WO2015012018A1 - トーショナルダンパー用epdm組成物 - Google Patents
トーショナルダンパー用epdm組成物 Download PDFInfo
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- WO2015012018A1 WO2015012018A1 PCT/JP2014/065960 JP2014065960W WO2015012018A1 WO 2015012018 A1 WO2015012018 A1 WO 2015012018A1 JP 2014065960 W JP2014065960 W JP 2014065960W WO 2015012018 A1 WO2015012018 A1 WO 2015012018A1
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- Prior art keywords
- weight
- epdm
- parts
- carbon black
- polymer
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 68
- 239000006229 carbon black Substances 0.000 claims abstract description 54
- 229920000642 polymer Polymers 0.000 claims abstract description 41
- 229920000098 polyolefin Polymers 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 16
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 12
- 239000011630 iodine Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000010521 absorption reaction Methods 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000006237 Intermediate SAF Substances 0.000 claims description 5
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000003505 terpenes Chemical class 0.000 claims description 4
- 235000007586 terpenes Nutrition 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 10
- 239000005977 Ethylene Substances 0.000 abstract description 6
- 235000019241 carbon black Nutrition 0.000 description 45
- 229920001971 elastomer Polymers 0.000 description 30
- 239000005060 rubber Substances 0.000 description 30
- 230000000704 physical effect Effects 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 12
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 235000019198 oils Nutrition 0.000 description 10
- 238000013016 damping Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- 150000001993 dienes Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 230000003993 interaction Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- 241001441571 Hiodontidae Species 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- -1 methylene norbornene Chemical compound 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical group CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical group CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical group CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical group CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical group CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical group CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- PMAAOHONJPSASX-UHFFFAOYSA-N 2-butylperoxypropan-2-ylbenzene Chemical group CCCCOOC(C)(C)C1=CC=CC=C1 PMAAOHONJPSASX-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- GPNLWUFFWOYKLP-UHFFFAOYSA-N s-(1,3-benzothiazol-2-yl)thiohydroxylamine Chemical compound C1=CC=C2SC(SN)=NC2=C1 GPNLWUFFWOYKLP-UHFFFAOYSA-N 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical group CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F15/00—Suppression of vibrations in systems; Means or arrangements for avoiding or reducing out-of-balance forces, e.g. due to motion
- F16F15/10—Suppression of vibrations in rotating systems by making use of members moving with the system
- F16F15/12—Suppression of vibrations in rotating systems by making use of members moving with the system using elastic members or friction-damping members, e.g. between a rotating shaft and a gyratory mass mounted thereon
- F16F15/121—Suppression of vibrations in rotating systems by making use of members moving with the system using elastic members or friction-damping members, e.g. between a rotating shaft and a gyratory mass mounted thereon using springs as elastic members, e.g. metallic springs
- F16F15/124—Elastomeric springs
- F16F15/126—Elastomeric springs consisting of at least one annular element surrounding the axis of rotation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- 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
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F15/00—Suppression of vibrations in systems; Means or arrangements for avoiding or reducing out-of-balance forces, e.g. due to motion
- F16F15/10—Suppression of vibrations in rotating systems by making use of members moving with the system
- F16F15/12—Suppression of vibrations in rotating systems by making use of members moving with the system using elastic members or friction-damping members, e.g. between a rotating shaft and a gyratory mass mounted thereon
- F16F15/121—Suppression of vibrations in rotating systems by making use of members moving with the system using elastic members or friction-damping members, e.g. between a rotating shaft and a gyratory mass mounted thereon using springs as elastic members, e.g. metallic springs
- F16F15/124—Elastomeric springs
Definitions
- the present invention relates to an EPDM composition for a torsional damper, and more particularly to an EPDM composition for a torsional damper that achieves high attenuation and has a balance of physical properties required for the torsional damper.
- the torsional damper is attached to the crankshaft for the purpose of reducing engine vibration (reducing torsional vibration of the crankshaft).
- a hub vibrating body
- an annular mass member damper wheel
- the torsional damper in the middle is required to have a function of absorbing the change in angular velocity between the two. Therefore, the main function of the torsional damper is to reduce the torsional vibration of the crankshaft by matching the torsional direction natural frequency of the torsional damper with the natural frequency generated in the crankshaft. Prevention and noise reduction.
- the natural frequency of the torsional damper is determined by the spring constant of rubber and the inertial mass of the vibration ring.
- the rubber material used for the torsional damper is required to have a hardness variation (type A durometer) of about Hs 50 to 80 °.
- the rubber elastic body has good heat resistance and good temperature dependence of the spring constant (vibration characteristics (E) so that the change in natural frequency due to operating temperature is reduced and vibration can be absorbed in a wide temperature range. ') The temperature characteristics are good).
- the current mainstream torsional damper is a fitting type manufactured by press-fitting rubber vulcanized and molded between a hub attached to a crankshaft and a vibration ring. Since the vibration ring is prevented from slipping due to the compressive stress of the fitting torsional damper, it is required that the reduction of the repulsive stress accompanying the fitting compression is small over time.
- Patent Document 1 (a) at least one EPDM, the propylene content (C3 / (C2 + C3)) in the total amount of ethylene / propylene of the copolymer rubber is 35 to 50% by weight, and 100 parts by weight of EPDM having a Mooney viscosity (ML100) of 40 or more, (b) an ⁇ -olefin polymer represented by the general formula CH 2 ⁇ CHR (where R is an alkyl group having 3 to 12 carbon atoms)
- a crosslinked product of an EPDM composition comprising 5 to 50 parts by weight of an ⁇ -olefin oligomer having a number average molecular weight Mn of 300 to 1,400 and (c) 1 to 10 parts by weight of an organic peroxide crosslinking agent is used as a damper.
- the EPDM composition cross-linked product improves the temperature dependence of the spring constant in the low temperature region, has good damping characteristics at normal use temperatures, suppresses vibration amplification at the resonance point, and has good durability
- Patent Document 2 proposes a rubber composition for a heat-resistant conveyor belt comprising 5 to 25 parts by weight of ethylene- ⁇ -olefin oil per 100 parts by weight of ethylene propylene rubber. According to the above EPDM composition, there is a description that wear resistance and crack resistance can be improved by blending ethylene- ⁇ -olefin oil as a softening agent.
- Patent Document 3 100 parts by weight of oil-extended EPDM (as EPDM), 20 to 150 parts by weight of an ethylene- ⁇ -olefin copolymer having a number average molecular weight Mn of 10,000 or less, and 10 to 150 parts by weight of an ester plasticizer.
- the EPDM composition vulcanized with a sulfur-based vulcanizing agent achieves low hardness (JIS A is 10 or less) and high attenuation.
- the present inventor pays attention to the steric hindrance of the polymer, the interaction of the polymer side chain, and the interaction between the polymer and carbon black as factors affecting the improvement of the damping characteristics in the rubber composition. It has been found that by selecting from grades, ISAF grades, or ISAF-LS grades, and adding a liquid polyolefin oligomer having good compatibility with EPDM, the interaction with the polymer is produced and the damping is increased.
- the present inventor focused on the fact that EPDM materials can be adjusted in physical properties by varying the polymer composition and molecular weight, and as a result, the optimum polymer molecular weight and polymer composition could be determined.
- the inventors have found that it is possible to provide an EPDM composition having a balanced physical property in response to the requirements of the torsional damper.
- an object of the present invention is to provide an EPDM composition for a torsional damper that achieves high attenuation and has a balanced physical property required for the torsional damper.
- an EPDM polymer (B) a liquid polyolefin oligomer; (C) an EPDM composition comprising carbon black, With respect to 100 parts by weight of the EPDM polymer in which the propylene content in the total amount of ethylene / propylene of the EPDM polymer (a) is 35 to 50 wt%, 5 to 30 parts by weight of a liquid polyolefin oligomer in which the number average molecular weight Mn of the liquid polyolefin oligomer (b) is in the range of 3,000 to 4,000,
- the nitrogen adsorption specific surface area of the carbon black is 100 ⁇ 150m 2 / g of (c)
- carbon black 10 to 120 of iodine adsorption amount is 110 ⁇ 160mg / g
- DBP oil absorption amount is in the range of 70 ⁇ 135cm 3 / 100g
- An EPDM composition for torsional dampers comprising: parts by weight.
- the hardness Hs is 50 ° to 80 °
- the temperature dependence of the spring constant is good
- the hot physical properties at high temperature are good
- the EPDM polymer (a) used in the present invention is mainly composed of an ethylene / propylene / non-conjugated diene terpolymer polymer. From the viewpoint of durability, hot physical properties, temperature dependence of spring constant, and repulsive stress at the time of fitting, propylene content (C3 / (C2 + C3)) in the total amount of ethylene (C2) and propylene (C3) is 35 to 50 wt. As the index of the polymer molecular weight, those having Mooney viscosity (ML 1 + 4 (125 ° C.)) adjusted to 25 to 70 are preferably used.
- the propylene content (C3 / (C2 + C3)) in the total amount of ethylene (C2) and propylene (C3) is adjusted to 40 to 45 wt%, and the Mooney viscosity (ML 1 + 4 (125 ° C.)) is adjusted to 25 to 65. It has been done.
- Adjusting the propylene ratio in the total amount of ethylene (C2) and propylene (C3) of the EPDM polymer of (a) is because the propylene content of the polymer increases, so that This is preferable because the amount of composition deformation can be reduced. Further, in the region of the above propylene ratio, the pseudo cross-linking points increase with the increase in the molecular weight of the polymer, which is preferable because the repulsion stress when the rubber is compressed increases.
- the Mooney viscosity (ML 1 + 4 (125 ° C.) is preferably in the range of 25 to 70.
- non-conjugated dienes examples include dicyclopentadiene (DCPD), 1,4-hexadiene (1,4-HD), dicyclooctadiene (DCOD), methylene norbornene, and ethylidene norbornene (ENB).
- DCPD dicyclopentadiene
- 1,4-hexadiene (1,4-HD) 1,4-hexadiene
- DCOD dicyclooctadiene
- methylene norbornene methylene norbornene
- ENB ethylidene norbornene
- the EPDM polymer (a) of the present invention preferably contains 7% by weight or more of a diene component.
- the EPDM polymer (a) of the present invention has a propylene content (C3 / (C2 + C3)) in the total amount of ethylene (C2) and propylene (C3) of 35 to 35 as shown in Table 1 below.
- 50 wt%, diene component is 7 wt% or more, and Mooney viscosity (ML 1 + 4 (125 ° C.)) is preferably in the range of 25 to 70. Even when used alone, a plurality of them are appropriately combined and used as an EPDM mixture. May be.
- JSR EP As a commercial product of EPDM used as the EPDM polymer of (a) of the present invention, for example, “JSR EP” series manufactured by JSR Corporation and the like can be mentioned.
- the nitrogen adsorption specific surface area of 100 ⁇ 150m 2 / g, iodine adsorption amount 110 ⁇ 160mg / g, DBP oil absorption amount of carbon black in the range of 70 ⁇ 135cm 3 / 100g using is preferably a nitrogen adsorption specific surface area of 106 ⁇ 142m 2 / g, iodine adsorption amount 111 ⁇ 139mg / g, DBP oil absorption amount is carbon black in the range of 75 ⁇ 115cm 3 / 100g.
- the primary particle diameter of carbon black used in the present invention is preferably in the range of 10 to 29 nm, more preferably in the range of 10 to 25 nm.
- SAF carbon black and SAF-HS carbon are used.
- furnace black such as black, ISAF carbon black, ISAF-HM carbon black, ISAF-LM carbon black, ISAF-HS carbon black, or ISAF-LS carbon black can be selected and used. Of these, ISAF-LS carbon black is preferred.
- the nitrogen adsorption specific surface area, the iodine adsorption amount and the DBP adsorption amount are typical indexes showing the characteristics of carbon black
- the nitrogen adsorption specific surface area is based on JIS K6217
- the iodine adsorption amount is based on JIS K6221.
- the DBP oil absorption is a value measured according to JIS K6221 method A (mechanical method).
- Nitrogen adsorption specific surface area is an index of total specific surface area including pores of carbon black, along with iodine adsorption amount.
- the DBP absorption amount indirectly quantifies the structure by measuring the void ratio between individual aggregates having a positive correlation with the structure. Nitrogen adsorption specific surface area, iodine adsorption amount, and DBP adsorption amount have great effects on the reinforcing properties, extrusion properties, dispersibility, coloring power, viscosity, and conductivity when blended in rubber compositions. give.
- the primary particle size is the average diameter measured and calculated by electron micrographs of the small spherical components (contained by microcrystals that cannot be separated) that make up the carbon black aggregate. This is published by the Carbon Black Association. Carbon Black Yearbook 1998, NO. 48 is the same as that described as the definition of the particle diameter. Moreover, when calculating the primary particle diameter in the present invention, an arithmetic average is used.
- the use of carbon black having a small particle size can be preferably used because the interaction between the polymer and carbon has a positive effect on the improvement of the damping characteristics of the rubber composition.
- Carbon black that can be preferably used in the present invention can be obtained as a commercial product, “SAF Carbon / Seast 9” manufactured by Tokai Carbon Co., Ltd. (nitrogen adsorption specific surface area: 142 m 2 / g, iodine adsorption amount: 139 mg).
- the carbon black is added in the range of 10 to 120 parts by weight, preferably in the range of 20 to 100 parts by weight, per 100 parts by weight of the EPDM polymer (a). This is because if the blending amount of carbon black is less than 10 parts by weight, the effect of high attenuation is small, and if it exceeds 120 parts by weight, a problem occurs in kneadability.
- the above-mentioned number of carbons may be added and other carbon blacks may be blended.
- Liquid polyolefin oligomer In the present invention, at least one liquid polyolefin oligomer is added.
- liquid polyolefin oligomer a copolymer of ethylene and ⁇ -olefin having a number average molecular weight Mn in the range of 3,000 to 4,000 is used in the present invention.
- the number average molecular weight Mn is preferably 3,500 to 3,900, more preferably 3,600 to 3,800.
- the number average molecular weight Mn of the polyolefin oligomer is less than 3,000, the attenuation characteristic is deteriorated, and when it exceeds 4,000, the low temperature characteristic is deteriorated.
- the liquid polyolefin oligomer is added in a proportion of 5 to 30 parts by weight, preferably 10 to 30 parts by weight, per 100 parts by weight of the EPDM polymer (a). This is because if the liquid polyolefin oligomer part by weight is less than 5 parts by weight, the high damping effect is small and roll processability deteriorates, and if it exceeds 30 parts by weight, problems arise in kneadability and workability.
- liquid polyolefin oligomer used in the present invention examples include “Lucant HC-2000” manufactured by Mitsui Chemicals, Inc. (number average molecular weight Mn: 3,700, 100 ° C. kinematic viscosity 2,000 mm 2 / s, viscosity index 300, sulfur And less than 0.1% by mass).
- a tackifying resin compatible with EPDM is preferably 1 to 20 parts by weight, more preferably 1 to 10 parts by weight. You may add in the ratio of a part.
- the tackifying resin include aromatic modified terpene resins.
- plasticizers include, for example, petroleum-based softeners such as process oil, lubricating oil, paraffinic oil, castor oil, fatty oil-based softeners such as tanse oil, rapeseed oil, coconut oil, dibutyl phthalate, dioctyl phthalate, dioctyl Examples thereof include ester plasticizers such as adipate and dioctyl sebacate, and hydrocarbon oligomers.
- petroleum-based softeners such as process oil, lubricating oil, paraffinic oil, castor oil, fatty oil-based softeners such as tanse oil, rapeseed oil, coconut oil, dibutyl phthalate, dioctyl phthalate, dioctyl
- ester plasticizers such as adipate and dioctyl sebacate, and hydrocarbon oligomers.
- ⁇ Filler> As the filler blended in the EPDM composition of the present invention, an inorganic filler, an organic filler, or the like that is usually blended in rubber is used in addition to the carbon black.
- ⁇ Crosslinking agent> As a crosslinking agent mix
- sulfur-based crosslinking agents in addition to sulfur, 4,4′-dithiodimorpholine, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, 2-mercaptoimidazoline, tetramethylthiuram monosulfide, N-cyclohexyl-2 -Sulfur-donating compounds such as benzothiazol sulfenamide, dibenzothiazyl disulfide, and polymer polysulfide are used.
- organic peroxide crosslinking agent examples include 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-butyl peroxide, and dicumyl.
- additives that can be added to the EPDM composition of the present invention include commonly used anti-aging agents (for example, polymerized-2,2,4-trimethyl-1,2-dihydroquinoline, 2-mercaptobenzimidazole), auxiliary agents ( For example, acid acceptors such as zinc oxide and stearic acid) and hydrotalcite may be used.
- anti-aging agents for example, polymerized-2,2,4-trimethyl-1,2-dihydroquinoline, 2-mercaptobenzimidazole
- auxiliary agents For example, acid acceptors such as zinc oxide and stearic acid
- hydrotalcite may be used.
- the rubber composition is prepared by kneading using a kneader such as an intermix, kneader, Banbury mixer or an open roll, and the vulcanization thereof is performed by a vulcanizing press, a compression molding machine, an injection. Using a molding machine, etc., it is generally performed by heating to about 150 to 200 ° C. for about 3 to 60 minutes. If necessary, oven vulcanization (secondary vulcanization) at about 120 to 200 ° C. for about 1 to 24 hours. ) Is also done.
- a kneader such as an intermix, kneader, Banbury mixer or an open roll
- the EPDM polymer of (a) is EPDM-1 to 4 (each diene component is 5-ethylidene-2-norbornene (ENB)) having the characteristic values described in Table 1 below, or a blend And use.
- EPDM-1 (“KELTAN 4703” manufactured by Lanxess) 40 parts by weight EPDM-4 (“JSR EP33” manufactured by JSR) 60 parts by weight ISAF-LS carbon black (“Seast 600” manufactured by Tokai Carbon Co., Ltd.) 80 parts by weight liquid polyolefin oligomer (number average molecular weight Mn: 3700) ("Lucant HC2000” manufactured by Mitsui Chemicals, Inc.) 10 parts by weight zinc white 5 parts by weight stearic acid 0.5 parts by weight quinoline antioxidant 0.5 parts by weight liquid polybutadiene 5 parts by weight aromatic modified terpene resin 10 parts by weight dicumyl peroxide (DCP) 3.3 parts by weight sulfur 0.05 part by weight
- DCP dicumyl peroxide
- Mooney scorch The minimum Mooney viscosity Vm and scorch times t5 and t35 were measured using a “Rotorless Mooney Viscometer (RLM-1 type)” manufactured by Toyo Seiki Co., Ltd. under a test temperature of 125 ° C.
- Hot physical properties As in the case of normal physical properties, a standard test piece conforming to JIS K6251: 2010 was prepared, and a tensile tester equipped with a thermostatic bath in which the ambient temperature of the jig holding the test piece was maintained at 120 ° C. The test piece was allowed to stand for 10 minutes in a thermostatic bath, and then the tensile strength Tb (MPa) and the elongation Eb (%) were measured according to JIS K 6251. A case where Tb (MPa) was in the range of 4 or more and an Eb (%) in the range of 100 or more was evaluated as ⁇ , and a case where both were not satisfied was evaluated as ⁇ .
- Kneadability / workability Regarding kneadability / workability the following items (1) to (3) were evaluated, and those satisfying all three items were evaluated as “good”, and those not satisfying any one item were evaluated as “x”.
- the kneading time is within 30 minutes.
- the rubber fabric is in close contact without leaving the roll, the bank rotates smoothly, and has good roll processability.
- Damping characteristics (tan ⁇ ) Tan tension at 200 Hz was measured at 60 ° C. and 120 ° C. under tensile conditions using a viscoelastic spectrometer manufactured by UBM. A value of 0.150 or more can be evaluated as good, and preferably 0.155 or more.
- Example 2 In Example 1, a crosslinked rubber sample was molded and evaluated in the same manner except that the blending amount of EPDM polymer (a) was changed to 40 parts by weight of EPDM-2 and 60 parts by weight of EPDM-4. The results are shown in Table 3.
- Example 3 In Example 1, a crosslinked rubber sample was molded and evaluated in the same manner except that the blending amount of EPDM polymer (a) was changed to 40 parts by weight of EPDM-3 and 60 parts by weight of EPDM-4. The results are shown in Table 3.
- Example 4 the EPDM polymer of (a) is composed of 100 parts by weight of EPDM-1, 90 parts by weight of ISAF-LS carbon black, and 20 parts by weight of liquid polyolefin oligomer (Mn: 3700).
- a crosslinked rubber sample was molded in the same manner except for the above and evaluated in the same manner, and the results are shown in Table 3.
- Example 5 In Example 1, a crosslinked rubber sample was molded in the same manner except that the EPDM polymer of (a) was changed to 100 parts by weight of EPDM-4, and evaluated in the same manner. The results are shown in Table 3.
- Example 6 In Example 1, except that the EPDM polymer of (a) was changed to 100 parts by weight of EPDM-3, a crosslinked rubber sample was molded in the same manner and evaluated in the same manner. The results are shown in Table 3.
- Example 7 In Example 1, the blending amount of the EPDM polymer in (a) was changed to 40 parts by weight of EPDM-3, 60 parts by weight of EPDM-4, and 20 parts by weight of the blending amount of the liquid polyolefin oligomer (Mn: 3700). Similarly, a crosslinked rubber sample was molded and evaluated in the same manner, and the results are shown in Table 3.
- Example 8 A crosslinked rubber sample was similarly molded and evaluated in the same manner as in Example 1 except that the blending amount of the liquid polyolefin oligomer (Mn: 3700) was changed to 30 weight. The results are shown in Table 3.
- Example 1 In Example 1, the amount of the EPDM polymer blended in (a) was changed to 40 parts by weight of EPDM-3, 60 parts by weight of EPDM-4, and 0 parts by weight of the liquid polyolefin oligomer. Samples were molded and evaluated in the same manner, and the results are shown in Table 3.
- Example 2 In Example 1, the blending amount of the EPDM polymer of (a) was 40 parts by weight of EPDM-3, 60 parts by weight of EPDM-4, 80 parts by weight of ISAF-LS carbon black, FEF carbon black (“Seast” manufactured by Tokai Carbon Co., Ltd. G-SO ”)) was changed to 80 parts by weight and the amount of the liquid polyolefin oligomer was changed to 0 part by weight. A crosslinked rubber sample was molded and evaluated in the same manner, and the results are shown in Table 3.
- Example 3 In Example 1, the blending amount of the EPDM polymer of (a) was 40 parts by weight of EPDM-3, 60 parts by weight of EPDM-4, 80 parts by weight of ISAF-LS carbon black (HAC carbon black “N330L” manufactured by Cabot Corporation). ) A crosslinked rubber sample was similarly molded and evaluated in the same manner except that the blending amount of the liquid polyolefin oligomer was changed to 0 part by weight to 80 parts by weight. The results are shown in Table 3.
- Example 4 a crosslinked rubber sample was molded in the same manner except that 80 parts by weight of ISAF-LS carbon black was changed to 80 parts by weight of HAF carbon black (“N330L” manufactured by Cabot Corporation), and evaluated in the same manner. It is shown in Table 3.
- Example 5 (Comparative Example 5) In Example 1, a crosslinked rubber sample was molded and evaluated in the same manner except that the blending amount of the liquid polyolefin oligomer (Mn: 3700) was changed to 40 weight, and the results are shown in Table 3.
- Example 6 a crosslinked rubber sample was molded in the same manner except that 10 parts by weight of the liquid polyolefin oligomer (Mn: 3700) was changed to 10 parts by weight of the liquid polyolefin oligomer (Mn: 2600) (“Lucant HC600” manufactured by Mitsui Chemicals). The results were similarly evaluated, and the results are shown in Table 3.
- Comparative Example 1 since the content of the liquid polyolefin oligomer is 0, the damping characteristics, kneading properties and processability are deteriorated as compared with the Examples. In Comparative Examples 2 and 3, since FEF carbon black and HAF carbon black having a large particle diameter are used, it can be seen that the attenuation characteristics are worse than those in Comparative Example 1.
- Comparative Example 5 since the content of the liquid polyolefin oligomer was increased to 40 parts by weight as compared with Examples 1 to 3, the damping characteristics were good, but the kneadability / workability deteriorated. I understand that.
- Comparative Example 6 in which the number average molecular weight of the liquid polyolefin oligomer is 2,600, it can be confirmed that the attenuation characteristics are deteriorated even when the blending amount is 10 parts by weight.
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Abstract
Description
そして、例えばクランクシャフトの軸端に取付けられるハブ(振動体)とその外周に配置された環状の質量部材(ダンパーホイール)とを、ゴムからなる弾性体を介して結合する構成となっている。
(b)液状ポリオレフィンオリゴマーと、
(c)カーボンブラックとからなるEPDM組成物であって、
前記(a)のEPDMポリマーのエチレン・プロピレン合計量中のプロピレン含量が35~50wt%であるEPDMポリマー100重量部に対して、
前記(b)の液状ポリオレフィンオリゴマーの数平均分子量Mnが3,000~4,000の範囲にある液状ポリオレフィンオリゴマー5~30重量部と、
前記(c)のカーボンブラックの窒素吸着比表面積が100~150m2/g、よう素吸着量が110~160mg/g、DBP吸油量が70~135cm3/100gの範囲にあるカーボンブラック10~120重量部とを含有することを特徴とするトーショナルダンパー用EPDM組成物。
本発明に用いられる(a)のEPDMポリマーとしては、エチレン/プロピレン/非共役ジエン3元共重合体ポリマーを主成分にしたものである。耐久性、熱間物性、ばね定数の温度依存性、嵌合時の反発応力の観点から、エチレン(C2)とプロピレン(C3)合計量中のプロピレン含量(C3/(C2+C3))が35~50wt%であって、ポリマー分子量の指標としては、ムーニー粘度(ML1+4(125℃))が25~70に調整されたものが好適に用いられる。
本発明で用いられるカーボンブラックは、窒素吸着比表面積が100~150m2/g、よう素吸着量が110~160mg/g、DBP吸油量が70~135cm3/100gの範囲にあるカーボンブラックが用いられ、好ましくは、窒素吸着比表面積が106~142m2/g、よう素吸着量が111~139mg/g、DBP吸油量が75~115cm3/100gの範囲にあるカーボンブラックである。
本発明においては、少なくとも一種類の液状ポリオレフィンオリゴマーを添加する。
本発明のEPDM組成物に配合される可塑剤としては、通常のゴムや熱可塑性エラストマーに使用されるものを用いることができる。可塑剤の例としては、例えばプロセスオイル、潤滑油、パラフィン系オイルなどの石油系軟化剤、ひまし油、あまに油、ナタネ油、ヤシ油などの脂肪油系軟化剤、ジブチルフタレート、ジオクチルフタレート、ジオクチルアジペート、ジオクチルセバセートなどのエステル系可塑剤、炭化水素系オリゴマーなどが挙げられる。
本発明のEPDM組成物に配合される充填剤としては、上記カーボンブラック以外に、通常ゴムに配合されているような無機充填剤、有機充填剤などが用いられる。
本発明のEPDM組成物に配合される架橋剤としては、硫黄系架橋剤または有機過酸化物架橋剤の何れも用いることができ、1種でも、これらを併用して用いても良い。
本発明のEPDM組成物に添加できるその他添加剤としては、一般に用いられる老化防止剤(例えばポリメライズド-2,2,4-トリメチル-1,2-ジヒドロキノリン、2-メルカプトベンゾイミダゾール)、助剤(例えば酸化亜鉛、ステアリン酸)、ハイドロタルサイト等の受酸剤等を使用してもよい。
本発明において、ゴム組成物の調製は、インターミックス、ニーダ、バンバリーミキサ等の混練機またはオープンロールなどを用いて混練することによって行われ、それの加硫は加硫プレス、圧縮成形機、射出成形機等を用いて、一般に約150~200℃に約3~60分間程度加熱することによって行われ、必要に応じて約120~200℃で約1~24時間オーブン加硫(二次加硫)することも行われる。
EPDM-1(Lanxess社製「KELTAN4703」) 40重量部
EPDM-4(JSR社製「JSR EP33」) 60重量部
ISAF-LSカーボンブラック(東海カーボン社製「シースト600」)
80重量部
液状ポリオレフィンオリゴマー(数平均分子量Mn:3700)(三井化学社製「ルーカントHC2000」 10重量部
亜鉛華 5重量部
ステアリン酸 0.5重量部
キノリン系老化防止剤 0.5重量部
液状ポリブタジエン 5重量部
芳香族変性テルペン樹脂 10重量部
ジクミルパーオキサイド(DCP) 3.3重量部
硫黄 0.05重量部
得られた試験片について、各物性を下記の方法で測定し、その測定結果を表3に示した。
試験温度125℃の温度条件で、最低ムーニー粘度Vm、スコーチタイムt5、t35を東洋精機社製「ロータレス・ムーニ・ビスコメータ(RLM-1型)」を用いて測定した。
硬さHs:JIS K6253:1997に準拠(タイプAデュロメータ)
引張強さTb(MPa):JIS K6251:2010に準拠
伸びEb(%):JIS K6251:2010に準拠
(a)常態物性値の変化(JIS K6257:2010準拠)
150℃下で、70時間経過後に常態物性値がどのように変化したかを評価した。具体的には、硬さ(硬度)Hsについては上記常態物性との変化値ΔHs(ポイント)を示した。引張強さTbについては、常態物性との変化率ΔTb(%)で示し、伸びEbも常態物性との変化率ΔEb(%)で示した。ΔHs≦7、ΔTb(%)≧-20、ΔEb(%)≧-30であれば良好な耐熱性を示している。
(b)圧縮永久歪(JIS K6262:2006準拠)
150℃で70時間において圧縮永久歪を測定した。圧縮永久歪が30%以下の場合良好であり、25%以下がより望ましい。
常態物性の場合と同様にJIS K6251:2010に準拠した標準試験片を調製し、この試験片を掴む治具の周辺雰囲気温度が120℃に保たれた恒温槽を備えた引張試験機を用い、恒温槽中に試験片を10分間放置後、JIS K 6251に従い、引張強さTb(MPa)、伸びEb(%)を測定した。Tb(MPa)が4以上、Eb(%)が100以上の範囲にあるものを○、両方満たさないものを×と評価した。
混練性・加工性については下記の項目(1)~(3)を評価し、3項目とも満足するものを○、いずれか1項目でも満たさないものを×と評価した。
(1)混練時間が30分以内であること。
(2)生地排出後の混練機の汚染が無いこと。
(3)ゴム生地がロールから離れること無く密着しており、バンクがスムーズに回転し、良好なロール加工性を有すること。
引張条件下、60℃および120℃において、100Hzにおける貯蔵弾性率E’をUBM社製粘弾性スペクトロメータを用いて測定し、60℃対比で120℃におけるE’変化率が36%以下のものを○、そうで無いものを×と評価した。
引張条件下、60℃および120℃において、200Hzにおけるtanδを、UBM社製粘弾性スペクトロメータを用いて測定した。その値が0.150以上のものは良好と評価でき、好ましくは0.155以上である。
実施例1において、(a)のEPDMポリマー配合量を、EPDM-2を40重量部、EPDM-4を60重量部と変更した以外は同様に架橋ゴム試料を成形し、同様に評価し、その結果を表3に示した。
実施例1において、(a)のEPDMポリマー配合量を、EPDM-3を40重量部、EPDM-4を60重量部と変更した以外は同様に架橋ゴム試料を成形し、同様に評価し、その結果を表3に示した。
実施例1において、(a)のEPDMポリマーを、EPDM-1を100重量部に、ISAF-LSカーボンブラックの配合量を90重量部、液状ポリオレフィンオリゴマー(Mn:3700)の配合量を20重量部と変更した以外は同様に架橋ゴム試料を成形し、同様に評価し、その結果を表3に示した。
実施例1において、(a)のEPDMポリマーを、EPDM-4を100重量部と変更した以外は同様に架橋ゴム試料を成形し、同様に評価し、その結果を表3に示した。
実施例1において、(a)のEPDMポリマーを、EPDM-3を100重量部と変更した以外は同様に架橋ゴム試料を成形し、同様に評価し、その結果を表3に示した。
実施例1において、(a)のEPDMポリマー配合量を、EPDM-3を40重量部、EPDM-4を60重量部、液状ポリオレフィンオリゴマー(Mn:3700)の配合量を20重量部と変更した以外は同様に架橋ゴム試料を成形し、同様に評価し、その結果を表3に示した。
実施例1において、液状ポリオレフィンオリゴマー(Mn:3700)の配合量を30重量へ変更した以外は同様に架橋ゴム試料を成形し、同様に評価し、その結果を表3に示した。
実施例1において、(a)のEPDMポリマー配合量を、EPDM-3を40重量部、EPDM-4を60重量部、液状ポリオレフィンオリゴマーの配合量を0重量部と変更した以外は同様に架橋ゴム試料を成形し、同様に評価し、その結果を表3に示した。
実施例1において、(a)のEPDMポリマー配合量を、EPDM-3を40重量部、EPDM-4を60重量部、ISAF-LSカーボンブラック80重量部をFEFカーボンブラック(東海カーボン社製「シーストG-SO」)80重量部へ、液状ポリオレフィンオリゴマーの配合量を0重量部へ変更した以外は同様に架橋ゴム試料を成形し、同様に評価し、その結果を表3に示した。
実施例1において、(a)のEPDMポリマー配合量を、EPDM-3を40重量部、EPDM-4を60重量部、ISAF-LSカーボンブラック80重量部をHAFカーボンブラック(キャボット社製「N330L」)80重量部へ、液状ポリオレフィンオリゴマーの配合量を0重量部へ変更した以外は同様に架橋ゴム試料を成形し、同様に評価し、その結果を表3に示した。
実施例1において、ISAF-LSカーボンブラック80重量部をHAFカーボンブラック(キャボット社製「N330L」)80重量部へ変更した以外は同様に架橋ゴム試料を成形し、同様に評価し、その結果を表3に示した。
実施例1において、液状ポリオレフィンオリゴマー(Mn:3700)の配合量を40重量へ変更した以外は同様に架橋ゴム試料を成形し、同様に評価し、その結果を表3に示した。
実施例1において、液状ポリオレフィンオリゴマー(Mn:3700)10重量部を液状ポリオレフィンオリゴマー(Mn:2600)(三井化学社製「ルーカントHC600」)10重量へ変更した以外は同様に架橋ゴム試料を成形し、同様に評価し、その結果を表3に示した。
表3より、(a)のEPDMポリマーのエチレン・プロピレン合計量中のプロピレン含量が35~50wt%の範囲にあるEPDM 100重量部と、数平均分子量Mnが3,000~4,000である液状ポリオレフィンオリゴマー5~30重量部と、ISAF-LSカーボンブラック80~90重量部よりなるEPDM組成物は、硬度60~80°であり、減衰特性tanδが0.150以上を満たし、耐熱性、熱間物性、振動特性が良好であり、またその他の常態物性、混練性、加工性においても問題なく良好であることが確認された。
Claims (3)
- (a)EPDMポリマーと、
(b)液状ポリオレフィンオリゴマーと、
(c)カーボンブラックとからなるEPDM組成物であって、
前記(a)のEPDMポリマーのエチレン・プロピレン合計量中のプロピレン含量が35~50wt%であるEPDMポリマー100重量部に対して、
前記(b)の液状ポリオレフィンオリゴマーの数平均分子量Mnが3,000~4,000の範囲にある液状ポリオレフィンオリゴマー5~30重量部と、
前記(c)のカーボンブラックの窒素吸着比表面積が100~150m2/g、よう素吸着量が110~160mg/g、DBP吸油量が70~135cm3/100gの範囲にあるカーボンブラック10~120重量部とを含有することを特徴とするトーショナルダンパー用EPDM組成物。 - 前記(c)のカーボンブラックが、SAFカーボンブラック、ISAFカーボンブラック、又はISAF-LSカーボンブラックの何れかから選ばれる少なくとも1種であることを特徴とする請求項1記載のトーショナルダンパー用EPDM組成物。
- 芳香族変性テルペン樹脂を1~20重量部含有することを特徴とする請求項1又は2記載のトーショナルダンパー用EPDM組成物。
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