水性懸濁液（Ｓ１）中のシリカの粒子径は１５μｍであった。
(Preparation of aqueous silica suspension (S1))
The silica wet cake and pure water obtained in Production Example 1 of silica are mixed while pulverizing the silica wet cake using a homogenizer so that the silica solid content concentration in the aqueous suspension is 15%, and the silica An aqueous suspension (S1) was obtained. The particle diameter of silica in the aqueous suspension (S1) was 15 μm.
（シリカの水性懸濁液（Ｓ２）の調整）
シリカの製造例１で得られたシリカ湿ケーク及び純水を、水性懸濁液中のシリカ固形分濃度が１５％になるように、ホモジナイザーを用いてシリカ湿ケークを粉砕しながら混合し、次いで、カチオン性高分子（ポリジアリルジメチルアンモニウムクロライド）をシリカ固形分１００重量部に対して３重量部となるように混合し、カチオン性高分子を含有するシリカ水性懸濁液（Ｓ２）を得た。水性懸濁液（Ｓ２）中のシリカの粒子径は１５μｍであった。
(Preparation of aqueous silica suspension (S2))
The silica wet cake obtained in silica production example 1 and pure water were mixed while grinding the silica wet cake using a homogenizer so that the silica solids concentration in the aqueous suspension was 15%, and then mixed. The cationic polymer (polydiallyldimethylammonium chloride) was mixed to 3 parts by weight with respect to 100 parts by weight of the silica solid content to obtain an aqueous silica suspension (S2) containing the cationic polymer. . The particle diameter of silica in the aqueous suspension (S2) was 15 μm.
（シリカの水性懸濁液（Ｓ３）の調整）
シリカの製造例１で得られたシリカ湿ケーク及び純水を、水性懸濁液中のシリカ固形分濃度が１５％になるように、ホモジナイザーを用いてシリカ湿ケークを粉砕しながら混合し、次いで、カチオン性界面活性剤（セチルトリメチルアンモニウムブロマイド）をシリカ固形分１００重量部に対して３重量部となるように混合し、カチオン性界面活性剤を含有するシリカ水性懸濁液（Ｓ３）を得た。水性懸濁液（Ｓ３）中のシリカの粒子径は１６μｍであった
(Preparation of aqueous silica suspension (S3))
The silica wet cake obtained in silica production example 1 and pure water were mixed while grinding the silica wet cake using a homogenizer so that the silica solids concentration in the aqueous suspension was 15%, and then mixed. , Cationic surfactant (cetyltrimethylammonium bromide) is mixed to 3 parts by weight with respect to 100 parts by weight of silica solid content to obtain an aqueous silica suspension (S3) containing the cationic surfactant. It was. The particle size of silica in the aqueous suspension (S3) was 16 μm.
（シリカの製造例２）
温度調節機付きの１ｍ3 ステンレス製反応容器に珪酸ナトリウム水溶液（ＳｉＯ2 濃度：１０ｇ／Ｌ、モル比：ＳｉＯ2 ／Ｎａ2 Ｏ＝３．４１）１５０重量部を投入し、９５℃に昇温した。次に、２２％硫酸７８重量部と珪酸ナトリウム水溶液（ＳｉＯ2 濃度：９０ｇ／Ｌ、モル比：ＳｉＯ2 ／Ｎａ2 Ｏ＝３．４１）４６１重量部を同時に１９０分かけて投入した。１０分間熟成後、２２％硫酸１５部を１５分かけて投入した。上記反応は反応液温度を８５℃に保持し、反応液を常時撹拌しながら行い、最終的に反応液のｐＨが３．１のシリカスラリーを得た。得られたシリカスラリーをフィルタープレスで水洗、ろ過し、シリカ固形分が２３％のシリカ湿ケークを得た。ここで、得られたシリカ湿ケークの一部を乾燥し、シリカ粉末（Ｂ）を得た。このシリカ粉末（Ｂ）のＢＥＴ比表面積（ＳBET ）は１００ｍ2 ／ｇ、ＣＴＡＢ比表面積（ＳCTAB）は９３ｍ2 ／ｇ、吸油量は１６５ｍｌ／１００ｇであった。
(Silica Production Example 2)
A 1 m 3 stainless steel reaction vessel equipped with a temperature controller was charged with 150 parts by weight of an aqueous sodium silicate solution (SiO 2 concentration: 10 g / L, molar ratio: SiO 2 / Na 2 O = 3.41), and the temperature was raised to 95 ° C. did. Next, 78 parts by weight of 22% sulfuric acid and 461 parts by weight of an aqueous sodium silicate solution (SiO 2 concentration: 90 g / L, molar ratio: SiO 2 / Na 2 O = 3.41) were added simultaneously over 190 minutes. After aging for 10 minutes, 15 parts of 22% sulfuric acid was added over 15 minutes. The above reaction was carried out while maintaining the reaction solution temperature at 85 ° C. and constantly stirring the reaction solution, and finally a silica slurry having a reaction solution pH of 3.1 was obtained. The obtained silica slurry was washed with a filter press and filtered to obtain a silica wet cake having a silica solid content of 23%. Here, a part of the obtained silica wet cake was dried to obtain silica powder (B). The silica powder (B) had a BET specific surface area (S BET ) of 100 m 2 / g, a CTAB specific surface area (S CTAB ) of 93 m 2 / g, and an oil absorption of 165 ml / 100 g.
（シリカの水性懸濁液（Ｓ４）の調整）
シリカの製造例２で得られたシリカ湿ケーク及び純水を、上記Ｓ１の製造の項と同様に処理して、シリカ固形分濃度が１５％のシリカ水性懸濁液（Ｓ４）を得た。水性懸濁液（Ｓ４）中のシリカの粒子径は１７μｍであった。
(Preparation of aqueous silica suspension (S4))
The silica wet cake and pure water obtained in Silica Production Example 2 were treated in the same manner as in the production of S1 to obtain an aqueous silica suspension (S4) having a silica solid content concentration of 15%. The particle diameter of silica in the aqueous suspension (S4) was 17 μm.
（伸展油エマルジョン（ＥＯ−１〜ＥＯ−６）の調整）
伸展油としてＥｎｅｒｔｈｅｎｅ１８４９Ａ（ブリティッシュペトロリアム社製）、表１に示す界面活性剤及び純水を、表１に示す割合になるようにホモジナイザーを用いて混合し、伸展油エマルジョン（ＥＯ−１〜ＥＯ−５）を得た。純水及び伸展油は６０℃に加温したものを用いた。
(Adjustment of extension oil emulsion (EO-1 to EO-6))
As an extender oil, 1818A (manufactured by British Petroleum Co., Ltd.), a surfactant shown in Table 1 and pure water were mixed using a homogenizer so as to have the ratio shown in Table 1, and an extender oil emulsion (EO-1 to EO-5) was mixed. ) Pure water and extender oil heated to 60 ° C. were used.
（シリカ含有伸展油エマルジョン（Ｓ／Ｏ−１〜Ｓ／Ｏ−６）の調整）
上記シリカの水性懸濁液、伸展油エマルジョン及び純水を、表２に示す割合になるようにホモジナイザーを用いて混合し、Ｓ／Ｏ−１〜Ｓ／Ｏ−６を得た。得られたエマルジョンの粘度及び安定性の評価結果を表２に示す。得られたエマルジョンの一部は、１日間放置して、シリカ及び伸展油の分散状態を下記のように評価した。
シリカの沈降が見られず、伸展油も全く分離していない ・・・ ○
シリカが沈降、もしくは伸展油が分離している ・・・ ×
(Preparation of silica-containing extended oil emulsion (S / O-1 to S / O-6))
The aqueous suspension of silica, the extended oil emulsion, and pure water were mixed using a homogenizer so as to have the ratio shown in Table 2 to obtain S / O-1 to S / O-6. Table 2 shows the evaluation results of the viscosity and stability of the obtained emulsion. A part of the obtained emulsion was allowed to stand for 1 day, and the dispersion state of silica and extending oil was evaluated as follows.
No sedimentation of silica was observed, and no extended oil was separated.
Silica is settled or extension oil is separated ... ×
（実施例１）
ゴムラテックス（Ｌｘ１）５００重量部を純水１０００重量部で希釈し、５０℃に昇温した。次に、上記希釈されたゴムラテックスに、シリカ含有伸展油エマルジョン（Ｓ／Ｏ１）８２４重量部を撹拌下、添加した。この時のｐＨは８．５であった。
次に、上記混合液に１０％硫酸を添加しｐＨを低下させ、共凝固を進行させた。ｐＨを７以下にすると上澄み液が透明になり始め、さらに１０％硫酸を添加し最終的にｐＨを６程度にした。なお、混合液の温度は５０℃に維持して行った
得られた凝固物をろ過し、７０℃で真空乾燥して、伸展油及びシリカを含有したゴム組成物（Ａ）を得た。上記ゴム組成物（Ａ）中のシリカの含有率は、ゴム固形分１００重量部に対して６９．３重量部であった。
得られたゴム組成物（Ａ）は、表３に示す配合量になるように、シランカップリング剤（ＫＢＥ−８４６、信越化学工業製）、パラフィンワックス、ステアリン酸、酸化亜鉛、老化防止剤（ノクラック６Ｃ：大内新興化学工業社製）を加えて、バンバリーミキサー（東洋精機製ラボプラストミル型式１００Ｃ ミキサータイプＢ−２５０）を用いて３分間混練した。混錬終了時の温度は１４０℃であった。次いで、加硫促進剤（ノクセラーＣＺ，大内新興化学工業社製）、及び硫黄を加えて、バンバリーミキサー（東洋精機製ラボプラストミル型式１００Ｃ ミキサータイプＢ−２５０）を用いて、７０℃で１分間混練した。次いで、得られた混練物を１６０℃で１５分プレス加硫して試験片を作製し、各物性を測定した。結果を表３に示す。
Example 1
500 parts by weight of rubber latex (Lx1) was diluted with 1000 parts by weight of pure water and heated to 50 ° C. Next, 824 parts by weight of a silica-containing extending oil emulsion (S / O1) was added to the diluted rubber latex with stirring. The pH at this time was 8.5.
Next, 10% sulfuric acid was added to the mixed solution to lower the pH, and co-coagulation proceeded. When the pH was adjusted to 7 or less, the supernatant liquid began to become transparent, and 10% sulfuric acid was further added to finally adjust the pH to about 6. The temperature of the mixed liquid was maintained at 50 ° C. The obtained solidified product was filtered and vacuum dried at 70 ° C. to obtain a rubber composition (A) containing an extending oil and silica. The content of silica in the rubber composition (A) was 69.3 parts by weight with respect to 100 parts by weight of the rubber solid content.
The obtained rubber composition (A) was blended with silane coupling agent (KBE-846, manufactured by Shin-Etsu Chemical Co., Ltd.), paraffin wax, stearic acid, zinc oxide, anti-aging agent ( Nocrack 6C (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) was added and kneaded for 3 minutes using a Banbury mixer (Laboplast Mill model 100C mixer type B-250 manufactured by Toyo Seiki Co., Ltd.). The temperature at the end of kneading was 140 ° C. Then, a vulcanization accelerator (Noxeller CZ, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) and sulfur are added, and a Banbury mixer (Laborplast Mill model 100C mixer type B-250 manufactured by Toyo Seiki Co., Ltd.) is used at 70 ° C. Kneaded for a minute. Next, the obtained kneaded material was press vulcanized at 160 ° C. for 15 minutes to prepare a test piece, and each physical property was measured. The results are shown in Table 3.
実施例２
ゴムラテックス（Ｌｘ１）５００重量部を純水５００重量部で希釈し、５０℃に昇温した。 次に、上記希釈されたゴムラテックスに、シリカ含有伸展油エマルジョン（Ｓ／Ｏ２）１２９０重量部を撹拌下、添加した。この時のｐＨは７．８であった。
次に、上記混合液に１０％硫酸を添加しｐＨを低下させ、共凝固を進行させた。ｐＨを７以下にすると上澄み液が透明になり始め、さらに１０％硫酸を添加し最終的にｐＨを６程度にした。なお、混合液の温度は５０℃に維持して行った。
得られた凝固物をろ過し、７０℃で真空乾燥して、伸展油及びシリカを含有したゴム組成物（Ｂ）を得た。上記ゴム組成物（Ｂ）中のシリカの含有率は、ゴム固形分１００重量部に対して１３８．５重量部であった。
得られたゴム組成物（Ｂ）は、表３に示す配合量になるように、ＳＢＲ１、各種添加剤を配合し、実施例１と同様に混練した。次いで、得られた混練物を６０℃で１５分プレス加硫して試験片を作製し、各物性を測定した。結果を表３に示す。
Example 2
500 parts by weight of rubber latex (Lx1) was diluted with 500 parts by weight of pure water and heated to 50 ° C. Next, 1290 parts by weight of a silica-containing extending oil emulsion (S / O 2) was added to the diluted rubber latex with stirring. The pH at this time was 7.8.
Next, 10% sulfuric acid was added to the mixed solution to lower the pH, and co-coagulation proceeded. When the pH was adjusted to 7 or less, the supernatant liquid began to become transparent, and 10% sulfuric acid was further added to finally adjust the pH to about 6. The temperature of the mixed solution was maintained at 50 ° C.
The obtained solidified product was filtered and vacuum-dried at 70 ° C. to obtain a rubber composition (B) containing an extending oil and silica. The content of silica in the rubber composition (B) was 138.5 parts by weight with respect to 100 parts by weight of the rubber solid content.
The obtained rubber composition (B) was blended with SBR1 and various additives so as to have the blending amounts shown in Table 3, and kneaded in the same manner as in Example 1. Next, the obtained kneaded material was press vulcanized at 60 ° C. for 15 minutes to prepare a test piece, and each physical property was measured. The results are shown in Table 3.
実施例３
実施例１において、シリカ含有伸展油エマルジョン（Ｓ／Ｏ１）の代りに（Ｓ／Ｏ３）を用いた以外は、実施例１と同様に行い、伸展油及びシリカを含有したゴム組成物（Ｃ）を得た。混合物（Ｃ）中のシリカの含有率は、ゴム固形分１００重量部に対して６９．０重量部であった。
得られたゴム組成物（Ｃ）は、表３に示す配合量になるように、各種添加剤を配合し実施例１と同様に混練した。次いで、得られた混練物を６０℃で１５分プレス加硫して試験片を作製し、各物性を測定した。結果を表３に示す。
Example 3
In Example 1, except that (S / O3) was used in place of the silica-containing extending oil emulsion (S / O1), the same procedure as in Example 1 was performed, and the rubber composition (C) containing the extending oil and silica was used. Got. The content rate of the silica in a mixture (C) was 69.0 weight part with respect to 100 weight part of rubber solid content.
The obtained rubber composition (C) was kneaded in the same manner as in Example 1 with various additives blended so as to have the blending amounts shown in Table 3. Next, the obtained kneaded material was press vulcanized at 60 ° C. for 15 minutes to prepare a test piece, and each physical property was measured. The results are shown in Table 3.
実施例４
実施例１において、シリカ含有伸展油エマルジョン（Ｓ／Ｏ１）の代りに（Ｓ／Ｏ４）を用いた以外は、実施例１と同様に行い、伸展油及びシリカを含有したゴム組成物（Ｄ）を得た。混合物（Ｄ）中のシリカの含有率は、ゴム固形分１００重量部に対して６９．５重量部であった。
得られたゴム組成物（Ｄ）は、表３に示す配合量になるように、各種添加剤を配合し、実施例１と同様に混練した。次いで、得られた混練物を６０℃で１５分プレス加硫して試験片を作製し、各物性を測定した。結果を表３に示す。
Example 4
In Example 1, except that (S / O4) was used instead of the silica-containing extending oil emulsion (S / O1), the same procedure as in Example 1 was carried out, and the rubber composition (D) containing the extending oil and silica was used. Got. The content rate of the silica in a mixture (D) was 69.5 weight part with respect to 100 weight part of rubber solid content.
The obtained rubber composition (D) was blended with various additives so as to have the blending amounts shown in Table 3, and kneaded in the same manner as in Example 1. Next, the obtained kneaded material was press vulcanized at 60 ° C. for 15 minutes to prepare a test piece, and each physical property was measured. The results are shown in Table 3.
実施例５
５０℃に昇温した純水１３００重量部に、ゴムラテックス（Ｌｘ１）５００重量部、伸展油エマルジョン（ＥＯ１）５７重量部、シリカ水性懸濁液（Ｓ１）４６７重量部を同時に混合した。この時のｐＨは８．５であった。
次に、上記混合液に１０％硫酸を添加しｐＨを低下させ、共凝固を進行させた。ｐＨを７以下にすると上澄み液が透明になり始め、さらに１０％硫酸を添加し最終的にｐＨを６程度にした。なお、混合液の温度は５０℃に維持して行った。
得られた凝固物をろ過し、７０℃で真空乾燥して、伸展油及びシリカを含有したゴム組成物（Ｅ）を得た。上記ゴム組成物（Ｅ）中のシリカの含有率は、ゴム固形分１００重量部に対して６９．３重量部であった。
得られたゴム組成物（Ｅ）は、表３に示す配合量になるように、各種添加剤を配合し、実施例１と同様に混練した。次いで、得られた混練物を６０℃で１５分プレス加硫して試験片を作製し、各物性を測定した。結果を表３に示す。
Example 5
500 parts by weight of rubber latex (Lx1), 57 parts by weight of an extended oil emulsion (EO1), and 467 parts by weight of an aqueous silica suspension (S1) were mixed at the same time with 1300 parts by weight of pure water heated to 50 ° C. The pH at this time was 8.5.
Next, 10% sulfuric acid was added to the mixed solution to lower the pH, and co-coagulation proceeded. When the pH was adjusted to 7 or less, the supernatant liquid began to become transparent, and 10% sulfuric acid was further added to finally adjust the pH to about 6. The temperature of the mixed solution was maintained at 50 ° C.
The obtained coagulated product was filtered and vacuum-dried at 70 ° C. to obtain a rubber composition (E) containing an extending oil and silica. The content rate of the silica in the said rubber composition (E) was 69.3 weight part with respect to 100 weight part of rubber solid content.
The obtained rubber composition (E) was kneaded in the same manner as in Example 1 by blending various additives so as to have the blending amounts shown in Table 3. Next, the obtained kneaded material was press vulcanized at 60 ° C. for 15 minutes to prepare a test piece, and each physical property was measured. The results are shown in Table 3.
実施例６
ゴムラテックス（Ｌｘ１）５００重量部を純水１０００重量部で希釈し、さらに、シリカ水性懸濁液（Ｓ１）４６７重量部を加え、５０℃に昇温した。次いで、伸展油エマルジョン（ＥＯ１）を攪拌下、５７重量部添加した。この時のｐＨは８．５であった。
次に、上記混合液に１０％硫酸を添加しｐＨを低下させた。ｐＨを７以下にすると共凝固が進行し、上澄み液が透明になるまでさらに１０％硫酸を添加し、最終的にｐＨを６程度にした。なお、混合液の温度は５０℃に維持して行った
得られた凝固物をろ過し、７０℃で真空乾燥して、伸展油及びシリカを含有したゴム組成物（Ｆ）を得た。上記ゴム組成物（Ｆ）中のシリカの含有率は、ゴム固形分１００重量部に対して６９．２重量部であった。
得られたゴム組成物（Ｆ）は、表３に示す配合量になるように、各種添加剤を配合し、実施例１と同様に混練した。次いで、得られた混練物を６０℃で１５分プレス加硫して試験片を作製し、各物性を測定した。結果を表３に示す。
Example 6
500 parts by weight of rubber latex (Lx1) was diluted with 1000 parts by weight of pure water, 467 parts by weight of an aqueous silica suspension (S1) was further added, and the temperature was raised to 50 ° C. Subsequently, 57 parts by weight of the extension oil emulsion (EO1) was added with stirring. The pH at this time was 8.5.
Next, 10% sulfuric acid was added to the mixed solution to lower the pH. When the pH was reduced to 7 or less, co-coagulation proceeded, and 10% sulfuric acid was further added until the supernatant became transparent, and finally the pH was adjusted to about 6. The temperature of the mixed solution was maintained at 50 ° C. The obtained coagulated product was filtered and vacuum-dried at 70 ° C. to obtain a rubber composition (F) containing extending oil and silica. The content of silica in the rubber composition (F) was 69.2 parts by weight with respect to 100 parts by weight of the rubber solid content.
The obtained rubber composition (F) was kneaded in the same manner as in Example 1 by blending various additives so as to have the blending amounts shown in Table 3. Next, the obtained kneaded material was press vulcanized at 60 ° C. for 15 minutes to prepare a test piece, and each physical property was measured. The results are shown in Table 3.
実施例７
ゴムラテックス（Ｌｘ１）５００重量部を純水１２００重量部で希釈し、５０℃に昇温した。 次に、上記希釈されたゴムラテックスに、シリカ含有伸展油エマルジョン（Ｓ／Ｏ５）６２４重量部を撹拌下、添加した。この時のｐＨは８．５であった。
次に、上記混合液に１０％硫酸を添加しｐＨを低下させた。ｐＨを７以下にすると共凝固が進行し、上澄み液が透明になるまでさらに１０％硫酸を添加し、最終的にｐＨを６程度にした。なお、混合液の温度は５０℃に維持して行った
得られた凝固物をろ過し、７０℃で真空乾燥して、伸展油及びシリカを含有したゴム組成物（Ｇ）を得た。上記ゴム組成物（Ｇ）中のシリカの含有率は、ゴム固形分１００重量部に対して６９．１重量部であった。
得られたゴム組成物（Ｇ）は、表３に示す配合量になるように、各種添加剤を配合し、実施例１と同様に混練した。次いで、得られた混練物を６０℃で１５分プレス加硫して試験片を作製し、各物性を測定した。結果を表３に示す。
Example 7
500 parts by weight of rubber latex (Lx1) was diluted with 1200 parts by weight of pure water and heated to 50 ° C. Next, 624 parts by weight of a silica-containing extending oil emulsion (S / O5) was added to the diluted rubber latex with stirring. The pH at this time was 8.5.
Next, 10% sulfuric acid was added to the mixed solution to lower the pH. When the pH was reduced to 7 or less, co-coagulation proceeded, and 10% sulfuric acid was further added until the supernatant became transparent, and finally the pH was adjusted to about 6. The temperature of the mixed solution was maintained at 50 ° C. The obtained coagulated product was filtered and vacuum-dried at 70 ° C. to obtain a rubber composition (G) containing an extending oil and silica. The content of silica in the rubber composition (G) was 69.1 parts by weight with respect to 100 parts by weight of the rubber solid content.
The obtained rubber composition (G) was blended with various additives so as to have the blending amounts shown in Table 3, and kneaded in the same manner as in Example 1. Next, the obtained kneaded material was press vulcanized at 60 ° C. for 15 minutes to prepare a test piece, and each physical property was measured. The results are shown in Table 3.
比較例１
シリカの水性懸濁液（Ｓ２）４６７重量部を純水１０００重量部で希釈し、５０℃に昇温した。次に、予め準備しておいたゴムラテックス（Ｌｘ１）５００重量部、伸展油エマルジョン（ＥＯ５）５７重量部の混合物を撹拌下、添加してシリカとゴムの共凝固物を含む混合液を得た。この時のｐＨは７．２であった。
次に、上記混合液に１０％硫酸を添加しｐＨを低下させた。ｐＨを６．５以下にして凝固を完結させた。混合液の温度は５０℃に維持して行った。なお、上記ゴムラテックス（Ｌｘ１）と伸展油エマルジョン（ＥＯ５）の混合物は不安定であるため、シリカ水性懸濁液に添加するまでは６０℃に保持し攪拌しておいた。
得られた凝固物をろ過し、７０℃で真空乾燥して、伸展油及びシリカを含有したゴム組成物（Ｈ）を得た。上記ゴム組成物（Ｈ）中のシリカの含有率は、ゴム固形分１００重量部に対して６９．３重量部であった。
得られたゴム組成物（Ｈ）は、表３に示す配合量になるように、各種添加剤を配合し、実施例１と同様に混練した。次いで、得られた混練物を６０℃で１５分プレス加硫して試験片を作製し、各物性を測定した。結果を表４に示す。
Comparative Example 1
467 parts by weight of an aqueous silica suspension (S2) was diluted with 1000 parts by weight of pure water, and the temperature was raised to 50 ° C. Next, a mixture of 500 parts by weight of a prepared rubber latex (Lx1) and 57 parts by weight of an extended oil emulsion (EO5) was added with stirring to obtain a mixed solution containing a co-coagulated product of silica and rubber. . The pH at this time was 7.2.
Next, 10% sulfuric acid was added to the mixed solution to lower the pH. The pH was set to 6.5 or less to complete the coagulation. The temperature of the mixture was maintained at 50 ° C. Since the mixture of the rubber latex (Lx1) and the extender oil emulsion (EO5) is unstable, the mixture was kept at 60 ° C. and stirred until it was added to the silica aqueous suspension.
The obtained coagulated product was filtered and vacuum-dried at 70 ° C. to obtain a rubber composition (H) containing an extending oil and silica. The content rate of the silica in the said rubber composition (H) was 69.3 weight part with respect to 100 weight part of rubber solid content.
The obtained rubber composition (H) was kneaded in the same manner as in Example 1 by blending various additives so as to have the blending amounts shown in Table 3. Next, the obtained kneaded material was press vulcanized at 60 ° C. for 15 minutes to prepare a test piece, and each physical property was measured. The results are shown in Table 4.
比較例２
シリカの水性懸濁液（Ｓ３）４６７重量部を純水１０００重量部で希釈し、５０℃に昇温した。次に、予め準備しておいたゴムラテックス（Ｌｘ１）５００重量部、伸展油エマルジョン（ＥＯ５）５７重量部の混合物を撹拌下、添加してシリカとゴムの共凝固物を含む混合液を得た。この時のｐＨは８．５であった。
次に、上記混合液に１０％硫酸を添加しｐＨを低下させた。ｐＨを７以下にすると共凝固が進行し、上澄み液が透明になるまでさらに１０％硫酸を添加し、最終的にｐＨを６程度にした。なお、混合液の温度は５０℃に維持して行った。なお、上記ゴムラテックス（Ｌｘ１）と伸展油エマルジョン（ＥＯ５）の混合物は不安定であるため、６０℃に保持し攪拌しておいた。
得られた凝固物をろ過し、７０℃で真空乾燥して、伸展油及びシリカを含有したゴム組成物（Ｉ）を得た。上記ゴム組成物（Ｉ）中のシリカの含有率は、ゴム固形分１００重量部に対して６９．３重量部であった。
得られたゴム組成物（Ｉ）は、表３に示す配合量になるように、各種添加剤を配合し、実施例１と同様に混練した。次いで、得られた混練物を６０℃で１５分プレス加硫して試験片を作製し、各物性を測定した。結果を表４に示す。
Comparative Example 2
467 parts by weight of an aqueous silica suspension (S3) was diluted with 1000 parts by weight of pure water and heated to 50 ° C. Next, a mixture of 500 parts by weight of a prepared rubber latex (Lx1) and 57 parts by weight of an extended oil emulsion (EO5) was added with stirring to obtain a mixed solution containing a co-coagulated product of silica and rubber. . The pH at this time was 8.5.
Next, 10% sulfuric acid was added to the mixed solution to lower the pH. When the pH was reduced to 7 or less, co-coagulation proceeded, and 10% sulfuric acid was further added until the supernatant became transparent, and finally the pH was adjusted to about 6. The temperature of the mixed solution was maintained at 50 ° C. In addition, since the mixture of the rubber latex (Lx1) and the extending oil emulsion (EO5) is unstable, the mixture was kept at 60 ° C. and stirred.
The obtained coagulated product was filtered and vacuum-dried at 70 ° C. to obtain a rubber composition (I) containing an extending oil and silica. The content rate of the silica in the said rubber composition (I) was 69.3 weight part with respect to 100 weight part of rubber solid content.
The obtained rubber composition (I) was blended with various additives so as to have the blending amounts shown in Table 3, and kneaded in the same manner as in Example 1. Next, the obtained kneaded material was press vulcanized at 60 ° C. for 15 minutes to prepare a test piece, and each physical property was measured. The results are shown in Table 4.
比較例３
固形ゴムＳＢＲ１、シリカ粉末（Ａ）を、表４に示す配合量になるように各種添加剤を配合し、実施例１と同様に混練、加硫して試験片を作製し、各物性を測定した。比較例３の測定値を１００とする指数で表した。
Comparative Example 3
Various additives were blended with the solid rubber SBR1 and silica powder (A) so as to have the blending amounts shown in Table 4, and test pieces were prepared by kneading and vulcanizing in the same manner as in Example 1 and measuring each physical property. did. The measured value of Comparative Example 3 is expressed as an index with 100 as the value.
本発明によれば、スチレンブタジエン共重合ゴムなどのジエン系ゴム中に伸展油、シリカを高度に分散させた耐スコーチ性に優れたゴム組成物を容易に効率よく製造することができ、得られたゴム組成物は、引張強度や耐摩耗性などの物性にすぐれている。さらに、このゴム組成物を架橋することにより、上記物性が一層すぐれたものになるため、この特性を生かす各種用途、例えば、トレッド、アンダートレッド、カーカス、サイドウオール、ビード部などのタイヤ用部材；ホース、窓枠、ベルト、靴底、防振ゴム、自動車部品、免震ゴムなどのゴム部材；耐衝撃性ポリスチレン、ＡＢＳ樹脂等の樹脂強化ゴム部材；などに好適に利用することいができ、なかでも、タイヤ用部材として好適であり、低燃費タイヤのタイヤトレッドとして特に好適である。
According to the present invention, it is possible to easily and efficiently produce a rubber composition excellent in scorch resistance in which an extension oil and silica are highly dispersed in a diene rubber such as a styrene-butadiene copolymer rubber. The rubber composition is excellent in physical properties such as tensile strength and wear resistance. Furthermore, since the above physical properties are further improved by crosslinking the rubber composition, various uses that make use of this characteristic, for example, tire members such as treads, undertreads, carcass, side walls, and bead parts; Rubber members such as hoses, window frames, belts, shoe soles, anti-vibration rubber, automobile parts, seismic isolation rubbers; resin-reinforced rubber members such as impact-resistant polystyrene and ABS resin; Especially, it is suitable as a member for tires, and is particularly suitable as a tire tread of a low fuel consumption tire.
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| JP2013199528A (en) * | 2012-03-23 | 2013-10-03 | Toyo Tire & Rubber Co Ltd | Wet master batch containing silica and method of manufacturing the same |
| CN103665729A (en) * | 2012-09-18 | 2014-03-26 | 中国石油天然气股份有限公司 | Oil-extended styrene-butadiene rubber containing nano silicon dioxide on surface, composition and preparation method thereof |
| CN103665484A (en) * | 2012-09-18 | 2014-03-26 | 中国石油天然气股份有限公司 | Oil-extended styrene-butadiene rubber, and composition and preparation method thereof |
| CN114634661A (en) * | 2020-12-15 | 2022-06-17 | 韩华道达尔有限公司 | Method for producing rubber composition, and tire produced by using same |
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| JP2002241507A (en) * | 2000-12-12 | 2002-08-28 | Jsr Corp | Diene-based rubber/inorganic compound composite and method for producing the same and rubber composition containing the same |
| JP2003138025A (en) * | 2001-11-06 | 2003-05-14 | Tokuyama Corp | Process for producing silica-filled rubber |
| JP2004256801A (en) * | 2003-02-03 | 2004-09-16 | Nippon Zeon Co Ltd | Silica-filled rubber composition and molded article |
| JP2005112918A (en) * | 2003-10-03 | 2005-04-28 | Tokuyama Corp | Rubber composition |
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| JP2002241507A (en) * | 2000-12-12 | 2002-08-28 | Jsr Corp | Diene-based rubber/inorganic compound composite and method for producing the same and rubber composition containing the same |
| JP2003138025A (en) * | 2001-11-06 | 2003-05-14 | Tokuyama Corp | Process for producing silica-filled rubber |
| JP2004256801A (en) * | 2003-02-03 | 2004-09-16 | Nippon Zeon Co Ltd | Silica-filled rubber composition and molded article |
| JP2005112918A (en) * | 2003-10-03 | 2005-04-28 | Tokuyama Corp | Rubber composition |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013199528A (en) * | 2012-03-23 | 2013-10-03 | Toyo Tire & Rubber Co Ltd | Wet master batch containing silica and method of manufacturing the same |
| CN103665729A (en) * | 2012-09-18 | 2014-03-26 | 中国石油天然气股份有限公司 | Oil-extended styrene-butadiene rubber containing nano silicon dioxide on surface, composition and preparation method thereof |
| CN103665484A (en) * | 2012-09-18 | 2014-03-26 | 中国石油天然气股份有限公司 | Oil-extended styrene-butadiene rubber, and composition and preparation method thereof |
| CN114634661A (en) * | 2020-12-15 | 2022-06-17 | 韩华道达尔有限公司 | Method for producing rubber composition, and tire produced by using same |
| JP2022094898A (en) * | 2020-12-15 | 2022-06-27 | ハンファ トータル ペトロケミカル カンパニー リミテッド | Method for manufacturing rubber composition, rubber composition manufactured by the method, and tire manufactured by using the same |
| CN114634661B (en) * | 2020-12-15 | 2024-03-26 | 韩华道达尔能源有限公司 | Method for producing rubber composition, rubber composition and tire produced by using the same |
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