JPH03296506A - Chlorinated ethylene-alpha-olefin copolymer rubber and composition containing same - Google Patents
Chlorinated ethylene-alpha-olefin copolymer rubber and composition containing sameInfo
- Publication number
- JPH03296506A JPH03296506A JP2099392A JP9939290A JPH03296506A JP H03296506 A JPH03296506 A JP H03296506A JP 2099392 A JP2099392 A JP 2099392A JP 9939290 A JP9939290 A JP 9939290A JP H03296506 A JPH03296506 A JP H03296506A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer rubber
- weight
- olefin copolymer
- rubber
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 135
- 239000005060 rubber Substances 0.000 title claims abstract description 134
- 229920000089 Cyclic olefin copolymer Polymers 0.000 title claims abstract description 73
- 239000004711 α-olefin Substances 0.000 title claims abstract description 73
- 239000000203 mixture Substances 0.000 title claims description 21
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 60
- 239000000460 chlorine Substances 0.000 claims abstract description 51
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 51
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 229920001577 copolymer Polymers 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 34
- 239000005977 Ethylene Substances 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 238000005660 chlorination reaction Methods 0.000 claims description 11
- 239000012744 reinforcing agent Substances 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 description 31
- -1 chlorinated ethylene compound Chemical class 0.000 description 20
- 238000000034 method Methods 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 12
- 150000001451 organic peroxides Chemical class 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 230000032683 aging Effects 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000004636 vulcanized rubber Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 239000004604 Blowing Agent Substances 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 229920005601 base polymer Polymers 0.000 description 3
- 239000004035 construction material Substances 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012772 electrical insulation material Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 238000010060 peroxide vulcanization Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group 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
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 229920005637 ethylene/1-butene copolymer elastomer Polymers 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 125000006353 oxyethylene group Chemical group 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 2
- 229960003656 ricinoleic acid Drugs 0.000 description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 2
- 238000010057 rubber processing Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 2
- 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
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- JILNIZGVLASAPX-UHFFFAOYSA-N 2,3-bis(sulfanylmethyl)but-2-ene-1,4-dithiol Chemical compound SCC(CS)=C(CS)CS JILNIZGVLASAPX-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- LPFZJDLQTAOHCU-UHFFFAOYSA-N 2,6-bis(sulfanyl)-1,3-dihydrotriazine-4-thione Chemical compound SN1NC(S)=CC(=S)N1 LPFZJDLQTAOHCU-UHFFFAOYSA-N 0.000 description 1
- YFGKDYFYYPZZLE-UHFFFAOYSA-N 2-anilino-6-sulfanyl-1,3-dihydrotriazine-4-thione Chemical compound N1C(S)=CC(=S)NN1NC1=CC=CC=C1 YFGKDYFYYPZZLE-UHFFFAOYSA-N 0.000 description 1
- IECMYBBHIXMQIG-UHFFFAOYSA-N 2-butoxy-6-sulfanyl-1,3-dihydrotriazine-4-thione Chemical compound CCCCON1NC(S)=CC(=S)N1 IECMYBBHIXMQIG-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-UHFFFAOYSA-N 0.000 description 1
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- JANFCFFNYNICBG-UHFFFAOYSA-N 4-n-naphthalen-1-ylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC2=CC=CC=C12 JANFCFFNYNICBG-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- LYUSNQSJVGCXFK-UHFFFAOYSA-N C(C)N(N1NC=CC=N1)CC Chemical compound C(C)N(N1NC=CC=N1)CC LYUSNQSJVGCXFK-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- LULCPJWUGUVEFU-UHFFFAOYSA-N Phthiocol Natural products C1=CC=C2C(=O)C(C)=C(O)C(=O)C2=C1 LULCPJWUGUVEFU-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- JJEJDZONIFQNHG-UHFFFAOYSA-N [C+4].N Chemical compound [C+4].N JJEJDZONIFQNHG-UHFFFAOYSA-N 0.000 description 1
- MYDXELWIGVWGSK-UHFFFAOYSA-N [I].C1C2C(=CC)CC1C=C2 Chemical compound [I].C1C2C(=CC)CC1C=C2 MYDXELWIGVWGSK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- UETLMBWMVIQIGU-UHFFFAOYSA-N calcium azide Chemical compound [Ca+2].[N-]=[N+]=[N-].[N-]=[N+]=[N-] UETLMBWMVIQIGU-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011294 coal tar pitch 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
- 238000009841 combustion method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- QNNPHOLOYSXYNU-UHFFFAOYSA-N dicyclohexylazanium;benzoate Chemical compound OC(=O)C1=CC=CC=C1.C1CCCCC1NC1CCCCC1 QNNPHOLOYSXYNU-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000004664 distearyldimethylammonium chloride (DHTDMAC) Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass 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
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 235000012907 honey Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 230000001617 migratory effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 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
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical class [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- TVVPMLFGPYQGTG-UHFFFAOYSA-M tetramethylphosphanium;iodide Chemical compound [I-].C[P+](C)(C)C TVVPMLFGPYQGTG-UHFFFAOYSA-M 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003568 thioethers Chemical class 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
- NDLIRBZKZSDGSO-UHFFFAOYSA-N tosyl azide Chemical compound CC1=CC=C(S(=O)(=O)[N-][N+]#N)C=C1 NDLIRBZKZSDGSO-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、塩素化エチレン・α−オレフィン共重合ゴム
及びその組成物に関し、更に詳しくは加工性、耐熱性、
ゴム弾性に優れ、ゴム製品の長寿命化に極めて有、益で
ある塩素化エチレン・ａ−オレフィン共重合ゴム及びそ
の組成物に関するものである。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to chlorinated ethylene/α-olefin copolymer rubber and compositions thereof, and more particularly, to improvements in processability, heat resistance,
The present invention relates to a chlorinated ethylene/a-olefin copolymer rubber and a composition thereof, which have excellent rubber elasticity and are extremely useful for extending the life of rubber products.
［従来の技術］
塩素化エチレン・α−オレフィン系共重合ゴムは、すで
に知られており、例えばＲｕｂｂｅｒ Ｃｈｅｗ。[Prior Art] Chlorinated ethylene/α-olefin copolymer rubber is already known, such as Rubber Chew.
Ｔｅｃｈｎｏｌ、４９ ３５３ （１９７６）、特開昭
６０−９９１４９号公報、特開平１−１８２３４０号公
報などに開示されている。Technol, 49 353 (1976), Japanese Unexamined Patent Publication No. 60-99149, Japanese Unexamined Patent Publication No. 1-182340, and the like.
塩素化エチレン・α−オレフィン系共重合ゴムは耐オゾ
ン性、耐熱老化性に優れたゴムであるが、上記に開示さ
れた技術について追試したところ、加硫が早ければ耐熱
性に劣り、耐熱性が良ければ加硫が遅く加工性に劣り、
且つゴム弾性に劣るという問題のあることが判明した。Chlorinated ethylene/α-olefin copolymer rubber is a rubber that has excellent ozone resistance and heat aging resistance, but when we further tested the technology disclosed above, we found that if the vulcanization was too early, the heat resistance would be poor, and the heat resistance would be poor. If it is good, vulcanization will be slow and workability will be poor.
It was also found that there was a problem in that the rubber elasticity was poor.
［発明が解決しようとする課題］
本発明の目的は、上記問題を解消するもので、加硫速度
が早く、且つ熱安定性、耐熱老化性、ゴム弾性等に優れ
た新規な塩素化エチレン・α−オレフィン共重合ゴム及
びその組成物を提供することにある。[Problems to be Solved by the Invention] The purpose of the present invention is to solve the above-mentioned problems, and to provide a novel chlorinated ethylene compound that has a fast vulcanization rate and is excellent in heat stability, heat aging resistance, rubber elasticity, etc. An object of the present invention is to provide an α-olefin copolymer rubber and a composition thereof.
［課題を解決するための手段］
本発明によれば塩素化エチレン・ａ−オレフィン共重合
ゴムであって、塩素含量が２０〜４０重量％、結合塩素
のうち一級の炭素に結合した塩素が塩素化エチレン・α
−オレフィン共重合ゴムを基準にして０．６重量％以上
、三級の炭素に結合した塩素が１．６重量％以下であり
、ムーニー粘度［ＭＬ１＋、（１２１”Ｃ）］が１０−
１９０であることを特徴とした塩素化エチレン・α−オ
レフィン共重合ゴムが提供される。[Means for Solving the Problems] According to the present invention, there is provided a chlorinated ethylene/a-olefin copolymer rubber having a chlorine content of 20 to 40% by weight, and of the combined chlorine, the chlorine bonded to the primary carbon is chlorine. Ethylene α
- 0.6% by weight or more based on the olefin copolymer rubber, 1.6% by weight or less of chlorine bonded to tertiary carbon, and Mooney viscosity [ML1+, (121"C)] of 10-
190 is provided.
前記塩素化エチレン・ａ−オレフィン共重合ゴムは、塩
素化前のエチレン・α−オレフィン共重合ゴムのエチレ
ン単位とα−オレフィン単位との組成比がモル基準で８
５／１５乃至９５１５であることが好適である。The chlorinated ethylene/α-olefin copolymer rubber has a composition ratio of ethylene units to α-olefin units of 8 on a molar basis in the ethylene/α-olefin copolymer rubber before chlorination.
Preferably, it is between 5/15 and 9515.
また塩素化エチレン・α−オレフィン共重合ゴムのα−
オレフィンが炭素数で３乃至２０であることが好適であ
る。In addition, α- of chlorinated ethylene/α-olefin copolymer rubber
It is preferred that the olefin has 3 to 20 carbon atoms.
本発明によれば、また前記塩素化エチレン・α−オレフ
ィン共重合ゴム１００重量部に対し（ａ）３００重量部
までの補強剤、（ｂ）２００重量部までの軟化剤、及び
（ｃ）該共重合ゴム１００ｇ当り５．Ｏ×１０−’乃至
５．ＯＸｌ［ｌ−”モルの割合に相当する重量部の加硫
剤を配合してなる組成物が提供される。According to the present invention, based on 100 parts by weight of the chlorinated ethylene/α-olefin copolymer rubber, (a) up to 300 parts by weight of a reinforcing agent, (b) up to 200 parts by weight of a softener, and (c) the 5. per 100g of copolymer rubber. O x 10-' to 5. A composition is provided which contains a vulcanizing agent in parts by weight corresponding to the proportion of OXl[l-'' moles.
［発明の実施態様］
本発明の塩素化エチレン・α−オレフィン共重合ゴムに
使用されるエチレン・α−オレフィン共重合ゴム（ベー
スポリマー）、ベースポリマーから本発明の塩素化エチ
レン・α−オレフィン共重合ゴムの製造方法とゴムの特
徴、特性、及び加硫ゴム組成物について、以下順次説明
する。[Embodiments of the invention] Ethylene/α-olefin copolymer rubber (base polymer) used in the chlorinated ethylene/α-olefin copolymer rubber of the present invention, chlorinated ethylene/α-olefin copolymer rubber of the present invention from the base polymer The method for producing polymerized rubber, the characteristics and characteristics of the rubber, and the vulcanized rubber composition will be sequentially explained below.
エチレン・α−オレフィン共重合ゴム
本発明における塩素化エチレン・α−オレフィン共重合
ゴムにおいて、ベースポリマーとして使用されるエチレ
ン・α−オレフィン共重合ゴムは次の通りである。Ethylene/α-olefin Copolymer Rubber In the chlorinated ethylene/α-olefin copolymer rubber of the present invention, the ethylene/α-olefin copolymer rubber used as the base polymer is as follows.
使用するα−オレフィンとしては、炭素数で３乃至２０
のものが選ばれ、プロピレン、ｌ−ブテン、４−メチル
ペンテン−１、ヘキセン、オクテン、デセン、ドデセン
などが例示できる。好適にはｌ−ブテン、ｌ−ヘキセン
が使用される。The α-olefin used has 3 to 20 carbon atoms.
Among them are propylene, 1-butene, 4-methylpentene-1, hexene, octene, decene, dodecene, and the like. L-butene and l-hexene are preferably used.
エチレン・α−オレフィン共重合ゴム中のエチレン単位
とα−オレフィン単位との組成比（エチレン／α−オレ
フィン）はモル基準で８５／１５乃至９５１５、好まし
くは８９／１１乃至９３／７のものである。The composition ratio of ethylene units to α-olefin units (ethylene/α-olefin) in the ethylene/α-olefin copolymer rubber is 85/15 to 9515, preferably 89/11 to 93/7 on a molar basis. be.
エチレン・α−オレフィン共重合ゴムは、上記成分の他
に、他の重合可能な成分を共重合していてもよく、特に
エチレン／α−オレフィン単位の総重ｆｘｏｏｇに対し
、５−ビニル−２−ノルボルネンを最大３０ ｆｆ１Ｕ
ａｏｌ含有しているのが好ましい。In addition to the above-mentioned components, the ethylene/α-olefin copolymer rubber may have other polymerizable components copolymerized therein. In particular, 5-vinyl-2 - Up to 30 ff1U of norbornene
Preferably, it contains aol.
エチレン・α−オレフィン共重合ゴムは、上記各成分を
ランダム重合させて得られたゴム状重合体であり、それ
自体公知の方法で製造される。Ethylene/α-olefin copolymer rubber is a rubbery polymer obtained by random polymerization of the above components, and is produced by a method known per se.
エチレン・α−オレフィン共重合ゴムの分子量は、塩素
化エチレン・α−オレフィン共重合ゴムのムーニー粘度
により規定されるが、塩素化前のエチレン・α−オレフ
ィン共重合ゴムとしては、通常１３５℃におけるデカリ
ン中の極限粘度［η〕で０．５乃至６．０の範囲に入る
ものから選ばれる。The molecular weight of the ethylene/α-olefin copolymer rubber is determined by the Mooney viscosity of the chlorinated ethylene/α-olefin copolymer rubber, but the molecular weight of the ethylene/α-olefin copolymer rubber before chlorination is usually It is selected from those having an intrinsic viscosity [η] in the range of 0.5 to 6.0 in decalin.
塩素化エチレン・α−オレフィン共重合ゴムは、上記に
より得られたエチレン・α−オレフィン共重合ゴムを塩
素化することにより得られ塩素化エチレン・α−オレフ
ィン北重合ゴムのエチレン・α−オレフィン共重合ゴム
の塩素化反応は、共重合ゴムを溶媒中に溶解し、光或い
は有機過酸化物を触媒として分子状塩素を接触させて製
造することができる。この際、溶媒として四塩化炭素、
クロロホルム、シクロヘキサン、トリクロルエタン、テ
トラクロルエチレン、四塩化ケイ素、ニトロメタン等が
例示で籾る。塩素に対しての安定性、安全性等の点から
四塩化炭素、クロロホルムなどが好ましい。Chlorinated ethylene/α-olefin copolymer rubber is obtained by chlorinating the ethylene/α-olefin copolymer rubber obtained above. The chlorination reaction of polymerized rubber can be produced by dissolving the copolymerized rubber in a solvent and bringing it into contact with molecular chlorine using light or an organic peroxide as a catalyst. At this time, carbon tetrachloride as a solvent,
Examples include chloroform, cyclohexane, trichloroethane, tetrachloroethylene, silicon tetrachloride, and nitromethane. Carbon tetrachloride, chloroform, etc. are preferable from the viewpoint of stability against chlorine, safety, etc.
塩素化反応後の処理は、通常衣のように行われる。まず
、溶液中の分子状塩素、塩化水素を脱気し、次にメタノ
ールなどの塩素化エチレン・α−オレフィン共重合ゴム
の貧溶媒中に投入し、沈澱物をろ過し、この貧溶媒で洗
浄し乾燥させるとか或いは溶液を薄膜状にして溶媒を熱
で除く方法などが例示できる。塩素化の程度を調節する
には、分子状塩素の使用量、反応時間、反応温度、触媒
の量などを調節することによって行われる。The treatment after the chlorination reaction is usually carried out like a cloth. First, molecular chlorine and hydrogen chloride in the solution are degassed, and then the solution is poured into a poor solvent of chlorinated ethylene/α-olefin copolymer rubber such as methanol, and the precipitate is filtered and washed with this poor solvent. For example, methods include drying the solution, or forming the solution into a thin film and removing the solvent with heat. The degree of chlorination is controlled by adjusting the amount of molecular chlorine used, reaction time, reaction temperature, amount of catalyst, etc.
塩素化エチレン・α−オレフィン共重合ゴム本発明の塩
素化エチレン・α−オレフィン共重合ゴムは、塩素含量
が２０〜４０重量％、好ましくは２５〜３５重量％以下
であり、またムーニ粘度［ＭＬＩ−４（１２１℃）］は
、成形性、作業性の見地から１０〜１９０、好ましくは
２０〜１５０、更に好ましくは３０〜１２０のものであ
る。Chlorinated ethylene/α-olefin copolymer rubber The chlorinated ethylene/α-olefin copolymer rubber of the present invention has a chlorine content of 20 to 40% by weight, preferably 25 to 35% by weight or less, and has a Mooney viscosity [MLI -4 (121°C)] is 10 to 190, preferably 20 to 150, and more preferably 30 to 120 from the viewpoint of moldability and workability.
更に、塩素化エチレン・α−オレフィン共重合ゴムを基
準として結合塩素のうち一級の炭素に結合した塩素が０
．６重量％以上、三級の炭素に結合した塩素がり、６重
量％以下であり、好ましくは一級の炭素に結合した塩素
が０．７重量％以上、三級の炭素に結合した塩素が１．
４重量％以下であることが、本発明の最大要件である。Furthermore, based on chlorinated ethylene/α-olefin copolymer rubber, the amount of chlorine bonded to primary carbon among the bonded chlorine is 0.
．． 6% by weight or more of chlorine bonded to tertiary carbon, and 6% by weight or less of chlorine bonded to tertiary carbon, preferably 0.7% or more of chlorine bonded to primary carbon, and 1.7% by weight of chlorine bonded to tertiary carbon.
The maximum requirement of the present invention is that the content is 4% by weight or less.
本発明の要件を達成するためには、原料となるエチレン
・α−オレフィン共重合ゴムが前述のように制限される
ほか、溶媒の選択、反応溶液の濃度、塩素化反応の温度
の調節が必要となる。In order to achieve the requirements of the present invention, in addition to the above-mentioned limitations on the raw material ethylene/α-olefin copolymer rubber, it is necessary to select the solvent, adjust the concentration of the reaction solution, and adjust the temperature of the chlorination reaction. becomes.
前記要件において、塩素含量が２０重量％を下まわると
塩素化により期待できる耐油性、難燃性、接着性の効果
が十分に発揮されない、また４０重量％を上まわると溶
融流動性が低下し、成形性、加工性等が悪くなる。In the above requirements, if the chlorine content is less than 20% by weight, the oil resistance, flame retardance, and adhesive effects that can be expected from chlorination will not be sufficiently exhibited, and if it exceeds 40% by weight, the melt fluidity will decrease. , moldability, processability, etc. deteriorate.
一級の炭素に結合した塩素が塩素化エチレン・α−オレ
フィン共重合ゴムを基準として０．６重量％を下まわる
と加硫が遅くなり実用に適さない。If the amount of chlorine bonded to primary carbon is less than 0.6% by weight based on the chlorinated ethylene/α-olefin copolymer rubber, vulcanization slows down and is not suitable for practical use.
また三級の炭素に結合した塩素が１．６重量％を上まわ
ると耐熱性が低下する。Furthermore, if the amount of chlorine bonded to tertiary carbon exceeds 1.6% by weight, heat resistance decreases.
ムーニー粘度［ＭＬＩ−４（１２１℃）１が上記範囲よ
り小さい場合には、塩素化エチレン・α−オレフィン共
重合ゴムの強度が不十分となり、一方上記範囲より大き
い場合には溶融流動性が低下し、成形性、加工性が悪化
し、また他のゴムや樹脂と均一にブレンドしにくくなる
。If the Mooney viscosity [MLI-4 (121°C) 1 is smaller than the above range, the strength of the chlorinated ethylene/α-olefin copolymer rubber will be insufficient, while if it is larger than the above range, the melt fluidity will decrease. However, moldability and processability deteriorate, and it becomes difficult to blend uniformly with other rubbers and resins.
本発明の塩素化エチレン・α−オレフィン共重合ゴムは
、従来公知の塩素化エチレン・α−オレフィン系共重合
ゴムと比較して加硫が速く加工性に優れ、耐熱性、耐熱
老化性に優れるという特徴を持っている。The chlorinated ethylene/α-olefin copolymer rubber of the present invention vulcanizes quickly, has excellent processability, and has excellent heat resistance and heat aging resistance compared to conventionally known chlorinated ethylene/α-olefin copolymer rubbers. It has the following characteristics.
本発明の塩素化エチレン・α−オレフィン共重合ゴムは
、未加硫状態においては熱可塑性ゴムとして使用できる
。また、未加硫の塩素化エチレン・α−オレフィン共重
合ゴムは、柔軟性に冨み、溶融流動特性にも優れること
から、各種の樹脂とも容易にブレンドすることができ、
例えば、塩化ビニル樹脂、ポリスチレン、ＡＳ樹脂、Ａ
ＢＳ樹脂などのスチレン系樹脂、ポリプロピレンなとの
耐衝撃性改良、軟質乃至半硬質塩化ビニル樹脂の非移行
性可塑剤、ポリエチレン、ポリプロピレンなどのポリオ
レフィン用難燃化剤などとして有効に用いることができ
る。The chlorinated ethylene/α-olefin copolymer rubber of the present invention can be used as a thermoplastic rubber in an unvulcanized state. In addition, unvulcanized chlorinated ethylene/α-olefin copolymer rubber is highly flexible and has excellent melt flow characteristics, so it can be easily blended with various resins.
For example, vinyl chloride resin, polystyrene, AS resin, A
It can be effectively used to improve the impact resistance of styrene resins such as BS resin and polypropylene, as a non-migratory plasticizer for soft to semi-hard vinyl chloride resins, and as a flame retardant for polyolefins such as polyethylene and polypropylene. .
本発明の塩素化エチレン・α−オレフィン共重合ゴムは
、加硫状態においてその特性が最も良く発揮される。加
硫物は、通常のゴムを加硫する時と同様に、未加硫の配
合ゴムを一度調整し次いで該配合ゴムを意図する形に成
形した後に加硫を行うことにより製造される。The chlorinated ethylene/α-olefin copolymer rubber of the present invention exhibits its properties best in a vulcanized state. The vulcanizate is produced by preparing an unvulcanized compounded rubber, molding the compounded rubber into an intended shape, and then vulcanizing it, in the same way as in the case of vulcanizing ordinary rubber.
本発明においては、本発明になる塩素化エチレン・α−
オレフィン共重合ゴムに加えてゴムを製造する上での加
工性および要求性能に応じて、それ自体公知の配合剤、
例えば加硫剤、加硫助剤、ゴム用補強剤、充填剤、軟化
剤、金属活性化剤、オキシメチレン構造を持つ化合物、
スコーチ防止剤、老化防止剤、加工助剤等を配合するこ
とがで籾る。In the present invention, chlorinated ethylene α-
In addition to olefin copolymer rubber, compounding agents known per se, depending on the processability and required performance in manufacturing rubber,
For example, vulcanizing agents, vulcanization aids, rubber reinforcing agents, fillers, softeners, metal activators, compounds with oxymethylene structures,
It can be mixed with anti-scorch agents, anti-aging agents, processing aids, etc.
本発明の組成物の加硫方法としては、トリアジン加硫、
有機過酸化物加硫などが有効である。The method of vulcanizing the composition of the present invention includes triazine vulcanization,
Organic peroxide vulcanization is effective.
トリアジン加硫を行う場合、加硫剤としては下記−数式
（１）で表されるトリアジン化合物が使用される。When performing triazine vulcanization, a triazine compound represented by the following formula (1) is used as a vulcanizing agent.
（式中、Ｒ，は−ＮＲ２Ｒ３，−０Ｒ２または一５Ｒ，
を表し、ここで８２、Ｒ３はそれぞれ水素原子、未置換
もしくは置換アルキル基、または未置換もしくは置換ア
リール基を表すものとする）
このような−数式（１）で表されるトリアジンチオール
類として具体的には、トリアジン−２，４，６−トリチ
オール、２−ジブチルアミノトリアジン−４６ジチオー
ル、２−フェニルアミノトリアジン−４，６−ジチオー
ル、２−へキシルアミノトリアジン−４６−ジチオール
、２−ジエチルアミノトリアジン−４，６−ジチオール
、２−ブトキシトリアジン−４，６−ジチオールなどを
挙げることができる。(In the formula, R is -NR2R3, -0R2 or -5R,
(where 82 and R3 each represent a hydrogen atom, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted aryl group) Specifically, triazine-2,4,6-trithiol, 2-dibutylaminotriazine-46dithiol, 2-phenylaminotriazine-4,6-dithiol, 2-hexylaminotriazine-46-dithiol, 2-diethylaminotriazine Examples include -4,6-dithiol and 2-butoxytriazine-4,6-dithiol.
加硫剤は、塩素化エチレン・α−オレフィン共重合ゴム
１００ｇあたり５．ＯＸ １０−’乃至５．０×１Ｏ−
２モル、好ましくは１．５ ×１０−３乃至２．Ｏ×１
０−２モル、更に好ましくは、３．ＯＸ １０−’乃至
１．３×１０一２モルの割合で配合される。加硫剤の配
合量が上記範囲よりも小さい場合には、好適なゴム弾性
を有する加硫物が得られず、また上記範囲よりも多量に
配合すると伸びが低下し実用に供し難くなる傾向がある
。The vulcanizing agent is 5.5% per 100g of chlorinated ethylene/α-olefin copolymer rubber. OX 10-' to 5.0×1O-
2 mol, preferably 1.5 x 10-3 to 2. O×1
0-2 mol, more preferably 3. It is blended in a proportion of OX 10-' to 1.3 x 10-12 moles. If the blending amount of the vulcanizing agent is smaller than the above range, a vulcanizate with suitable rubber elasticity cannot be obtained, and if it is blended in a larger amount than the above range, the elongation tends to decrease and it becomes difficult to put it into practical use. be.
加硫剤としてトリアジン化合物を使用するとぎは加硫助
剤が添加される。加硫助剤は加硫速度を加工成形上実用
的なものとするために添加される。加硫助剤としては、
酸解離定数（ｐＫａ）が７以上の有機塩基、あるいは有
機塩基を発生しうる化合物が、塩素化エチレン・α−オ
レフィン共重合ゴム１００ｇに対して５ Ｘ １０−４
〜２ Ｘ １０−’モル、好ましくはｌ×１０−’〜ｌ
×１０−”モル、１ｆＩ！単独であるいは２種以上混合
して用いられる。When a triazine compound is used as a vulcanizing agent, a vulcanizing aid is added. The vulcanization aid is added to make the vulcanization rate practical for processing and molding. As a vulcanization aid,
An organic base with an acid dissociation constant (pKa) of 7 or more, or a compound capable of generating an organic base, is added in an amount of 5 x 10-4 per 100 g of chlorinated ethylene/α-olefin copolymer rubber.
~2 x 10-' mol, preferably l x 10-' ~ l
x10-'' mole, 1fI! Can be used alone or in combination of two or more.
これらの加硫助剤としては、１．８−ジアザ−ビシクロ
（５，４，０）−ウンデセン−７、ラウリルアミン、ベ
ンジルアミン、ジベンジルアミン、Ｎ−メチルモルホリ
ン、ジシクロヘキシルアミン、ジブチルジチオカルバミ
ン酸亜鉛、ペンタメチレンジチオカルバミン酸ピペリジ
ン塩、Ｎ−シクロへキシル−２−ベンゾチアゾリルスル
フェンアミド、安息香酸・ジシクロヘキシルアミン塩、
安息香酸・ピペリジン塩、ジペンタメチレンチウラムテ
トラスルフィド、テトラメチルチウラムジスルフィド、
ヨウ化テトラメチルホスホニウム、塩化テトラメチルア
ンモニウム、臭化テトラブチルホスホニウム、臭化テト
ラブチルアンモニウム、ジステアリルジメチルアンモニ
ウムクロライドなどのオニウム塩が例示できる。These vulcanization aids include 1,8-diaza-bicyclo(5,4,0)-undecene-7, laurylamine, benzylamine, dibenzylamine, N-methylmorpholine, dicyclohexylamine, zinc dibutyldithiocarbamate. , pentamethylene dithiocarbamic acid piperidine salt, N-cyclohexyl-2-benzothiazolyl sulfenamide, benzoic acid dicyclohexylamine salt,
Benzoic acid/piperidine salt, dipentamethylenethiuram tetrasulfide, tetramethylthiuram disulfide,
Examples include onium salts such as tetramethylphosphonium iodide, tetramethylammonium chloride, tetrabutylphosphonium bromide, tetrabutylammonium bromide, and distearyldimethylammonium chloride.
有機過酸化物加硫を行う場合、加硫剤としてはジクミル
ペルオキシド、２，５−ジメチル−２，５−ジ（第三ブ
チルペルオキシ）ヘキサン、２．５−ジメチル−２，５
−ジ（ベンゾイルペルオキシ）ヘキサン、２．５−ジメ
チル−２，５−ジ（第三ブチルペルオキシ）ヘキシン−
３、ジ第三ブチルペルオキシド、ジ第三ブヂルベルオキ
シ−３，３，５−トリメチルシクロヘキサン、第三ブチ
ルヒドロペルオキシドを例示できるが、なかでもジクミ
ルペルオキシド、ジ第三ブチルペルオキシド、ジ第三ブ
チルペルオキシ−３゜３．５−トリメチルシクロヘキサ
ンが好ましく使用される。When performing organic peroxide vulcanization, the vulcanizing agent is dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5
-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane-
3. Examples include di-tert-butyl peroxide, di-tert-butylperoxy-3,3,5-trimethylcyclohexane, and tert-butyl hydroperoxide, among which dicumyl peroxide, di-tert-butyl peroxide, and di-tert-butyl peroxide. 3°3.5-trimethylcyclohexane is preferably used.
有機過酸化物の使用量は、塩素化エチレン・α−オレフ
ィン共重合ゴム１００ｇに対して通常５、Ｏｘ １０−
’ 〜５．Ｏｘ １０−’モル、好ましくは１．ＯＸ１
Ｏ−３〜３．０ ×１０−’モルに選ぶ。The amount of organic peroxide used is usually 5, Ox 10- per 100 g of chlorinated ethylene/α-olefin copolymer rubber.
'~5. Ox 10-' mol, preferably 1. OX1
O-3 to 3.0 x 10-' mol.
加硫剤として有機過酸化物を使用するときは、加硫助剤
の併用が好ましい。加硫助剤としては硫黄、ｐ−キノン
ジオキシムなどのキノンジオキシム系、ポリエチレング
リコールジメタクリレートなどのメタクリレート系、ジ
アリルフタレート、トリアリルシアヌレートなどのアリ
ル系、その他マレイミド系、ジビニルベンゼンなどが例
示される。このような加硫助剤は使用する有機過酸化物
１モルに対し局ないし２°モル、好ましくは約等モル使
用する。When using an organic peroxide as a vulcanizing agent, it is preferable to use a vulcanizing aid in combination. Examples of vulcanization aids include sulfur, quinone dioxime types such as p-quinone dioxime, methacrylate types such as polyethylene glycol dimethacrylate, allyl types such as diallyl phthalate and triallyl cyanurate, other maleimide types, and divinylbenzene. be done. Such a vulcanization aid is used in an amount of 1 to 2 mol, preferably about the same mol, per mol of the organic peroxide used.
ゴム用補強剤としては、例えばＳＲＦ、ＧＰＥ、ＦＥＦ
ＭＡＦ、ＨＡＦ、ｌ５ＡＦ、ＳＡＦ、ＦＴ、ＭＴなどの
各種カーボンブラック、微粉けい酸などが適宜用いられ
る。これら補強剤は、塩素化エチレン・α−オレフィン
共重合ゴム１００重量部当り通常３００重量部以下、好
ましくは１５０重量部以下の量で配合される。３００重
量部を上まわるときは、加工性が低下する。Examples of rubber reinforcing agents include SRF, GPE, and FEF.
Various carbon blacks such as MAF, HAF, 15AF, SAF, FT, and MT, finely divided silicic acid, and the like are used as appropriate. These reinforcing agents are generally blended in an amount of 300 parts by weight or less, preferably 150 parts by weight or less, per 100 parts by weight of the chlorinated ethylene/α-olefin copolymer rubber. When it exceeds 300 parts by weight, processability decreases.
充填剤としては、例えば軽質炭酸カルシウム、重質炭酸
カルシウム、タルク、クレーなどが用いられる。また着
色のために無機顔料、有機顔料などが用いられる。これ
らの充填剤及び顔料は、塩素化エチレン・α−オレフィ
ン共重合ゴム１００重量部当り通常３００重量部以下、
好ましくは１５０重量部以下の量で配合される。As the filler, for example, light calcium carbonate, heavy calcium carbonate, talc, clay, etc. are used. Also, inorganic pigments, organic pigments, etc. are used for coloring. These fillers and pigments are usually 300 parts by weight or less per 100 parts by weight of chlorinated ethylene/α-olefin copolymer rubber,
It is preferably blended in an amount of 150 parts by weight or less.
また軟化剤としては、例えばプロセスオイル、潤滑油、
パラフィン、流動パラフィン、石油アスファルト、ワセ
リンなどの石油系物質、コールタール、コールタールピ
ッチなどのコールタール類、ヒマシ油、アマニ油、ナタ
ネ油、大豆油、ヤシ油などの脂肪油、トール油、蜜ロウ
、カルナウバロウ、ラノリンなとのロウ類、リシノール
酸、バルミチン酸、ステアリン酸、ステアリン酸バリウ
ム、ステアリン酸カルシウムなどの脂肪酸またはその金
属塩、石油樹脂、クマロンインデン樹脂、アタクチック
ポリプロピレンなとの合成高分子物質、ジオクチルフタ
レート、ジオクチルアジペート、ジオクチルセパケート
などのエステル系可塑剤、その他マイクロクリスタリン
ワックス、サブ（ファクチス）、液状ポリブタジェン、
変性液状ポリブタジェン、液状チオコール等を挙げるこ
とができる。In addition, as a softening agent, for example, process oil, lubricating oil,
Petroleum-based substances such as paraffin, liquid paraffin, petroleum asphalt, and petrolatum, coal tar such as coal tar and coal tar pitch, fatty oils such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil, tall oil, and honey. Synthesis of waxes such as wax, carnauba wax and lanolin, fatty acids or their metal salts such as ricinoleic acid, valmitic acid, stearic acid, barium stearate, and calcium stearate, petroleum resin, coumaron indene resin, and atactic polypropylene. Molecular substances, ester plasticizers such as dioctyl phthalate, dioctyl adipate, dioctyl sepacate, other microcrystalline waxes, sub(factice), liquid polybutadiene,
Examples include modified liquid polybutadiene and liquid thiocol.
これらの軟化剤は、一般に塩素化エチレン・α−オレフ
ィン共重合ゴム１００重量部当たり２００重量部以下、
好ましくは７０重量部以下の量で適宜配合される。軟化
剤の量が２００重量部を上まわるときは、ゴム弾性、耐
熱性、耐熱老化性が低下し好ましくない。These softeners are generally 200 parts by weight or less per 100 parts by weight of chlorinated ethylene/α-olefin copolymer rubber,
It is preferably blended in an amount of 70 parts by weight or less. When the amount of the softener exceeds 200 parts by weight, the rubber elasticity, heat resistance, and heat aging resistance deteriorate, which is not preferable.
金属活性化剤として、酸化マグネシウム、高級脂肪酸亜
鉛、鉛丹、リサージ、酸化カルシウム等を使用し得る。As a metal activator, magnesium oxide, higher fatty acid zinc, red lead, litharge, calcium oxide, etc. can be used.
これらの金属活性化剤は、塩素化エチレン・α−オレフ
ィン共重合ゴム１００重量部当たり３〜１５重量部、好
ましくは５〜１０重量部の範囲で使用するのがよい。These metal activators are preferably used in an amount of 3 to 15 parts by weight, preferably 5 to 10 parts by weight, per 100 parts by weight of the chlorinated ethylene/α-olefin copolymer rubber.
また、各様なゴム加工工程に対処するためには、オキシ
エチレン構造を持つ化合物の添加およびスコーチ防止剤
の添加が推奨できる。In addition, in order to deal with various rubber processing steps, it is recommended to add compounds having an oxyethylene structure and scorch inhibitors.
オキシエチレン構造を持つ化合物としては、エチレング
リコール、ジエチレングリコール、ポリエチレングリコ
ール、プロピレングリコール、ポリプロピレングリコー
ルなどが例示でき、通常これらは塩素化エチレン・α−
オレフィン共重合ゴム１００重量部に対し０．１〜１０
重量部、好ましくは１〜５重量部用いられる。Examples of compounds with an oxyethylene structure include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, and polypropylene glycol, which are usually chlorinated ethylene/α-
0.1 to 10 per 100 parts by weight of olefin copolymer rubber
Parts by weight are used, preferably 1 to 5 parts by weight.
スコーチ防止剤としては公知のスコーチ防止剤を用いる
ことができ、無水マレイン酸、チオイミド系化合物、ス
ルフェンアミド系化合物、スルホンアミド系化合物など
を例示できる。上記成分は通常塩素化エチレン・α−オ
レフィン共重合ゴム１００重量部に対し０．２〜５重量
部、好ましくは０．３〜３重量部の割合で用いられる。As the scorch inhibitor, a known scorch inhibitor can be used, and examples thereof include maleic anhydride, thioimide compounds, sulfenamide compounds, and sulfonamide compounds. The above components are usually used in an amount of 0.2 to 5 parts by weight, preferably 0.3 to 3 parts by weight, per 100 parts by weight of the chlorinated ethylene/α-olefin copolymer rubber.
また、老化防止剤を使用すれば、本発明の塩素化エチレ
ン・α−オレフィン共重合物組成物製品の材料寿命を長
くすることが可能であることも通常のゴムにおけると同
様である。この場合に使用される老化防止剤としては、
例えばフェニルナフチルアミン、 Ｎ、Ｎ’−ジー２−
ナフチル−ｐ−フェニレンジアミンなどの芳香族第二ア
ミン系、ジブチルヒドロキシトルエン、テトラキス［メ
チレン（３，５−ジ−ｔ−ブチル−４−ヒドロキシ）ヒ
ドロシンナメート］メタンなどのフェノール系安定剤、
ビス［２−メチル−４−（３−ｎ−アルキルチオブロビ
オニルオキシ）−５−ｔ−プチルフェニルコスルフィド
などのチオエーテル系安定剤、ジブチルジチオカルバミ
ン酸ニッケルなどのジチオカルバミン酸塩系安定剤など
が単独あるいは２種以上の併用で配合される。Further, if an anti-aging agent is used, it is possible to extend the material life of the chlorinated ethylene/α-olefin copolymer composition product of the present invention, as in the case of ordinary rubber. Anti-aging agents used in this case include:
For example, phenylnaphthylamine, N,N'-di2-
Aromatic secondary amines such as naphthyl-p-phenylenediamine, phenolic stabilizers such as dibutylhydroxytoluene, tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane,
Thioether stabilizers such as bis[2-methyl-4-(3-n-alkylthiobrobionyloxy)-5-t-butylphenylcosulfide, dithiocarbamate stabilizers such as nickel dibutyldithiocarbamate, etc. are used alone. Alternatively, two or more types may be used in combination.
このような老化防止剤の使用量は塩素化エチレン・α−
オレフィン共重合ゴム１００重量部に対して通常０．１
〜５重量部、好ましくは０．５〜３重量部の割合で選ぶ
。The amount of such anti-aging agent used is chlorinated ethylene/α-
Usually 0.1 per 100 parts by weight of olefin copolymer rubber
-5 parts by weight, preferably 0.5-3 parts by weight.
次に加工助剤としては、通常のゴムの加工に使用される
ものが使用でき、リシノール酸、ステアリン酸、パルミ
チン酸、ラウリン酸、ステアリン酸バリウム、ステアリ
ン酸カルシウム、ステアリン酸亜鉛、上記酸のエステル
類など、高級脂肪酸、その塩およびそのエステル類など
を例示できる。これらの加工助剤は通常の場合には、塩
素化エチレン・α−オレフィン共重合ゴム１００重量部
に対して約１０重量部まで、好ましくは約１〜５重量部
用いられる。Next, as processing aids, those used in normal rubber processing can be used, including ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, calcium stearate, zinc stearate, and esters of the above acids. Examples include higher fatty acids, salts thereof, and esters thereof. These processing aids are usually used in an amount of up to about 10 parts by weight, preferably about 1 to 5 parts by weight, based on 100 parts by weight of the chlorinated ethylene/α-olefin copolymer rubber.
次にゴム配合物は、例えば次のような方法で調製される
。塩素化エチレン・α−オレフィン共ｍ合ゴムおよび補
強剤、充填剤、顔料、軟化剤などの添加剤をバンバリー
ミキサ−などのミキサー類を用いて約８０〜１７０℃の
温度で約３〜１０分間混練した後、加硫剤、加硫助剤を
オーブンロールの如きロール類を用いて追加混合し、ロ
ール温度約４０〜８０℃で約５〜３０分間混練して分出
し、リボン状またはシート状のゴム配合物を調製する。Next, a rubber compound is prepared, for example, by the following method. The chlorinated ethylene/α-olefin co-molar rubber and additives such as reinforcing agents, fillers, pigments, and softeners are mixed at a temperature of about 80 to 170°C for about 3 to 10 minutes using a mixer such as a Banbury mixer. After kneading, a vulcanizing agent and a vulcanizing aid are further mixed using rolls such as an oven roll, and kneaded for about 5 to 30 minutes at a roll temperature of about 40 to 80°C to form a ribbon or sheet. A rubber compound is prepared.
或いは塩素化エチレン・α−オレフィン共重合ゴムおよ
び配合剤を約８０〜１００℃に加熱された押出機に直接
供給し、滞留時間を約０．５〜５分間とることにより、
ベレット状のゴム配合物を調製することもできる。Alternatively, by directly feeding the chlorinated ethylene/α-olefin copolymer rubber and the compounding agent to an extruder heated to about 80 to 100°C and allowing a residence time of about 0.5 to 5 minutes,
It is also possible to prepare rubber compounds in the form of pellets.
このようにして調製された未加硫ゴム配合物は、例えば
、押出成形機、カレンダーロール、プレス成形機などに
より所望の形状に成形され、成形と同時にまたはその成
形品を加硫槽内で、通常的１５０〜２７０℃の温度に約
１〜３０分間加熱する方法により加硫される。The unvulcanized rubber compound thus prepared is molded into a desired shape using, for example, an extrusion molding machine, a calendar roll, a press molding machine, etc., and the molded product is molded simultaneously with the molding or in a vulcanization tank. Vulcanization is typically carried out by heating at a temperature of 150 to 270°C for about 1 to 30 minutes.
加硫槽としては、スチーム加硫かん、熱空気加硫槽、ガ
ラスピーズ流動床、溶融塩加硫槽、マイクロ波加硫禮な
どが単独或いは組合わせて使用される。As the vulcanization tank, a steam vulcanization tank, a hot air vulcanization tank, a glass beads fluidized bed, a molten salt vulcanization tank, a microwave vulcanization tank, etc. are used singly or in combination.
加硫物はそのもの自体でも電気絶縁材、自動車工業部品
、工業用ゴム製品、土木建材用品、ゴム弓布として有用
である。Vulcanized products themselves are useful as electrical insulation materials, automobile industrial parts, industrial rubber products, civil engineering and construction materials, and rubber bow cloth.
電気絶縁材としては、プラグキャップ、イグニッション
キャップ、デイストリビューターキャップなどの自動車
エンジン周辺のキャップ類、コンデンサーキャップ、舶
用電線、自動車用イグニッションケーブルなどの電線の
通電部を円筒状に被覆した絶縁層、ケーブルジヨイント
カバーなどに具体的に使用される。Electrical insulating materials include caps around automobile engines such as plug caps, ignition caps, and distributor caps, capacitor caps, insulating layers that cover current-carrying parts of electric wires such as marine electric wires, and automobile ignition cables in a cylindrical shape. Specifically used for cable joint covers, etc.
自動車工業部品としては、ラジェーターホース、フュー
エルホースなどのホース類、またバンパー、バンパーフ
ィラー、バンパーストリップ、バンパーサイドガード、
オーバーライダー、サイドプロテクションモールなどの
自動車外装部品、各種ウェザ−ストリップ類、ブーツ、
ボールジヨイントシール、各種防振ゴムなどに使用でき
工業用ゴム製品としては、ロール、バッキング、ライニ
ング、ベルトなどに使用できる。Automotive industry parts include hoses such as radiator hoses and fuel hoses, as well as bumpers, bumper fillers, bumper strips, bumper side guards,
Automotive exterior parts such as overriders and side protection moldings, various weather strips, boots,
It can be used for ball joint seals, various anti-vibration rubbers, and other industrial rubber products such as rolls, backings, linings, and belts.
また土木建材用としてはルーフィングシート、耐熱ベル
ト、建築用ガスケット、ハイウェイジヨイントシールな
どに使用される。It is also used for civil engineering and construction materials such as roofing sheets, heat-resistant belts, construction gaskets, and highway joint seals.
ゴム引布としては、防水布、天幕、レジャーシートなど
に使用される。Rubberized fabrics are used for waterproof fabrics, awnings, leisure sheets, etc.
更に、加硫に先立ってゴム配合物中に発泡剤および必要
に応じて発泡助剤を配合し、断熱材、クツション材、シ
ーリング材、防音材、電気絶縁材などに使用し得る発泡
加硫物とすることもできる。Furthermore, a foaming agent and, if necessary, a foaming aid are added to the rubber compound prior to vulcanization to create a foamed vulcanizate that can be used for insulation materials, cushioning materials, sealing materials, soundproofing materials, electrical insulation materials, etc. It is also possible to do this.
発泡剤としては、例えば炭酸水素ナトリウム、炭酸ナト
リウム、炭酸水素アンモニウム、炭素アンモニウム、亜
硝酸アンモニウムなどの無機発泡剤、Ｎ、Ｎ“−ジメチ
ル−Ｎ、Ｎ−ジニトロソテレフタルアミド、Ｎ−Ｎ“−
ジニトロソペンタメチレンテトラミンなどのニトロソ化
合物：アゾジカルボンアミド、アゾビスイソブチロニト
リル、アゾシクロヘキシルニトリル、アゾジアミノベン
ゼン、バリウムアゾジカルボキシレートなどのアゾ化合
物：ベンゼンスルホニルヒドラジド、トルエンスルホニ
ルヒドラジド、ｐ、ｐ’−オキシビス（ベンゼンスルホ
ニルヒドラジド）、ジフェニルスルホン−３，３°−ジ
スルホニルヒドラジドなどのスルホニルヒドラジド化合
物；カルシウムアジド、４．４°−ジフェニルジスルホ
ニルアジド、ｐ−トルエンスルホニルアジドなどのアジ
ド化合物が挙げられ、特にニトロソ化合物、アゾ化合物
およびアジド化合物が好んで使用される。Examples of the blowing agent include inorganic blowing agents such as sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate, ammonium carbon, ammonium nitrite, N, N"-dimethyl-N, N-dinitrosoterephthalamide, N-N"-
Nitroso compounds such as dinitrosopentamethylenetetramine: Azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate: benzenesulfonyl hydrazide, toluenesulfonylhydrazide, p, p Examples include sulfonyl hydrazide compounds such as '-oxybis(benzenesulfonylhydrazide) and diphenylsulfone-3,3°-disulfonylhydrazide; azide compounds such as calcium azide, 4.4°-diphenyldisulfonyl azide, and p-toluenesulfonyl azide. Among them, nitroso compounds, azo compounds and azide compounds are particularly preferred.
これらの発泡剤は、塩素化エチレン・α−オレフィン共
重合ゴム１００重量部当り通常約０．５〜３０重量部、
好ましくは約１〜２０重量部の割合で配合され、一般に
見掛比重的０．０３〜０７程度の発泡体を形成させる。These blowing agents are usually about 0.5 to 30 parts by weight per 100 parts by weight of chlorinated ethylene/α-olefin copolymer rubber,
It is preferably blended in an amount of about 1 to 20 parts by weight, and generally forms a foam having an apparent specific gravity of about 0.03 to 0.7.
発泡剤と共に使用することもでする発泡助剤としては、
サリチル酸、フタル酸、ステアリン酸などの有機酸ある
いは尿素またはその誘導体などが使用され、発泡剤の分
解温度の低下、分解促進、気泡の均一化などの動きを示
す。Foaming aids that can also be used with blowing agents include:
Organic acids such as salicylic acid, phthalic acid, and stearic acid, or urea or its derivatives are used, and exhibit actions such as lowering the decomposition temperature of the blowing agent, accelerating decomposition, and making bubbles uniform.
［発明の作用効果］
本発明の塩素化エチレン・α−オレフィン共重合ゴムと
その組成物における塩素化エチレン・α−オレフィン共
重合ゴムは、前記した通り塩素含量が２０〜４０重量％
であること、結合塩素のうち一級炭素に結合した塩素が
該共重合ゴムを基準にして０．６重量％以上であり三級
炭素に結合した塩素が１６重量％以下であること、ムー
ニー粘度［ＭＬｌ＃４（１２１℃）］が１０〜１９０で
あることが特徴である。[Operations and Effects of the Invention] As described above, the chlorinated ethylene/α-olefin copolymer rubber in the chlorinated ethylene/α-olefin copolymer rubber of the present invention and its composition has a chlorine content of 20 to 40% by weight.
of the combined chlorine, the amount of chlorine bonded to primary carbon is 0.6% by weight or more based on the copolymer rubber, and the amount of chlorine bonded to tertiary carbon is not more than 16% by weight, Mooney viscosity [ MLl#4 (121°C)] is 10 to 190.
塩素含量が２０〜４０重量％であることが耐オゾン性、
耐熱性、耐油性、難燃性、接着性、ゴム弾性等において
バランスのとれた良好な性状を与えている。塩素含量が
上記範囲より小さいと塩素化により期待できる耐油性、
難燃性、接着性等の効果が十分発揮できなくなり、上記
範囲より大艶くなるとムーニー粘度が余りに大きい場合
と同様に溶融流動性が低下し成形性、加工性が悪くなる
。Ozone resistance is achieved by having a chlorine content of 20 to 40% by weight.
It provides well-balanced properties in terms of heat resistance, oil resistance, flame retardancy, adhesiveness, rubber elasticity, etc. If the chlorine content is lower than the above range, the oil resistance that can be expected due to chlorination,
Effects such as flame retardancy and adhesion cannot be sufficiently exhibited, and when the gloss becomes greater than the above range, melt flowability decreases and moldability and processability deteriorate, as in the case where the Mooney viscosity is too high.
結合塩素のうち、−級炭素に結合した塩素が０．６重量
％以上であり、三級炭素に結合した塩素が１．６重量％
以上であることが本発明の塩素化エチレン・α−オレフ
ィン共重合ゴムの最大の特徴であるが、この特徴が加硫
速度を早くし、且つ熱安定性、加硫ゴムの耐熱老化性を
著しく向上させている。−級炭素に結合した塩素が０．
６重量％未満、あまりに少ないと加硫が遅くなり実用に
適さなくなり、また三級炭素に結合した塩素が１．６
Ｊｉ量％をこえる、即ちあまりに多いと耐熱安定性、加
硫ゴムの耐熱老化性が低下する。Of the combined chlorine, the amount of chlorine bonded to -class carbon is 0.6% by weight or more, and the amount of chlorine bonded to tertiary carbon is 1.6% by weight.
The above is the greatest feature of the chlorinated ethylene/α-olefin copolymer rubber of the present invention, and this feature increases the vulcanization rate and significantly improves the thermal stability and heat aging resistance of the vulcanized rubber. Improving. The amount of chlorine bonded to -class carbon is 0.
Less than 6% by weight. If the amount is too low, vulcanization will slow down and become unsuitable for practical use, and chlorine bonded to tertiary carbon will
If the amount of Ji exceeds %, that is, if it is too large, the heat resistance stability and heat aging resistance of the vulcanized rubber will decrease.
ムーニー粘度［ＭＬｌ−４（１２１℃）］が１０〜１９
０であることが、バランスのとれた良好な物性で、成形
性、加工性を良好にしている。ムーニー粘度が上記範囲
より小さい場合には、ゴムの強度が十分でなく、一方大
きい場合には、溶融流動性が低下し成形性、加工性が悪
化し、また他のゴムや樹脂との混和性が低下する。Mooney viscosity [MLl-4 (121°C)] is 10 to 19
A value of 0 means good, well-balanced physical properties, and good moldability and workability. If the Mooney viscosity is smaller than the above range, the strength of the rubber will not be sufficient, while if it is larger, the melt fluidity will decrease, moldability and processability will deteriorate, and miscibility with other rubbers and resins will deteriorate. decreases.
本発明の塩素化エチレン・α−オレフィン共重合ゴムは
、トリアジン加硫、有機過酸化物加硫が有効であり、加
硫ゴム組成物は、塩素化エチレン・α−オレフィン共重
合ゴム１００重量部当り、３００重量部までの補強剤、
２００重量部までの軟化剤、及び該共重合ゴム１００ｇ
当り５、Ｏ×１０−’乃至５．Ｏｘ １０−’モルの割
合に相当する重量部の加硫剤を配合した組成物を特徴と
することによって、加硫が速く、加工性、熱安定性に優
れ、加硫ゴム物性の強度、ゴム弾性が良好であり、特に
耐熱老化性、耐候性、耐久性に優れたゴム製品を得るこ
とができる。Triazine vulcanization and organic peroxide vulcanization are effective for the chlorinated ethylene/α-olefin copolymer rubber of the present invention, and the vulcanized rubber composition contains 100 parts by weight of the chlorinated ethylene/α-olefin copolymer rubber. up to 300 parts by weight of reinforcing agent,
Up to 200 parts by weight of softener and 100 g of the copolymer rubber
5 per hit, O x 10-' to 5. The composition is characterized by containing a part by weight of a vulcanizing agent corresponding to a proportion of 10-' moles of Ox, and as a result, vulcanization is fast, processability and thermal stability are excellent, and the strength of the physical properties of the vulcanized rubber is improved. It is possible to obtain a rubber product that has good elasticity and is particularly excellent in heat aging resistance, weather resistance, and durability.
本発明における塩素化エチレン・α−オレフィン共重合
物とその組成物は、上述のように優れた効果を有し、耐
オゾン性、耐熱性、耐候性、耐薬品性、耐油性、難燃性
、耐寒性、明色性、耐退色性等に優れているところから
、前記したように、電気絶縁材、自動車工業部品、工業
用ゴム製品、土木建材用品、ゴム引布その他に有効に使
用することができる。The chlorinated ethylene/α-olefin copolymer and its composition in the present invention have excellent effects as described above, and have ozone resistance, heat resistance, weather resistance, chemical resistance, oil resistance, and flame retardancy. As mentioned above, it is effectively used in electrical insulation materials, automobile industrial parts, industrial rubber products, civil engineering and construction materials, rubberized fabrics, etc. due to its excellent cold resistance, brightness, and fading resistance. be able to.
［実施例］ 次に実施例に基づいて本発明を説明する。[Example] Next, the present invention will be explained based on examples.
実施例 １
エチレン・１−ブテン共重合ゴムを公知の方法で重合し
た。この共重合ゴムの組成を１３Ｃ−ＮＭＲで測定した
ところエチレン単位と１−ブテン単位のモル比が９０７
１０であった０次に１３５℃のデカリン中で極限粘度［
η］を測定した。［η］は１．５であった。Example 1 Ethylene/1-butene copolymer rubber was polymerized by a known method. The composition of this copolymer rubber was measured by 13C-NMR, and the molar ratio of ethylene units to 1-butene units was 907.
The intrinsic viscosity [
η] was measured. [η] was 1.5.
この共重合ゴム３００ｇと有機過酸化物であるバーブチ
ル０１．ｌ１ｍ ｍｏｌを５１のクロロホルムに溶解し
、攪拌機、温度計を備えたオートクレーブに該溶液を入
れた０反応液を７０℃に保ちながら反応器内へ塩素ガス
を２８／ｗｉｎ、の割合で導入し、３時間反応を行った
。その後、窒素ガスを反応器へ通じて、系中に残った塩
素ガス、塩化水素を除去した。次に、これをエバポレー
ターで濃縮し、更に５０℃の真空乾燥機で４８時間減圧
乾燥し、十分脱溶媒した。300 g of this copolymer rubber and 01.0 g of barbutyl, an organic peroxide. 1 mmol was dissolved in 51 chloroform, and the solution was placed in an autoclave equipped with a stirrer and a thermometer.While maintaining the reaction solution at 70°C, chlorine gas was introduced into the reactor at a rate of 28/win. The reaction was carried out for 3 hours. Thereafter, nitrogen gas was passed through the reactor to remove chlorine gas and hydrogen chloride remaining in the system. Next, this was concentrated using an evaporator and further dried under reduced pressure in a vacuum dryer at 50° C. for 48 hours to thoroughly remove the solvent.
製造した塩素化エチレン・α−オレフィン共重合ゴムの
性状を次のようにして測定した。The properties of the produced chlorinated ethylene/α-olefin copolymer rubber were measured as follows.
ムーニー粘度 ＭＬ１＋、（１２１℃）ＪＩＳ Ｋ６
３００に：従い、島原製作所製ＭＳＶ−２００型ムーニ
ー粘度計を用いて測定した。Mooney viscosity ML1+, (121℃) JIS K6
300: Accordingly, it was measured using a Mooney viscometer MSV-200 manufactured by Shimabara Seisakusho.
塩素含量 ボンベ燃焼法により測定した。Chlorine content Measured by cylinder combustion method.
結合塩素の分布
０．１ ｇの塩素化エチレン・α−オレフィン共重合ゴ
ムを５１の無水テトラヒドロフランに溶かし、１１００
ＩＩ１のリチウムアルミニウムデュウテライドを加え、
オートクレーブに入れ１００℃に保温し３週間放置した
。この、反応液を希塩酸で処理し、ベンゼンでポリマー
分を抽出し、硫酸マグネシウムで乾燥、ろ過し、真空乾
燥機で脱溶媒した。このポリマーを１３Ｃ−ＮＭＲで測
定し結合塩素の分布を定量した。Distribution of combined chlorine Dissolve 0.1 g of chlorinated ethylene/α-olefin copolymer rubber in 51% anhydrous tetrahydrofuran,
Add II1 lithium aluminum deuteride,
It was placed in an autoclave and kept at 100°C for 3 weeks. This reaction solution was treated with dilute hydrochloric acid, the polymer component was extracted with benzene, dried over magnesium sulfate, filtered, and the solvent was removed using a vacuum dryer. This polymer was measured by 13C-NMR to quantify the distribution of bound chlorine.
熱安定性
島原製作所製熱分析装置を用いて、加熱減量開始温度を
求めた。試験条件は、空気雰囲気中で、昇温速度は３０
℃／分であった。Thermal stability The heating loss start temperature was determined using a thermal analyzer manufactured by Shimabara Seisakusho. The test conditions were an air atmosphere and a temperature increase rate of 30
°C/min.
次に、以下の手順で配合ゴム、加硫ゴムを作製し試験に
供した。先ず、８インチオーブンロール（日豊ロール社
製）を使用して、表１に示す処方で配合物を作製した。Next, a compounded rubber and a vulcanized rubber were prepared according to the following procedure and subjected to a test. First, a formulation was prepared using an 8-inch oven roll (manufactured by Nippo Roll Co., Ltd.) according to the formulation shown in Table 1.
混練に要した時間は１５分間であった。The time required for kneading was 15 minutes.
表 １
配合物
重量部
口高品名 協和マグ１５０ ［協和化学社製］２）商品
名 ジースト ＳＯ［東海カーボン社製］３′商品名
サンセン４２４０
［日本サンオイル製］
４）ジブチルアミノトリアジン２．４−ジチオール［三
協化成社製］
この配合物を厚さ５簡■で分出しした。この分出しシー
トを用いてＪＩＳ Ｋ６３００に従って、加硫速度の
指標であるムーニースコーチ時間（ｔｓ）を求めた。続
いて、この分出しシートからプレス成形機（コータキ社
製ゴム用１５０ｔブレス成形機）を使用して、２ｍｍの
加硫シートを作成した。プレス条件は、１６０℃で２０
分間であった。加硫シートについて、ＪＩＳ Ｋ６３
０１に従って、スプリング式硬さ（Ａ形） （ＨｓＪ
Ｉ ＳＡ）、引張強さ（ＴＢ）、伸び（ＥＢ）、及び永
久伸び（ｐｓ）を測定した。Table 1 Compound weight part name Product name Kyowa Mag 150 [manufactured by Kyowa Kagaku Co., Ltd.] 2) Product name Geast SO [manufactured by Tokai Carbon Co., Ltd.] 3' Product name
Sansen 4240 [manufactured by Nippon Sunoil] 4) Dibutylaminotriazine 2,4-dithiol [manufactured by Sankyo Kasei Co., Ltd.] This blend was divided into 5-inch thick pieces. Mooney scorch time (ts), which is an index of vulcanization rate, was determined using this dispensing sheet according to JIS K6300. Subsequently, a 2 mm vulcanized sheet was created from this dispensed sheet using a press molding machine (150 t press molding machine for rubber manufactured by Kotaki Co., Ltd.). Pressing conditions were 160℃ and 20℃.
It was a minute. Regarding vulcanized sheets, JIS K63
According to 01, spring type hardness (A type) (HsJ
ISA), tensile strength (TB), elongation (EB), and permanent elongation (ps) were measured.
更に、加硫シート試験片を１５０℃のエアーオーブン中
で７０時間放置した後、引張強さの保持率（ＡＲ（ＴＢ
））及び伸びの保持率（ＡＲ（ＥＢ））をＪＩＳ Ｋ
６３０１に従って測定した。Furthermore, after leaving the vulcanized sheet test piece in an air oven at 150°C for 70 hours, the tensile strength retention rate (AR (TB
)) and elongation retention rate (AR(EB)) according to JIS K
Measured according to 6301.
これらの結果を表２に示す。These results are shown in Table 2.
実施例 ２
実施例１で原料となるエチレン・ｌ−ブテン共重合ゴム
の代わりに下記のエチレン・ｌ−ブテン共重合ゴムを用
いた以外は、実施例１と同様に行った。Example 2 The same procedure as in Example 1 was conducted except that the following ethylene/l-butene copolymer rubber was used instead of the ethylene/l-butene copolymer rubber used as the raw material in Example 1.
エチレン単位／ｌ−ブテン単位（モル比） ８７／１３
極限粘度 ［η］１．６
結果は表２に示す。Ethylene unit/l-butene unit (molar ratio) 87/13
Intrinsic viscosity [η] 1.6 The results are shown in Table 2.
実施例 ３
実施例１で原料となるエチレン・ｌ−ブテン共重合ゴム
の代わりに下記のエチレン・ｌ−ブテン共重合ゴムを用
いた以外は、実施例１と同様に行った。Example 3 The same procedure as in Example 1 was conducted except that the following ethylene/l-butene copolymer rubber was used instead of the ethylene/l-butene copolymer rubber used as the raw material in Example 1.
エチレン単位／ｌ−ブテン隼位（そル比） ９３／７極
限粘度 ［η］１．５
結果は表２に示す。Ethylene unit/l-butene ratio (sol ratio) 93/7 Intrinsic viscosity [η] 1.5 The results are shown in Table 2.
実施例 ４
実施例１で、塩素化反応時間を３時間２５分とした以外
は実施例１と同様に行った。Example 4 The same procedure as in Example 1 was conducted except that the chlorination reaction time was changed to 3 hours and 25 minutes.
結果は、表２に示す。The results are shown in Table 2.
実施例 ５
実施例１で、塩素化反応時間を２時間４０分とした以外
は実施例１と同様に行った。Example 5 The same procedure as in Example 1 was conducted except that the chlorination reaction time was changed to 2 hours and 40 minutes.
結果は、表２に示す。The results are shown in Table 2.
実施例 ６
実施例１で原料となるエチレン・ｌ−ブテン共重合ゴム
の代わりに下記のエチレン・ｌ−ブテン共重合ゴムを用
いた以外は、実施例２と同様に行った。Example 6 The same procedure as in Example 2 was carried out except that the following ethylene/l-butene copolymer rubber was used instead of the ethylene/l-butene copolymer rubber used as the raw material in Example 1.
エチレン単位／１−ブテン阜位（モル比） ９０／１０
極限粘度 ［η］２．３
結果は表２に示す。Ethylene unit/1-butene position (mole ratio) 90/10
Intrinsic viscosity [η]2.3 The results are shown in Table 2.
実施例 フ
実施例１で原料となるエチレン・１−ブテン共重合ゴム
の代わりに下記のエチレン・１−ヘキセン共重合ゴムを
用いた以外は、実施例１と同様に行った。Example F The same procedure as in Example 1 was carried out except that the following ethylene/1-hexene copolymer rubber was used instead of the ethylene/1-butene copolymer rubber used as the raw material.
エチレン単位／１−ヘキセン単位（モル比）０７１０ 極限粘度 ［η］１．９ 結果は表２に示す。Ethylene unit/1-hexene unit (molar ratio) 0710 Intrinsic viscosity [η] 1.9 The results are shown in Table 2.
比較例 １
実施例１で原料となるエチレン・ｌ−ブテン共重合ゴム
の代わりに下記に示すエチレン・プロピレン共重合ゴム
を用いた以外は、実施例１と同様に行った。Comparative Example 1 The same procedure as in Example 1 was conducted except that the ethylene/propylene copolymer rubber shown below was used instead of the ethylene/l-butene copolymer rubber used as the raw material in Example 1.
エチレン単位／プロピレン単位（モル比）０７３０ 極限粘度 ［η］１．７ 結果は表２に示す。Ethylene unit/propylene unit (molar ratio) 0730 Intrinsic viscosity [η] 1.7 The results are shown in Table 2.
比較例 ２
実施例１で原料となるエチレン・ｌ−ブテン共重合ゴム
の代わりに下記に示すエチレン・プロピレン・非共役ジ
エン共重合ゴムを用いた以外は、実施例１と同様に行っ
た。Comparative Example 2 The same procedure as in Example 1 was conducted except that the ethylene/propylene/non-conjugated diene copolymer rubber shown below was used instead of the ethylene/l-butene copolymer rubber used as the raw material in Example 1.
エチレン単位／プロピレン単位（モル比）７０／３０ 極限粘度 ［η］２．２ 非共役ジエンの種類 ５−エチリデン ２−ノルボルネン ヨウ素価 ｌＯ 結果は表２に示す。Ethylene unit/propylene unit (mole ratio) 70/30 Intrinsic viscosity [η]2.2 Type of non-conjugated diene 5-ethylidene 2-Norbornene Iodine value lO The results are shown in Table 2.
比較例 ３
実施例１で原料となるエチレン・ｌ−ブテン共重合ゴム
の代わりに下記に示すポリエチレンを用いた以外は、実
施例１と同様に行った。Comparative Example 3 The same procedure as in Example 1 was conducted except that polyethylene shown below was used instead of the ethylene/l-butene copolymer rubber used as the raw material in Example 1.
比重 ０．９７ 極限粘度 ［η］１．４ 結果は表２に示す。Specific gravity 0.97 Intrinsic viscosity [η] 1.4 The results are shown in Table 2.
実施例 ８
実施例１で反応溶媒を四塩化炭素とした以外は、実施例
１と同様に行った。Example 8 The same procedure as in Example 1 was conducted except that carbon tetrachloride was used as the reaction solvent.
結果は、表２に示す。The results are shown in Table 2.
実施例 ９
実施例１で反応溶媒をクロルベンゼンとした以外は、実
施例１と同様に行った。Example 9 The same procedure as in Example 1 was carried out except that chlorobenzene was used as the reaction solvent.
結果は、表２に示す。The results are shown in Table 2.
比較例 ４
実施例１で、反応溶媒をｔｅｒｔ−ブチルベンゼンとし
、反応時間を３時間１０分とした以外は実施例１と同様
に行った。Comparative Example 4 The same procedure as in Example 1 was conducted except that the reaction solvent was tert-butylbenzene and the reaction time was 3 hours and 10 minutes.
結果は、表２に示す。The results are shown in Table 2.
実施例 １０
実施例１で反応温度を２５℃とし有機過酸化物のかわり
に２０Ｗ畳色光蛍光灯を照射し、反応時間を３時間３０
分とした以外は、実施例１と同様に行った。Example 10 The reaction temperature was changed to 25°C in Example 1, 20W tatami color fluorescent lamp was irradiated instead of the organic peroxide, and the reaction time was 3 hours and 30 minutes.
The same procedure as in Example 1 was carried out except that the sample was divided into minutes.
結果は、表２に示す。The results are shown in Table 2.
実施例 １１
実施例８で反応温度を１００℃とし有機過酸化物として
パーブチルＬを１．３ｍ ｍｏｌ用いた以外は、実施例
８と同様に行った。Example 11 The same procedure as in Example 8 was conducted except that the reaction temperature was 100° C. and 1.3 mmol of Perbutyl L was used as the organic peroxide.
結果は、表２に示す。The results are shown in Table 2.
比較例 ５
実施例１で反応溶媒をクロルベンゼンとし、１００ｇの
共重合ゴムを５Ｊ２の溶媒に溶解し、反応温度を２５℃
とし、有機過酸化物のかわりに２０Ｗ昼色光蛍光灯を照
射し、反応時間を３時間３０分とした以外は、実施例１
と同様に行った。Comparative Example 5 In Example 1, the reaction solvent was chlorobenzene, 100 g of copolymer rubber was dissolved in 5J2 solvent, and the reaction temperature was 25°C.
Example 1 except that a 20W daylight fluorescent lamp was used instead of the organic peroxide and the reaction time was 3 hours and 30 minutes.
I did the same thing.
結果は、表２に示す。The results are shown in Table 2.
表２に示す結果から明らかなように本発明の実施例では
、塩素化エチレン・α−オレフィン共重合ゴムは、ムー
ニー粘度ＭＬ、□（１２１℃）が３１〜１２８で１０〜
１９０の範囲内にあり、塩素含量が２５〜３５重量％で
２０〜４０重量％の範囲内にあり、結合塩素の分布にお
ける１級炭素結合塩素が０．７〜１．４重量％で０．６
重量％以上であり３級炭素結合塩素が０．６〜１．４重
量％で１．６重量％以下である。そして実施例は、いづ
れも熱安定性に優れ、また加硫速度が速（加工性に優れ
、更に加硫ゴム物性の常態、耐熱老化性においても優れ
た結果が得られている。As is clear from the results shown in Table 2, in the examples of the present invention, the chlorinated ethylene/α-olefin copolymer rubber had a Mooney viscosity ML, □ (121°C) of 31 to 128, and 10 to 10.
190, the chlorine content is in the range of 25 to 35% by weight and 20 to 40% by weight, and the primary carbon bonded chlorine in the bonded chlorine distribution is 0.7 to 1.4% by weight and 0. 6
% by weight or more, and tertiary carbon-bonded chlorine is 0.6 to 1.4 weight % and 1.6 weight % or less. All of the examples have excellent thermal stability, a fast vulcanization rate (excellent workability), and excellent results in the normal physical properties of the vulcanized rubber and heat aging resistance.
これに対し比較例１及び２では、塩素化エチレン・α−
オレフィン共重合ゴムは、ムーニー粘度と塩素含量は実
施例と同様の範囲内にあり、結合塩素の分布における１
級炭素結合塩素も実施例と同様０．６重量％以上である
が３級炭素結合塩素が２、１．２．２重量％と１．６重
量％をこえている。そのため、加硫速さは実施例と同様
でも、熱安定性が低下し、加硫ゴム物性において強度が
劣り、また耐熱老化性の低下が著しい。On the other hand, in Comparative Examples 1 and 2, chlorinated ethylene・α-
The Mooney viscosity and chlorine content of the olefin copolymer rubber are within the same range as in the examples, and the olefin copolymer rubber has a
The amount of chlorine bonded to class carbon is 0.6% by weight or more as in the example, but the amount of chlorine bonded to tertiary carbon is 2, 1.2.2% by weight, which exceeds 1.6% by weight. Therefore, even though the vulcanization rate is the same as in the examples, the thermal stability is lower, the physical properties of the vulcanized rubber are poorer in strength, and the heat aging resistance is significantly lower.
比較例３の塩素化ポリエチレンでは、結合塩素の分布は
１級炭素結合塩素及び３級炭素結合塩素共に０．１重量
％以下であり、熱安定性は良いが加硫速度が極端に遅く
加工性に劣り、加硫ゴム物性においても引張強度が劣り
永久伸びが大でゴム弾性に劣っている。比較例４及び５
の塩素化エチレン・ａ−オレフィン共重合ゴムは、結合
塩素の分布の１級炭素結合塩素が０．３重量％で０．６
重量％未満であり３級炭素結合塩素が２．０及び２．１
重量％で１．６重量％をこえており、加硫速度が遅くな
り熱安定性が低下し、加硫ゴム物性においても耐熱老化
性が著しく低下していることが理解される。In the chlorinated polyethylene of Comparative Example 3, the distribution of combined chlorine is 0.1% by weight or less for both primary carbon-bonded chlorine and tertiary carbon-bonded chlorine, and although the thermal stability is good, the vulcanization rate is extremely slow and processability is poor. In terms of physical properties of vulcanized rubber, it has poor tensile strength, high permanent elongation, and poor rubber elasticity. Comparative examples 4 and 5
The chlorinated ethylene/a-olefin copolymer rubber has a bonded chlorine distribution of 0.3% by weight of primary carbon bonded chlorine and 0.6% by weight.
Less than 2.0 and 2.1% by weight of tertiary carbon-bonded chlorine
It is understood that the vulcanization rate exceeds 1.6% by weight, the vulcanization rate slows down, the thermal stability decreases, and the heat aging resistance of the vulcanized rubber is significantly decreased.
Claims (4)
って、塩素含量が２０〜４０重量％、結合塩素のうち一
級の炭素に結合した塩素が塩素化エチレン・α−オレフ
ィン共重合ゴムを基準にして０．６重量％以上、三級の
炭素に結合した塩素が１．６重量％以下であり、ムーニ
ー粘度［ＭＬ＿１＿＋＿４（１２１℃）］が１０〜１９
０であることを特徴とした塩素化エチレン・α−オレフ
ィン共重合ゴム。(1) Chlorinated ethylene/α-olefin copolymer rubber with a chlorine content of 20 to 40% by weight, with chlorine bonded to primary carbon among the combined chlorine based on chlorinated ethylene/α-olefin copolymer rubber 0.6% by weight or more, 1.6% by weight or less of chlorine bonded to tertiary carbon, and Mooney viscosity [ML_1_+_4 (121°C)] of 10 to 19
A chlorinated ethylene/α-olefin copolymer rubber characterized by having a
のエチレン単位とα−オレフィン単位との組成比がモル
基準で８５／１５乃至９５／５であることを特徴とする
請求項１記載の塩素化エチレン・α−オレフィン共重合
ゴム。(2) The composition of claim 1, wherein the composition ratio of ethylene units and α-olefin units in the ethylene/α-olefin copolymer rubber before chlorination is from 85/15 to 95/5 on a molar basis. Chlorinated ethylene/α-olefin copolymer rubber.
を特徴とする請求項１記載の塩素化エチレン・α−オレ
フィン共重合ゴム。(3) The chlorinated ethylene/α-olefin copolymer rubber according to claim 1, wherein the α-olefin has 3 to 20 carbon atoms.
共重合ゴム１００重量部に対し（ａ）３００重量部まで
の補強剤（ｂ）２００重量部までの軟化剤、及び（ｃ）
該共重合ゴム１００ｇ当り５．０×１０＾−＾４乃至５
．０×１０＾−＾２モルの割合に相当する重量部の加硫
剤を配合してなる組成物。(4) Based on 100 parts by weight of the chlorinated ethylene/α-olefin copolymer rubber according to claim 1, (a) up to 300 parts by weight of a reinforcing agent, (b) up to 200 parts by weight of a softener, and (c)
5.0 x 10^-^4 to 5 per 100g of the copolymer rubber
．． A composition containing part by weight of a vulcanizing agent corresponding to a ratio of 0x10^-^2 moles.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9939290A JP2904861B2 (en) | 1990-04-17 | 1990-04-17 | Chlorinated ethylene / α-olefin copolymer rubber and composition thereof |
| CA002040570A CA2040570A1 (en) | 1990-04-17 | 1991-04-16 | Chlorinated ethylene-.alpha.-olefin copolymer rubber and composition thereof |
| KR1019910006163A KR930011665B1 (en) | 1990-04-17 | 1991-04-17 | Chlorinated ethylene-alpha-olefin copolymer rubber and composition thereof |
| DE69112689T DE69112689T2 (en) | 1990-04-17 | 1991-04-17 | Ethylene-alpha-olefin elastomer and its composition. |
| EP91303422A EP0453262B1 (en) | 1990-04-17 | 1991-04-17 | Chlorinated ethylene-alpha-olefin copolymer rubber and composition thereof |
| US07/686,381 US5206305A (en) | 1990-04-17 | 1991-04-17 | Chlorinated ethylene-alpha-olefin copolymer rubber and composition thereof |
| AT91303422T ATE127502T1 (en) | 1990-04-17 | 1991-04-17 | ETHYLENE-ALPHA-OLEFIN ELASTOMER AND COMPOSITION MADE THEREFROM. |
| US07/957,864 US5237010A (en) | 1990-04-17 | 1992-10-08 | Chlorinated ethylene-α-olefin copolymer rubber and composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9939290A JP2904861B2 (en) | 1990-04-17 | 1990-04-17 | Chlorinated ethylene / α-olefin copolymer rubber and composition thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03296506A true JPH03296506A (en) | 1991-12-27 |
| JP2904861B2 JP2904861B2 (en) | 1999-06-14 |
Family
ID=14246227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9939290A Expired - Fee Related JP2904861B2 (en) | 1990-04-17 | 1990-04-17 | Chlorinated ethylene / α-olefin copolymer rubber and composition thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2904861B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004506803A (en) * | 2000-08-18 | 2004-03-04 | デュポン ダウ エラストマーズ エルエルシー | Curable composition of chlorinated polyolefin elastomer |
-
1990
- 1990-04-17 JP JP9939290A patent/JP2904861B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004506803A (en) * | 2000-08-18 | 2004-03-04 | デュポン ダウ エラストマーズ エルエルシー | Curable composition of chlorinated polyolefin elastomer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2904861B2 (en) | 1999-06-14 |
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