JPWO2019176797A1 - アクリロニトリル・ブタジエンゴム組成物および当該組成物層を含む積層体 - Google Patents
アクリロニトリル・ブタジエンゴム組成物および当該組成物層を含む積層体 Download PDFInfo
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- JPWO2019176797A1 JPWO2019176797A1 JP2020506478A JP2020506478A JPWO2019176797A1 JP WO2019176797 A1 JPWO2019176797 A1 JP WO2019176797A1 JP 2020506478 A JP2020506478 A JP 2020506478A JP 2020506478 A JP2020506478 A JP 2020506478A JP WO2019176797 A1 JPWO2019176797 A1 JP WO2019176797A1
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- Prior art keywords
- layer
- vinyl acetate
- ethylene
- acetate copolymer
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- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 125
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 88
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 88
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical class C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003475 lamination Methods 0.000 claims abstract 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 claims description 13
- 238000010030 laminating Methods 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 9
- 239000005062 Polybutadiene Substances 0.000 abstract description 5
- 229920002857 polybutadiene Polymers 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 84
- -1 unsaturated silane compound Chemical class 0.000 description 29
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 26
- 238000004073 vulcanization Methods 0.000 description 21
- 229920001577 copolymer Polymers 0.000 description 19
- 230000003712 anti-aging effect Effects 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 14
- 239000011787 zinc oxide Substances 0.000 description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 12
- 239000005977 Ethylene Substances 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000004132 cross linking Methods 0.000 description 11
- 239000004088 foaming agent Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 9
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 9
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 9
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000006057 Non-nutritive feed additive Substances 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 238000005187 foaming Methods 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 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 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- 239000012190 activator Substances 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 235000019241 carbon black Nutrition 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- BOOBDAVNHSOIDB-UHFFFAOYSA-N (2,3-dichlorobenzoyl) 2,3-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC(C(=O)OOC(=O)C=2C(=C(Cl)C=CC=2)Cl)=C1Cl BOOBDAVNHSOIDB-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- GWQOYRSARAWVTC-UHFFFAOYSA-N 1,4-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=C(C(C)(C)OOC(C)(C)C)C=C1 GWQOYRSARAWVTC-UHFFFAOYSA-N 0.000 description 2
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical class CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 150000001540 azides Chemical class 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FALCQDAWENTNHF-UHFFFAOYSA-N ethenyl(2-methoxyethoxy)silane Chemical compound COCCO[SiH2]C=C FALCQDAWENTNHF-UHFFFAOYSA-N 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 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
- 238000002715 modification method Methods 0.000 description 2
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 150000002978 peroxides Chemical class 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
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 2
- PFBLRDXPNUJYJM-UHFFFAOYSA-N tert-butyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(C)(C)C PFBLRDXPNUJYJM-UHFFFAOYSA-N 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 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
- FUPAJKKAHDLPAZ-UHFFFAOYSA-N 1,2,3-triphenylguanidine Chemical compound C=1C=CC=CC=1NC(=NC=1C=CC=CC=1)NC1=CC=CC=C1 FUPAJKKAHDLPAZ-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- LLZHXQRNOOAOFF-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione;zinc Chemical compound [Zn].C1=CC=C2NC(S)=NC2=C1 LLZHXQRNOOAOFF-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- CQSQUYVFNGIECQ-UHFFFAOYSA-N 1-n,4-n-dimethyl-1-n,4-n-dinitrosobenzene-1,4-dicarboxamide Chemical compound O=NN(C)C(=O)C1=CC=C(C(=O)N(C)N=O)C=C1 CQSQUYVFNGIECQ-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- STUPOYLSQNMUKA-UHFFFAOYSA-N 1h-imidazol-2-yl-(2-sulfanylphenyl)methanone Chemical compound SC1=CC=CC=C1C(=O)C1=NC=CN1 STUPOYLSQNMUKA-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
- JDICEKWSLNPYSN-UHFFFAOYSA-N 2-(2,4-dinitrophenyl)-1,3-benzothiazole-4-thiol Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC=C1C1=NC2=C(S)C=CC=C2S1 JDICEKWSLNPYSN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 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
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 1
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- KCSOBOZCMQBPFM-UHFFFAOYSA-N 4-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=C2C=CC=CC2=CC=1)C1=CC=C(C=CC=C2)C2=C1 KCSOBOZCMQBPFM-UHFFFAOYSA-N 0.000 description 1
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- 239000004604 Blowing Agent Substances 0.000 description 1
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- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 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
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- 229910000576 Laminated steel Inorganic materials 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
- KFFQABQEJATQAT-UHFFFAOYSA-N N,N'-dibutylthiourea Chemical compound CCCCNC(=S)NCCCC KFFQABQEJATQAT-UHFFFAOYSA-N 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2331/00—Polyvinylesters
- B32B2331/04—Polymers of vinyl acetate, e.g. PVA
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2597/00—Tubular articles, e.g. hoses, pipes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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- C—CHEMISTRY; METALLURGY
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Abstract
Description
本発明の積層体を構成するアクリロニトリル・ブタジエンゴム(NBR)層(以下、「NBR層」と略称する場合がある。)、およびアクリロニトリル・ブタジエンゴム組成物(以下、「NBR組成物」と略称する場合がある。)を構成するアクリロニトリル・ブタジエンゴム(NBR)は、アクリロニトリルとブタジエンとを乳化重合して得られるジエン系合成ゴムである。NBRは一般的にアクリロニトリルの結合量によって、極高(43%以上)、高(36〜42%)、中高(31〜35%)、中(25〜30%)、低(24%以下)の5段階に分類され、中高が汎用タイプである。
本発明に係わるNBRに配合されるシラン変性エチレン・酢酸ビニル共重合体は、エチレン・酢酸ビニル共重合体に不飽和シラン化合物をグラフト変性してなる変性共重合体である。不飽和シラン化合物のグラフト量は、通常0.01〜5重量%、好ましくは0.02〜3重量%である。
エチレン・酢酸ビニル共重合体にグラフトされる不飽和シラン化合物としては、種々公知の化合物、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニル(β−メトキシエトキシ)シラン、ビニルトリアセトキシシラン等のビニルシラン類、アクリロキシプロピルトリメトキシシラン、メタクリロキシプロピルトリメトキシシラン等のアクリル系シラン類等を挙げることができる。
本発明のNBR組成物は、上記NBR:100質量部に対して、上記シラン変性エチレン・酢酸ビニル共重合体を0〜50質量部、好ましくは2〜50質量部、より好ましくは5〜20質量部含む組成物である。
本発明に係わるNBRに配合されるフィラーは、NBRに配合される公知のゴム補強剤であり、通常、カーボンブラック、無機補強剤と呼称されている無機物である。
架橋剤として、ジクミルペルオキシドを用いる場合、架橋助剤を併用してもよい。架橋助剤としては、例えば、イオウ;p−キノンジオキシム等のキノンジオキシム系架橋助剤;エチレングリコールジメタクリレート、トリメチロールプロパントリメタクリレート等のアクリル系架橋助剤;ジアリルフタレート、トリアリルイソシアヌレート等のアリル系架橋助剤;マレイミド系架橋助剤;ジビニルベンゼン;酸化亜鉛(例えば、ZnO#1・酸化亜鉛2種(JIS規格(K−1410))、ハクスイテック(株)製)、酸化マグネシウム、亜鉛華〔例えば、「META−Z102」(商品名;井上石灰工業(株)製)などの酸化亜鉛〕、活性亜鉛華等の金属酸化物が挙げられる。
本発明に係わる軟化剤としては、例えば、プロセスオイル、潤滑油、パラフィン油、流動パラフィン、石油アスファルト、ワセリン等の石油系軟化剤;コールタール等のコールタール系軟化剤;ヒマシ油、アマニ油、ナタネ油、大豆油、ヤシ油等の脂肪油系軟化剤;蜜ロウ、カルナウバロウ等のロウ類;ナフテン酸、パイン油、ロジンまたはその誘導体;テルペン樹脂、石油樹脂、クマロンインデン樹脂等の合成高分子物質;ジオクチルフタレート、ジオクチルアジペート等のエステル系軟化剤;その他、マイクロクリスタリンワックス、液状ポリブタジエン、変性液状ポリブタジエン、炭化水素系合成潤滑油、トール油、サブ(ファクチス)が挙げられ、これらのうちでは、石油系軟化剤が好ましく、プロセスオイルが特に好ましい。
本発明に係わるNBRに、老化防止剤(安定剤)を配合することにより、これから形成されるシールパッキンの寿命を長くすることができる。このような老化防止剤として、従来公知の老化防止剤、例えば、アミン系老化防止剤、フェノール系老化防止剤、イオウ系老化防止剤などがある。
加本発明に係わる加工助剤としては、一般に加工助剤としてゴムに配合されるものを広く使用することができる。具体的には、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、ステアリン酸亜鉛、ステアリン酸カルシウム、ラウリン酸亜鉛またはエステル類等が挙げられる。これらのうち、ステアリン酸が好ましい。
本発明に係わる活性剤としては、例えば、ジ−n−ブチルアミン、ジシクロヘキシルアミン、モノエラノールアミン等のアミン類;ジエチレングリコール、ポリエチレングリコール、レシチン、トリアリルートメリレート、脂肪族カルボン酸または芳香族カルボン酸の亜鉛化合物等の活性剤;過酸化亜鉛調整物;クタデシルトリメチルアンモニウムブロミド、合成ハイドロタルサイト、特殊四級アンモニウム化合物が挙げられる。
本発明に係わるNBRを用いて形成された積層体は、非発泡体であってもよいし、発泡体であってもよい。積層体が発泡体である場合にはNBR組成物には発泡剤が含まれていることが好ましい。
本発明の積層体を構成するエチレン・酢酸ビニル共重合体鹸化物は、エチレン・ビニルアルコール共重合体とも称されているエチレンとビニルアルコールとの共重合体である。
本発明の積層体を構成するエチレン・酢酸ビニル共重合体は、エチレンと酢酸ビニルとの共重合体であって、共重合体中に存在する酢酸ビニル含量が通常、共重合体中に存在する酢酸ビニル含量が通常、5〜50重量%、好ましくは5〜40重量%の範囲にある。
エチレン・酢酸ビニル共重合体にグラフトされる不飽和シラン化合物としては、種々公知の化合物、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニル(β−メトキシエトキシ)シラン、ビニルトリアセトキシシラン等のビニルシラン類、アクリロキシプロピルトリメトキシシラン、メタクリロキシプロピルトリメトキシシラン等のアクリル系シラン類等を挙げることができる。
本発明の積層体は、上記NBR組成物層と上記エチレン・酢酸ビニル共重合体鹸化物層とが積層されてなる積層体である。
(1)NBR:商品名Nipol 1042、結合アクリロニトリル(AN)量:33.5%、ML(1+4)100℃:77.5、非汚染性、比重:0.98[日本ゼオン(株)製]
(2)エチレン・酢酸ビニル共重合体
(2−1)エチレン・酢酸ビニル共重合体
エチレン・酢酸ビニル共重合体(EVA−1)として、商品名 エバフレック 銘柄EVA150 MFR:30g/10分、VA含有量:33重量%および密度:960kg/m3 三井・デュポンポリケミカル株式会社製を用いた。
(2−2)シラン変性エチレン・酢酸ビニル共重合体
実施例で用いたシラン変性エチレン・酢酸ビニル共重合体(変性EVA)は、以下の製造例1で製造した。
エチレン・酢酸ビニル共重合体〔商品名エバフレックス 銘柄EV260(MFR:6g/10分、密度:950kg/m3、酢酸ビニル含有量:28重量% 三井・デュポンポリケミカル製)を100質量部、ビニルトリメトキシシラン:1.7質量部、ジクミルパーオキサイド:0.15質量部、及び、ドデシルメルカプタン:0.03質量部を混合し、65mmφの多軸押出機に供給して押出温度200℃以上で溶融混練して押出した後、冷却ペレット化してシラン変性エチレン・酢酸ビニル共重合体(変性EVA)を得た。
エチレン・酢酸ビニル共重合体鹸化物からなるフィルムとして、EVOH 商品面F101B [(株)クラレ社製]融点:180℃、厚さ:100μmのフィルムを用いた(EVOHフィルム)。
(NBR組成物の調製)
第一段階として、BB−2型バンバリーミキサー(神戸製鋼所製)を用いて、上記NBRを30秒間素練りし、次いでこれに、NBR:100質量部に対して5質量部の酸化亜鉛(井上石灰工業(株)製)と、40質量部のFEFカーボンブラック(旭#60UG、旭カーボン(株)社製)及び1質量部のステアリン酸を140℃で2分間混練した。その後、ラムを上昇させ掃除を行ない、さらに、1分間混練を行ない、約150℃で排出し、第一段階の配合物を得た。
(T型剥離試験用の積層体の作製)
上記NBR組成物の調製で得られたNBR組成物をシート状に分出した。次に分出したNBR組成物シート50gを、延伸ポリエチレンテレフタレートフィルム(東レ製 商品名:ルミラー)で共重合体組成物シートの上下を挟んだ。ルミラーフィルムで上下が挟まれたNBR組成物シートを、50トンプレス成形機を用いて、120℃で2分間プレスし、t(厚さ)=1mm、20cm四方のNBR組成物シートを作製した。
実施例1で用いた変性EVAに替えて、EVA−1を用いる以外は、実施例1と同様に行い積層体を得た。評価結果を表1に示す。
実施例1において、中間層に用いた変性EVAを用いずに、シート(層1)とフィルム(層3)とを直接積層して積層体を得た。評価結果を表1に示す。
実施例1で用いたノクセラーNS−P及び硫黄に替えて、ジクミルパーオキサイド40%マスターバッチ(DCP−40C、日油(株)製)を用いる以外は、実施例1と同様に行い積層体を得た。評価結果を表1に示す。
実施例3で用いた変性EVAに替えて、EVA−1を用いる以外は、実施例3と同様に行い積層体を得た。評価結果を表1に示す。
実施例3において、中間層に用いた変性EVAを用いずに、シート(層1)とフィルム(層3)とを直接積層して積層体を得た。評価結果を表1に示す。
(NBR組成物の調製)
第一段階として、BB−2型バンバリーミキサー(神戸製鋼所製)を用いて、上記NBRを30秒間素練りし、次いでこれに、NBR:100質量部に対して10質量部のシラン変性EVAと、5質量部の酸化亜鉛(井上石灰工業(株)製)と、40質量部のFEFカーボンブラック(旭#60UG、旭カーボン(株)社製)及び1質量部のステアリン酸を140℃で2分間混練した。その後、ラムを上昇させ掃除を行ない、さらに、1分間混練を行ない、約150℃で排出し、第一段階の配合物を得た。
(T型剥離試験用の積層体の作製)
上記NBR組成物の調製で得られたNBR組成物をシート状に分出した。次に分出したNBR組成物シート50gを、延伸ポリエチレンテレフタレートフィルム(東レ製 商品名:ルミラー)で共重合体組成物シートの上下を挟んだ。ルミラーフィルムで上下が挟まれたNBR組成物シートを、50トンプレス成形機を用いて、120℃で2分間プレスし、t(厚さ)=1mm、20cm四方のNBR組成物シートを作製した。
実施例5で用いたノクセラーNS−P及び硫黄に替えて、ジクミルパーオキサイド40%マスターバッチ(DCP−40C、日油(株)製)を用いる以外は、実施例5と同様に行い、NBR組成物および積層体を得た。
実施例5で用いたNBR組成物に替えて、シラン変性EVAを配合しないNBR組成物を用いる以外は実施例5と同様に行い、NBR組成物およびその積層体を得た。
実施例6で用いたNBR組成物に替えて、シラン変性EVAを配合しないNBR組成物を用いる以外は実施例6と同様に行い、NBR組成物およびその積層体を得た。
Claims (6)
- アクリロニトリル・ブタジエンゴム、および当該アクリロニトリル・ブタジエンゴム100質量部に対して、シラン変性エチレン・酢酸ビニル共重合体を0〜50質量部含むことを特徴とするアクリロニトリル・ブタジエンゴム組成物。
- 請求項1に記載の組成物を含むアクリロニトリル・ブタジエンゴム層とエチレン・酢酸ビニル共重合体鹸化物層とが、エチレン・酢酸ビニル共重合体層を介して積層されていることを特徴とする積層体。
- 上記エチレン・酢酸ビニル共重合体層がシラン変性エチレン・酢酸ビニル共重合体を含むことを特徴とする請求項2に記載の積層体。
- アクリロニトリル・ブタジエンゴム、および当該アクリロニトリル・ブタジエンゴム100質量部に対して、シラン変性エチレン・酢酸ビニル共重合体を2〜50質量部含むことを特徴とする請求項1に記載のアクリロニトリル・ブタジエンゴム組成物。
- さらにジクミルペルオキシドを1.7〜20質量部含むことを特徴とする請求項1または請求項4に記載のアクリロニトリル・ブタジエンゴム組成物。
- 請求項4または5に記載のアクリロニトリル・ブタジエンゴム組成物からなる層とエチレン・酢酸ビニル共重合体鹸化物層とが積層されていることを特徴とする積層体。
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JPH09124803A (ja) * | 1995-08-28 | 1997-05-13 | Daicel Huels Ltd | 複合部材およびその製造方法 |
JP2002019030A (ja) * | 2000-07-05 | 2002-01-22 | Gomuno Inaki Kk | 燃料油不透過性ゴム積層体 |
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US20210079199A1 (en) | 2021-03-18 |
WO2019176797A1 (ja) | 2019-09-19 |
TWI788539B (zh) | 2023-01-01 |
EP3766929A4 (en) | 2021-12-15 |
EP3766929B1 (en) | 2023-02-22 |
TW201940571A (zh) | 2019-10-16 |
KR102422863B1 (ko) | 2022-07-19 |
KR20200108077A (ko) | 2020-09-16 |
EP3766929A1 (en) | 2021-01-20 |
JP7075479B2 (ja) | 2022-05-25 |
CN111836853A (zh) | 2020-10-27 |
CN111836853B (zh) | 2022-06-28 |
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