WO2019069904A1 - 変性液状ジエン系ゴム - Google Patents
変性液状ジエン系ゴム Download PDFInfo
- Publication number
- WO2019069904A1 WO2019069904A1 PCT/JP2018/036839 JP2018036839W WO2019069904A1 WO 2019069904 A1 WO2019069904 A1 WO 2019069904A1 JP 2018036839 W JP2018036839 W JP 2018036839W WO 2019069904 A1 WO2019069904 A1 WO 2019069904A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rubber
- liquid diene
- modified liquid
- mass
- diene rubber
- Prior art date
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 217
- 239000005060 rubber Substances 0.000 title claims abstract description 217
- 239000007788 liquid Substances 0.000 title claims abstract description 184
- 150000001993 dienes Chemical class 0.000 title abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 152
- 125000000524 functional group Chemical group 0.000 claims abstract description 61
- 239000000945 filler Substances 0.000 claims abstract description 34
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 25
- 239000011324 bead Substances 0.000 claims abstract description 21
- 239000003566 sealing material Substances 0.000 claims abstract description 17
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 16
- 239000000155 melt Substances 0.000 claims abstract description 12
- 229920003244 diene elastomer Polymers 0.000 claims description 152
- 239000003795 chemical substances by application Substances 0.000 claims description 57
- 150000001875 compounds Chemical class 0.000 claims description 54
- -1 diene anhydride Chemical class 0.000 claims description 54
- 239000007787 solid Substances 0.000 claims description 41
- 239000005011 phenolic resin Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000009257 reactivity Effects 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 description 57
- 239000003822 epoxy resin Substances 0.000 description 54
- 229920000647 polyepoxide Polymers 0.000 description 54
- 238000006116 polymerization reaction Methods 0.000 description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- 239000000047 product Substances 0.000 description 42
- 238000000034 method Methods 0.000 description 39
- 229920005989 resin Polymers 0.000 description 38
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- 238000006243 chemical reaction Methods 0.000 description 36
- 230000003712 anti-aging effect Effects 0.000 description 34
- 229920001195 polyisoprene Polymers 0.000 description 32
- 229920000642 polymer Polymers 0.000 description 32
- 238000004519 manufacturing process Methods 0.000 description 30
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 29
- 239000000243 solution Substances 0.000 description 27
- 238000004073 vulcanization Methods 0.000 description 25
- 239000003921 oil Substances 0.000 description 23
- 235000019198 oils Nutrition 0.000 description 23
- 229920002554 vinyl polymer Polymers 0.000 description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 20
- 229920003048 styrene butadiene rubber Polymers 0.000 description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 19
- 230000001070 adhesive effect Effects 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 17
- 239000000853 adhesive Substances 0.000 description 17
- 239000002174 Styrene-butadiene Substances 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
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- 239000011342 resin composition Substances 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 150000001339 alkali metal compounds Chemical class 0.000 description 12
- 239000003431 cross linking reagent Substances 0.000 description 12
- 244000043261 Hevea brasiliensis Species 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 229910052783 alkali metal Inorganic materials 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
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- 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 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 229920002857 polybutadiene Polymers 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- 229920003986 novolac Polymers 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 150000003512 tertiary amines Chemical class 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 238000007259 addition reaction Methods 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 7
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 229920006337 unsaturated polyester resin Polymers 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 description 6
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- 239000000178 monomer Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 5
- 125000004018 acid anhydride group Chemical group 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 125000002897 diene group Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 5
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- 150000003464 sulfur compounds Chemical class 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
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- 238000005452 bending Methods 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
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- 125000003277 amino group Chemical group 0.000 description 3
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- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 3
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
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- 150000008282 halocarbons Chemical class 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
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- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 235000013875 sodium salts of fatty acid Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical class [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
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- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-O trimethylammonium Chemical compound C[NH+](C)C GETQZCLCWQTVFV-UHFFFAOYSA-O 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 235000016804 zinc Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C15/00—Tyre beads, e.g. ply turn-up or overlap
- B60C15/06—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead
- B60C15/0603—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead characterised by features of the bead filler or apex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/28—Reaction with compounds containing carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
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- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
- C08C19/36—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups with carboxy radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
- C08C19/38—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups with hydroxy radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/08—Isoprene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C2001/005—Compositions of the bead portions, e.g. clinch or chafer rubber or cushion rubber
- B60C2001/0058—Compositions of the bead apexes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0607—Rubber or rubber derivatives
Definitions
- the present invention relates to a modified liquid diene rubber and a composition containing the modified liquid diene rubber.
- a rubber composition containing solid rubber, liquid rubber, oil and the like has excellent tackiness, and a crosslinked product obtained by crosslinking this has conventionally had excellent adhesion to adherends and the like. It is used as a sealing material, an adhesive for various members, and the like in various industrial applications such as automotive applications (see, for example, Patent Documents 1 to 4). Further, in order to improve the adhesion of the rubber composition to metals etc., a method is known in which a modified liquid rubber modified with a functional group is used as the liquid rubber (see, for example, Patent Documents 2 and 4) .
- the components of the rubber composition are first mixed and stored in a sealed container or the like, and this sealing is performed when used It is common to apply the rubber composition to a substrate or the like from a container using a cartridge gun or the like and to crosslink the rubber composition.
- JP-A-59-006272 Japanese Patent Application Laid-Open No. 05-194922 Japanese Patent Application Laid-Open No. 05-059345 Japanese Patent Application Publication No. 2004-099651
- the conventional rubber composition is excellent in pumpability, drip resistance, processability, and reactivity, and rubber elasticity of a cured product obtained from the rubber composition and adhesion to various substrates. It was difficult to produce an excellent rubber composition.
- the present invention has been made in view of the above-described circumstances, and is excellent in pumpability, drip resistance, processability, and reactivity, and rubber elasticity, mechanical characteristics (stiffness), and various properties of the obtained cured product.
- a modified liquid diene rubber and a rubber composition containing the modified liquid diene rubber which is excellent in adhesion to a substrate, and suitably used for sealing materials, adhesives, tire bead fillers and the like.
- a modified liquid diene rubber having a functional group (a) derived from an acid anhydride and satisfying all the following requirements (I) to (III).
- the functional group equivalent of the functional group (a) is in the range of 400 to 3,500 g / eq.
- II When measured by gel permeation chromatography (GPC), the polystyrene equivalent number average molecular weight (Mn) is in the range of 5,000 to 20,000.
- Mn polystyrene equivalent number average molecular weight
- the melt viscosity at 38 ° C. is 3 Pa ⁇ s or more, and the following X is 6100 K or more.
- the modified liquid diene rubber (A) is a reaction product of a unsaturated diene-modified liquid diene rubber and a compound represented by the following chemical formula (2) or (3): Modified liquid diene rubber (A) described.
- R a -OH (2) (In the above formula (2), R a is a hydrogen atom or an alkyl group which may be substituted.)
- R b 2 -NH (3) (In the above formula (3), R b is a hydrogen atom or an alkyl group which may be substituted, and a plurality of R b may be the same or different.)
- a rubber composition comprising the modified liquid diene rubber (A) according to [1] or [2] and a solid rubber (B).
- a rubber composition for a tire bead filler comprising the rubber composition according to [4].
- a modified liquid diene rubber suitable for a rubber composition having excellent pumpability, drip resistance, processability and reactivity is obtained, and a cured product obtained from the rubber composition has rubber elasticity, It has excellent mechanical properties (rigidity) and adhesion to various substrates. Therefore, the rubber composition of the present invention can be suitably used as a sealing material, adhesion of various members, adhesive, tire bead filler and the like.
- the modified liquid diene rubber (A) of the present invention is a liquid polymer having a functional group (a) derived from an acid anhydride and satisfying all the requirements of the following (I) to (III) Say (I) The functional group equivalent of the functional group (a) is in the range of 400 to 3,500 g / eq. (II) When measured by gel permeation chromatography (GPC), the polystyrene equivalent number average molecular weight (Mn) is in the range of 5,000 to 20,000. (III) The melt viscosity at 38 ° C. is 3 Pa ⁇ s or more, and the following X is 6100 K or more.
- a rubber composition containing such a modified liquid diene rubber (A) and a solid rubber (B) described later is excellent in pumping property, drip resistance, processability, and reactivity, and the obtained rubber of a cured product It has excellent elasticity, mechanical properties (rigidity) and adhesion to various substrates.
- the rubber elasticity can be represented, for example, by storage elastic modulus, and the reactivity represents the reactivity of the functional group, and by being excellent in reactivity, the hardness and adhesion of the obtained cured product become excellent. .
- the modified liquid diene rubber (A) can be produced, for example, by adding a modified compound corresponding to a functional group (a) derived from an acid anhydride to an unmodified liquid diene rubber (A ′).
- a modified compound corresponding to a functional group (a) derived from an acid anhydride to an unmodified liquid diene rubber (A ′).
- a ′ As the non-modified liquid diene rubber (A ') as a raw material of the modified liquid diene rubber (A), a polymer obtained by polymerizing a conjugated diene (a1) by a method described later is preferable.
- conjugated dienes (a1) include butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, chloroprene and the like.
- conjugated dienes butadiene and isoprene are preferable.
- These conjugated dienes may be used alone or in combination of two or more.
- the unmodified liquid diene rubber (A ') may be one obtained by copolymerizing an aromatic vinyl compound (a2) in addition to the above-mentioned conjugated diene (a1).
- aromatic vinyl compound (a2) include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene , 4-dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene 2-vinylnaphthalene, vinyl anthracene, N, N-diethyl
- the ratio of the aromatic vinyl compound (a2) unit to the total of the units derived from the conjugated diene (a1) and the aromatic vinyl compound (a2) in the above-mentioned unmodified liquid diene rubber (A ′) is the processing of the composition From the viewpoint of properties, adhesion, etc., 70% by mass or less is preferable, 60% by mass or less is more preferable, and 50% by mass or less is still more preferable.
- the unmodified liquid diene rubber (A ′) can be produced, for example, by an emulsion polymerization method or a solution polymerization method.
- an emulsion polymerization method a known method or a method according to a known method can be applied.
- a monomer containing a predetermined amount of conjugated diene is emulsified and dispersed in the presence of an emulsifier, and emulsion polymerization is performed by a radical polymerization initiator.
- Examples of the emulsifier include long-chain fatty acid salts having 10 or more carbon atoms and rosin acid salts.
- Examples of long-chain fatty acid salts include potassium salts or sodium salts of fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid.
- a dispersion medium water is usually used, and a water-soluble organic solvent such as methanol or ethanol may be included as long as the stability during polymerization is not inhibited.
- a water-soluble organic solvent such as methanol or ethanol
- the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides, hydrogen peroxide and the like.
- a chain transfer agent may be used to adjust the molecular weight of the resulting unmodified liquid diene rubber (A ').
- chain transfer agents include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, thioglycolic acid, diterpenes, terpinenol, ⁇ -terpinene, ⁇ -methylstyrene dimer and the like.
- the temperature of the emulsion polymerization can be appropriately set depending on the type of the radical polymerization initiator to be used, etc., but is usually in the range of 0 to 100 ° C., preferably in the range of 0 to 60 ° C.
- the polymerization mode may be either continuous polymerization or batch polymerization.
- the polymerization reaction can be terminated by the addition of a polymerization terminator.
- a polymerization terminator examples include amine compounds such as isopropylhydroxylamine, diethylhydroxylamine and hydroxylamine, quinone compounds such as hydroquinone and benzoquinone, and sodium nitrite.
- an anti-aging agent may be added as required.
- a salt such as sodium chloride, calcium chloride, potassium chloride or the like is used as a coagulant, and if necessary, nitric acid, sulfuric acid etc.
- An unmodified liquid diene rubber is obtained by coagulating the unmodified liquid diene rubber (A ') while adding an acid to adjust the pH of the coagulation system to a predetermined value, and separating the dispersion medium. Recover (A '). Then, after washing with water and dehydration, drying is performed to obtain the unmodified liquid diene rubber (A ').
- a latex and an extender oil in the form of an emulsified dispersion may be mixed in advance and recovered as an oil-extended non-modified liquid diene rubber (A ').
- a known method or a method according to a known method can be applied.
- a known method or a method according to a known method can be applied.
- the solvent examples include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene, Aromatic hydrocarbons such as toluene and xylene can be mentioned.
- aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane
- alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane
- benzene Aromatic hydrocarbons such as toluene and xylene can be mentioned.
- anionically polymerizable active metal examples include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; lanthanoid rare earth metals such as lanthanum and neodymium .
- Organic alkali metal compounds are preferred as the anionically polymerizable active metal compound.
- Organic alkali metal compounds include, for example, organic monolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, stilbene lithium; dilithiomethane, dilithionaphthalene And polyfunctional organolithium compounds such as 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane and 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene and the like.
- organic alkali metal compounds organic lithium compounds are preferable, and organic monolithium compounds are more preferable.
- the amount of the organic alkali metal compound used can be appropriately set according to the molecular weight, melt viscosity, etc. of the unmodified liquid diene rubber (A ') and the modified liquid diene rubber (A), but the total amount including conjugated diene It is usually used in an amount of 0.01 to 3 parts by mass based on 100 parts by mass of the body.
- the organic alkali metal compound can also be used as an organic alkali metal amide by reacting with a secondary amine such as dibutylamine, dihexylamine, dibenzylamine and the like.
- Polar compounds are generally used in anionic polymerization to adjust the microstructure (e.g. vinyl content) of conjugated diene units without quenching the reaction.
- polar compounds include ether compounds such as dibutyl ether, tetrahydrofuran, ethylene glycol diethyl ether and the like; tertiary amines such as N, N, N ', N'- tetramethyl ethylene diamine and trimethylamine; alkali metal alkoxides, phosphine compounds and the like It can be mentioned.
- the polar compound is generally used in an amount of 0.01 to 1000 mol per 1 mol of the organic alkali metal compound.
- the temperature of solution polymerization is usually in the range of ⁇ 80 to 150 ° C., preferably in the range of 0 to 100 ° C., more preferably in the range of 10 to 90 ° C.
- the polymerization mode may be either batchwise or continuous.
- the polymerization reaction can be terminated by the addition of a polymerization terminator.
- the polymerization terminator include alcohols such as methanol and isopropanol.
- the obtained polymerization reaction solution is poured into a poor solvent such as methanol to precipitate an unmodified liquid diene rubber (A ′) or the polymerization reaction solution is washed with water, separated, and dried to obtain the above-mentioned undried product.
- Modified liquid diene rubber (A ') can be isolated.
- the solution polymerization method is preferable as a method for producing the non-modified liquid diene rubber (A ′).
- the unmodified liquid diene rubber (A ') obtained in this manner may be modified with the functional group described later (in the state of not being hydrogenated) as it is, but it is contained in the liquid diene rubber. Modification may be performed after hydrogenating at least a portion of the unsaturated bonds.
- the unmodified liquid diene rubber (A ') is modified with a functional group (a) derived from an acid anhydride and used as a modified liquid diene rubber (A).
- a functional group (a) derived from an acid anhydride examples include an acid anhydride group such as an unsaturated carboxylic acid anhydride group, an unsaturated carboxylic acid ester group derived from the acid anhydride group, and an unsaturated carboxylic acid amide group Unsaturated carboxylic acid imide group etc. are mentioned.
- the method for producing the modified liquid diene rubber (A) is not particularly limited, for example, the above-mentioned unmodified liquid diene rubber (A ') is modified with a compound corresponding to the functional group (a) derived from the acid anhydride. It can be produced by a grafting reaction which is added as a compound.
- Examples of the compound corresponding to the unsaturated carboxylic acid anhydride group include unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride.
- Examples of the compound corresponding to the unsaturated carboxylic acid ester group include unsaturated carboxylic acid esters such as maleic acid ester, fumaric acid ester, itaconic acid ester, glycidyl (meth) acrylate and hydroxyethyl (meth) acrylate.
- Examples of the compound corresponding to the unsaturated carboxylic acid amide group include unsaturated carboxylic acid amides such as maleic acid amide, fumaric acid amide and itaconic acid amide.
- unsaturated carboxylic acid imide group unsaturated carboxylic acid imides, such as maleic acid imide and itaconic acid imide, etc. are mentioned, for example.
- maleic anhydride was added as a modifying compound to unmodified liquid diene rubber (A ') from the viewpoint of economy and sufficient properties of the rubber composition and the crosslinked product of the present invention.
- a maleic anhydride modified liquid diene rubber is preferable, a maleic anhydride modified liquid polybutadiene and a maleic anhydride modified liquid polyisoprene are more preferable, and a maleic anhydride modified liquid polyisoprene is more preferable.
- the method for adding the modifying compound to the unmodified liquid diene rubber (A ') is not particularly limited.
- the unmodified liquid diene rubber corresponds to the functional group (a) derived from the acid anhydride.
- a compound for example, an acid anhydride such as unsaturated carboxylic acid anhydride, and optionally, a radical catalyst may be added, and heating may be performed in the presence or absence of an organic solvent.
- hydrocarbon solvents such as n-butane, n-hexane, n-heptane, cyclohexane, benzene, toluene and xylene are preferable.
- radical catalyst used in the above method di-s-butylperoxydicarbonate, t-amyl peroxypivalate, t-amylperoxy-2-ethylhexanoate, azobisisobutyronitrile etc. may be mentioned. Be Among these radical catalysts, azobisisobutyronitrile is preferred.
- the unsaturated carboxylic anhydride is added to the unmodified liquid diene rubber (A ′) to obtain the unsaturated carboxylic anhydride modified liquid diene rubber, the unsaturated carboxylic anhydride is further added.
- Acid anhydride modified liquid diene rubber and water or alcohol represented by Ra- OH (2) (in formula (2), Ra is a hydrogen atom or an alkyl group which may be substituted), or Ammonia represented by R b 2 -NH (3) (in formula (3), R b is a hydrogen atom or an alkyl group which may be substituted, and a plurality of R b may be the same or different)
- an amine or the like is reacted to produce an unsaturated carboxylic acid ester modified liquid diene rubber, an unsaturated carboxylic acid amide modified liquid diene rubber, or an unsaturated carboxylic acid imide modified liquid diene rubber, which is modified liquid Jie It may be used as a system rubber (A).
- the compounds represented by the formulas (2) and (3) are not particularly limited, but in view of easiness of modification reaction, alcohols having 1 to 20 carbon atoms are preferable, and saturated alcohols having 1 to 20 carbon atoms are preferable. Is more preferred, and methanol, ethanol, propanol, butanol, 3-methylbutanol and 3-methyl-1,3-butanediol are more preferred.
- a (meth) acryloyl group modified liquid diene rubber is produced using a hydroxyl group-containing (meth) acrylate as a compound represented by the formula (2) to be reacted with an unsaturated carboxylic acid modified liquid diene rubber.
- the meta) acryloyl group modified liquid diene rubber may be used as the modified liquid diene rubber (A).
- the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate. These hydroxyl group-containing (meth) acrylates Among them, 2-hydroxyethyl (meth) acrylate is preferable.
- the functional group equivalent of the functional group (a) derived from the acid anhydride of the modified liquid diene rubber (A) is in the range of 400 to 3,500 g / eq, preferably 600 to 2,500 g / eq. And more preferably 700 to 2,300 g / eq.
- the functional group equivalent of the functional group (a) derived from the acid anhydride of the modified liquid diene rubber (A) is in the above range, both the dripping resistance at normal temperature and the pumping property at high temperature can be compatible, and further A composition is obtained which shows excellent adhesion to various substrates after curing and high stiffness.
- the functional group equivalent of the functional group (a) derived from the acid anhydride in the present specification means the molecular weight of the modified liquid diene rubber (A) per one functional group (a).
- a reaction of adding a modifying compound is performed at an appropriate reaction temperature for a sufficient reaction time.
- the temperature in the reaction of adding maleic anhydride to unmodified liquid diene rubber (A ′) is preferably 100 to 200 ° C., and more preferably 120 ° C. to 180 ° C.
- the reaction time is preferably 3 to 200 hours, more preferably 4 to 100 hours, and still more preferably 5 to 50 hours.
- the functional group equivalent of the functional group (a) added in the modified liquid diene rubber (A) can also be calculated based on the addition reaction rate of the modified compound, infrared spectroscopy, nuclear magnetic resonance It can also be determined using various analytical instruments such as spectroscopy.
- the addition reaction rate of the modified compound of the modified liquid diene rubber (A) is preferably 40 to 100 mol%, more preferably 60 to 100 mol%, and still more preferably 80 to 100 mol%, Even more preferably 100 mol%.
- the modified compound or the low molecular weight compound derived from the modified compound is less likely to remain in the modified liquid diene rubber (A) to be obtained.
- An adverse effect such as metal corrosion which is considered to be derived from an acidic component such as maleic anhydride can be further suppressed.
- the rate of addition reaction of the modifying compound is an unreacted modification by comparing the acid value before and after washing in the sample after the modification reaction.
- the amount of compound can be calculated and determined.
- the amount of modifying compound added to the modified liquid diene rubber (A) is not strictly limited, but from the viewpoint of sufficiently exhibiting the characteristics of the obtained rubber composition and crosslinked product, the unmodified polymer
- the range of 0.05 to 40 parts by mass is preferable with respect to 100 parts by mass, the range of 0.1 to 30 parts by mass is more preferable, and the range of 0.1 to 20 parts by mass is more preferable.
- the amount of modifying compound added is more than 40 parts by mass, the flexibility and strength of the resulting crosslinked product tend to decrease, and when the amount of modifying compound added is less than 0.05 parts by mass, the adhesiveness of the resulting crosslinked product decreases. There is a tendency to
- the amount of modifying compound added to the modifying liquid diene rubber (A) can also be calculated based on the rate of addition reaction of the modifying compound, and various analyzes such as infrared spectroscopy and nuclear magnetic resonance spectroscopy. It can also be determined using an instrument.
- the position at which the functional group is introduced may be at the polymerization end, or may be the side chain of the polymer chain.
- the functional groups may be contained singly or in combination of two or more. Therefore, the modified liquid diene rubber (A) may be modified with one type of modifying compound, or may be modified with two or more types of modifying compounds.
- the number average molecular weight (Mn) of the modified liquid diene rubber (A) is 5,000 to 20,000, preferably 6,000 to 18,000, more preferably 6,000 to 16,000, and 6,000. -14,000 is more preferable, and 8,000 to 12,000 is even more preferable.
- Mn of the modified liquid diene rubber (A) is in the above range, a composition having excellent moldability and exhibiting good rubber elasticity and rigidity after curing can be obtained.
- Mn of the modified liquid diene rubber (A) is a polystyrene-equivalent number average molecular weight obtained from measurement of gel permeation chromatography (GPC).
- the molecular weight distribution (Mw / Mn) of the modified liquid diene rubber (A) is preferably 1.0 to 2.0, more preferably 1.0 to 1.5, still more preferably 1.0 to 1.2, 0 to 1.1 are more preferred.
- Mw / Mn is in the above-mentioned range, both the dripping resistance at normal temperature and the pumping property at high temperature can be compatible, and a composition having excellent formability and less bleeding out of low molecular weight components can be obtained.
- molecular weight distribution (Mw / Mn) means the ratio of the weight average molecular weight (Mw) / number average molecular weight (Mn) of polystyrene conversion calculated
- an unmodified liquid diene rubber Purification of (A ′) may be sufficient to sufficiently remove components that inhibit the reaction of adding the modified compound.
- washing with water or warm water, or an organic solvent or supercritical fluid carbon dioxide represented by methanol, acetone or the like is preferable.
- the modified liquid diene rubber (A) having a specific molecular weight distribution it is also effective to add an antiaging agent at the time of the reaction of adding the modified compound, in addition to the washing.
- Preferred anti-aging agents used at this time are 2,6-di-t-butyl-4-methylphenol (BHT), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4 ' -Thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol) (AO-40), 3,9-bis [1,1-dimethyl-2 -[3- (3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (AO-80), 2 , 4-Bis [(octylthio) methyl] -6-methylphenol (BHT), 2,2'-methylenebis
- Antiaging agents are classified according to their mechanism of action into primary chain inhibition type primary antiaging agents and peroxide decomposition type secondary antiaging agents.
- a modified liquid diene rubber (A) having a specific molecular weight distribution in the present invention it acts as a primary anti-aging agent from the viewpoint of suppressing side reactions due to radicals generated during the reaction of adding a modifying compound.
- Phenolic anti-aging agents and amine anti-aging agents are preferred.
- the modified liquid diene rubber (A) as one component of the rubber composition for a tire bead filler described later.
- the phenolic anti-aging agent is inferior to the amine anti-aging agent in anti-aging effect, it does not cause the above-mentioned coloring problem. Therefore, the modified liquid diene rubber (A) to which the modifying compound is added in the presence of a phenolic antioxidant is a composition other than the rubber composition for a tire bead filler, for example, a rubber composition for sealing material described later, epoxy It is preferable to use as one component of the resin composition.
- the addition amount of the antiaging agent is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the unmodified liquid diene rubber (A ') or the modified liquid diene rubber (A). Part is more preferred.
- the temperature in the reaction of adding maleic anhydride to the unmodified liquid diene rubber (A ') is preferably 100 to 200 ° C, more preferably 120 to 180 ° C.
- the glass transition temperature (Tg) of the modified liquid diene rubber (A) is the vinyl content of the unit derived from the conjugated diene (a1), the type of conjugated diene (a1), and the unit derived from monomers other than conjugated diene Although it may vary depending on the content etc., -100 to 30 ° C. is preferable, -100 to 20 ° C. is more preferable, and -100 to 10 ° C. is more preferable.
- Tg is in the above range, for example, the processability and adhesion of the rubber composition become good. Further, the increase in viscosity can be suppressed and the handling becomes easy.
- the vinyl content of the modified liquid diene rubber (A) is preferably 99 mol% or less, more preferably 90 mol% or less, still more preferably 50 mol% or less, and 20 mol% or less Is further more preferable, and 10 mol% or less is particularly preferable.
- the vinyl content of the modified liquid diene rubber (A) is preferably 1 mol% or more, more preferably 3 mol% or more, and still more preferably 5 mol% or more.
- the modified liquid diene rubber (A) may be used alone or in combination of two or more.
- the "vinyl content" refers to a 1,2- or 3,4- bond in a total of 100 mol% of conjugated diene (a1) units contained in the modified liquid diene rubber.
- the total mole percent of conjugated diene units (conjugated diene units having bonds other than 1,4-bonds) is meant.
- the vinyl content is determined by using 1 H-NMR to conjugated diene units linked by 1,4-links with peaks derived from conjugated diene units linked by 1,2- or 3,4-links. It can be calculated from the area ratio of the derived peaks.
- the vinyl content of the modified liquid diene rubber (A) is, for example, the kind of solvent used when producing the unmodified liquid diene rubber (A ′), the polar compound used according to need, and the polymerization A desired value can be obtained by controlling the temperature or the like.
- the melt viscosity of the modified liquid diene rubber (A) measured at 38 ° C. is 3 Pa ⁇ s or more, preferably in the range of 3 to 200 Pa ⁇ s, more preferably in the range of 3 to 100 Pa ⁇ s, still more preferably It is in the range of 5 to 50 Pa ⁇ s.
- the melt viscosity of the modified liquid diene rubber (A) at 38 ° C. is within the above range, the dripping resistance of the modified liquid diene rubber (A) and the composition thereof becomes good.
- the melt viscosity of the modified liquid diene rubber (A) is not particularly limited as long as the requirements of the present invention are satisfied, but preferably 25 Pa ⁇ s or less, more preferably 20 Pa ⁇ s or less, and further preferably Is 10 Pa ⁇ s or less. Moreover, Preferably it is 1.0 Pa.s or more, More preferably, it is 1.3 Pa.s or more, More preferably, it is 1.5 Pa.s or more.
- the melt viscosity of the modified liquid diene rubber (A) at 60 ° C. is within the above range, the pumping properties of the modified liquid diene rubber (A) and the composition thereof become good.
- the melt viscosity of the modified liquid diene rubber (A) is a value determined by the method described in the examples described later.
- X (K) is 6100 K or more, preferably 6200 K or more, and more preferably 6400 K or more.
- X (K) may be 12000 K or less, preferably 10000 K or less, more preferably 9000 K or less, and still more preferably 8000 K or less.
- X (K) is a melt viscosity ⁇ (Pa ⁇ s) 2 point measured at 38 ° C. and 60 ° C.
- X (K) can be considered to approximately represent E / R in the above formula (1), and E / R is obtained by dividing the apparent activation energy required for flow by the gas constant It is a value.
- X (K) of the present invention is in the above range, the change in melt viscosity with temperature becomes large, and the modified liquid diene rubber (A) or its composition in which the dripping resistance at normal temperature and the flowability at high temperature are compatible It becomes possible to design things.
- the rubber component contains the above-mentioned modified liquid diene rubber (A).
- the rubber component in the present invention is a component comprising a modified liquid diene rubber, an unmodified liquid diene rubber optionally contained, and the following solid rubber (B) optionally contained.
- the rubber component of the rubber composition according to the present invention may be, for example, the modified liquid diene rubber (A) and the following solid rubber (A) when it is composed only of the liquid diene rubber containing the above-mentioned modified liquid diene rubber (A). B) may be included.
- this rubber component may be composed of 1 to 99% by mass of liquid diene rubber (A) and 99 to 1% by mass of solid rubber (B), Preferably, 1 to 95% by mass of liquid diene rubber (A) and 99 to 5% by mass of solid rubber (B), more preferably 10 to 90% by mass of liquid diene rubber (A) and 90 to 10 solid rubber (B) It is composed of, preferably, 20 to 80% by mass of liquid diene rubber (A) and 80 to 20% by mass of solid rubber (B).
- the mixing ratio of the liquid diene rubber (A) and the solid rubber (B) is in the above range, the processability and the adhesiveness of the rubber composition become good.
- Solid rubber (B) used in the rubber composition of the present invention is a rubber which can be handled in solid form at 20 ° C., and the Mooney viscosity ML 1 + 4 at 100 ° C. of the solid rubber (B) is usually 20 to 200.
- the solid rubber (B) include natural rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber, acrylonitrile-butadiene copolymer rubber, chloroprene rubber, ethylene propylene And rubber and butyl rubber.
- the weight average molecular weight (Mw) of the solid rubber (B) is preferably 80,000 or more, preferably 100,000 to 3,000,000, from the viewpoint of sufficiently exhibiting the characteristics of the obtained rubber composition. It is more preferable to be within the range.
- the weight average molecular weight in this specification is a weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).
- the natural rubber examples include natural rubber generally used in the tire industry such as SMR, SIR, STR, TSR such as STR, high purity natural rubber, epoxidized natural rubber, hydroxylated natural rubber, hydrogenated natural rubber And modified natural rubber such as grafted natural rubber.
- SMR20, STR20 and RSS # 3 are preferable in terms of less variation in quality and availability.
- These natural rubbers may be used alone or in combination of two or more.
- polyisoprene rubber examples include Ziegler catalysts such as titanium tetrahalide-trialkylaluminum-based, diethylaluminum chloride-cobalt-based, trialkylaluminum-boron trifluoride-nickel-based, diethylaluminum chloride-nickel-based; It is polymerized using an organic alkali metal compound in the same manner as a lanthanide rare earth metal catalyst such as triethylaluminum-organic acid neodymium-Lewis acid system, or solution-polymerized styrene-butadiene copolymer rubber (hereinafter also referred to as S-SBR).
- Ziegler catalysts such as titanium tetrahalide-trialkylaluminum-based, diethylaluminum chloride-cobalt-based, trialkylaluminum-boron trifluoride-nickel-based, diethylaluminum chloride-nickel-based
- polyisoprene rubber can be used.
- a polyisoprene rubber polymerized with a Ziegler-based catalyst is preferred because of its high cis content.
- the vinyl content of the polyisoprene rubber is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. When the vinyl content exceeds 50% by mass, the flexibility at low temperature of the rubber composition tends to deteriorate.
- the lower limit of the vinyl content is not particularly limited.
- the glass transition temperature varies depending on the vinyl content, but is preferably ⁇ 20 ° C. or less, more preferably ⁇ 30 ° C. or less.
- the weight average molecular weight (Mw) of the polyisoprene rubber is preferably 90,000 to 2,000,000, and more preferably 150,000 to 1,500,000. When Mw is in the above range, processability and mechanical strength become good.
- the polyisoprene rubber is a multifunctional modifier such as tin tetrachloride, silicon tetrachloride, an alkoxysilane having an epoxy group in the molecule, or an amino group, as long as the effect of the present invention is not impaired. It may have a branched structure or a polar functional group by using a modifying agent such as containing alkoxysilane.
- polybutadiene rubber examples include Ziegler-based catalysts such as titanium tetrahalide-trialkylaluminum-based, diethylaluminum chloride-cobalt-based, trialkylaluminum-boron trifluoride-nickel-based, diethylaluminum chloride-nickel-based;
- Ziegler-based catalysts such as titanium tetrahalide-trialkylaluminum-based, diethylaluminum chloride-cobalt-based, trialkylaluminum-boron trifluoride-nickel-based, diethylaluminum chloride-nickel-based
- a commercially available polybutadiene rubber polymerized using a lanthanoid rare earth metal catalyst such as an aluminum-organic acid neodymium-Lewis acid system or an organic alkali metal compound in the same manner as S-SBR can be used.
- Polybutadiene rubber polymerized with a Ziegler-based catalyst is preferred because
- the vinyl content of the polybutadiene rubber is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. When the vinyl content exceeds 50% by mass, the flexibility at low temperature of the rubber composition tends to deteriorate.
- the lower limit of the vinyl content is not particularly limited.
- the glass transition temperature varies depending on the vinyl content, but is preferably ⁇ 40 ° C. or less, more preferably ⁇ 50 ° C. or less.
- the weight average molecular weight (Mw) of the polybutadiene rubber is preferably 90,000 to 2,000,000, and more preferably 150,000 to 1,500,000. When Mw is in the above range, processability and mechanical strength become good.
- the polybutadiene rubber is a multifunctional modifier such as tin tetrachloride, silicon tetrachloride, alkoxysilane having an epoxy group in the molecule, or an amino group-containing, as long as the effects of the present invention are not impaired. It may have a branched structure or a polar functional group by using a modifier such as alkoxysilane.
- styrene-butadiene copolymer rubber (hereinafter, also referred to as SBR), an appropriate one can be used according to the application etc. Specifically, one having a styrene content of 0.1 to 70% by mass is preferable 5 to 50% by mass is more preferable, and 10 to 40% by mass is more preferable.
- the vinyl content is preferably 0.1 to 60% by mass, and more preferably 0.1 to 55% by mass.
- the weight average molecular weight (Mw) of SBR is preferably 100,000 to 2,500,000, more preferably 150,000 to 2,000,000, and 200,000 to 1,500,000. It is further preferred that When it is in the above range, it is possible to achieve both processability and mechanical strength.
- the glass transition temperature of the SBR used in the present invention determined by differential thermal analysis is preferably ⁇ 95 to 0 ° C., and more preferably ⁇ 95 to ⁇ 5 ° C. By setting the glass transition temperature to the above range, the increase in viscosity can be suppressed, and the handling becomes easy.
- the SBR that can be used in the present invention is obtained by copolymerizing styrene and butadiene.
- There are no particular restrictions on the method for producing SBR and any of emulsion polymerization, solution polymerization, gas phase polymerization and bulk polymerization can be used, but among these production methods, emulsion polymerization and solution polymerization are preferred. .
- Emulsion polymerization styrene-butadiene copolymer rubber (hereinafter, also referred to as E-SBR) can be produced by a known emulsion polymerization method according to a known method or a known method. For example, it can be obtained by emulsifying and dispersing predetermined amounts of styrene and butadiene monomers in the presence of an emulsifying agent, and then performing emulsion polymerization with a radical polymerization initiator.
- S-SBR can be prepared by conventional solution polymerization methods, for example using an active metal that can be anionically polymerized in a solvent to polymerize styrene and butadiene, optionally in the presence of polar compounds.
- the solvent examples include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene, Aromatic hydrocarbons such as toluene and the like can be mentioned. It is preferable to use these solvents in the range in which the monomer concentration is usually 1 to 50% by mass.
- anionically polymerizable active metal examples include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; lanthanoid rare earth metals such as lanthanum and neodymium .
- alkali metals and alkaline earth metals are preferable, and alkali metals are more preferable.
- organic alkali metal compounds are more preferably used.
- organic alkali metal compound examples include organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, stilbenelithium, etc .; dilithiomethane, 1,4-dilithiobutane, 1,4 -Multifunctional organolithium compounds such as dilithio-2-ethylcyclohexane and 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene and the like. Among them, organic lithium compounds are preferable, and organic monolithium compounds are more preferable.
- the amount of the organic alkali metal compound used is appropriately determined by the required molecular weight of S-SBR.
- organic alkali metal compounds can also be used as organic alkali metal amides by reacting with secondary amines such as dibutylamine, dihexylamine, dibenzylamine and the like.
- the polar compound is not particularly limited as long as it is generally used to adjust the microstructure of the butadiene moiety or the distribution of styrene in the copolymer chain without deactivating the reaction in anionic polymerization, for example, Ether compounds such as dibutyl ether, tetrahydrofuran, ethylene glycol diethyl ether and the like; tertiary amines such as tetramethyl ethylene diamine and trimethylamine; alkali metal alkoxides, phosphine compounds and the like.
- Ether compounds such as dibutyl ether, tetrahydrofuran, ethylene glycol diethyl ether and the like
- tertiary amines such as tetramethyl ethylene diamine and trimethylamine
- alkali metal alkoxides, phosphine compounds and the like alkali metal alkoxides, phosphine compounds and the like.
- the temperature of the polymerization reaction is usually in the range of ⁇ 80 to 150 ° C., preferably 0 to 100 ° C., and more preferably 30 to 90 ° C.
- the polymerization mode may be either batchwise or continuous.
- the polymerization reaction can be terminated by adding an alcohol such as methanol or isopropanol as a polymerization terminator.
- the target S-SBR can be recovered by directly separating the solvent from the polymerization solution after termination of the polymerization reaction by drying or steam stripping.
- the polymerization solution and the extender oil may be mixed in advance and recovered as an oil-extended rubber.
- SBR As said SBR, you may use the modified SBR by which the functional group was introduce
- a functional group an amino group, alkoxy silyl group, a hydroxyl group, an epoxy group, a carboxyl group etc. are mentioned, for example.
- modified SBR for example, tin tetrachloride, tetrachlorosilane, dimethyldichlorosilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, which can react with the polymerization active end before adding the polymerization terminator.
- Coupling agents such as 3-aminopropyltriethoxysilane, tetraglycidyl-1,3-bisaminomethylcyclohexane, 2,4-tolylene diisocyanate, 4,4'-bis (diethylamino) benzophenone, N-vinyl pyrrolidone, etc.
- tin tetrachloride tetrachlorosilane
- dimethyldichlorosilane dimethyldiethoxysilane
- tetramethoxysilane tetraethoxysilane
- tetraethoxysilane
- the position of the polymer at which the functional group is introduced may be a polymerization terminal or a side chain of a polymer chain.
- styrene-isoprene copolymer rubber acrylonitrile-butadiene copolymer rubber, chloroprene rubber, ethylene propylene rubber (EPM, EPDM, etc.) and butyl rubber, commercially available products can be used without particular limitation.
- the rubber composition of the present invention may contain a filler.
- the filler is blended for the purpose of improving mechanical strength, improving physical properties such as heat resistance or weather resistance, adjusting hardness, increasing the amount of rubber, and the like.
- the filler include calcium carbonate, calcium oxide, magnesium hydroxide, magnesium oxide, magnesium oxide, magnesium carbonate, aluminum hydroxide, barium sulfate, barium oxide, titanium oxide, iron oxide, zinc oxide, zinc carbonate, wax clay, kaolin Clay and clay such as calcined clay, mica, diatomaceous earth, carbon black, silica, glass fiber, carbon fiber, fibrous filler, inorganic filler such as glass balloon, crosslinked polyester, polystyrene, styrene-acrylic copolymer resin, or urea
- the resin particle formed from resin, such as resin, a synthetic fiber, and a natural fiber etc. are mentioned.
- grain can take various shapes, such as spherical shape, according to a desired physical property etc.
- the filler when the filler is in the form of particles, it may be either solid particles or hollow particles depending on the desired physical properties and the like, or core-shell type particles formed of a plurality of materials and the like. May be These fillers may be surface-treated with various compounds such as fatty acids, resin acids, fatty acid esters, and silane coupling agents.
- fillers calcium carbonate, carbon black and silica are preferable, and calcium carbonate and carbon black are more preferable, from the viewpoints of the reinforcing property of the obtained rubber composition and the crosslinked product thereof, the cost and the handling ease.
- These fillers may be used alone or in combination of two or more.
- the content of the filler relative to 100 parts by mass of the rubber component is preferably 0.1 to 1500 parts by mass, more preferably 1 to 1300 parts by mass, still more preferably 5 to 1000 parts by mass, 800 parts by weight are even more preferred.
- the rubber composition of the present invention containing the modified liquid diene rubber (A) and the solid rubber (B) as the rubber component, 100 parts by mass of the rubber component containing the modified liquid diene rubber (A) and the solid rubber (B)
- the content of the filler is preferably 0.1 to 1500 parts by mass, more preferably 1 to 1300 parts by mass, still more preferably 5 to 1000 parts by mass, and still more preferably 10 to 800 parts by mass.
- the processability and adhesiveness of a rubber composition are favorable in content of a filler being in the said range.
- the rubber composition of the present invention may contain an oil.
- the oil is added mainly to improve the processability of the rubber composition of the present invention and the dispersibility of other additives, and to bring the properties of the rubber composition into a desired range.
- As said oil mineral oil, vegetable oil, a synthetic oil etc. are mentioned.
- mineral oils include paraffinic oils, naphthenic oils and aromatic oils.
- vegetable oils include castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, peanut oil and the like.
- synthetic oils include ethylene / ⁇ -olefin oligomers, liquid paraffin and the like.
- oils paraffinic oils, naphthenic oils and aromatic oils are preferred, and naphthenic oils are more preferred. These oils may be used alone or in combination of two or more.
- the content of oil relative to 100 parts by mass of the rubber component is preferably 0.1 to 500 parts by mass, more preferably 1 to 450 parts by mass, still more preferably 5 to 400 parts by mass, and 8 to 350 Parts by weight are even more preferred.
- the rubber composition of the present invention containing the modified liquid diene rubber (A) and the solid rubber (B) as the rubber component, 100 parts by mass of the rubber component containing the modified liquid diene rubber (A) and the solid rubber (B)
- the content of oil is preferably 0.1 to 500 parts by mass, more preferably 1 to 450 parts by mass, still more preferably 5 to 400 parts by mass, and still more preferably 8 to 350 parts by mass.
- the processability and adhesiveness of a rubber composition are favorable in content of oil being in the said range.
- the rubber composition of the present invention may further contain a crosslinking agent to crosslink the rubber component.
- a crosslinking agent for example, sulfur, sulfur compound, oxygen, organic peroxide, phenol resin, amino resin, quinone and quinone dioxime derivative, halogen compound, aldehyde compound, alcohol compound, epoxy compound, metal halide and organic metal Halide, a silane compound, etc. are mentioned.
- the sulfur compound include morpholine disulfide, alkylphenol disulfide and the like.
- organic peroxide cyclohexanone peroxide, methylacetoacetate peroxide, t-butylperoxyisobutyrate, t-butylperoxybenzoate, benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, di-t- Examples include butyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene and the like. These crosslinking agents may be used alone or in combination of two or more.
- the cross-linking agent is usually contained in an amount of 0.1 to 10 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 0.8 to 10 parts by mass, per 100 parts by mass of the rubber component contained in the rubber composition. Ru.
- the crosslinking agent contains a modified liquid diene rubber (A) and a solid rubber (B) as rubber components from the viewpoint of mechanical properties of a crosslinked product, a solid rubber (B) and a modified liquid diene rubber (
- the amount is usually 0.1 to 10 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 0.8 to 10 parts by mass, with respect to 100 parts by mass of the rubber component consisting of A).
- the rubber composition of the present invention may further contain a vulcanization accelerator when, for example, sulfur, a sulfur compound or the like is contained as a crosslinking agent for crosslinking (vulcanizing) the rubber.
- vulcanization accelerators include guanidine compounds, sulfenamide compounds, thiazole compounds, thiuram compounds, thiourea compounds, dithiocarbamic acid compounds, aldehyde-amine compounds, aldehyde-ammonia compounds, imidazoline compounds Compounds, xanthate compounds and the like can be mentioned. These vulcanization accelerators may be used alone or in combination of two or more.
- the above-mentioned vulcanization accelerator is usually contained in an amount of 0.1 to 15 parts by mass, preferably 0.1 to 10 parts by mass, per 100 parts by mass of the rubber component contained in the rubber component.
- the above-mentioned vulcanization accelerator contains a modified liquid diene rubber (A) and a solid rubber (B) as a rubber component, a rubber component comprising the solid rubber (B) and the modified liquid diene rubber (A)
- the amount is usually 0.1 to 15 parts by mass, preferably 0.1 to 10 parts by mass, per 100 parts by mass.
- the rubber composition of the present invention contains, for example, sulfur, a sulfur compound, or the like as a crosslinking agent for crosslinking (vulcanizing) the rubber, it may further contain a vulcanization aid.
- a vulcanization assistant include fatty acids such as stearic acid, metal oxides such as zinc flower, and fatty acid metal salts such as zinc stearate. These vulcanization aids may be used alone or in combination of two or more.
- the above-mentioned vulcanization auxiliary is contained usually in an amount of 0.1 to 15 parts by mass, preferably 0.5 to 10 parts by mass, with respect to the rubber component contained in the rubber composition.
- vulcanization auxiliary contains a modified liquid diene rubber (A) and a solid rubber (B) as a rubber component, a rubber component comprising the solid rubber (B) and the modified liquid diene rubber (A)
- the amount is usually 0.1 to 15 parts by mass, preferably 0.5 to 10 parts by mass.
- crosslinking agents may be used instead of or in addition to the above-mentioned crosslinking agent, optionally added vulcanization accelerator, and optionally added vulcanization assistant And the like may be crosslinked.
- a crosslinking agent etc. of the rubber composition of this invention the combination of a phenol resin (C) and a hardening
- the combination of the phenolic resin (C) and the curing agent (D) is preferably used in a rubber composition for tire bead filler.
- the phenol resin (C) and the curing agent (D) will be described in detail in the description of the rubber composition for tire bead filler.
- the combination of epoxy resin and tertiary amine is preferably used in the rubber composition for sealing material.
- the epoxy resin and tertiary amine will be described in detail in the description of the sealing material.
- the rubber composition of the present invention aims at improvement in processability, fluidity, etc. within the range that does not inhibit the effects of the invention, and if necessary, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, C9 resin, Tackifying resins such as rosin resins, coumarone-indene resins, and phenol resins may be contained.
- the rubber composition of the present invention is an anti-aging agent, an antioxidant, and a light-stabilizing agent as needed for the purpose of improving the weather resistance, heat resistance, oxidation resistance, etc.
- Agents scorch inhibitors, functional group-containing compounds, waxes, lubricants, plasticizers, processing aids, pigments, dyes, dyes, other colorants, flame retardants, antistatic agents, matting agents, antiblocking agents, UV absorbers
- antioxidant examples include hindered phenol compounds, phosphorus compounds, lactone compounds, hydroxyl compounds and the like.
- examples of the antiaging agent include amine-ketone compounds, imidazole compounds, amine compounds, phenol compounds, sulfur compounds and phosphorus compounds.
- a functional group-containing compound may be added to improve the adhesion, adhesion and the like of the rubber composition and the adherend.
- the functional group-containing compound include functional group-containing alkoxysilanes such as N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane and ⁇ -glycidoxypropyltrimethoxysilane, 2-hydroxyethylacryloyl phosphate, Examples include functional group-containing acrylates and methacrylates such as 2-hydroxyethyl methacryloyl phosphate, nitrogen-containing acrylate, and nitrogen-containing methacrylate. From the viewpoint of adhesion and adhesion, an epoxy group is a preferred embodiment as the functional group.
- the pigment examples include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine blue, bengala, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride and sulfate; and organic pigments such as azo pigment and copper phthalocyanine pigment Be
- antistatic agent examples include hydrophilic compounds such as quaternary ammonium salts, polyglycols and ethylene oxide derivatives.
- the flame retardant includes, for example, chloroalkyl phosphate, dimethyl-methyl phosphonate, bromine-phosphorus compound, ammonium polyphosphate, neopentyl bromide polyether, brominated polyether. These additives may be used alone or in combination of two or more.
- the method for producing the rubber composition of the present invention is not particularly limited as long as the above components can be uniformly mixed.
- the apparatus used for producing the rubber composition includes, for example, a tangential or intermeshing internal mixer such as a kneader ruder, Brabender, Banbury mixer, internal mixer, etc., single screw extruder, twin screw extruder, mixing roll , Rollers and the like.
- the above-mentioned mixing can be carried out under normal pressure and in an air atmosphere, but it is preferable to carry out under reduced pressure or nitrogen atmosphere from the viewpoint of preventing bubbles from being mixed in the composition at the time of mixing. It is preferable that the rubber composition of the present invention obtained by thus uniformly dispersing each component is stored in a closed container or the like until use.
- the rubber composition of the present invention is a preferred embodiment to be used as a rubber composition for tire bead filler.
- the rubber composition for a tire bead filler preferably contains a phenolic resin (C) and a curing agent (D) in addition to the modified liquid diene rubber (A) and the solid rubber (B).
- a phenol resin (C) used for the rubber composition for tire bead fillers of this invention a novolak-type phenol resin etc. are mentioned, for example.
- the novolak type phenol resin phenol-formaldehyde resin, resorcinol-formaldehyde resin, cresol resin and the like can be mentioned.
- novolac type phenolic resin those modified with rosin oil, tall oil, cashew oil, linoleic acid, oleic acid, linoleic acid, etc., those modified with aromatic hydrocarbons such as xylene, mesitylene, nitrile It may be one modified by rubber such as rubber.
- curing agent (D) used for the rubber composition for tire bead fillers of this invention hexamethylene tetramine, hexamethoxymethylmelamine etc. are mentioned, for example. Among them, hexamethyltetramine is preferred.
- the content of the modified liquid diene rubber (A) with respect to 100 parts by mass of the solid rubber (B) is the formability and vulcanization.
- the amount is preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass, and still more preferably 4 to 12 parts by mass from the viewpoint of the later rigidity and strength. When the amount is less than 1 part by mass, sufficient moldability and rigidity after vulcanization may not be obtained. When the amount is more than 20 parts by mass, mechanical strength of the vulcanized product may be reduced.
- the content of the phenolic resin (C) relative to 100 parts by mass of the solid rubber (B) is the hardness and toughness after vulcanization. From the point of point of view, it is preferably 5 to 40 parts by mass, and more preferably 15 to 25 parts by mass. If the amount is less than 5 parts by mass, the hardness after vulcanization may decrease and the rigidity may be impaired. If the amount is more than 40 parts by mass, the toughness may be lost and the vulcanized product may become brittle.
- the content of the curing agent (D) relative to 100 parts by mass of the solid rubber (B) has a hardness and low fuel consumption after vulcanization. From the viewpoint of the properties, it is preferably 0.5 to 2.0 parts by mass. If the amount is less than 0.5 parts by mass, the hardness after vulcanization may decrease and the rigidity may be impaired. If the amount is more than 2.0 parts by mass, the energy loss at the time of deformation may increase and the fuel efficiency may be deteriorated. is there.
- the rubber composition of the present invention is used as a rubber composition for tire bead fillers, other optional components (for example, carbon black, a vulcanizing agent, and crosslinking) contained in the rubber composition of the present invention as components other than the above.
- Agents, vulcanization accelerators, oils, processing aids, plasticizers, anti-aging agents, etc. are included in the rubber composition of the present invention as components other than the above.
- the above rubber composition of the present invention is an embodiment suitable for use as a rubber composition for a sealing material.
- the sealing material is preferably one embodiment of the following crosslinked product.
- the rubber composition for a sealing material preferably contains the above-mentioned crosslinking agent and the like.
- the rubber composition for a sealing material may contain a combination of an epoxy resin and a tertiary amine instead of, or in addition to, the above-mentioned crosslinking agent and the like.
- epoxy resin examples include biphenyl type epoxy resin, naphthalene type epoxy resin, diphenyl ether type epoxy resin, diphenyl thioether type epoxy resin, hydroquinone type epoxy resin, biphenyl novolac type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin Resin, bisphenol A novolac epoxy resin, trisphenol epoxy resin, tetraphenylolethane epoxy resin, dicyclopentadiene epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, etc. may be mentioned.
- the tertiary amine examples include triethylamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol.
- Crosslinked product After the rubber composition of the present invention is applied to a base material such as oil-faced steel sheet as required, it is crosslinked to obtain a crosslinked product.
- the crosslinking conditions of the rubber composition can be appropriately set according to the application etc. However, for example, a crosslinked product can be produced by performing a crosslinking reaction in a temperature range of 130 ° C. to 250 ° C. for 10 minutes to 60 minutes. .
- the rubber composition of the present invention is used in an automobile manufacturing line, the rubber composition of the present invention is applied to desired portions of various members (for example, gaps between flanges of a plurality of frame members).
- the crosslinked product can be formed on a desired site by crosslinking with the generated heat.
- the crosslinked product obtained from the rubber composition of the present invention is excellent in adhesion, and can be suitably used, for example, for automobile parts.
- modified liquid diene rubber (A) of the present invention can be used as one component of a curable resin composition together with the curable resin (E).
- the curable resin (E) contained in the said curable resin composition, according to a use etc., an appropriate thing can be selected and used.
- the curable resin (E) is a curable compound having a relatively small molecular weight, a curable oligomer, or a mixture thereof, and the curable resin (E) has functions of heat, light, catalyst, etc. Causes a curing reaction to form a three-dimensional network structure.
- an epoxy resin unsaturated polyester resin, an epoxy (meth) acrylate resin, ester (meth) acrylate resin, a phenol resin, a urea resin, a melamine resin, a urethane resin, a silicon resin, an imide, for example Resin, furan resin, alkyd resin, allyl resin, diallyl phthalate resin etc. are mentioned.
- epoxy resin examples include biphenyl type epoxy resin, naphthalene type epoxy resin, diphenyl ether type epoxy resin, diphenyl thioether type epoxy resin, hydroquinone type epoxy resin, biphenyl novolac type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin Resin, bisphenol A novolac epoxy resin, trisphenol epoxy resin, tetraphenylolethane epoxy resin, dicyclopentadiene epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, etc. may be mentioned. These epoxy resins may be used alone or in combination of two or more.
- unsaturated polyester resin As said unsaturated polyester resin, ortho-type unsaturated polyester resin, iso-type unsaturated polyester resin, bisphenol-type unsaturated polyester resin etc. are mentioned, for example. These unsaturated polyester resins may be used alone or in combination of two or more.
- curable resins (E) an epoxy resin and an unsaturated polyester resin are preferable, and an epoxy resin is more preferable, from the viewpoint of availability and basic physical properties of a cured product.
- the modified liquid diene rubber (A) is used per 100 parts by mass of the curable resin (E).
- the content is preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass, and more preferably 4 to 12 parts by mass from the viewpoints of moldability, heat resistance after curing, strength, and impact resistance. More preferably, it is a part.
- the amount is less than 1 part by mass, sufficient moldability and impact resistance after curing may not be obtained.
- the amount is more than 20 parts by mass, the mechanical strength of the cured product may be reduced.
- the curable resin composition may further contain a resin curing agent (F) capable of curing the curable resin (E).
- a resin curing agent capable of curing the curable resin (E).
- the curable resin (E) is an epoxy resin, as such a curing agent, polyaddition type epoxy such as aliphatic polyamine, alicyclic polyamine, aromatic polyamine, acid anhydride type compound, phenol novolac resin, etc.
- Curing agents Epoxy curing agents such as catalyst type epoxy curing agents such as aromatic tertiary amines, imidazole compounds (eg, 2-ethyl-4-methylimidazole etc.) and Lewis acid complexes can be used.
- the content of the resin curing agent (F) is 0.5 to 5.0 from the viewpoint of curing speed and physical properties of the cured product with respect to 100 parts by mass of the curable resin (E). It is preferable that it is a mass part. If the amount is less than 0.5 parts by mass, the curing rate may not be sufficient, and the heat resistance, strength and the like of the cured product may be impaired. If the amount is more than 5.0 parts by mass, the curable resin composition may be cured It may adversely affect the physical properties of things.
- the above-mentioned curable composition is exemplified as a component which can be contained in the rubber composition of the present invention as a component other than the above; filler; anti-aging agent, antioxidant, light stabilizer, functional group-containing compound, wax, lubricant , Plasticizers, processing aids, pigments, dyes, dyes, other colorants, flame retardants, antistatic agents, matting agents, antiblocking agents, UV absorbers, mold release agents, foaming agents, antibacterial agents, antifungal agents And additives such as perfumes, dispersants and solvents.
- the said curable resin composition can mix uniformly curable resin (E), modified
- the said curable composition can produce hardened
- a temperature suitable for the curable resin composition containing the curable resin (E) may be selected, and curing may be performed for an appropriate time.
- cured material the transfer molding method, the injection molding method, the compression molding method etc. are mentioned, for example.
- the curable resin composition for example, a cured product excellent in heat resistance, impact resistance and mechanical properties can be obtained. Therefore, the said curable resin composition and the hardened
- the curable resin composition and the cured product can be used, for example, in the field of electric and electronics, in the field of construction and civil engineering, in the field of transportation and transportation (in the field of automobiles, etc.).
- More specific applications include, for example, adhesives for fiber-reinforced composites (adhesives for fiber-reinforced composites for concrete, adhesives for fiber-reinforced composites for transportation devices such as automobiles, railway vehicles, and aircraft, various sports goods Adhesives for fiber reinforced composite materials), adhesives for assembly (adhesives for assembly of parts in transportation equipment such as cars, railway vehicles and aircraft), etc .; anticorrosion / waterproof coatings for water and sewage, for metals Various paints such as anticorrosion paint; paint primers for construction and civil engineering, paint primers such as paint primers for transportation equipment such as cars, railway cars and aircrafts; lining materials for metal, lining materials for concrete, lining materials for tanks etc. Various lining materials; Various repair materials such as crack repair material for concrete; Printed wiring board, insulation board, Conductor sealing material, like various electric and electronic parts, such as packaging materials.
- Comparative Production Example 1 Liquid Polyisoprene (A'-1)
- the sufficiently dried pressure vessel is replaced with nitrogen, and 600 g of cyclohexane and 212 g of sec-butyllithium (10.5 mass% cyclohexane solution) are charged in the pressure vessel, and the temperature is raised to 70 ° C. While controlling the temperature to 70 ° C., 2050 g of isoprene was added and polymerized for 1 hour. Thereafter, methanol was added to stop the polymerization reaction to obtain a polymerization solution (2862 g). Water was added to the obtained polymerization reaction solution and stirred, and the polymerization reaction solution was washed with water.
- Comparative Production Example 2 Liquid Polyisoprene (A'-2) The sufficiently dried pressure vessel is replaced with nitrogen, and 600 g of n-hexane and 21.9 g of n-butyllithium (17 mass% hexane solution) are charged into the pressure vessel, heated to 70 ° C., and then stirred While controlling the polymerization temperature to be 70 ° C., 2050 g of isoprene was added and polymerization was carried out for 1 hour. Thereafter, methanol was added to stop the polymerization reaction to obtain a polymerization solution (2672 g). Water was added to the obtained polymerization reaction solution and stirred, and the polymerization reaction solution was washed with water.
- polymer (A′-3) liquid polyisoprene (hereinafter also referred to as “polymer (A′-3)”).
- polymer (A'-3) liquid polyisoprene (hereinafter also referred to as “polymer (A′-3)).
- polymer (A'-3) 1.5 parts by mass of the polymer (A'-3), 1.5 parts by mass of maleic anhydride and 0.1 parts by mass of BHT (2,6-di-t-butyl-4-methylphenol, manufactured by Honshu Chemical Industry Co., Ltd.) Were added and reacted at 160.degree. C.
- a "-1" maleic anhydride-modified liquid polyisoprene (hereinafter also referred to as” polymer (A "-1)").
- the reaction rate of maleic anhydride determined by acid value titration is 99% or more, and the equivalent of the functional group (a) derived from the acid anhydride in the polymer (A ′ ′-1) is 6,700 g / eq. there were.
- the reaction rate of maleic anhydride determined by acid value titration is 99% or more, and the equivalent of the functional group (a) derived from the acid anhydride in the polymer (A ′ ′ ⁇ 2) is 2,100 g / eq.
- the reaction rate of the maleic anhydride-derived functional group in the polymer (A ′ ′-2) was 100%, which was calculated from the infrared absorption spectrum.
- the measuring method and calculation method of each physical properties are as follows.
- the vinyl content of the liquid diene rubber obtained in each production example was measured using 1 H-NMR (500 MHz) manufactured by Nippon Denshi Co., Ltd. at a concentration of 50 mg of sample / weight chloroform / 1 mL and the number of integrations 1024 times.
- the vinyl content was calculated from the area ratio of the peak of the double bond derived from the vinylated diene compound to the peak of the double bond derived from the non-vinylated diene compound in the obtained spectrum.
- melt viscosity The melt viscosities at 38 ° C. and 60 ° C. of the polymers obtained in Production Examples 1 to 4 and Comparative Production Examples 1 to 4 were measured using a Brookfield viscometer (manufactured by BROOKFIELD ENGINEERING LABS. INC.).
- reaction rate of acid anhydride group The reaction rate of the acid anhydride group in the case of reacting the compound represented by the chemical formula (2) or (3) with the acid anhydride modified liquid diene rubber is expressed by Fourier transform infrared spectrophotometer FT / IR-4200 ( It calculated according to the following formula from the infrared absorption spectrum before and behind the reaction measured using JASCO Corporation make.
- reaction ratio of acid anhydride group (%)] [1 ⁇ (peak intensity ratio of functional group derived from acid anhydride after reaction) / (peak intensity ratio of functional group derived from acid anhydride before reaction) )] ⁇ 100
- this mixture is again put into a Banbury mixer, a curing agent (D), sulfur and a vulcanization accelerator are added, and the rubber composition is obtained by kneading for 75 seconds so that the starting temperature is 50 ° C and the reaching temperature is 100 ° C.
- a curing agent (D) sulfur and a vulcanization accelerator are added, and the rubber composition is obtained by kneading for 75 seconds so that the starting temperature is 50 ° C and the reaching temperature is 100 ° C.
- Mooney viscosity The Mooney viscosity (ML1 + 4) of the rubber composition before vulcanization was measured at 130 ° C. according to JIS K6300 as an index of processability of the rubber composition.
- the Mooney viscosity in Table 2 is a relative value when the value of Comparative Example 1 is 100. The smaller the numerical value, the better the processability of the composition.
- the obtained rubber composition is press-formed (145 ° C., 15 to 25 minutes) to prepare a cross-linked product (vulcanized rubber) sheet (thickness 2 mm), and the hardness, breaking energy and storage are based on the following method.
- the modulus of elasticity was evaluated. The results are shown in Table 3.
- the hardness was measured with a type D hardness tester in accordance with JIS K6253 using the crosslinked product sheets produced in Examples and Comparative Examples.
- the numerical values of the respective examples and the comparative examples are relative values when the value of the comparative example 1 in Table 3 is 100. The larger the numerical value, the smaller the deformation of the composition and the better the rigidity.
- (Storage elastic modulus) A test piece of 40 mm long ⁇ 5 mm wide is cut out from the sheet of the rubber composition prepared in the examples and comparative examples, and measurement temperature 30 ° C., frequency 10 Hz, static strain 10 using a dynamic viscoelasticity measuring device manufactured by GABO. The storage modulus was measured under the conditions of% and dynamic strain of 2%.
- the numerical values of the respective examples and the comparative examples are relative values when the value of the comparative example 1 in Table 3 is 100. The larger the numerical value, the smaller the deformation of the composition and the better the rigidity.
- Example 5 using modified liquid polyisoprene satisfying the requirements of the present invention, and modified liquid polyisoprene obtained in Comparative Production Example 4 having the same functional group equivalent as in Example 5 and not satisfying the requirements of (III)
- the Mooney viscosity is lower in both Example 5 and Comparative Example 6 than in Comparative Example 1, and the processability is improved. It is further excellent in processability than that.
- the storage elastic modulus is also sufficiently improved in both of Example 5 and Comparative Example 6 as compared with Comparative Example 1, it is understood that in Example 5, the formability at 500 / s is further improved.
- Example 3 using a liquid polyisoprene modified with maleic anhydride and Example 6 using a liquid polyisoprene further modified with methanol, the formability of 500 / s is compared with Example 3. Is superior, while Example 6 is superior in terms of storage elastic modulus, and it is possible to use properly depending on the required performance.
- Example 7 in which the functional group equivalent is 2,100 g / eq and Example 7 in which the functional group equivalent is 1,100 g / eq and Comparative Example 1 the hardness and the breaking energy in both Examples 5 and 7 are better than in Comparative Example 1.
- the hardness, the energy at break and the storage elastic modulus are all improved in Example 7 while the formability at 500 / s is better in Example 5,
- Example 8 to 11 and Comparative Examples 7 to 9 The modified liquid diene rubber (A) or a diene rubber, a terpene resin, an antiaging agent, an epoxy resin and a tertiary amine are compounded according to the compounding ratio (parts by mass) described in Table 4, and a kneader is used to obtain 50 ° C. The mixture was kneaded to obtain a rubber composition. Each evaluation was performed about the obtained rubber composition based on the following method. The results are shown in Table 5.
- the rubber composition prepared in the example or comparative example is coated on a 1 mm thick stainless steel plate (SUS 304) as an adherend at a thickness of 20 ⁇ m and heat treated at 120 ° C. for 30 minutes, and then the rubber composition layer is 15 mm ⁇ 12 mm
- the test piece was cut into a size of 1 mm, and a 1 kg weight was attached to the test piece, and the time until the weight dropped was measured according to JIS Z 0237 under conditions of 25 ° C. or 40 ° C. The longer the time it takes for the weight to fall, the better the holding power.
- the shear adhesion was measured according to JIS K 6850.
- the test material used was a stainless steel plate (SUS304) or an aluminum plate (A5052) having a thickness of 1 mm.
- the composition was applied to the above substrate to a thickness of 1 mm, and then crosslinked under conditions of 120 ° C. for 30 minutes to prepare a sample, and shear adhesion was measured.
- the tensile speed at the time of measuring shear adhesion was 50 mm / min. In comparison with the adhesive force of Comparative Example 8, the following criteria were evaluated.
- Example 12 to 15 and Comparative Examples 10 to 12 Modified liquid diene rubber (A) or diene rubber, solid rubber (B), calcium carbonate, naphthenic oil, stearic acid, zinc flower and anti-aging agent according to the blending ratio (parts by mass) described in Table 6 It compounded and knead
- the shear adhesion was measured according to JIS K 6850.
- the test material was a stainless steel plate (SUS304), an aluminum plate (A5052) or a polyethylene plate (HDPE, Shore hardness D60), and a 1 mm thick material was used.
- the composition was applied to the above substrate to a thickness of 1 mm, and then crosslinked under the conditions of 150 ° C. for 30 minutes to prepare a sample, and the shear adhesion was measured.
- the tensile speed at the time of measuring shear adhesion was 50 mm / min. In comparison with the adhesion of Comparative Example 11, the evaluation was made according to the following criteria.
- Examples 16 to 18 and Comparative Examples 13 and 14 The modified liquid diene rubber (A) and the epoxy resin were mixed for 4 minutes in a rotation and revolution stirring degassing machine (manufactured by Shinky Co., Ltd.) according to the mixing ratio (parts by mass) described in Table 8 and defoamed for 2 minutes.
- the epoxy resin curing agent was further added to this mixture, mixed for 4 minutes, and defoamed for 2 minutes to obtain an epoxy resin composition.
- the temperature is raised to 150 ° C. at a temperature rising rate of 30 ° C./hour for 4 hours at 60 ° C., and cured for 4 hours to produce a cured epoxy resin product.
- the viscosity, deflection temperature under load, flexural strength, flexural modulus, flexural strain, and Izod impact strength were evaluated based on the following methods. The results are shown in Table 8.
- viscosity The viscosity of the mixture of the modified liquid diene rubber (A) and the epoxy resin was measured according to JIS K 7117-2 using TVE-22LT manufactured by Toki Sangyo Co., Ltd. The measurement conditions are as follows. Temperature: 23 ° C Rotor: 3 ° ⁇ R9.7 ⁇ Number of revolutions: 0.5 rpm ⁇ Measurement time: Measured for 1 minute after standing for 1 minute
- the deflection temperature under load of the obtained cured epoxy resin product was measured using a heat distortion tester No. 4 manufactured by Yasuda Seiki Co., Ltd. It was measured according to JIS K 7191-2 (Flatwise, method A) using 148-HD-PC.
- cured material is excellent in heat resistance, so that deflection temperature under load is high.
- the Izod impact strength of the obtained epoxy resin cured product was measured according to JIS K 7110 using a digital impact tester DG-UB type manufactured by Toyo Seiki Seisaku-sho, Ltd. The measurement conditions are as follows. The higher the Izod impact strength, the better the obtained epoxy resin cured product is in impact resistance. ⁇ Test specimen: 80 mm ⁇ 10 mm ⁇ 4 mm, without notch ⁇ Measurement condition: Hammer / 1.0 J
- the rubber composition obtained in the present invention is excellent in workability, and a crosslinked product obtained from this rubber composition is also excellent in adhesiveness, and thus can be suitably used for bonding of sealing materials, various members, etc. It is useful for adhesives, various industrial products such as automobiles, and daily necessities.
- the rubber composition of the present invention can be suitably used as a tire bead filler and is useful.
- the curable resin composition containing the modified liquid diene rubber (A) of the present invention can improve heat resistance, mechanical properties and impact resistance without impairing the properties of the curable resin, It is useful.
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Abstract
Description
〔1〕酸無水物に由来する官能基(a)を有し、下記(I)~(III)の要件をすべて満たす変性液状ジエン系ゴム(A)。
(I)官能基(a)の官能基当量が400~3,500g/eqの範囲にある。
(II)ゲルパーミエーションクロマトグラフィー(GPC)で測定した際、ポリスチレン換算の数平均分子量(Mn)が5,000~20,000の範囲にある。
(III)38℃における溶融粘度が3Pa・s以上であり、下記Xが6100K以上である。X(K):ブルックフィールド型粘度計を用いて測定される38℃及び60℃における溶融粘度η(Pa・s)2点を、1/T(K-1)を横軸、Ln[η/(Pa・s)]を縦軸とするグラフにプロットした際の、該2点を通る直線の傾き。(但し、Tは温度(K)である。)
〔2〕 変性液状ジエン系ゴム(A)が、不飽和カルボン酸無水物変性された液状ジエン系ゴムと下記化学式(2)又は(3)で示される化合物との反応物である〔1〕に記載の変性液状ジエン系ゴム(A)。
Ra-OH (2)
(上記式(2)中、Raは水素原子又は置換されていてもよいアルキル基である。)
Rb 2-NH (3)
(上記式(3)中、Rbは水素原子又は置換されていてもよいアルキル基であり、複数あるRbは同一でも異なっていてもよい。)
〔3〕 〔1〕又は〔2〕に記載の変性液状ジエン系ゴム(A)を含む組成物。
〔4〕 〔1〕又は〔2〕に記載の変性液状ジエン系ゴム(A)と固形ゴム(B)とを含むゴム組成物。
〔5〕 〔4〕に記載のゴム組成物を含むシーリング材。
〔6〕 〔4〕に記載のゴム組成物を含むタイヤビードフィラー用ゴム組成物。
〔7〕固形ゴム(B)100質量部と、〔1〕又は〔2〕に記載の変性液状ジエン系ゴム(A)1~20質量部と、フェノール系樹脂(C)5~40質量部と、硬化剤(D)0.5~2.0質量部とを含む、〔6〕に記載のタイヤビードフィラー用ゴム組成物。
本発明の変性液状ジエン系ゴム(A)とは、液状の重合体であり、酸無水物に由来する官能基(a)を有し、下記(I)~(III)の要件をすべて満たす物をいう。
(I)官能基(a)の官能基当量が400~3,500g/eqの範囲にある。
(II)ゲルパーミエーションクロマトグラフィー(GPC)で測定した際、ポリスチレン換算の数平均分子量(Mn)が5,000~20,000の範囲にある。
(III)38℃における溶融粘度が3Pa・s以上であり、下記Xが6100K以上である。
X(K):ブルックフィールド型粘度計を用いて測定される38℃及び60℃における溶融粘度η(Pa・s)2点を、1/T(K-1)を横軸、Ln[η/(Pa・s)]を縦軸とするグラフにプロットした際の、該2点を通る直線の傾き。(但し、Tは温度(K)である。)
変性液状ジエン系ゴム(A)の原料となる上記未変性の液状ジエン系ゴム(A’)としては、共役ジエン(a1)を後述の方法で重合して得られる重合体が好ましい。共役ジエン(a1)としては、例えば、ブタジエン、イソプレン、2,3-ジメチルブタジエン、2-フェニルブタジエン、1,3-ペンタジエン、2-メチル-1,3-ペンタジエン、1,3-ヘキサジエン、1,3-オクタジエン、1,3-シクロヘキサジエン、2-メチル-1,3-オクタジエン、1,3,7-オクタトリエン、ミルセン、及びクロロプレンなどが挙げられる。これら共役ジエンの中でも、ブタジエン、及びイソプレンが好ましい。これら共役ジエンは、1種単独で用いてもよく、2種以上を併用してもよい。
上記乳化重合法としては、公知又は公知に準ずる方法を適用できる。例えば、所定量の共役ジエンを含む単量体を乳化剤の存在下に乳化分散し、ラジカル重合開始剤により乳化重合する。
ラジカル重合開始剤としては、例えば過硫酸アンモニウムや過硫酸カリウムのような過硫酸塩、有機過酸化物、過酸化水素等が挙げられる。
アニオン重合可能な活性金属化合物としては、有機アルカリ金属化合物が好ましい。有機アルカリ金属化合物としては、例えば、メチルリチウム、エチルリチウム、n-ブチルリチウム、sec-ブチルリチウム、t-ブチルリチウム、ヘキシルリチウム、フェニルリチウム、スチルベンリチウム等の有機モノリチウム化合物;ジリチオメタン、ジリチオナフタレン、1,4-ジリチオブタン、1,4-ジリチオ-2-エチルシクロヘキサン、1,3,5-トリリチオベンゼン等の多官能性有機リチウム化合物;ナトリウムナフタレン、カリウムナフタレン等が挙げられる。これら有機アルカリ金属化合物の中でも有機リチウム化合物が好ましく、有機モノリチウム化合物がより好ましい。
上記未変性の液状ジエン系ゴム(A’)の製造方法としては、上記方法の中でも、溶液重合法が好ましい。
不飽和カルボン酸エステル基に対応する化合物としては、例えば、マレイン酸エステル、フマル酸エステル、イタコン酸エステル、グリシジル(メタ)アクリレート、ヒドロキシエチル(メタ)アクリレートなどの不飽和カルボン酸エステルが挙げられる。
不飽和カルボン酸イミド基に対応する化合物としては、例えば、マレイン酸イミド、イタコン酸イミドなどの不飽和カルボン酸イミドなどが挙げられる。
変性液状ジエン系ゴム(A)の酸無水物に由来する官能基(a)の官能基当量は、400~3,500g/eqの範囲であり、600~2,500g/eqであることが好ましく、700~2,300g/eqであることがより好ましい。変性液状ジエン系ゴム(A)の酸無水物に由来する官能基(a)の官能基当量が上記範囲にあることにより、常温下における耐液垂れ性と高温下におけるポンピング性を両立でき、更に硬化後に種々の基材への優れた接着性と、高い剛性を示す組成物が得られる。なお、本明細書における酸無水物に由来する官能基(a)の官能基当量とは、官能基(a)1個当たりの変性液状ジエン系ゴム(A)の分子量を意味する。
η=A・exp[T-1・E/R] ・・・(1)
(上記式(1)中、ηは温度T(K)における溶融粘度(Pa・s)、Rは気体定数(J・K-1・mol-1)、Eは流動活性化エネルギー(J・mol-1)、Aは定数(Pa・s)である。)
本発明のゴム組成物においては、ゴム成分は上述した変性液状ジエン系ゴム(A)を含んでいる。本発明でゴム成分とは、変性液状ジエン系ゴム、必要に応じて含まれる未変性の液状ジエン系ゴム、及び必要に応じて含まれる下記固形ゴム(B)からなる成分である。本発明のゴム組成物のゴム成分としては、例えば、上述した変性液状ジエン系ゴム(A)を含む液状ジエン系ゴムのみから構成される場合、変性液状ジエン系ゴム(A)及び下記固形ゴム(B)を含む場合などがある。
本発明のゴム組成物で用いる固形ゴム(B)とは、20℃において固形状で取り扱うことができるゴムをいい、固形ゴム(B)の100℃におけるムーニー粘度 ML1+4は通常20~200の範囲にある。上記固形ゴム(B)としては、例えば、天然ゴム、ポリイソプレンゴム、ポリブタジエンゴム、スチレン-ブタジエン共重合体ゴム、スチレン-イソプレン共重合体ゴム、アクリロニトリル-ブタジエン共重合体ゴム、クロロプレンゴム、エチレンプロピレンゴム及びブチルゴムなどが挙げられる。
なお、本明細書における重量平均分子量とは、ゲルパーミエーションクロマトグラフィー(GPC)で測定したポリスチレン換算の重量平均分子量である。
上記スチレン-イソプレン共重合体ゴム、アクリロニトリル-ブタジエン共重合体ゴム、クロロプレンゴム、エチレンプロピレンゴム(EPM、EPDM等)及びブチルゴムとしては、市販品を特に制限なく使用することができる。
本発明のゴム組成物には、フィラーが含まれていてもよい。フィラーとは、機械強度の向上、耐熱性又は耐候性等の物性の改良、硬度の調整、ゴムの増量等を目的として配合されるものである。上記フィラーとしては、例えば、炭酸カルシウム、酸化カルシウム、水酸化マグネシウム、酸化マグネシウム、 炭酸マグネシウム、水酸化アルミニウム、硫酸バリウム、酸化バリウム、酸化チタン、酸化鉄、酸化亜鉛、炭酸亜鉛、ろう石クレー、カオリンクレー及び焼成クレー等のクレー、マイカ、ケイソウ土、カーボンブラック、シリカ、ガラス繊維、カーボン繊維、繊維状フィラー、ガラスバルーン等の無機フィラー、架橋ポリエステル、ポリスチレン、スチレン-アクリル共重合体樹脂、又は尿素樹脂等の樹脂から形成された樹脂粒子、合成繊維、及び天然繊維などが挙げられる。
本発明のゴム組成物には、オイルが含まれていてもよい。オイルとは、主として本発明のゴム組成物の加工性、他の配合剤の分散性を向上するため、またゴム組成物の特性を所望の範囲とするために添加されるものである。上記オイルとしては、鉱物油、植物油、合成油などが挙げられる。
これらオイルは1種単独で用いてもよく、2種以上を併用してもよい。
本発明のゴム組成物は、そのゴム成分を架橋するために更に架橋剤を含有してもよい。架橋剤としては、例えば、硫黄、硫黄化合物、酸素、有機過酸化物、フェノール樹脂、アミノ樹脂、キノン及びキノンジオキシム誘導体、ハロゲン化合物、アルデヒド化合物、アルコール化合物、エポキシ化合物、金属ハロゲン化物及び有機金属ハロゲン化物、シラン化合物などが挙げられる。硫黄化合物としては、例えば、モルホリンジスルフィド、アルキルフェノールジスルフィドなどが挙げられる。有機過酸化物としては、シクロヘキサノンパーオキサイド、メチルアセトアセテートパーオキサイド、t-ブチルパーオキシイソブチレート、t-ブチルパーオキシベンゾエート、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、ジクミルパーオキサイド、ジ-t-ブチルパーオキサイド、1,3-ビス(t-ブチルパーオキシイソプロピル)ベンゼンなどが挙げられる。これら架橋剤は1種単独で用いてもよく、2種以上を併用してもよい。
本発明のゴム組成物の他の架橋剤等としては、例えば、フェノール系樹脂(C)および硬化剤(D)の組み合わせ、エポキシ樹脂と3級アミンの組み合わせなどが挙げられる。
フェノール系樹脂(C)および硬化剤(D)の組み合わせは、タイヤビードフィラー用ゴム組成物で用いられることが好適である。フェノール樹脂(C)および硬化剤(D)については、タイヤビードフィラー用ゴム組成物に関する説明の中で、詳細に説明をする。
エポキシ樹脂および3級アミンの組み合わせは、シーリング材用ゴム組成物で用いられることが好適である。エポキシ樹脂および3級アミンについては、シーリング材に関する説明の中で、詳細に説明をする。
老化防止剤としては、例えば、アミン-ケトン系化合物、イミダゾール系化合物、アミン系化合物、フェノール系化合物、硫黄系化合物及びリン系化合物等が挙げられる。
難燃剤としては、例えば、クロロアルキルホスフェート、ジメチル-メチルホスホネート、臭素-リン化合物、アンモニウムポリホスフェート、ネオペンチルブロマイドーポリエーテル、臭素化ポリエーテルが挙げられる。これら添加剤は1種単独で用いられてもよく、2種以上を併用してもよい。
本発明のゴム組成物の製造方法は、上記各成分を均一に混合できれば特に限定されない。ゴム組成物の製造に用いる装置としては、例えば、ニーダールーダー、ブラベンダー、バンバリーミキサー、インターナルミキサー等の接線式又は噛合式の密閉式混練機、単軸押出機、二軸押出機、ミキシングロール、ローラーなどが挙げられる。上記混合は、常圧下、空気雰囲気下で行うことができるが、混合する際に組成物中に気泡が混在するのを防ぐ観点から、減圧下又は窒素雰囲気下で行うことが好ましい。このように均一に各成分を分散することにより得られた本発明のゴム組成物は、使用するまで密閉容器等で保存することが好ましい。
本発明のゴム組成物は、タイヤビードフィラー用ゴム組成物として用いることが好適な一態様である。かかるタイヤビードフィラー用ゴム組成物には、変性液状ジエン系ゴム(A)及び固形ゴム(B)に加えて、フェノール系樹脂(C)及び硬化剤(D)が含まれていることが好ましい。
本発明の上記ゴム組成物は、シーリング材用ゴム組成物として用いることが好適な一態様である。シーリング材は、下記の架橋物からなることが好ましい一態様である。シーリング材用ゴム組成物には、変性液状ジエン系ゴム(A)、必要に応じて含まれる固形ゴム(B)に加え、上述した架橋剤等が含まれていることが好ましい。また、シーリング材用ゴム組成物には、上述した架橋剤等に替え、あるいはこれらに加えて、エポキシ樹脂及び3級アミンの組み合わせが含まれるものであってもよい。
上記エポキシ樹脂としては、例えば、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂、ジフェニルチオエーテル型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビスフェノールA ノボラック型エポキシ樹脂、トリスフェノール型エポキシ樹脂、テトラフェニロールエタン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂などが挙げられる。
上記3級アミンとしては、例えば、トリエチルアミン、ベンジルジメチルアミン、2-(ジメチルアミノメチル)フェノール、2,4,6-トリス(ジメチルアミノメチル)フェノールなどが挙げられる。
本発明のゴム組成物を、必要に応じて油面鋼板等の基材等に塗布した後、これを架橋することにより架橋物を得ることができる。ゴム組成物の架橋条件は、その用途等に応じて適宜設定できるが、例えば130℃ ~250℃の温度範囲で、10分~60分間架橋反応を行うことにより、架橋物を作製することができる。例えば、自動車製造ラインで本発明のゴム組成物を用いる場合には、本発明のゴム組成物を各種部材の所望の部位(例えば、複数のフレーム部材のフランジ間の隙間)に塗布した後、車体の電着塗装工程で焼付乾燥を行う際に、その発生する熱により架橋することにより、所望の部位に架橋物を形成させることができる。
本発明の変性液状ジエン系ゴム(A)は、硬化性樹脂(E)とともに硬化性樹脂組成物の一成分として用いることができる。
<変性液状ジエン系ゴム(A)>
後述の製造例1~4で得られた変性液状ジエン系ゴム
<ジエン系ゴム>
合成イソプレンゴム:IR-2200(JSR株式会社製)
後述の比較製造例1~4で得られた(変性)液状ジエン系ゴム
<固形ゴム(B)>
天然ゴム :STR20
ポリブタジエンゴム :ジエンNF35R(旭化成株式会社製)
<フェノール系樹脂(C)>
固形ノボラックレジン:PR12686(住友ベークライト株式会社製)
<硬化剤(D)>
ヘキサメチレンテトラミン:ノクセラーH(大内新興化学工業株式会社製)
<任意成分>
オイル(TDAE):VivaTec500(H&R社製)
ナフテン系オイル :SUNTHENE 250(日本サン石油株式会社製)
カーボンブラック :ダイアブラックH(三菱ケミカル株式会社製)
炭酸カルシウム :白艶華CCR(白石カルシウム社製)
硫黄(1) :ミュークロンOT-20(四国化成工業株式会社)
硫黄(2) :微粉硫黄200メッシュ(鶴見化学工業株式会社製)
加硫促進剤(1) :サンセラーNS-G (三新化学工業株式会社製)
加硫促進剤(2) :ノクセラーDM (大内新興化学工業株式会社製)
加硫促進剤(3) :ノクセラーBG (大内新興化学工業株式会社製)
亜鉛華 :酸化亜鉛(堺化学工業株式会社製)
ステアリン酸 :ルナックS-20(花王株式会社製)
老化防止剤(1) :ノクラック6C(大内新興化学工業株式会社製)
老化防止剤(2) :アンテージRD(川口化学工業株式会社製)
老化防止剤(3) :ノクラックNS-6(大内新興化学工業株式会社製)
テルペン樹脂 :YS resin Px800(ヤスハラケミカル株式会社製)
エポキシ樹脂(1) :Araldite GY-260(ハンツマン・ジャパン株式会社製)
エポキシ樹脂(2):jER828(三菱ケミカル株式会社製)
3級アミン :Ancamine K-54(Evonik社製)
エポキシ硬化剤 :キュアゾール2E4MZ(四国化成工業株式会社製)
十分に乾燥した耐圧容器を窒素置換し、この耐圧容器に、シクロヘキサン600g、及びsec-ブチルリチウム(10.5質量%シクロヘキサン溶液)212gを仕込み、70℃に昇温した後、撹拌条件下、重合温度を70℃となるように制御しながら、イソプレン2050gを加えて1時間重合した。その後、メタノールを添加して重合反応を停止させ、重合溶液(2862g)を得た。得られた重合反応液に水を添加して撹拌し、水で重合反応液を洗浄した。撹拌を終了し、重合溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合反応液を70℃で12時間乾燥することにより、液状ポリイソプレン(以下、「重合体(A’-1)」ともいう)を得た。
重合体(A’-1)100質量部に無水マレイン酸5質量部とBHT(2,6-ジ-t-ブチル-4-メチルフェノール、本州化学工業株式会社製)0.1質量部を添加し、160℃で20時間反応させることにより、無水マレイン酸変性液状ポリイソプレン(A-1)(以下、「重合体(A-1)」ともいう)を得た。なお、酸価滴定により求めた無水マレイン酸の反応率は99%以上であり、重合体(A-1)における酸無水物に由来する官能基(a)の当量は2,100g/eqであった。
重合体(A’-1)100質量部に無水マレイン酸10質量部とBHT(2,6-ジ-t-ブチル-4-メチルフェノール、本州化学工業株式会社製)0.1質量部を添加し、160℃で20時間反応させることにより、無水マレイン酸変性液状ポリイソプレン(A-2)(以下、「重合体(A-2)」ともいう)を得た。なお、酸価滴定により求めた無水マレイン酸の反応率は99%以上であり、重合体(A-2)における酸無水物に由来する官能基(a)の当量は1,100g/eqであった。
重合体(A-1)に、付加された無水マレイン酸基に対して1.05モル当量のメタノールを加え、90℃で10時間反応させることにより、無水マレイン酸変性液状ポリイソプレン メチルエステル化物(A-3)(以下、「重合体(A-3)」ともいう)を得た。なお、赤外吸収スペクトルから算出した、重合体(A-3)中の無水マレイン酸由来官能基の反応率は100%であった。
重合体(A-2)に、付加された無水マレイン酸基に対して1.05モル当量のメタノールを加え、90℃で10時間反応させることにより、無水マレイン酸変性液状ポリイソプレン メチルエステル化物(A-4)(以下、「重合体(A-4)」ともいう)を得た。なお、赤外吸収スペクトルから算出した、重合体(A-4)中の無水マレイン酸由来官能基の反応率は100%であった。
十分に乾燥した耐圧容器を窒素置換し、この耐圧容器に、n-ヘキサン600g、及びn-ブチルリチウム(17質量%ヘキサン溶液)21.9gを仕込み、70℃に昇温した後、撹拌条件下、重合温度を70℃となるように制御しながら、イソプレン2050gを加えて1時間重合した。その後、メタノールを添加して重合反応を停止させ、重合溶液(2672g)を得た。得られた重合反応液に水を添加して撹拌し、水で重合反応液を洗浄した。撹拌を終了し、重合溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合反応液を70℃で12時間乾燥することにより、液状ポリイソプレン(以下、「重合体(A’-2)」ともいう)を得た。
十分に乾燥した耐圧容器を窒素置換し、この耐圧容器に、n-ヘキサン600g、及びn-ブチルリチウム(17質量%ヘキサン溶液)39.3gを仕込み、70℃に昇温した後、撹拌条件下、重合温度を70℃となるように制御しながら、イソプレン2050gを加えて1時間重合した。その後、メタノールを添加して重合反応を停止させ、重合溶液(2689g)を得た。得られた重合反応液に水を添加して撹拌し、水で重合反応液を洗浄した。撹拌を終了し、重合溶液相と水相とが分離していることを確認した後、水を分離した。洗浄終了後の重合反応液を70℃で12時間乾燥することにより、液状ポリイソプレン(以下、「重合体(A’-3)」ともいう)を得た。重合体(A’-3)100質量部に無水マレイン酸1.5質量部とBHT(2,6-ジ-t-ブチル-4-メチルフェノール、本州化学工業株式会社製)0.1質量部を添加し、160℃で20時間反応させることにより、無水マレイン酸変性液状ポリイソプレン(A”-1)(以下、「重合体(A”-1)」ともいう)を得た。なお、酸価滴定により求めた無水マレイン酸の反応率は99%以上であり、重合体(A”-1)における酸無水物に由来する官能基(a)の当量は6,700g/eqであった。
2)
重合体(A’-3)100質量部に無水マレイン酸5質量部とBHT(2,6-ジ-t-ブチル-4-メチルフェノール、本州化学工業株式会社製)0.1質量部を添加し、160℃で20時間反応させた後、付加された無水マレイン酸基に対して1.05モル当量のメタノールを加え、90℃で10時間反応させることにより、無水マレイン酸変性液状ポリイソプレン メチルエステル化物(A”-2)(以下、「重合体(A”-2)」ともいう)を得た。なお、酸価滴定により求めた無水マレイン酸の反応率は99%以上であり、重合体(A”-2)における酸無水物に由来する官能基(a)の当量は2,100g/eqであった。また、赤外吸収スペクトルから算出した、重合体(A”-2)中の無水マレイン酸由来官能基の反応率は100%であった。
製造例1~4及び比較製造例1~4で得られた重合体のMn及びMwはGPC(ゲルパーミエーションクロマトグラフィー)により標準ポリスチレン換算分子量で求め、Mw/Mnはこれらの値から算出した。測定装置及び条件は、以下の通りである。
・装置 :東ソー株式会社製 GPC装置「HLC-8320GPC」
・分離カラム :東ソー株式会社製 カラム「TSKgelSuperHZ4000」
・溶離液 :テトラヒドロフラン
・溶離液流量 :0.7mL/min
・サンプル濃度:5mg/10mL
・カラム温度 :40℃
各製造例で得た液状ジエン系ゴムのビニル含量を、日本電子株式会社製1H-NMR(500MHz)を使用し、サンプル/重クロロホルム=50mg/1mLの濃度、積算回数1024回で測定した。得られたスペクトルのビニル化されたジエン化合物由来の二重結合のピークと、ビニル化されていないジエン化合物由来の二重結合のピークとの面積比から、ビニル含量を算出した。
製造例1~4及び比較製造例1~4で得られた重合体の38℃及び60℃における溶融
粘度をブルックフィールド型粘度計(BROOKFIELD ENGINEERING LABS. INC.製)により測定した。
製造例1~4及び比較製造例1~4で得られた重合体10mgをアルミパンに採取し、示差走査熱量測定(DSC)により10℃/分の昇温速度条件においてサーモグラムを測定し、DDSCのピークトップの値をガラス転移温度(Tg)とした。
変性反応後の試料3gにトルエン180mL、エタノール20mLを加えて溶解した後、0.1N水酸化カリウムのエタノール溶液で中和滴定し酸価を求めた。
酸価(meq/g)=(A-B)×F/S
A:中和に要した0.1N水酸化カリウムのエタノール溶液滴下量(mL)
B:試料を含まないブランクでの0.1N水酸化カリウムのエタノール溶液滴下量(mL)
F:0.1N水酸化カリウムのエタノール溶液の力価
S:秤量した試料の質量(g)
〔変性化合物の付加反応率(%)〕=〔洗浄後の酸価(meq/g)〕/〔洗浄前の酸価(meq/g)〕×100
上記で求めた洗浄後の酸価から、下記式に従い、酸無水物に由来する官能基(a)の当量を算出した。
〔酸無水物に由来する官能基(a)の当量(g/eq)〕=1,000/〔洗浄後の酸価(meq/g)〕
化学式(2)又は(3)で示される化合物と、酸無水物変性液状ジエン系ゴムを反応させた場合における酸無水物基の反応率を、フーリエ変換赤外分光光度計FT/IR-4200(日本分光株式会社製)を用いて測定した反応前後の赤外吸収スペクトルから、下記式に従い算出した。
〔酸無水物基の反応率(%)〕=〔1-(反応後の酸無水物に由来する官能基のピーク強度比)/(反応前の酸無水物に由来する官能基のピーク強度比)〕×100
表2に記載した配合割合(質量部)にしたがって、変性液状ジエン系ゴム(A)又はジエン系ゴム、固形ゴム(B)、フェノール系樹脂(C)、オイル、カーボンブラック、亜鉛華、ステアリン酸及び老化防止剤を、それぞれ密閉式バンバリーミキサーに投入して開始温度50℃、樹脂温度が150℃となるように6分間混練した後、ミキサー外に取り出して室温まで冷却した。次いで、この混合物を再度バンバリーミキサーに入れ、硬化剤(D)、硫黄及び加硫促進剤を加えて開始温度50℃、到達温度100℃となるように75秒間混練することでゴム組成物を得た。
ゴム組成物の加工性の指標として、JIS K6300に準拠し、加硫前のゴム組成物のムーニー粘度(ML1+4)を130℃で測定した。
なお表2におけるムーニー粘度は、比較例1の値を100とした際の相対値である。数値が小さいほど当該組成物は加工性が良好である。
実施例及び比較例で作製したゴム組成物のシートを細かく刻み、ロングダイ(2φ/32mm)とショートダイ(2φ/0.25mm)を装着したツインキャピロ R6000(IMATEK社製)に投入し、120℃でせん断速度100/s及び500/sそれぞれにおいて押出し成形を行い、得られたストランドの形状から目視で成形性を評価した。
○:ストランドに寄りが確認されない
×:ストランドに寄りが確認される
実施例及び比較例で作製した架橋物シートを用いて、JIS K6253に準拠して、タイプD硬度計により硬度を測定した。各実施例及び比較例の数値は、表3の比較例1の値を100とした際の相対値である。なお、数値が大きいほど当該組成物は変形が小さく剛性に優れる。
実施例及び比較例で作製したゴム組成物のシートからJISダンベル状3号形試験片を打ち抜き、インストロン社製引張試験機を用いて、JIS K 6251に準じて引張破断エネルギーを測定した。各実施例及び比較例の数値は、表3の比較例1の値を100とした際の相対値である。なお、数値が大きいほど当該組成物は強度に優れる。
実施例及び比較例で作製したゴム組成物のシートから縦40mm×横5mmの試験片を切り出し、GABO社製動的粘弾性測定装置を用いて、測定温度30℃、周波数10Hz、静的歪み10%、動的歪み2%の条件で、貯蔵弾性率を測定した。各実施例及び比較例の数値は、表3の比較例1の値を100とした際の相対値である。なお、数値が大きいほど当該組成物は変形が小さく剛性に優れる。
表4に記載した配合割合(質量部)にしたがって、変性液状ジエン系ゴム(A)又はジエン系ゴム、テルペン樹脂、老化防止剤、エポキシ樹脂及び3級アミンを配合し、ニーダーを用いて50℃で混練してゴム組成物を得た。得られたゴム組成物について、下記の方法に基づき各評価を行った。結果を表5に示す。
実施例又は比較例で作製したゴム組成物を、被着体である1mm厚ステンレス板(SUS304)に20μm厚で塗工し、120℃で30分間熱処理した後、ゴム組成物層を15mm×12mmのサイズにカットして試験片とし、当該試験片に1kgの重りを取り付けて、25℃又は40℃の条件下にて、JIS Z 0237に準拠して重りが落下するまでの時間を測定した。重りが落下するまでの時間が長いほど、保持力に優れていることを示す。
JIS K 6850に準じてせん断接着力の測定を行った。試験材料はステンレス板(SUS304)又はアルミ板(A5052)で、厚さ1mmの物を用いた。組成物を厚さ1mmになるように上記基板に塗布した後、120℃、30分間の条件で架橋して試料を作製し、せん断接着力を測定した。せん断接着力を測定する際の引張り速度は50mm/分とした。比較例8の接着力と比べて、以下の基準で評価した。
A:比較例8の接着力の1.5倍以上
B:比較例8の接着力の0.75倍以上、1.5倍未満
C:比較例8の接着力の0.5倍以上、0.75倍未満
D:比較例8の接着力の0.5倍未満
得られたゴム組成物をカートリッジガンに充填しステンレス板(SUS304)上に塗布した時の、作業性を評価した。塗布し易く、糸引きが無いものを○、粘度が高く塗布しにくく、糸引きするものを×とした。
得られたゴム組成物をカートリッジガンに充填しステンレス板(SUS304)上に塗布した時の、液垂れを目視で評価した。液垂れが全く無いものを○、液垂れが確認されたものを×とした。
表6に記載した配合割合(質量部)にしたがって、変性液状ジエン系ゴム(A)又はジエン系ゴム、固形ゴム(B)、炭酸カルシウム、ナフテン系オイル、ステアリン酸、亜鉛華及び老化防止剤を配合し、ブラベンダーを用いて50℃で混練した。次いで、硫黄及び加硫促進剤を表6に示す割合で添加し、50℃で混練してゴム組成物を得た。得られたゴム組成物について、下記の方法に基づき各評価を行った。結果を表7に示す。
JIS K 6850に準じてせん断接着力の測定を行った。試験材料はステンレス板(SUS304)、アルミ板(A5052)又はポリエチレン板(HDPE、ショアー硬度D60)で、厚さ1mmの物を用いた。組成物を厚さ1mmになるように上記基板に塗布した後、150℃、30分間の条件で架橋して試料を作製し、せん断接着力を測定した。せん断接着力を測定する際の引張り速度は50mm/分とした。比較例11の接着力と比べて、以下の基準で評価した。
A:比較例11の接着力の1.5倍以上
B:比較例11の接着力の0.75倍以上、1.5倍未満
C:比較例11の接着力の0.5倍以上、0.75倍未満
D:比較例11の接着力の0.5倍未満
得られたゴム組成物をカートリッジガンに充填しステンレス板(SUS304)上に塗布した時の、作業性を評価した。塗布し易く、糸引きが無いものを○、粘度が高く塗布しにくく、糸引きするものを×とした。
表8に記載した配合割合(質量部)にしたがって、変性液状ジエン系ゴム(A)、エポキシ樹脂を自転公転撹拌脱泡機(シンキー株式会社製)で4分間混合し、2分間脱泡した。この混合物に、更にエポキシ樹脂硬化剤を添加し、4分間混合、2分間脱泡することでエポキシ樹脂組成物を得た。注型枠に得られたエポキシ樹脂組成物を流し込んだ後、60℃で4時間、更に昇温速度30℃/時間で150℃まで昇温し、4時間硬化することでエポキシ樹脂硬化物を作製し、下記の方法に基づき粘度、荷重たわみ温度、曲げ強度、曲げ弾性率、曲げひずみ、アイゾット衝撃強さを評価した。結果を表8に示す。
変性液状ジエン系ゴム(A)とエポキシ樹脂との混合物の粘度を、東機産業株式会社製TVE-22LTを用いて、JIS K 7117-2に準じて測定した。測定条件は以下の通りである。
・温度 :23℃
・ロータ :3°×R9.7
・回転数 :0.5rpm
・測定時間 :1分間静置後1分間測定
得られたエポキシ樹脂硬化物の荷重たわみ温度を、株式会社安田精機製作所製ヒートデストーションテスターNo.148-HD-PCを用い、JIS K 7191-2(フラットワイズ、A法)に準じて測定した。なお荷重たわみ温度が高いほど、得られたエポキシ樹脂硬化物は耐熱性に優れる。
得られたエポキシ樹脂硬化物の曲げ強度、曲げ弾性率、曲げひずみを、インストロン社製万能材料試験機5966型を用い、JIS K 7171に準じて測定した。測定条件は以下の通りである。なお曲げ強度、曲げ弾性率、曲げひずみが高いほど、得られたエポキシ樹脂硬化物は曲げ物性に優れる。
・試験片 :80mm×10mm×4mm
・試験速度 :2mm/分
・支点間距離 :64mm
得られたエポキシ樹脂硬化物のアイゾット衝撃強さを、株式会社東洋精機製作所製デジタル衝撃試験機DG-UB型を用い、JIS K 7110に準じて測定した。測定条件は以下の通りである。なおアイゾット衝撃強さが高いほど、得られたエポキシ樹脂硬化物は耐衝撃性に優れる。
・試験片 :80mm×10mm×4mm、ノッチ無し
・測定条件 :ハンマ/1.0J
Claims (7)
- 酸無水物に由来する官能基(a)を有し、下記(I)~(III)の要件をすべて満たす変性液状ジエン系ゴム(A)。
(I)官能基(a)の官能基当量が400~3,500g/eqの範囲にある。
(II)ゲルパーミエーションクロマトグラフィー(GPC)で測定した際、ポリスチレン換算の数平均分子量(Mn)が5,000~20,000の範囲にある。
(III)38℃における溶融粘度が3Pa・s以上であり、下記Xが6100K以上である。
X(K):ブルックフィールド型粘度計を用いて測定される38℃及び60℃における溶融粘度η(Pa・s)2点を、1/T(K-1)を横軸、Ln[η/(Pa・s)]を縦軸とするグラフにプロットした際の、該2点を通る直線の傾き。(但し、Tは温度(K)である。) - 変性液状ジエン系ゴム(A)が、不飽和カルボン酸無水物変性された液状ジエン系ゴムと下記化学式(2)又は(3)で示される化合物との反応物である請求項1に記載の変性液状ジエン系ゴム(A)。
Ra-OH (2)
(上記式(2)中、Raは水素原子又は置換されていてもよいアルキル基である。)
Rb 2-NH (3)
(上記式(3)中、Rbは水素原子又は置換されていてもよいアルキル基であり、複数あるRbは同一でも異なっていてもよい。) - 請求項1又は2に記載の変性液状ジエン系ゴム(A)を含む組成物。
- 請求項1又は2に記載の変性液状ジエン系ゴム(A)と固形ゴム(B)とを含むゴム組成物。
- 請求項4に記載のゴム組成物を含むシーリング材。
- 請求項4に記載のゴム組成物を含むタイヤビードフィラー用ゴム組成物。
- 固形ゴム(B)100質量部と、
請求項1又は2に記載の変性液状ジエン系ゴム(A)1~20質量部と、
フェノール系樹脂(C)5~40質量部と、
硬化剤(D)0.5~2.0質量部とを含む、請求項6に記載のタイヤビードフィラー用ゴム組成物。
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WO2022163359A1 (ja) * | 2021-01-26 | 2022-08-04 | 横浜ゴム株式会社 | シーラント材組成物およびそれを用いたタイヤ |
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KR20220099129A (ko) * | 2021-01-04 | 2022-07-13 | 현대자동차주식회사 | 자동차 내장재용 인조가죽, 및 이를 포함하는 자동차 내장재 |
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JP7273718B2 (ja) | 2023-05-15 |
CA3078383A1 (en) | 2019-04-11 |
US11773190B2 (en) | 2023-10-03 |
CN111148767B (zh) | 2023-01-10 |
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EP3693399A1 (en) | 2020-08-12 |
CN115819857A (zh) | 2023-03-21 |
TW201922894A (zh) | 2019-06-16 |
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