JPH0494930A - Rubber laminate - Google Patents
Rubber laminateInfo
- Publication number
- JPH0494930A JPH0494930A JP21392490A JP21392490A JPH0494930A JP H0494930 A JPH0494930 A JP H0494930A JP 21392490 A JP21392490 A JP 21392490A JP 21392490 A JP21392490 A JP 21392490A JP H0494930 A JPH0494930 A JP H0494930A
- Authority
- JP
- Japan
- Prior art keywords
- fluororubber
- nbr
- rubber
- laminate
- blended
- 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
- 229920001971 elastomer Polymers 0.000 title claims abstract description 29
- 239000005060 rubber Substances 0.000 title claims abstract description 29
- 229920001973 fluoroelastomer Polymers 0.000 claims abstract description 51
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 43
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 14
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 8
- 150000001993 dienes Chemical class 0.000 claims abstract description 7
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 6
- 235000019795 sodium metasilicate Nutrition 0.000 claims abstract description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000292 calcium oxide Substances 0.000 claims abstract description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 4
- 238000004073 vulcanization Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000004711 α-olefin Substances 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005977 Ethylene Substances 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003377 acid catalyst Substances 0.000 abstract description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 3
- 239000003513 alkali Substances 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 238000010030 laminating Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 239000000853 adhesive Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 13
- 230000032683 aging Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000013329 compounding Methods 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920002943 EPDM rubber Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 241000918728 Monotes Species 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 238000010059 sulfur vulcanization Methods 0.000 description 3
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 2
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical compound CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical compound FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 description 1
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical compound FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 description 1
- SKVZFDZSXCKKHQ-UHFFFAOYSA-N 1,1-difluoroethene;prop-1-ene Chemical group CC=C.FC(F)=C SKVZFDZSXCKKHQ-UHFFFAOYSA-N 0.000 description 1
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- PMAAOHONJPSASX-UHFFFAOYSA-N 2-butylperoxypropan-2-ylbenzene Chemical compound CCCCOOC(C)(C)C1=CC=CC=C1 PMAAOHONJPSASX-UHFFFAOYSA-N 0.000 description 1
- AGPJEGDSGBAREQ-UHFFFAOYSA-N 2-chloro-1,3,3,4,4,5,6,6,7,8,8,8-dodecafluorooct-1-ene Chemical compound FC(C(F)(F)F)C(C(C(C(C(=CF)Cl)(F)F)(F)F)F)(F)F AGPJEGDSGBAREQ-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 101001024605 Homo sapiens Next to BRCA1 gene 1 protein Proteins 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 241000357292 Monodactylus Species 0.000 description 1
- 102100037001 Next to BRCA1 gene 1 protein Human genes 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-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
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000010060 peroxide vulcanization Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、フッ素ゴム層とアクリロニトリルブタジェン
ゴム（以下ＩＮＢＲＪという）および／またはエチレン
−α−オレフィン（−非共役ジエン）共重合ゴム（以下
ｒＥＰ （Ｄ）Ｍｌという）層とが強固に加硫接着され
たゴム積層体に関するものである。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a fluororubber layer and acrylonitrile butadiene rubber (hereinafter referred to as INBRJ) and/or ethylene-α-olefin (-nonconjugated diene) copolymer rubber (hereinafter referred to as INBRJ). The present invention relates to a rubber laminate in which a layer (rEP (D)Ml) is firmly vulcanized and bonded.
［従来の技術］
フッ素ゴムは、耐油性、耐熱老化性、耐薬品性などの特
性に優れるため燃料ホースなどの素材として着目されて
いるが、ＮＢＲ，ＥＰ （Ｄ）Ｍなとの汎用ゴムに較べ
て高価である。このため、比較的耐油性が良好な汎用ゴ
ムであるＮＢＲあるいは耐熱老化性、耐薬品性が良好な
ＥＰ （Ｄ）Ｍとの積層体としての使用が考えられる。[Conventional technology] Fluororubber is attracting attention as a material for fuel hoses because of its excellent properties such as oil resistance, heat aging resistance, and chemical resistance. It is relatively expensive. Therefore, it is conceivable to use it as a laminate with NBR, which is a general-purpose rubber that has relatively good oil resistance, or EP (D)M, which has good heat aging resistance and chemical resistance.
しかし、一般にフッ素ゴムと他のゴムとの加硫接着は難
しく、特に三元系フッ素ゴムと他のゴムとの場合は加硫
接着が困難である。However, vulcanization bonding between fluororubber and other rubbers is generally difficult, and it is particularly difficult to vulcanize bonding between ternary fluororubber and other rubbers.
このため、フッ素ゴムとＮＢＲの加硫接着に関する種々
の特許が出願されており、フッ素ゴムに特定の加硫促進
剤を配合しＮＢＲに特定の金属酸化物を配合する発明（
特開昭６１−２４２８４０号公報）、フッ素ゴムにアク
リルゴムをブレンドする発明（特開昭６３−２１８３４
７号公報、特開平１−２４７１５８号公報）、エポキシ
樹脂またはその硬化剤を配合する発明（特開昭５５−５
１５５４号公報）などがある。For this reason, various patents have been filed regarding vulcanization adhesion between fluororubber and NBR, and there are inventions in which fluororubber is blended with a specific vulcanization accelerator and NBR is blended with a specific metal oxide (
JP-A No. 61-242840), invention of blending acrylic rubber with fluororubber (JP-A No. 63-21834)
No. 7, JP-A-1-247158), the invention of blending an epoxy resin or its curing agent (JP-A-55-5)
1554).
しかし、これらの公報に記載された方法では、フッ素ゴ
ム層にも何等かの配合剤を添加するため、より過酷な条
件の側に使用されるフッ素ゴムの物性の低下や加工性の
悪化がさけられない。However, in the methods described in these publications, some compounding agents are added to the fluororubber layer, so deterioration of the physical properties and processability of fluororubber used in harsher conditions can be avoided. I can't.
また、フッ素ゴムは配合の自由度が小さく、そのうえ多
くの場合フッ素ゴムとＮＢＲまたはＥＰ（Ｄ）Ｍの供給
メーカーは異なるので、ＮＢＲまたはＥＰ （Ｄ）Ｍの
配合のみを変更することによって、どのようなフッ素ゴ
ム配合物とも強固な加硫接着性が得られるＮＢＲまたは
ＥＰ （Ｄ）Ｍの配合技術は重要である。In addition, fluororubber has a small degree of freedom in formulation, and in many cases the suppliers of fluororubber and NBR or EP(D)M are different, so by changing only the formulation of NBR or EP(D)M, it is possible to The compounding technology of NBR or EP (D)M is important because it can provide strong vulcanization adhesion even with fluororubber compounds such as fluorocarbon rubber compounds.
フッ素ゴム層の配合を変更することなく、ＮＢＲ層のみ
の配合変更で加硫接着性を改良する方法として、ＮＢＲ
に酸化マグネシウムおよびシリカまたは珪酸塩またはエ
ポキシ樹脂を含有させる方法（特開昭５６−５３０６６
号公報）が提案されているが、接着力が十分でない。As a method of improving vulcanization adhesion by changing the formulation of only the NBR layer without changing the formulation of the fluororubber layer, NBR
A method of incorporating magnesium oxide and silica or silicate or epoxy resin into
No. 2) has been proposed, but the adhesive strength is not sufficient.
ＮＢＲまたはフッ素ゴムのどちらか一方の配合変更だけ
で加硫接着力を改良する方法として、カルボン酸の１．
８−ジアザビシクロ（５，４，０）ウンデセン−７塩を
添加、あるいはそれにシリカまたはエポキシ樹脂を併用
する方法（特開昭５８１６２３３５号公報）が提案され
ているが、積層体の耐熱老化性が劣り、またこれらの物
をＮＢＲに添加すると、スコーチ時間が短くて加工性が
悪い。As a method of improving vulcanized adhesive strength by changing the formulation of either NBR or fluororubber, 1. of carboxylic acid is used.
A method of adding 8-diazabicyclo(5,4,0)undecene-7 salt or using silica or epoxy resin together has been proposed (Japanese Patent Application Laid-open No. 58162335), but the heat aging resistance of the laminate is poor. Also, when these substances are added to NBR, the scorch time is short and processability is poor.
また、フッ素ゴム層と他のゴム層の加硫接着力を改良す
る方法として、１．８−ジアザビシクロ（５Ｌ ４．
０）ウンデセン−７の塩酸塩、スルホン酸塩、フェノー
ル塩および金属酸化物、水酸化物、炭酸塩を配合する方
法（特開昭６２−２８２９２８号公報）が提案されてい
るが、加硫接着力が不十分であり、また積層体の耐熱老
化性が大幅に劣る。In addition, as a method for improving the vulcanization adhesive strength between the fluororubber layer and other rubber layers, 1.8-diazabicyclo (5L 4.
0) A method of blending undecene-7 hydrochloride, sulfonate, phenol salt, and metal oxide, hydroxide, carbonate (Japanese Patent Application Laid-open No. 62-282928) has been proposed, but vulcanization adhesion The strength is insufficient, and the heat aging resistance of the laminate is significantly inferior.
［発明が解決しようとする課題］
本発明の目的は、フッ素ゴムの優れた性能を損なわずに
フッ素ゴムとＮＢＲおよび／またはＥＰ（Ｄ）Ｍとが強
固に加硫接着された積層体を得ることにある。[Problems to be Solved by the Invention] An object of the present invention is to obtain a laminate in which fluororubber and NBR and/or EP(D)M are firmly vulcanized and bonded without impairing the excellent performance of fluororubber. There is a particular thing.
［課題を解決するだめの手段］
本発明者らは、これらの問題点を解決すべく鋭意研究の
結果、本発明を完成させるに至った。[Means for Solving the Problems] As a result of intensive research to solve these problems, the present inventors have completed the present invention.
すなわち本発明は、フッ素ゴムを主成分とするゴム層と
ＮＢＲおよび／またはＥＰ（Ｄ）Ｍを主成分とするゴム
層とが強固に加硫接着されたゴム積層体であって、加硫
接着する前のＮＢＲおよび／またはＥＰ （Ｄ）Ｍを主
成分とする未加硫ゴム層に
（Ａ）水酸化カルシウム、炭酸ナトリウム、炭酸カリウ
ム、メタ珪酸ナトリウム、酸化カルシウムのうち少なく
とも一種のアルカリ性物質、
（Ｂ）下記一般式で示される化合物（イ）、（ロ）、お
よびそれらの塩から選ばれた少なくとも一種の化合物、
（イ） （ロ）
および
（Ｃ）有機過酸化物
を配合することを特徴とするゴム積層体を提供するもの
である。That is, the present invention provides a rubber laminate in which a rubber layer containing fluororubber as a main component and a rubber layer containing NBR and/or EP(D)M as a main component are firmly vulcanized and bonded. (A) at least one alkaline substance selected from calcium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, and calcium oxide; (B) At least one compound selected from compounds (a), (b), and salts thereof represented by the following general formula, (a), (b), and (C) an organic peroxide. The present invention provides a rubber laminate having the following characteristics.
以下、さらに本発明の詳細な説明する。The present invention will be further explained in detail below.
本発明で使用するフッ素ゴムとしては、高度にフッ素化
されたゴム状共重合体が適当である。これらの共重合体
としては、例えばビニリデンフルオライドとその他のフ
ッ素含有オレフィンとの共重合体である。フッ素含有オ
レフィンとしては、ヘキサフルオロプロペン、ペンタフ
ルオロプロペン、トリフルオロエチレン、トリフルオロ
クロロエチレン、テトラフルオロエチレン、ビニルフル
オライド、パーフルオロメチルビニルエーテル、パーフ
ルオロプロピルビニールエーテルなどがあり、これらの
一種または二種以上が共重合成分として用いられる。こ
れらのうち、ビニリデンフルオライド−へキサフルオロ
プロペン二元共重合体、ビニリデンフルオライド−テト
ラフルオロエチレン−ヘキサフルオロプロペン三元共重
合体、テトラフルオロエチレン−プロピレン二元共重合
体およびテトラフルオロエチレン−ビニリデンフルオラ
イド−プロピレン三元共重合体が好ましい。As the fluororubber used in the present invention, highly fluorinated rubbery copolymers are suitable. Examples of these copolymers include copolymers of vinylidene fluoride and other fluorine-containing olefins. Examples of fluorine-containing olefins include hexafluoropropene, pentafluoropropene, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, vinyl fluoride, perfluoromethyl vinyl ether, and perfluoropropyl vinyl ether. More than one species is used as a copolymerization component. Among these, vinylidene fluoride-hexafluoropropene binary copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropene terpolymer, tetrafluoroethylene-propylene binary copolymer, and tetrafluoroethylene-hexafluoropropene binary copolymer Vinylidene fluoride-propylene terpolymer is preferred.
フッ素ゴムには、その目的に応じて公知の配合剤が添加
される。また、必要に応じ前記（Ａ）、（Ｂ）、（Ｃ）
成分をフッ素ゴムに配合してもよい。Known compounding agents are added to the fluororubber depending on the purpose. In addition, if necessary, the above (A), (B), (C)
The components may be blended with fluororubber.
ＮＢＲとしてはアクリロニトリルとブタジェンとの共重
合体であって、少量のメタクリル酸などのアクリルモノ
マーおよび／または、第３成分としてエステル基や老化
防止機能を有するモノマーを共重合した三元系ポリマー
を含む。また、ＮＢＲの二重結合の一部が水素添加され
た水添ＮＢＲ１およびＮＢＲ＋：ＰＶＣまたはＥＰ （
Ｄ）Ｍをブレンドしたブレンドポリマーであってもよい
。NBR is a copolymer of acrylonitrile and butadiene, and includes a small amount of an acrylic monomer such as methacrylic acid and/or a ternary polymer copolymerized with an ester group or a monomer with an anti-aging function as a third component. . In addition, hydrogenated NBR1 and NBR+, in which some of the double bonds of NBR are hydrogenated: PVC or EP (
D) A blend polymer obtained by blending M may also be used.
また、本発明のＥＰ （Ｄ）Ｍは、エチレンとα−オレ
フィンとの共重合体であって、第３成分として非共役ジ
エンを含むものであってもよい。Further, the EP (D)M of the present invention is a copolymer of ethylene and α-olefin, and may contain a non-conjugated diene as a third component.
エチレン−α−オレフィン（−非共役ジエン）共重合ゴ
ムの成分であるα−オレフィンとしては、炭素数３〜２
０のα−オレフィンで、例えばプロピレン、１−ブテン
、１−ヘキセン、４−メチル１−ペンテン、３−メチル
−１−ペンテン、１−オクテン、１−デセン、１−ドデ
セン、１−テトラデセン、１−へキサデセン、１−オク
タデセン、１−エイコセンなどが用いられるか、好まし
くはプロピレン、１−ブテンである。The α-olefin that is a component of the ethylene-α-olefin (-nonconjugated diene) copolymer rubber has 3 to 2 carbon atoms.
0 α-olefins, such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -hexadecene, 1-octadecene, 1-eicosene, etc. are used, preferably propylene, 1-butene.
また、非共役ジエンとしては、例えば１，４ヘキサジエ
ン、ジシクロペンタジェン、５−エチリデン−２−ノル
ボルネン、２，５−ノルボルナジェンなどが用いられる
が、好ましくは５−エチリデン−２−ノルボルネンであ
る。Further, as the non-conjugated diene, for example, 1,4 hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 2,5-norbornadiene, etc. are used, and preferably 5-ethylidene-2-norbornene.
また、必要に応じて他のゴムや樹脂とブレンドして使用
することができる。他のゴムとしては、ハロゲン化ＥＰ
ＤＭＳＩ ＩＲ，ハロゲン化１１Ｒ。Moreover, it can be used by blending with other rubbers or resins as needed. Other rubbers include halogenated EP
DMSI IR, halogenated 11R.
ＳＢＲ，水添ＳＢＲ，水添ＮＢＲ，ＣＲ，液状ポリブタ
ジェンなどが挙げられ、樹脂としては、ポリプロピレン
、低密度および高密度ポリエチレン、リシンジオクタチ
ック１．２−ポリブタジエン、ポリスチレン、エチレン
−酢酸ビニル共重合体、アイオノマー樹脂などが挙げら
れる。SBR, hydrogenated SBR, hydrogenated NBR, CR, liquid polybutadiene, etc. are mentioned, and the resins include polypropylene, low density and high density polyethylene, lysine dioctatic 1,2-polybutadiene, polystyrene, ethylene-vinyl acetate copolymer. Examples include coalescence, ionomer resin, etc.
本発明では、ＮＢＲおよび／またはＥＰ（Ｄ）Ｍと接触
している面のフッ素ゴムから脱フツ酸を行なう際に発生
したフッ化水素を中和する目的で（Ａ）成分、すなわち
水酸化カルシウム、炭酸ナトリウム、炭酸カリウムまた
はメタ珪酸ナトリウム、酸化カルシウムのうち少なくと
も一種のアルカリ性物質が配合される。In the present invention, component (A), that is, calcium hydroxide, is used for the purpose of neutralizing hydrogen fluoride generated when dehydrating the fluororubber on the surface in contact with NBR and/or EP(D)M. , sodium carbonate, potassium carbonate, sodium metasilicate, and calcium oxide.
（Ａ）成分の配合量はＮＢＲおよび／またはＥＰ （Ｄ
）Ｍポリマー１００重量部当たり、０．５〜３０重量部
か好ましい。（Ａ）成分か０．５重量部未満の場合は接
着力が劣り、また３０重量部を超える場合はＮＢＲおよ
び／またはＥＰ（Ｄ）Ｍの加工性、物性に悪影響を及ぼ
し、好ましくない。さらに好ましくは５〜２０重量部で
ある。The blending amount of component (A) is NBR and/or EP (D
) It is preferably 0.5 to 30 parts by weight per 100 parts by weight of the M polymer. If the amount of component (A) is less than 0.5 parts by weight, the adhesive strength will be poor, and if it exceeds 30 parts by weight, it will adversely affect the processability and physical properties of NBR and/or EP(D)M, which is not preferable. More preferably, it is 5 to 20 parts by weight.
（Ａ）成分のうち、好ましいものは水酸化カルシウム、
メタ珪酸ナトリウムであり、さらに好ましいものは水酸
化カルシウムである。Among the components (A), preferred are calcium hydroxide,
Sodium metasilicate is more preferred, and calcium hydroxide is more preferred.
また、ＮＢＲおよび／またはＥＰ（Ｄ）Ｍと接触してい
る面のフッ素ゴムから脱フツ酸を行なう触媒として（Ｂ
）成分、すなわち１，８−ジアザビシクロ（５，４，０
）ウンデセン−７（以下、単に「ＤＢＵＪということが
ある）、１．５−ジアザビシクロ（４，３，０）ノネン
−５（以下、単にｒＤＢＮＪということがある）、また
はこれらの塩から選ばれた少なくとも一種の化合物が配
合される。In addition, (B
) component, i.e. 1,8-diazabicyclo(5,4,0
) Undecene-7 (hereinafter sometimes simply referred to as "DBUJ"), 1,5-diazabicyclo(4,3,0)nonene-5 (hereinafter sometimes simply referred to as rDBNJ), or salts thereof At least one compound is blended.
（Ｂ）成分の配合量はＮＢＲおよび／またはＥＰ （Ｄ
）Ｍポリマー１００重量部当たり、０．１〜５重量部が
好ましい。（Ｂ）成分が０．１重量部未満の場合は接着
力が劣り、また５重量部を超える場合はＮＢＲおよび／
またはＥＰ（Ｄ）Ｍの加工性、物性に悪影響を及ぼし、
好ましくない。The blending amount of component (B) is NBR and/or EP (D
) It is preferably 0.1 to 5 parts by weight per 100 parts by weight of the M polymer. If component (B) is less than 0.1 parts by weight, the adhesive strength will be poor, and if it exceeds 5 parts by weight, NBR and/or
or adversely affect the processability and physical properties of EP(D)M,
Undesirable.
さらに好ましくは０．５〜４重量部である。More preferably, it is 0.5 to 4 parts by weight.
ＤＢＵＳＤＢＮおよびそれらの塩としては、環状環の水
素原子が他の原１子または分子によって置換されたもの
であってもよい。塩としては塩酸塩、フェノール塩、カ
ルボン酸塩、スルホン酸塩が挙げられ、カルボン酸とし
てはオクチル酸、オレイン酸、ぎ酸、オルソフタール酸
、アジピン酸が、スルホン酸としてはベンゼンスルホン
酸、トルエンスルホン酸、ドデシルベンゼンスルホン酸
、ナフタレンスルホン酸、およびこれらの環状環の水素
原子か他の原子または分子で置換されたものが挙げられ
る。DBUSDBN and salts thereof may have a hydrogen atom in the cyclic ring replaced by another atom or molecule. Salts include hydrochloride, phenol salt, carboxylate, and sulfonate; carboxylic acids include octyl acid, oleic acid, formic acid, orthophthalic acid, and adipic acid; sulfonic acids include benzenesulfonic acid and toluenesulfone. Examples include acids, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and those in which the hydrogen atom of the cyclic ring of these is substituted with another atom or molecule.
ＤＢＵＳＤＢＮの塩は、塩酸塩、スルホン酸塩、フェノ
ール塩から選ばれた少なくとも一種の化合物であること
が好ましい。また、ＤＢＵ、ＤＢＮおよびそれらの塩の
うち、さらに好ましいものは、取扱いの安全性の面から
ＤＢＵおよびＤＢＮの塩酸塩、またはスルホン酸塩であ
る。The salt of DBUSDBN is preferably at least one compound selected from hydrochloride, sulfonate, and phenol salt. Further, among DBU, DBN and their salts, hydrochloride or sulfonate of DBU and DBN is more preferable from the viewpoint of handling safety.
同一の接着力を得るのに水酸化カルシウムを多く使用す
ればＤＢＵ塩は少なくてすみ、例えば水酸化カルシウム
１０重量部十ＤＢＵ塩２重量部使用した場合と同等の接
着力を得るのに、水酸化カルシウムを２０重量部使用し
た場合にはＤＢＵ塩は１重量部でよい。If more calcium hydroxide is used to obtain the same adhesive strength, less DBU salt is required.For example, to obtain the same adhesive strength as using 10 parts by weight of calcium hydroxide and 2 parts by weight of DBU salt, less water When 20 parts by weight of calcium oxide is used, 1 part by weight of DBU salt may be used.
また、脱フツ酸によって生成したフッ素ゴム中の二重結
合とＮＢＲおよび／またはＥＰ（Ｄ）Ｍとを架橋するた
めに、（Ｃ）成分、すなわち有機過酸化物が配合される
。ここで使用する有機過酸化物は、半減期１分を得る温
度が少なくとも１５０℃以上であることが好ましい。有
機過酸化物の半減期１分を得る温度が１５０℃未満であ
る場合は、フッ素ゴムとＮＢＲおよび／またはＥＰ（Ｄ
）Ｍとの界面に両ゴムの相互拡散によって接着に有効な
十分な厚さの界面層を形成する以前に加硫が完了してし
まうため、接着力がやや劣る。さらに好ましい温度は１
７０℃以上であり、通常使用するものは２００９Ｃ以下
である。In addition, component (C), that is, an organic peroxide, is blended in order to crosslink the double bonds in the fluororubber produced by dehydrofluoric acid and NBR and/or EP(D)M. The organic peroxide used here preferably has a half-life of 1 minute at a temperature of at least 150°C or higher. If the temperature at which the organic peroxide has a half-life of 1 minute is less than 150°C, fluororubber and NBR and/or EP(D
) Since vulcanization is completed before an interface layer of sufficient thickness for effective adhesion is formed at the interface with M due to mutual diffusion of both rubbers, the adhesive strength is somewhat inferior. A more preferable temperature is 1
The temperature is 70°C or higher, and the temperature normally used is 2009°C or lower.
（Ｃ）成分の配合量はＮＢＲおよび／またはＥＰ （Ｄ
）Ｍポリマー１００重量部当たり、０．５〜１５重量部
が好ましい。（Ｃ）成分が０．５重量部未満の場合、加
硫不足で物性、接着力が劣り、１５重量部を超える場合
は伸びが小さく、硬くなるため好ましくない。さらに好
ましいのは１〜１０重量部である。The blending amount of component (C) is NBR and/or EP (D
) It is preferably 0.5 to 15 parts by weight per 100 parts by weight of the M polymer. If component (C) is less than 0.5 parts by weight, vulcanization is insufficient, resulting in poor physical properties and adhesive strength, and if it exceeds 15 parts by weight, elongation is low and the resin becomes hard, which is not preferable. More preferred is 1 to 10 parts by weight.
好ましい有機過酸化物としては、１．３−ビス（ｔ−ブ
チルパーオキシイソプロピル）ベンゼン、ジクミルパー
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゜１−ビス（ｔ−ブチル
パーオキシ）３，３．５−トリメチルシクロヘキサン、
２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ
）ヘキシン（３）、ｔ−ブチルクミルパーオキサイド、
ジ−ｔ−ブチルパーオキサイドなどが挙げられる。これ
らのうち、さらに好ましいものは、１．３−ビス（ｔ−
ブチルパーオキシイソプロピル）ベンゼン、ジクミルパ
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、２゜５−ジメチル−２，５
−ジ（ｔ−ブチルパーオキシ）ヘキシン−（３）、ｔ−
ブチルクミルパーオキサイド、ジ−ｔ−ブチルパーオキ
サイドである。Preferred organic peroxides include 1,3-bis(t-butylperoxyisopropyl)benzene, dicumyl peroxide, 2.,5-dimethyl-2°5-di(t-butylperoxy)hexane, 1.゜1-bis(t-butylperoxy)3,3.5-trimethylcyclohexane,
2,5-dimethyl-2,5-di(t-butylperoxy)hexyne (3), t-butylcumyl peroxide,
Examples include di-t-butyl peroxide. Among these, 1,3-bis(t-
butylperoxyisopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2゜5-di(t-butylperoxy)hexane, 2゜5-dimethyl-2,5
-di(t-butylperoxy)hexyne-(3), t-
They are butylcumyl peroxide and di-t-butyl peroxide.
また、有機過酸化物を使用せず硫黄加硫した場合、接着
力は問題ないが、積層体の耐熱老化性が著しく劣るうえ
に、スコーチ時間が短すぎて実用に適さない。Further, when sulfur vulcanization is performed without using an organic peroxide, there is no problem in adhesive strength, but the heat aging resistance of the laminate is significantly inferior and the scorch time is too short to be suitable for practical use.
前記（Ａ）、（Ｂ）、（Ｃ）は加硫接着のための必須成
分であり、これ以外に、通常ＮＢＲおよび／またはＥＰ
（Ｄ）Ｍの配合に使用される配合剤を含んでよい。The above (A), (B), and (C) are essential components for vulcanization adhesion, and in addition to these, usually NBR and/or EP
(D) It may contain the compounding agent used for compounding M.
加硫接着する相手のフッ素ゴムとしては、本発明の主旨
からして特にその配合を限定しないし、またフッ素ゴム
の種類についても限定しない。本発明のＮＢＲおよび／
またはＥＰ （Ｄ）Ｍ配合物は、三元系フッ素ゴムに対
しても非常に強固な加硫接着力を得ることができる。The composition of the fluororubber to be vulcanized and bonded is not particularly limited in view of the gist of the present invention, and the type of fluororubber is not limited either. NBR of the present invention and/or
Alternatively, the EP (D)M compound can provide very strong vulcanization adhesion even to ternary fluororubber.
［実 施 例］
次に、実施例により本発明を説明するが、本発明はその
趣旨を超えない限り、実施例に限定されるものではない
。[Examples] Next, the present invention will be explained by examples, but the present invention is not limited to the examples unless it exceeds the spirit thereof.
表−１に従って４０°Ｃロール上でフッ素ゴムを混練り
した。また表−２に従ってＮＢＲを、表３に従ってＥＰ
ＤＭをバンバリーミキサ−で混練りした。混練りした未
加硫のゴム配合物を３ＩＩＩ１１厚さのシートにし、表
−４の組み合わせで重ね合わせ、１７０°Ｃで２０分間
プレス加硫した。得られた貼り合わせシートを２．５ｃ
ｍ幅に打ち抜き、ＪＩＳ Ｋ６８５４に従ってＴ型剥
離試験を行なった。結果を表−４に示す。The fluororubber was kneaded on a 40°C roll according to Table 1. Also, NBR according to Table 2 and EP according to Table 3.
DM was kneaded using a Banbury mixer. The kneaded unvulcanized rubber compound was made into a sheet of 3III11 thickness, stacked in the combinations shown in Table 4, and press-vulcanized at 170°C for 20 minutes. 2.5c of the obtained laminated sheet
It was punched out to a width of m, and a T-peel test was conducted according to JIS K6854. The results are shown in Table 4.
また、積層体の耐熱老化性を比較するために表−１のＢ
のフッ素ゴム配合物と表−２のＮＢＲ配合物、表−３の
ＥＰＤＭ配合物のうち、イ、ハ、ネ、ソ、ツ、うとを重
ね合わせ、１７０℃で２０分プレス加硫して積層体を作
り、ＪＩＳ Ｋ６３０１に従って耐熱老化試験を行な
った。積層体の厚みはフッ素ゴム層０．３ｍｍ、ＮＢＲ
層、ＥＰＤＭ層１．７ｍｍ、合計２、Ｏｍｍであり、老
化試験の条件はギヤ−オーブン１冫０
老化前後の物性の変化率を表−５に示す。In addition, in order to compare the heat aging resistance of the laminate,
Of the fluororubber compound, the NBR compound in Table 2, and the EPDM compound in Table 3, A, C, Ne, S, T, and U were stacked together and laminated by press vulcanization at 170°C for 20 minutes. A body was prepared and a heat aging test was conducted according to JIS K6301. The thickness of the laminate is 0.3 mm of fluororubber layer, NBR
The EPDM layer had a thickness of 1.7 mm, a total thickness of 2.0 mm, and the aging test conditions were a gear oven of 1.0 mm.The rate of change in physical properties before and after aging is shown in Table 5.
また、ＮＢＲ，ＥＰＤＭの加工性を比較するために、表
−２のＮＢＲ配合物、表−３のＥＰＤＭ配合物のうち、
イ、ハ、ネ、ソ、ツ、うのムーニースコーチ時間を表−
５に示す。In addition, in order to compare the processability of NBR and EPDM, among the NBR blends in Table 2 and the EPDM blends in Table 3,
Table of moony scorch times for a, ha, ne, so, tsu, and u.
5.
実施例１〜６は、本発明の特定の配合剤配合のＮＢＲ層
と種々のフッ素ゴム層とを加硫接着した例である。フッ
素ゴムの加硫系、配合剤に関係なくよく接着しており、
三元系のフッ素ゴムともよく接着している。Examples 1 to 6 are examples in which NBR layers containing specific ingredients of the present invention and various fluororubber layers were vulcanized and bonded. It adheres well regardless of the fluororubber vulcanization system or compounding agent.
It also adheres well to ternary fluororubber.
比較例１、２は、ＮＢＲの配合に（Ａ）成分または（Ｂ
）成分を使用しなかった例であり、全く接着していない
。In Comparative Examples 1 and 2, component (A) or (B) was added to the NBR formulation.
) component was not used, and there was no adhesion at all.
実施例７〜１１は、実施例２において（Ａ’）成分の水
酸化カルシウムを無水炭酸ナトリウム、メタ珪酸ナトリ
ウムに置き換えた例、およびシリカと併用した例である
。シリカと併用した場合、接着力がやや低下するが、Ｎ
ＢＲの物性または加工性上、必要なら併用することは可
能である。Examples 7 to 11 are examples in which calcium hydroxide in component (A') in Example 2 was replaced with anhydrous sodium carbonate or sodium metasilicate, and examples in which calcium hydroxide was used in combination with silica. When used in combination with silica, the adhesive strength decreases slightly, but N
It is possible to use them together if necessary in view of the physical properties or processability of BR.
一方、比較例３、４は、実施例２において（Ａ）成分の
アルカリ性物質の替わりにシリカのみを使用した例であ
る。酸性のシリカ、塩基性シリカに関係なく、はとんど
接着しない。On the other hand, Comparative Examples 3 and 4 are examples in which only silica was used in place of the alkaline substance as component (A) in Example 2. Regardless of whether it is acidic silica or basic silica, it rarely adheres.
実施例１２〜１４は、実施例２において脱フツ酸触媒で
ある（Ｂ）成分の種類を変更した例であり、いずれもよ
く接着している。Examples 12 to 14 are examples in which the type of component (B), which is the dehydrofluoric acid catalyst, was changed in Example 2, and all adhered well.
比較例５、６は、それぞれ実施例１０、実施例２におい
て（Ｃ）成分の有機過酸化物の替わりに硫黄加硫系を用
いた例である。有機過酸化物の場合と異なり、水酸化カ
ルシウムにシリカを併用しても接着力は低下しない。し
かし、表−５に示すとおり、本発明の実施例に比べ積層
体の耐熱老化性は大幅に劣り、ＮＢＲ層のスコーチ時間
が短い。Comparative Examples 5 and 6 are examples in which a sulfur vulcanization system was used in place of the organic peroxide as component (C) in Example 10 and Example 2, respectively. Unlike the case of organic peroxides, the adhesion strength does not decrease even when silica is used in combination with calcium hydroxide. However, as shown in Table 5, the heat aging resistance of the laminate was significantly inferior compared to the examples of the present invention, and the scorch time of the NBR layer was short.
また実施例１５〜１８は、実施例２において有機過酸化
物の種類を変更した例であるが、半減期１分を得る温度
が１５０℃以下の有機過酸化物を使用した場合は、接着
力がやや劣る。Further, Examples 15 to 18 are examples in which the type of organic peroxide was changed in Example 2, but when using an organic peroxide whose half-life of 1 minute is 150°C or lower, the adhesive strength is slightly inferior.
また実施例１９は、本発明の特定の配合剤配合のＥＰＤ
Ｍ層とフッ素ゴム層とを加硫接着した例であるが、良く
接着している。In addition, Example 19 shows that EPD with a specific formulation of the present invention
This is an example in which the M layer and the fluororubber layer are vulcanized and bonded, and they are well bonded.
比較例７は、実施例１９において（Ｂ）成分のＤＢＵ塩
を使用しなかった例であり、全く接着していない。Comparative Example 7 is an example in which the DBU salt of component (B) in Example 19 was not used, and there was no adhesion at all.
また比較例８は、実施例１９において（Ｃ）成分の有機
過酸化物の替わりに硫黄加硫系を用いた例である。表−
４、表−５かられかるとおり接着力は優れているが、積
層体の耐熱老化性が大幅に劣り、ＥＰＤＭ層のスコーチ
時間が短い。Comparative Example 8 is an example in which a sulfur vulcanization system was used in place of the organic peroxide of component (C) in Example 19. Table -
4. As shown in Table 5, the adhesive strength is excellent, but the heat aging resistance of the laminate is significantly inferior, and the scorch time of the EPDM layer is short.
以下余白
表−１
フン素ゴム配合処方
１）Ａ＋ＤｕＰｏｎｔ社製、フッ素ゴム ハイドノーＡ
（二元系フッ素ゴム）２） Ｂ −Ｐｏｎｔ社製、フ
ッ素ゴム ハイド／−Ｂ（三元系フッ素ゴム）３）Ｅ−
４３０＋ＤｕＰｏｎｔ社製、フッ素ゴム バイトノーＥ
−４３０（ポリオール系加硫酸入り二元系フッ素ゴム）
４） ＧＦ ：Ｄｕ Ｐｏｎｔ社製、７ノ素ゴム ベイ
ト：／−ＧＦ（パーオキサイド加硫系）５）ＴＮ５０
モノテフルオス社製、フッ素ゴム テクノ７０ノＴＮ
−５０５（三元系７）素ゴム）
６）２００・旭硝子製、フッ素ゴム アフラス２００７
）ＤＩＡＫ Ｎｉｌ ヘキサメチレフノアミツカー
バメイト８）ＤＩＡＫ ｍ７ トリアリルイソノアヌ
レート９）キュラティブ＃２０ ＋ Ｄｕ Ｐｏｎｔ社
製、加硫促進剤 多［４級士スオニウム塩１０）キュラ
ティブ＃３０ ： Ｄｕ Ｐｏｎｔ社製、加硫剤、ノ
ヒトロキノ化合物１１）パーヘキノン２５Ｂ 日本油
陣製〔２，５−ツメチル−２５−ジ（ｔブチルパーオキ
／）ヘキノノ−（３）〕１２）テクノ７０７Ｍ１ モノ
テフルオス社製、ビスフェノールＡＦ ５０％品１３
）テクノ７０７Ｍ２ モノテフルオス社製、加硫促進剤
３０％品１４）パーカドックス−１４化薬アクノ■製
、１．３−ビス（ｔ−ブチルパーオキ／イノプロピル）
べ／ゼノ
ＮＢＲ： Ｎ２３Ｏ５、日本合成コム■製、結合ＡＮｌ
３７％ニブノールＶＮ３ 日本ノリカ■製、湿式ノリ
力、ｐＨ５，５〜６５カープレツクス＃１１２０ ／
オノギ製薬■製、湿式ノリ力、ｐＨ１０，６パーカトノ
クス１４／４０ 化薬アクｌ製、１，３−ビス（℃−
ブチルパーオキ／イソプロピル）ベノゼノー半減期１分
を得る温度 １８３℃カクヤミルＤ 化薬アクゾ製、ツ
クミルパーオキサイド−半減期１分を与える温度１７９
℃
カヤへキサＡＤ−４０化薬アクノ製、２５−ツメチル−
２，５−；；（＋−ブチルパーオキ／）ヘキサ／−半Ｉ
１１期１分を得る温度 １８１℃トリゴノノクス２９／
４０ 化薬アク／製、１．１−ビス（ｔ−プチルパー
オキノ） ３． ３． ５−トリメチル／クロヘキサ／
−半減期１分を得る温度 １５２℃力トノクスＢ 化薬
アクｌ製、べ／ノイルパーオキサイドー半減期１分を得
る温度１３０℃
表−４
実施例および比較例
注１）
プレス加硫取り出し時に剥離
以上の実施例に述べたとおり、本発明のＮＢＲ５よび／
またはＥＰ（Ｄ）Ｍは耐熱老化性、加工上が改良されて
おり、フッ素ゴムとの加硫接着性二優れている。Margin table below-1 Fluororubber compounding prescription 1) A+DuPont, fluororubber Hydno A
(Binary fluororubber) 2) B - manufactured by Pont, fluororubber Hyde/-B (ternary fluororubber) 3) E-
430+Fluororubber Byte No E manufactured by DuPont
-430 (binary fluororubber containing polyol-based sulfate)
4) GF: Manufactured by Du Pont, 7-node rubber Bait: /-GF (peroxide vulcanization type) 5) TN50
Manufactured by Monote Fluos, fluororubber Techno 70 TN
-505 (ternary system 7) raw rubber) 6) 200, manufactured by Asahi Glass, fluororubber Aflas 2007
) DIAK Nil hexamethylene phenoamic carbamate 8) DIAK m7 triallylisonoanurate 9) Curative #20 + Du Pont Co., Ltd., vulcanization accelerator poly [quaternary suonium salt 10) Curative #30: Du Pont Co., Ltd. product , vulcanizing agent, nohydroquino compound 11) Perhequinone 25B manufactured by Nippon Yujin [2,5-methyl-25-di(t-butylperoxy/)hequinono-(3)] 12) Techno 707M1 manufactured by Monote Fluos, bisphenol AF 50% product 13
) Techno 707M2 Manufactured by Monote Fluos, 30% vulcanization accelerator 14) Percadox-14 Manufactured by Kayaku Akuno ■, 1.3-bis (t-butyl peroxy/inopropyl)
Be/Xeno NBR: N23O5, manufactured by Nippon Gosei Com■, bonded ANl
37% Nibnol VN3, manufactured by Nippon Norica ■, wet glue strength, pH 5.5-65 Carplex #1120 /
Manufactured by Onogi Pharmaceutical ■, wet glue strength, pH 10.6 Perkatonox 14/40 Manufactured by Kayaku Acl, 1,3-bis (℃-
Butyl peroxide/isopropyl) benozeno Temperature that gives a half-life of 1 minute 183℃ Kakuyamil D Tsukumil peroxide manufactured by Kayaku Akzo - Temperature that gives a half-life of 1 minute 179
℃ Kayahexa AD-40 manufactured by Akuno, 25-methyl-
2,5-;;(+-butylperoxy/)hex/-half I
Temperature to obtain 11th period 1 minute 181℃ Trigononox 29/
40 Kayaku Aku/manufactured by 1.1-bis(t-butylperokino) 3. 3. 5-trimethyl/chlorohexa/
- Temperature to obtain a half-life of 1 minute: 152°C Tortonox B Made by Kayaku Acl, be/noyl peroxide - Temperature to obtain a half-life of 1 minute: 130°C Table 4 Examples and Comparative Examples Note 1) At press vulcanization removal Peeling As described in the above examples, NBR5 and/or
Alternatively, EP(D)M has improved heat aging resistance and processability, and has excellent vulcanization adhesion to fluororubber.
［発明の効果］
本発明の方法により、フッ素ゴムとＮＢＲおよ〈／また
はＥＰ （Ｄ）Ｍとが強固に加硫接着されニゴム積層体
が得られる。[Effects of the Invention] According to the method of the present invention, a fluororubber and NBR and/or EP (D)M are firmly vulcanized and bonded to each other to obtain a Ni-rubber laminate.
本発明の方法によれば、フッ素ゴムの加工性、１性を損
なうことがな（、また積層体としての耐３老化性も優れ
ている。According to the method of the present invention, the processability and properties of the fluororubber are not impaired (also, the laminate has excellent aging resistance).
本発明により製造される積層体の具体的用途と−では、
各種ホース類、例えば燃料油用ホース、−イルホース、
ガス用ホース、ブレーキ曲用ホースなどが挙げられ、工
業部品、自動車、航空機などへの利用が挙げられる。Specific uses of the laminate produced according to the present invention include:
Various hoses, such as fuel oil hoses, oil hoses,
Examples include gas hoses and brake bend hoses, and applications include industrial parts, automobiles, and aircraft.
特許出願人 日本合成ゴム株式会社Patent applicant: Japan Synthetic Rubber Co., Ltd.
Claims (1)
リル−ブタジエンゴムおよび／またはエチレン−α−オ
レフィン（−非共役ジエン）共重合ゴムを主成分とする
ゴム層とが強固に加硫接着されたゴム積層体であって、
加硫接着する前のアクリロニトリル−ブタジエンゴムお
よび／またはエチレン−α−オレフィン（−非共役ジエ
ン）共重合ゴムを主成分とする未加硫ゴム層に （Ａ）水酸化カルシウム、炭酸ナトリウム、炭酸カリウ
ム、メタ珪酸ナトリウム、酸化カ ルシウムのうち少なくとも一種のアルカリ 性物質、 （Ｂ）下記一般式で示される化合物（イ）、（ロ）、お
よびそれらの塩から選ばれた少 なくとも一種の化合物、 ▲数式、化学式、表等があります▼ （イ） ▲数式、化学式、表等があります▼ （ロ） および （Ｃ）有機過酸化物 を配合することを特徴とするゴム積層体。(1) A rubber layer mainly composed of fluororubber and a rubber layer mainly composed of acrylonitrile-butadiene rubber and/or ethylene-α-olefin (-nonconjugated diene) copolymer rubber are firmly vulcanized and bonded. A rubber laminate,
(A) Calcium hydroxide, sodium carbonate, potassium carbonate in an unvulcanized rubber layer mainly composed of acrylonitrile-butadiene rubber and/or ethylene-α-olefin (-nonconjugated diene) copolymer rubber before vulcanization adhesion. , sodium metasilicate, and calcium oxide; (B) at least one compound selected from compounds (a), (b) represented by the following general formulas, and salts thereof; ▲Mathematical formula, chemical formula , tables, etc. ▼ (A) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (B) And (C) A rubber laminate characterized by blending an organic peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21392490A JPH0494930A (en) | 1990-08-13 | 1990-08-13 | Rubber laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21392490A JPH0494930A (en) | 1990-08-13 | 1990-08-13 | Rubber laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0494930A true JPH0494930A (en) | 1992-03-27 |
Family
ID=16647302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21392490A Pending JPH0494930A (en) | 1990-08-13 | 1990-08-13 | Rubber laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0494930A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995019880A1 (en) * | 1994-01-24 | 1995-07-27 | Nippon Zeon Co., Ltd. | Laminate of vulcanizable rubber composition layers, process for producing rubber laminate, and rubber laminate |
| JP2008238818A (en) * | 2001-06-04 | 2008-10-09 | Saint-Gobain Performance Plastics Corp | Multilayer polymeric article with mutual crosslinkage polymer layers and method of making the same |
| WO2009157361A1 (en) * | 2008-06-26 | 2009-12-30 | ユニマテック株式会社 | Rubber laminate |
| JP2019171745A (en) * | 2018-03-29 | 2019-10-10 | 三井化学株式会社 | Laminate and application thereof |
| WO2020090981A1 (en) * | 2018-11-02 | 2020-05-07 | 三井化学株式会社 | LAYERED PRODUCT INCLUDING ETHYLENE-α-OLEFIN-NON-CONJUGATED POLYENE COPOLYMER COMPOSITION LAYER AND USE THEREOF |
| WO2020204081A1 (en) * | 2019-04-04 | 2020-10-08 | Ａｇｃ株式会社 | Multilayer body |
-
1990
- 1990-08-13 JP JP21392490A patent/JPH0494930A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995019880A1 (en) * | 1994-01-24 | 1995-07-27 | Nippon Zeon Co., Ltd. | Laminate of vulcanizable rubber composition layers, process for producing rubber laminate, and rubber laminate |
| JP2008238818A (en) * | 2001-06-04 | 2008-10-09 | Saint-Gobain Performance Plastics Corp | Multilayer polymeric article with mutual crosslinkage polymer layers and method of making the same |
| WO2009157361A1 (en) * | 2008-06-26 | 2009-12-30 | ユニマテック株式会社 | Rubber laminate |
| JP5177226B2 (en) * | 2008-06-26 | 2013-04-03 | ユニマテック株式会社 | Rubber laminate |
| US8574717B2 (en) | 2008-06-26 | 2013-11-05 | Unimatec Co., Ltd. | Rubber laminate |
| JP2019171745A (en) * | 2018-03-29 | 2019-10-10 | 三井化学株式会社 | Laminate and application thereof |
| WO2020090981A1 (en) * | 2018-11-02 | 2020-05-07 | 三井化学株式会社 | LAYERED PRODUCT INCLUDING ETHYLENE-α-OLEFIN-NON-CONJUGATED POLYENE COPOLYMER COMPOSITION LAYER AND USE THEREOF |
| KR20210068096A (en) * | 2018-11-02 | 2021-06-08 | 미쓰이 가가쿠 가부시키가이샤 | Laminate comprising layer of ethylene/α-olefin/non-conjugated polyene copolymer composition and use thereof |
| CN112969589A (en) * | 2018-11-02 | 2021-06-15 | 三井化学株式会社 | Laminate comprising layer of ethylene-alpha-olefin-nonconjugated polyene copolymer composition and use thereof |
| JPWO2020090981A1 (en) * | 2018-11-02 | 2021-09-30 | 三井化学株式会社 | Laminates containing ethylene / α-olefin / non-conjugated polyene copolymer composition layers and their uses |
| WO2020204081A1 (en) * | 2019-04-04 | 2020-10-08 | Ａｇｃ株式会社 | Multilayer body |
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