JPS62243631A - Thermoplastic elastomer composition - Google Patents
Thermoplastic elastomer compositionInfo
- Publication number
- JPS62243631A JPS62243631A JP8715286A JP8715286A JPS62243631A JP S62243631 A JPS62243631 A JP S62243631A JP 8715286 A JP8715286 A JP 8715286A JP 8715286 A JP8715286 A JP 8715286A JP S62243631 A JPS62243631 A JP S62243631A
- Authority
- JP
- Japan
- Prior art keywords
- group
- resin
- rubber
- nitrile rubber
- nylon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims description 16
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 29
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 28
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 23
- 125000003277 amino group Chemical group 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 10
- 125000004018 acid anhydride group Chemical group 0.000 claims abstract description 9
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000178 monomer Substances 0.000 abstract description 20
- -1 amino, carboxyl Chemical group 0.000 abstract description 13
- 229920001778 nylon Polymers 0.000 abstract description 13
- 239000004677 Nylon Substances 0.000 abstract description 12
- 150000001451 organic peroxides Chemical class 0.000 abstract description 11
- 239000003431 cross linking reagent Substances 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 229920000571 Nylon 11 Polymers 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 4
- 229920000098 polyolefin Polymers 0.000 abstract description 2
- 239000004593 Epoxy Substances 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 25
- 239000005060 rubber Substances 0.000 description 17
- 239000004743 Polypropylene Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 7
- 239000000806 elastomer Substances 0.000 description 6
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 1
- POPVUKGJWNLYGW-UHFFFAOYSA-N (hydroxyamino) hydrogen sulfate Chemical compound ONOS(O)(=O)=O POPVUKGJWNLYGW-UHFFFAOYSA-N 0.000 description 1
- AYWSZYFQXSLSFY-UHFFFAOYSA-N 1,2-dihydrotriazine-5,6-dithione Chemical compound SC1=CN=NN=C1S AYWSZYFQXSLSFY-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- SPPWGCYEYAMHDT-UHFFFAOYSA-N 1,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C(C)C)C=C1 SPPWGCYEYAMHDT-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 1
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- SALQMMXSINGXMI-UHFFFAOYSA-N 4-nitrosoaniline Chemical compound NC1=CC=C(N=O)C=C1 SALQMMXSINGXMI-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 208000000474 Poliomyelitis Diseases 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004959 Rilsan Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical class C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical compound CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 210000001520 comb Anatomy 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction 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
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 229920006229 ethylene acrylic elastomer Polymers 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は機械的強度に優れ、かつ耐油性、耐クリープ性
、成形性に優れた熱可塑性エラストマー組成物に関し、
さらに詳しくは官能基を有するオレフィン系樹脂とポリ
アミド樹脂および官能基を有するニトリル系ゴムを必須
成分とし、架橋剤により部分的に架橋させた熱可塑性エ
ラストマー組成物に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a thermoplastic elastomer composition that has excellent mechanical strength, oil resistance, creep resistance, and moldability.
More specifically, the present invention relates to a thermoplastic elastomer composition containing an olefin resin having a functional group, a polyamide resin, and a nitrile rubber having a functional group as essential components, and partially crosslinked with a crosslinking agent.
結晶性の樹脂、例えばポリオレフィン樹脂あるいはポリ
アミド樹脂にニジストマーをブレンドして熱可塑性エラ
ストマーとする手法が近年広く試みられている。熱可塑
性エラストマーとすることにより熱可塑性樹脂と同様に
取扱え、成形ができかつ再加工ができ、従来の加硫ゴム
のように加硫工程を必要とせず、成形サイクルが短縮で
きる利点があるためで、その上に優れた物性を有する熱
可塑性ニジストマー組成物を得んとしている。BACKGROUND ART In recent years, a method of blending a crystalline resin, such as a polyolefin resin or a polyamide resin, with a nydistomer to produce a thermoplastic elastomer has been widely attempted. By making it a thermoplastic elastomer, it can be handled in the same way as a thermoplastic resin, can be molded and reprocessed, does not require a vulcanization process like conventional vulcanized rubber, and has the advantage of shortening the molding cycle. The present invention aims to obtain a thermoplastic nidistomer composition which also has excellent physical properties.
ポリオレフィン樹脂は柔軟性、成形性に優れ、かつ比較
的安価であるため、これを用いたブレンドが広く検討さ
れており、特に相溶性の良好なエチレン−α−オレフィ
ン系共重合コム(以下1!JI) (LIM類と略す)
とのブレンド物について数多くの報告がある。しかしこ
れらブレンド物は樹脂成分、ゴム成分ともに耐油性に乏
しく、このため得られた熱可塑性エラストマー組成物も
耐油性の乏しいものとなっている。これに対し耐油性の
改良を目的に、ポリオレフィン樹脂にE P CQ M
類とともにニトリル系ゴムを混合する方法(例えば特開
昭54−100443、特開昭56−2332など)、
またポリオレフィン樹脂とニトリル系ゴムの二成分系で
耐油性エラストマーを得る方法も報告されている(特開
昭52−73950、特開昭56−143233など)
。しかしこれらの方法ではポリオレフィンとゴム量の界
面での接着が十分とはいい難く、機械的強度も低い。Polyolefin resins have excellent flexibility and moldability, and are relatively inexpensive, so blends using them have been widely studied, and in particular, ethylene-α-olefin copolymer combs (hereinafter referred to as 1!) with good compatibility are being studied. JI) (abbreviated as LIM)
There are many reports on blends with. However, these blends have poor oil resistance in both the resin component and the rubber component, and therefore the obtained thermoplastic elastomer composition also has poor oil resistance. On the other hand, for the purpose of improving oil resistance, E P CQ M was added to polyolefin resin.
A method of mixing nitrile rubber with the above (for example, JP-A-54-100443, JP-A-56-2332, etc.),
In addition, a method for obtaining an oil-resistant elastomer using a two-component system of polyolefin resin and nitrile rubber has also been reported (JP-A-52-73950, JP-A-56-143233, etc.).
. However, in these methods, adhesion at the interface between the polyolefin and the rubber amount is not sufficient, and the mechanical strength is also low.
一方、ポリアミド樹脂は耐薬品性、機械的強度に優れ、
数多くの用途に利用さ゛れ、その用途拡大を目的に柔軟
性付与が試みられた。その1つの方法としてポリアミド
樹脂との相溶性が良好ナニトリル系ゴムをブレンドする
方法がある(例えば特公昭55−44108、特開昭5
2−104566など)。 これにはニトリル系ゴムに
ポリアミドと反応するような官能基、例えばカルボキシ
ル基あるいはアミノ基を導入することによって機械的強
度が良好となることが開示されている。しかしながらポ
リアミド樹脂とニトリル系ゴムよりなる熱可塑性ニジス
トマー組成物は硬度が高く、エラストマーとして用いう
る硬度になるまでゴム量を増すと機械的強度が低下し、
捷た耐湿性および圧縮成形時の金型離れ性が劣るという
問題がある。On the other hand, polyamide resin has excellent chemical resistance and mechanical strength.
It has been used for many purposes, and attempts have been made to make it flexible in order to expand its uses. One method is to blend nanitrile rubber, which has good compatibility with polyamide resin (for example, Japanese Patent Publication No. 55-44108;
2-104566 etc.). This document discloses that mechanical strength can be improved by introducing into nitrile rubber a functional group that reacts with polyamide, such as a carboxyl group or an amino group. However, a thermoplastic nydistomer composition made of polyamide resin and nitrile rubber has high hardness, and when the amount of rubber is increased to the point where it can be used as an elastomer, the mechanical strength decreases.
There are problems with poor moisture resistance and poor mold release properties during compression molding.
近年、その高性能化から自動車用途を中心に材料への要
求特性は一段と厳しいものとなっており、機械的強度が
良好で耐油性、耐クリープ性に優れ、かつ成形性の良好
な熱可塑性エラストマーが要望されるようになってきた
。In recent years, due to improved performance, the required properties of materials mainly for automotive applications have become even more stringent, and thermoplastic elastomers have good mechanical strength, excellent oil resistance, creep resistance, and good moldability. is now in demand.
本発明者らはこれらの点に鑑み、鋭意研究した結果、官
能基を有する単量体で変性したオレフィン系樹脂にポリ
アミド樹脂および官能基を有するニトリル系ゴムをブレ
ンドすることにより、良好な機械的強度を有し、かつ耐
油性、耐クリープ性に優れ、良好な成形性を有する熱可
塑性エラストマー組成物を製造できることを見い出した
。すなわち本発明は下記のオレフィン系樹脂(A)、ポ
リアミド樹脂(J3)およびニトリル系ゴム0を混合し
、混合割合が(囚+ω月/(C)が15/85〜70/
30 (重量比)であり、囚/CB)が10//90〜
90/10 (重量比)で、ある熱可塑性エラストマー
組成物を提供するものである。In view of these points, the present inventors conducted intensive research and found that by blending an olefin resin modified with a monomer having a functional group with a polyamide resin and a nitrile rubber having a functional group, good mechanical properties were obtained. It has been found that it is possible to produce a thermoplastic elastomer composition that has strength, excellent oil resistance and creep resistance, and good moldability. That is, in the present invention, the following olefin resin (A), polyamide resin (J3), and nitrile rubber are mixed, and the mixing ratio is (Primary + ω month/(C) is 15/85 to 70/
30 (weight ratio) and prisoner/CB) is 10//90 ~
A thermoplastic elastomer composition is provided in a 90/10 (weight ratio).
囚エポキシ基、ヒドロキシル基、アミノ基、カルボキシ
ル基および酸無水物基から選ばれた少なくとも1種の官
能基を有する変性オレフィン系樹脂
■)ポリアミド樹脂
(C)エポキシ基、ヒドロキシル基、アミノ基、カルボ
キシル基および酸無水物基から選ばれた少なくとも1種
の官能基を有するニトリル系ゴム
本発明に使用する変性されたポリオレフィン系樹脂(4
)は、エチレン、プロピレン、1−ブテンなどのα−オ
レフィンモノマーを単独または共重合させることにより
得られる結晶性ポリオから選ばれた少なくとも1種の単
量体を付加させることによシ得ることができる。Modified olefin resin having at least one functional group selected from epoxy groups, hydroxyl groups, amino groups, carboxyl groups, and acid anhydride groups ■) Polyamide resin (C) Epoxy groups, hydroxyl groups, amino groups, carboxyl groups Nitrile rubber having at least one functional group selected from groups and acid anhydride groups Modified polyolefin resin (4) used in the present invention
) can be obtained by adding at least one monomer selected from crystalline polio obtained by copolymerizing α-olefin monomers such as ethylene, propylene, and 1-butene. can.
カルボキシル基または酸無水物基を含有する単量体とし
て具体的にはアクリル酸、メタクリル酸、マレイン酸、
無水マレイン酸、フマル酸、イタコン酸、無水イタコン
酸などのα、β−不飽和カルポン酸またはその酸無水物
があげられる。Specifically, monomers containing carboxyl groups or acid anhydride groups include acrylic acid, methacrylic acid, maleic acid,
Examples include α,β-unsaturated carboxylic acids such as maleic anhydride, fumaric acid, itaconic acid, and itaconic anhydride, or acid anhydrides thereof.
エポキシ基含有単量体としては、グリシジル(メタ)ア
クリレート、アリルグリシジルエーテル、ビニルグリシ
ジルエーテルなどがあげられる。ヒドロキシル基含有単
量体としては、1−ヒドロキシブロビル(メタ)アクリ
レート、2−ヒドロキシプロピル(メタ)アクリレート
、ヒドロキシエチル(メタ)アクリレートなどがあげら
れる。Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, allyl glycidyl ether, and vinyl glycidyl ether. Examples of the hydroxyl group-containing monomer include 1-hydroxybrobyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and hydroxyethyl (meth)acrylate.
アミノ基含有単量体としては、ジメチルアミノエチル(
メタ)アクリレート、ジエチルアミノエチル(メタ)ア
クリレート、ジブチルアミノエチル(メタ)アクリレー
トなどの3級アミノ基含有単量体があげられる。As an amino group-containing monomer, dimethylaminoethyl (
Examples include tertiary amino group-containing monomers such as meth)acrylate, diethylaminoethyl (meth)acrylate, and dibutylaminoethyl (meth)acrylate.
また、上記重合性を有する単量体の他、付加反応性を有
する有機化合物類をも用いることが可能である。例えば
チオグリコール酸、2−メルカプトプロピオン酸、2−
メルカプトエタノール、2−アミノエタンチオールなど
のチオール類、p−ニトロソアニリン、p−ニトロンフ
ェノールなどのニトロソ化合物、および各種官能基を有
するハイドロシラン類等が挙げられる。Furthermore, in addition to the above monomers having polymerizability, it is also possible to use organic compounds having addition reactivity. For example, thioglycolic acid, 2-mercaptopropionic acid, 2-
Examples include thiols such as mercaptoethanol and 2-aminoethanethiol, nitroso compounds such as p-nitrosoaniline and p-nitronephenol, and hydrosilanes having various functional groups.
変性ポリオレフィン樹脂の製造方法は、オレフィン系樹
脂と官能基を有する単量体を150℃〜300℃の温度
でバンバリーミキサ−1二−ダーブレンダー等の混練り
機あるいは連続混練り機または押出様を用いて熱処理す
ることにより得られる。この場合、多少の有機パーオキ
サイドを併用してもよい。The method for producing modified polyolefin resin is to mix an olefin resin and a monomer having a functional group at a temperature of 150°C to 300°C using a kneading machine such as a Banbury mixer-1 two-dur blender, a continuous kneading machine, or an extrusion machine. It can be obtained by heat treatment using In this case, some organic peroxide may be used in combination.
また、変性されたポリオレフィン樹脂の官能基を用いて
他種の官能基に変更し、利用することもできる。例えば
無水マレイン酸で変性した変性ポリオレフィン樹脂を4
,4′−メチレンジアニリンあるいハ4.4’−メチレ
ンビスシクロヘキシルアミノ、ヘキサメチレンジアミノ
などと反応させることによりアミノ基に変更して用いる
ことができる。Furthermore, the functional groups of the modified polyolefin resin can be changed to other types of functional groups for use. For example, a modified polyolefin resin modified with maleic anhydride
, 4'-methylene dianiline, 4,4'-methylenebiscyclohexylamino, hexamethylene diamino, etc. to convert it into an amino group.
これら官能基を有するモノマーのオレフィン系樹脂への
付加量は樹脂100重量部当り0.01〜20重量部が
好ましく、更に好ましくは0.2〜5重量部である。0
.01重量部未満では良好な機械的強度が十分に得られ
ず、20重量部を超えるとゲル化により機械的強度が低
下し、加工性も悪化する。The amount of monomers having these functional groups added to the olefin resin is preferably 0.01 to 20 parts by weight, more preferably 0.2 to 5 parts by weight per 100 parts by weight of the resin. 0
.. If it is less than 0.01 parts by weight, sufficient mechanical strength cannot be obtained, and if it exceeds 20 parts by weight, mechanical strength will decrease due to gelation and processability will also deteriorate.
本発明で用いられるポリアミド樹脂(B)は一般にナイ
ロンと呼ばれているものであり、ジアミノとジカルボン
酸の重縮合物、W−アミノカルボン酸の重縮合物、ラク
タム類の重合物およびこれら化合物の共重合物等である
。それらの例としてはナイロン6、ナイロン6.6、ナ
イロン6.10、ナイロン6.11.ナイロン6.12
、ナイロン7、ナイロン9、ナイロン11、ナイロン1
2、ナイロン13、ナイロン4,6、およびナイロン6
/6.6などの共重縮合物あるいはこれらの混合物が挙
げられる。The polyamide resin (B) used in the present invention is generally called nylon, and includes polycondensates of diamino and dicarboxylic acids, polycondensates of W-aminocarboxylic acids, polymers of lactams, and polymers of these compounds. Copolymers, etc. Examples of these are nylon 6, nylon 6.6, nylon 6.10, nylon 6.11. nylon 6.12
, nylon 7, nylon 9, nylon 11, nylon 1
2, nylon 13, nylon 4, 6, and nylon 6
Examples include copolycondensates such as /6.6 and mixtures thereof.
中でも柔軟性の面からナイロン9、ナイロン11、ナイ
ロン12、ナイロン13等の炭素含量の高いナイロンが
好ましい。Among them, nylons with high carbon content, such as nylon 9, nylon 11, nylon 12, and nylon 13, are preferred from the viewpoint of flexibility.
本発明における変性されたニトリル系ゴム0で用いられ
る官能性単量体としては、前述の変性されたオレフィン
系樹脂の製造に用いられたと同じ各種単量体を用い、そ
のまま重合することができる。As the functional monomer used in the modified nitrile rubber 0 in the present invention, the same various monomers as those used in the production of the above-mentioned modified olefin resin can be used and polymerized as they are.
変性ニトリル系ゴム(C)を得るだめの重合は、通常の
乳化重合で行なわれ、単量体、乳化剤、開始剤、分子量
調節剤およびその他の重合薬剤は反応開始前に全量添加
しても、反応開始後任意に分割添加してもよく、また反
応途中に温度や攪拌などの操作条件を任意に変更するこ
ともできる。The polymerization to obtain the modified nitrile rubber (C) is carried out by ordinary emulsion polymerization, and even if monomers, emulsifiers, initiators, molecular weight regulators, and other polymerization agents are added in their entire amounts before the start of the reaction, It may be added in portions as desired after the start of the reaction, and operating conditions such as temperature and stirring may be arbitrarily changed during the reaction.
重合方式は、連続式、回分式のいずれであってもよい。The polymerization method may be either continuous or batch.
得られた重合体の分子量は特に制限はないが、ムーニー
粘度(M L !+4 、100℃)は20〜12(C
)が好ましい。20未満ではゴム弾性に乏しく、また1
20を超えると加工性が劣る。The molecular weight of the obtained polymer is not particularly limited, but the Mooney viscosity (M L !+4, 100°C) is 20 to 12 (C
) is preferred. If it is less than 20, the rubber elasticity is poor;
If it exceeds 20, workability will be poor.
上記ニトリル系ゴムΩの官能基含有単量体の含量は1.
0〜20重量係が好ましく、更に好ましくは3〜15重
量係である。1.0重量係未満では、変性ポリオレフィ
ン樹脂囚およびポリアミド樹脂(B)との反応性に乏し
く、良好な機械的強度が得られない。また20重量%を
越えると、弾性率の増大が著しくエラストマーとし−C
の特性に乏しくなる。The content of the functional group-containing monomer in the nitrile rubber Ω is 1.
The weight ratio is preferably 0 to 20, more preferably 3 to 15 weight. If the weight coefficient is less than 1.0, the reactivity with the modified polyolefin resin and the polyamide resin (B) will be poor, and good mechanical strength will not be obtained. Moreover, if it exceeds 20% by weight, the elastic modulus increases significantly and becomes an elastomer.
characteristics become poor.
共重合体中のアクリロニトリル単量体の含量は15〜5
0重量係であり、好ましくは25〜45重量係である。The content of acrylonitrile monomer in the copolymer is 15-5
0 weight ratio, preferably 25 to 45 weight ratio.
15重量%未満ではポリアミド樹脂との相溶性に劣り、
本発明の特徴である高い機械的強度を得るのは困難であ
り、50重量%を超えると弾性率の増大が著しく、エラ
ストマーとしての特性に乏しくなる。If it is less than 15% by weight, the compatibility with polyamide resin is poor;
It is difficult to obtain the high mechanical strength that is a feature of the present invention, and if it exceeds 50% by weight, the elastic modulus increases significantly and the properties as an elastomer become poor.
本発明におけるオレフィン系樹脂(A)、ポリアミド°
樹脂(B)およびニトリル系ゴム(C)の混合割合は(
囚+(B) ] /(C)が15/85〜70/30(
重量比)であシ、囚/a3)が10/90〜90/10
(重量比)である。Olefin resin (A) in the present invention, polyamide °
The mixing ratio of resin (B) and nitrile rubber (C) is (
Prisoner + (B) ] / (C) is 15/85 ~ 70/30 (
Weight ratio) is 10/90 to 90/10
(weight ratio).
オレフィン系樹脂(4)とポリアミド樹脂(B)の混合
割合は10/90〜90/10であシ、好ましくは30
/70〜70/30である。10/90より小さい場合
にはポリアミド樹脂の欠点である成形性が改善されず、
一方90/10より大きい場合、耐油性、機械的強度に
劣る。The mixing ratio of olefin resin (4) and polyamide resin (B) is 10/90 to 90/10, preferably 30/90 to 90/10.
/70 to 70/30. If it is smaller than 10/90, moldability, which is a drawback of polyamide resin, will not be improved;
On the other hand, if it is greater than 90/10, oil resistance and mechanical strength are poor.
ニトリル系ゴム(C)の混合割合としては(因子CB)
)/(C)が15/85〜.70/30、好ましくは
25/75〜70/30重量比であり、15/85より
小さい場合には、樹脂の本来の特性である熱可塑性に乏
しく成形が困難となる。また70/30より大きい場合
には、エラストマーとしてのゴム弾性に劣る。The mixing ratio of nitrile rubber (C) is (factor CB)
)/(C) from 15/85. The weight ratio is 70/30, preferably 25/75 to 70/30, and if it is less than 15/85, the thermoplasticity, which is the original property of the resin, will be poor and molding will be difficult. Moreover, when it is larger than 70/30, the rubber elasticity as an elastomer is poor.
本発明の組成物は部分的に架橋されていることによシ機
械的強度、耐油性、耐クリープ性の著しい効果がえられ
る。部分的な架橋を目的として添加される架橋剤として
は、通常ゴムの加硫剤として用いられるイオウおよびそ
の誘導体類または有機パーオキサイド類のいずれでも良
いが、効率の良さから有機パーオキサイド類が好ましい
。Because the composition of the present invention is partially crosslinked, remarkable effects on mechanical strength, oil resistance, and creep resistance can be obtained. The crosslinking agent added for the purpose of partial crosslinking may be either sulfur and its derivatives or organic peroxides, which are usually used as vulcanizing agents for rubber, but organic peroxides are preferred from the standpoint of efficiency. .
架橋剤として使用される有機パーオキサイドとしては2
,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)
ヘキサン−3,2,5−ジメチル−2,5−ジ(1−ブ
チルパーオキシ)ヘキサン、2.2′−ビス(t−ブチ
ルパーオキシ)p−ジイソプロピルベンゼン、ジクミル
パーオキサイド、ジ−t−ブチルパーオキサイド、t−
ブチルパーオキシベンゾエート、l、■−ビス(1−ブ
チルパーオキシ)−3,3,5−トリメチルシクロヘキ
サン、2,4−ジクロルベンゾイルパーオキサイド、ベ
ンゾイルパーオキサイド、p−クロルベンゾイルパーオ
キサイドなどがあるが、より好適には分解温度の高いも
のが選択使用される。The organic peroxide used as a crosslinking agent is 2
,5-dimethyl-2,5-di(t-butylperoxy)
Hexane-3,2,5-dimethyl-2,5-di(1-butylperoxy)hexane, 2,2'-bis(t-butylperoxy)p-diisopropylbenzene, dicumyl peroxide, di-t -butyl peroxide, t-
Examples include butyl peroxybenzoate, l,■-bis(1-butylperoxy)-3,3,5-trimethylcyclohexane, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, etc. However, those with a high decomposition temperature are more preferably selected and used.
有機パーオキサイドの添加量は用いられるエラストマー
組成物100重量部に対して0.3〜3.0重量部、好
ましくは0.5〜2.0重量部である。有機パーオキサ
イドの量が0.3重量部未満では、機械的強度、耐油性
、耐クリープ性が不十分である。また、有機パーオキサ
イドの量が3.0重量部を超えると架橋密度が高くなシ
、配合物の伸びが低下する。The amount of organic peroxide added is 0.3 to 3.0 parts by weight, preferably 0.5 to 2.0 parts by weight, based on 100 parts by weight of the elastomer composition used. If the amount of organic peroxide is less than 0.3 parts by weight, mechanical strength, oil resistance, and creep resistance will be insufficient. Furthermore, if the amount of organic peroxide exceeds 3.0 parts by weight, the crosslinking density will not be high and the elongation of the compound will be reduced.
ゴム成分の架橋に際して2官能のビニルモノマーなどを
共架橋剤として使用することができる。かかる共架橋剤
としては以下の化合物があげられる。エチレン・ジメタ
クリレート、1.3−ブチレン・ジメタクリレート、1
,4−ブチレンジメタクリレート、1,6−ヘキサンジ
オールジアクリレート、ポリエチレングリコールジメタ
クリレート、1,4−ブタンジオールジアクリレート、
1,6−ヘキサンジオールジアクリレート、2,2′−
ビス(4−メタクリロイルジェトキシフェニル)フロパ
ン、トリメチロールプロパントリメタクリレート、トリ
メチロールプロパントリアクリレート、ペンタエリスリ
トールトリアクリレート、ジビニルベンゼン、N 、
N’−メチレンビスアクリルアミド、p−キノンジオキ
シム、plp’−ジベンゾイルキノンジオキシム、トリ
アジンジチオール、トリアリルシアスレート、トリアリ
ルイソシアヌレート、ビスマレイイミドなどである。When crosslinking the rubber component, a bifunctional vinyl monomer or the like can be used as a co-crosslinking agent. Examples of such co-crosslinking agents include the following compounds. Ethylene dimethacrylate, 1,3-butylene dimethacrylate, 1
, 4-butylene dimethacrylate, 1,6-hexanediol diacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol diacrylate,
1,6-hexanediol diacrylate, 2,2'-
Bis(4-methacryloyljethoxyphenyl)furopane, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, divinylbenzene, N,
These include N'-methylenebisacrylamide, p-quinone dioxime, plp'-dibenzoylquinone dioxime, triazinedithiol, triallyl ciaslate, triallyl isocyanurate, bismaleimide, and the like.
本発明の熱可塑性エラストマー組成物はゴム及び樹脂に
慣用の補助添加剤を使用することができる。かかる補助
添加剤としては、一般に市販されている以下のものがあ
げられる。The thermoplastic elastomer compositions of the present invention can use auxiliary additives customary for rubbers and resins. Examples of such auxiliary additives include the following, which are generally commercially available.
ゴム用の軟化剤及び可塑剤、カーボンブラック、ホワイ
トカーボン、クレー、タルク、炭酸カルシウムなどのフ
ィラー、酸化防止剤、熱安定剤、紫外線吸収剤、着色剤
、加工助剤、滑剤などであシ、樹脂に主に用いられるチ
タン、雲母、カオリンなどの充てん剤、および難燃材等
も使用することが可能である。更に本発明の組成物には
、その物性を損なわない範囲において他の重合体を配合
することもできる。Softeners and plasticizers for rubber, fillers such as carbon black, white carbon, clay, talc, calcium carbonate, antioxidants, heat stabilizers, ultraviolet absorbers, colorants, processing aids, lubricants, etc. Fillers such as titanium, mica, and kaolin, which are mainly used in resins, and flame retardants can also be used. Furthermore, other polymers may be blended into the composition of the present invention within a range that does not impair its physical properties.
重合体としてはポリブタジェンゴム、インプレンゴム、
クロロプレンゴム、スチレン−ブタジェンゴム、アクリ
ロニトリル−ブタジェンゴム、エチレン−プロピレンゴ
ム、アクリルゴム、ヒドリンゴム、シリコーンゴム、フ
ッ素ゴム等の各種ゴム状重合体があシ、これらのうちオ
レフィン系樹脂との相溶性の良好なブタジェンゴム、エ
チレン−プロピレンゴム、またポリアミド樹脂と相溶性
の良好なアクリルゴム、ヒドリンゴムが好ましい。これ
ら配合される重合体についてもエポキシ基、ヒドロキシ
基、アミノ基、カルボキシル基および酸無水物基より選
ばれた少なくとも一種の官能基を有することが機械的強
度の面から好ましい。Polymers include polybutadiene rubber, imprene rubber,
There are various rubbery polymers such as chloroprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene rubber, acrylic rubber, hydrin rubber, silicone rubber, and fluorine rubber. Preferred are butadiene rubber, ethylene-propylene rubber, and acrylic rubber and hydrin rubber, which have good compatibility with polyamide resins. It is preferable from the viewpoint of mechanical strength that the polymers to be blended have at least one functional group selected from epoxy groups, hydroxy groups, amino groups, carboxyl groups, and acid anhydride groups.
また、ゴム状重合体の他、ポリエチレン、ポリプロピレ
ン、エチレン−アクリレート樹脂、ポリスチレン、ポリ
エステル樹脂、ポリカーボネート樹脂等各種樹脂を必要
に応じて用いることも可能である。これらの添加剤の配
合割合は適宜の範囲である。In addition to rubbery polymers, various resins such as polyethylene, polypropylene, ethylene-acrylate resin, polystyrene, polyester resin, and polycarbonate resin can also be used as needed. The blending ratio of these additives is within an appropriate range.
本発明の組成物はポリオレフィン系樹脂(A)、ポリア
ミド樹脂の)、ニトリル系ゴム0および架橋剤を種々の
方法で溶融混合することによシ調整できる。例えば(A
)CB) (C)および架橋剤を同時に混練シすること
もできるし、あらかじめ(4)と■を溶融混合した後0
を加えその後架橋剤を加えることもできる。また、これ
らの任意の段階で必要に応じて前記添加剤を添加するこ
ともできる。混合は各種押出様、バンバリーミキサ−、
ニーダ−、ロール等で150〜250℃の範囲で混練シ
することによって行なうことができ、好ましい混練方法
としては押出機を用いる方法である。The composition of the present invention can be prepared by melt-mixing a polyolefin resin (A), a polyamide resin), a nitrile rubber, and a crosslinking agent by various methods. For example, (A
)CB) (C) and the crosslinking agent can be kneaded at the same time, or (4) and
It is also possible to add a crosslinking agent after that. Moreover, the above-mentioned additives can be added at any of these stages as necessary. Mixing can be done using various types of extrusion, Banbury mixer,
This can be carried out by kneading in a kneader, rolls, etc. at a temperature of 150 to 250°C, and a preferred kneading method is a method using an extruder.
本発明の熱可塑性エラストマー組成物は、従来から公知
の種々の溶融成形法によシ、種々の形状に成形される。The thermoplastic elastomer composition of the present invention can be molded into various shapes by various conventionally known melt molding methods.
例えば射出成形、押出成形、圧縮成形などの方法が挙げ
られ、得られた成形品はその優れた性質を利用して各種
自動車用部品、工業用品等に利用することができる。Examples include methods such as injection molding, extrusion molding, and compression molding, and the obtained molded products can be used for various automobile parts, industrial products, etc. by taking advantage of their excellent properties.
以下実施例により本発明を説明するが、これらによって
何ら本発明が制限を受けるものではない。The present invention will be explained below with reference to examples, but the present invention is not limited by these in any way.
尚、以下の各側において部およびチはそれぞれ重量部、
重量部を示す。In addition, in each side below, parts and parts are parts by weight, respectively.
Parts by weight are shown.
実施例、比較例に使用した各成分は次の通りである。The components used in the Examples and Comparative Examples are as follows.
ポリプロピレン樹脂
P P (1) ;三菱油化■製 三菱ノープレンFW
変性ポリプロピレン樹脂
変性PP(1) ;PP(1)に無水マレイン酸1.0
部付加したもの。PP(1)100部に対して、無水マ
レイン酸2.0部、有機パーオ
キサイド(2,5−ジメチル−2,5−ジ(t−ブチル
パーオキシ)ヘキサ
ン)1.0部を密閉型混線機中であら
かじめ溶融したPPに加え、180℃
で6分間混練シすることにより得た。Polypropylene resin PP (1); Mitsubishi Noprene FW manufactured by Mitsubishi Yuka ■
Modified polypropylene resin Modified PP (1); Maleic anhydride 1.0 in PP (1)
Part added. To 100 parts of PP (1), 2.0 parts of maleic anhydride and 1.0 part of organic peroxide (2,5-dimethyl-2,5-di(t-butylperoxy)hexane) were mixed in a closed type. It was obtained by adding it to PP which had been melted in advance in a machine and kneading it at 180°C for 6 minutes.
変性P P(n) ; P P(1)にヒドロキシエチ
ルメタクリレート1.2部付加したもの。変
性PP(1)と同様の方法で無水マレイン酸1.0部の
代わりにヒドロキシエ
チルメタクリレート3.0部用いた。Modified P P (n); 1.2 parts of hydroxyethyl methacrylate added to P P (1). In the same manner as modified PP (1), 3.0 parts of hydroxyethyl methacrylate was used instead of 1.0 part of maleic anhydride.
変性PPQI) ;変性PP(1)にヘキサメチレンジ
アミノを反応させたもの。変性PP
(1)100部に対してヘキサメチレンジアミノ1.5
部を密閉型混練機中で変
性PP(r)溶融下に加え180℃で6分間混練りさせ
て得た。Modified PPQI): Modified PP (1) reacted with hexamethylene diamino. Modified PP (1) 1.5 hexamethylene diamino per 100 parts
A portion of the modified PP(r) was melted in a closed kneader and kneaded at 180° C. for 6 minutes.
アクリロニトリルブタジェンゴム
N B R(4) ;日本合成ゴム■製JSRN230
S結合AN量35チ ムーニー粘度
ML++4 (100℃) = 56
変性アクリロニトリルブタジエンゴム
変性NBJ■);カルボキシ変性NBR下記に示す重合
処方に従かい内容積20tのオートクレーブ中で30℃
にて重合を行なった。Acrylonitrile butadiene rubber NBR (4); JSRN230 manufactured by Japan Synthetic Rubber
S-bond AN amount: 35 cm Mooney viscosity ML++4 (100°C) = 56 Modified acrylonitrile butadiene rubber Modified NBJ■); Carboxy-modified NBR Follow the polymerization recipe shown below at 30°C in an autoclave with an internal volume of 20 tons.
Polymerization was carried out at
ブタジェン 55 部アクリロニトリ
ル 37
メタクリル酸 7
水 250
ドデシルベンゼンスルフオン酸ナトリウム 5
第3級ドデシルメルカプタン 0.5過硫
酸カリウム 0.27シアノエチル化ジ
エタノールアミノ 0.15水酸化カリウム
0.10重台率80チに達した後、単量体
100部当り0.2部のヒドロキシルアミノ硫酸塩を添
加し、重合を停止させた。つづいて加温し水蒸気蒸留に
より、残留単量体を除去した後、ゴム固形分100部当
シ老化防止剤としてアルキル化フェノール1部を添加し
、硫酸で酸性状態に保った塩化カルシウム水溶液で凝固
し、得られたクラムを水洗した後50℃で真空乾燥し、
評価用サンプルを作製した。Butadiene 55 parts Acrylonitrile 37 Methacrylic acid 7 Water 250
Sodium dodecylbenzenesulfonate 5
Tertiary dodecyl mercaptan 0.5 Potassium persulfate 0.27 Cyanoethylated diethanolamino 0.15 Potassium hydroxide
After reaching a weight ratio of 80 inches, 0.2 parts of hydroxylamino sulfate per 100 parts of monomer was added to stop the polymerization. Subsequently, after heating and steam distillation to remove residual monomers, 1 part of alkylated phenol was added as an anti-aging agent per 100 parts of rubber solid content, and coagulated with an aqueous calcium chloride solution maintained in an acidic state with sulfuric acid. After washing the obtained crumb with water, vacuum drying at 50°C,
A sample for evaluation was prepared.
合体を作成した。Created a union.
(以 下 余 白 )
ポリアミド樹脂(■);東し■製゛リルサン”ナイロン
−11
ポリアミド樹脂(■);東し■製”アミラン”ナイロン
−6
gPM;日本合成ゴム■製JSREPO2P変性EPM
;無水マレイン酸変性EPM日本合成ゴム■製JAR,
EPO2P
100重量部に対し、無水マレイン酸
1重量部、有機パーオキサイド(化
薬ヌーリー■製カヤヘキサAD)
0.2重量部をあらかじめよく攪拌し、555mφ押出
機を用いて200℃、30rpmで反応させた。(Left below) Polyamide resin (■); Rilsan" nylon-11 manufactured by Toshi ■ Polyamide resin (■); "Amilan" nylon-6 manufactured by Toshi ■ gPM; JSREPO2P modified EPM manufactured by Nippon Synthetic Rubber ■
;Maleic anhydride modified EPM JAR manufactured by Japan Synthetic Rubber,
To 100 parts by weight of EPO2P, 1 part by weight of maleic anhydride and 0.2 parts by weight of organic peroxide (Kayahexa AD manufactured by Kayaku Nouri ■) were thoroughly stirred in advance and reacted at 200°C and 30 rpm using a 555 mφ extruder. Ta.
実施例1〜4.比較例1〜4
表−2に示す配合処方により予め180℃に予(1)
〜(II)、NBFL(1)、変性NBR(1) 〜G
IDを入れ混練を行ない、均一に混練りされた後(およ
そ2分後)、所定量の有機過酸化物を添加し、約10分
間混練りを続け、添加した有機パーオキサイドを100
係作用させ熱可塑性エラストマー組成物を得た。得られ
た組成物を6インチ電熱ロールでシート化し、それをプ
レス成形することにより、評価用テストピースを作成し
た。Examples 1-4. Comparative Examples 1 to 4 Preheated to 180°C according to the formulation shown in Table 2 (1)
~(II), NBFL (1), modified NBR (1) ~G
After adding ID and kneading, and after being uniformly kneaded (after about 2 minutes), add a predetermined amount of organic peroxide and continue kneading for about 10 minutes.
A thermoplastic elastomer composition was obtained. The obtained composition was formed into a sheet using a 6-inch electric heating roll, and the sheet was press-molded to prepare a test piece for evaluation.
物性評価結果を表−2にまとめだ。Table 2 summarizes the physical property evaluation results.
なお、表中の永久伸びは耐クリープ性の指標として示し
たが、その測定は厚さl■の試料よりJIS1号ダンベ
ルにて打ち抜いたサンプルについてJISK6301に
準拠して行なった。測定に用いた伸長率は50チである
。また成形性は厚さ1■で153四方のテスト板を圧縮
成形(200℃で5分間プレス後、加圧したまま水冷)
を行なった際の金型からの取り外し易さを良、劣で評価
したものである。引張強さ、伸び、耐油性はJIS K
6301に準じて測定した。The permanent elongation in the table is shown as an index of creep resistance, and the measurement was carried out in accordance with JIS K6301 on a sample punched out with a JIS No. 1 dumbbell from a sample having a thickness of 1. The elongation rate used in the measurement was 50 inches. In addition, the moldability was evaluated by compression molding a 153 square test plate with a thickness of 1 inch (after pressing at 200℃ for 5 minutes, cooling with water while pressurized).
The ease of removal from the mold was evaluated as good or poor. Tensile strength, elongation, and oil resistance are JIS K
Measured according to 6301.
実施例5〜11 、比較例5〜8
配合処方として表3,4に示した成分を用いる以外は実
施例1と同じ方法で試料を作製し物性評価を行なった。Examples 5 to 11, Comparative Examples 5 to 8 Samples were prepared in the same manner as in Example 1, except that the ingredients shown in Tables 3 and 4 were used as the formulation, and the physical properties were evaluated.
表−2に示した実施例1〜4と比較例1〜4から本発明
の組成物は機械的強度、耐油性に優れ、良好な耐クリー
プ特性(永久伸び)を示している。変性をしていないポ
リオレフィン樹脂又は二) IJル系ゴムを用いた場合
機械的強度が劣り、ポリアミド樹脂を用いない場合は耐
油性も劣る。From Examples 1 to 4 and Comparative Examples 1 to 4 shown in Table 2, the compositions of the present invention have excellent mechanical strength and oil resistance, and exhibit good creep resistance (permanent elongation). If an unmodified polyolefin resin or 2) IJ rubber is used, the mechanical strength will be poor, and if a polyamide resin is not used, the oil resistance will be poor.
また表−3に示した実施例5 、6 、10 、11お
よび比較例5.6から本発明の範囲外のブレンド比の領
域では機械的強度、耐油性、耐クリープ性のバランスの
とれた組成物を得ることが困難であることがわかる。即
ち変性NB几の含量の多い比較例5では強度がえられず
、又変性NBl(の含量の少ない比較例6は機械的強度
良好でも耐クリープ性が劣る。Furthermore, from Examples 5, 6, 10, 11 and Comparative Examples 5.6 shown in Table 3, compositions with well-balanced mechanical strength, oil resistance, and creep resistance were obtained in the range of blend ratios outside the range of the present invention. It turns out that it is difficult to obtain things. That is, Comparative Example 5, which has a high content of modified NBl, does not have sufficient strength, and Comparative Example 6, which has a low content of modified NBl, has good mechanical strength but poor creep resistance.
表−4に示した実施例7はポリオレフィン系樹脂の一部
を未変性のままで用いた場合であり、実施例8,9はエ
チレン−プロピレンゴムt−併用した組成物であるが、
本発明の目的とする効果が認められる。特にエチレン−
プロピレンゴム等他種ポリマーを併用する際には、これ
らについても各種官能基を導入したものが好ましい。Example 7 shown in Table 4 is a case in which a part of the polyolefin resin is used unmodified, and Examples 8 and 9 are compositions in which ethylene-propylene rubber t- is used in combination.
The desired effects of the present invention are observed. Especially ethylene
When using other types of polymers such as propylene rubber, it is preferable that various functional groups are also introduced into these polymers.
比較例7は実施例1に対し未変性NBRを用い較例7及
び比較例8のようなポリアミド/ニトリルゴムの混合組
成物は高温時の金属粘着性が大であり、圧縮成形、射出
成形の際の金型離れ性に問題があるのに対し、本発明組
成物は良好な金型離れ性を示す。Comparative Example 7 uses unmodified NBR in contrast to Example 1, and the mixed compositions of polyamide/nitrile rubber such as Comparative Examples 7 and 8 have high metal tackiness at high temperatures and are difficult to use in compression molding and injection molding. In contrast, the composition of the present invention exhibits good mold release properties.
本発明の熱可塑性エラストマー組成物は、変性されたポ
リオレフィン系樹脂、ポリアミド樹脂及び特定のニトリ
ルゴムを特定の比率で使用したものであり、優れた機械
的強度と耐油性を種ブーツ類、ホース類、シール材料等
の自動車用部品、ベルト、パツキン等の工業用部品に広
く用いることができる。The thermoplastic elastomer composition of the present invention uses a modified polyolefin resin, a polyamide resin, and a specific nitrile rubber in a specific ratio, and has excellent mechanical strength and oil resistance. It can be widely used in automotive parts such as sealing materials, and industrial parts such as belts and packing.
Claims (3)
(B)およびニトリル系ゴム(C)を混合し、その混合
割合が{(A)+(B)}/(C)が15/85〜70
/30(重量比)であり、(A)/(B)が10/90
〜90/10(重量比)であることを特徴とする熱可塑
性エラストマー組成物。 (A)エポキシ基、ヒドロキシ基、アミノ基、カルボキ
シル基および酸無水物基から選ばれ た少なくとも1種の官能基を有する変性オ レフィン系樹脂 (B)ポリアミド樹脂 (C)エポキシ基、ヒドロキシ基、アミノ基、カルボキ
シル基および酸無水物基から選ばれ た少なくとも1種の官能基を有するニトリ ル系ゴム(1) The following olefin resin (A), polyamide resin (B) and nitrile rubber (C) are mixed, and the mixing ratio is {(A)+(B)}/(C) from 15/85 to 70
/30 (weight ratio), and (A)/(B) is 10/90
A thermoplastic elastomer composition having a weight ratio of ˜90/10 (weight ratio). (A) Modified olefin resin having at least one functional group selected from epoxy group, hydroxy group, amino group, carboxyl group, and acid anhydride group (B) Polyamide resin (C) Epoxy group, hydroxy group, amino group Nitrile rubber having at least one functional group selected from a group consisting of a carboxyl group, a carboxyl group, and an acid anhydride group.
オレフィン系樹脂であり、ニトリル系ゴム(C)がカル
ボキシル基および/または酸無水物基を有するニトリル
系ゴムである特許請求の範囲第(1)項記載の熱可塑性
エラストマー組成物。(2) The olefin resin (A) is a modified olefin resin having an amino group, and the nitrile rubber (C) is a nitrile rubber having a carboxyl group and/or an acid anhydride group. Thermoplastic elastomer composition according to item 1).
許請求の範囲第(1)項記載の熱可塑性エラストマー組
成物。(3) The thermoplastic elastomer composition according to claim (1), wherein the composition is partially crosslinked.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8715286A JPS62243631A (en) | 1986-04-17 | 1986-04-17 | Thermoplastic elastomer composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8715286A JPS62243631A (en) | 1986-04-17 | 1986-04-17 | Thermoplastic elastomer composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS62243631A true JPS62243631A (en) | 1987-10-24 |
Family
ID=13907007
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8715286A Pending JPS62243631A (en) | 1986-04-17 | 1986-04-17 | Thermoplastic elastomer composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS62243631A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20030069495A (en) * | 2002-02-20 | 2003-08-27 | 서동학 | Preparation of partially crosslinked polypropylene and copolymers thereof and compositions thereof |
EP2692802A4 (en) * | 2011-03-31 | 2014-12-17 | Nitta Corp | Belt |
-
1986
- 1986-04-17 JP JP8715286A patent/JPS62243631A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20030069495A (en) * | 2002-02-20 | 2003-08-27 | 서동학 | Preparation of partially crosslinked polypropylene and copolymers thereof and compositions thereof |
EP2692802A4 (en) * | 2011-03-31 | 2014-12-17 | Nitta Corp | Belt |
US9624372B2 (en) | 2011-03-31 | 2017-04-18 | Nitta Corporation | Belt |
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