JP5176267B2 - Nitrile rubber composition and cross-linked product - Google Patents
Nitrile rubber composition and cross-linked product Download PDFInfo
- Publication number
- JP5176267B2 JP5176267B2 JP2005252131A JP2005252131A JP5176267B2 JP 5176267 B2 JP5176267 B2 JP 5176267B2 JP 2005252131 A JP2005252131 A JP 2005252131A JP 2005252131 A JP2005252131 A JP 2005252131A JP 5176267 B2 JP5176267 B2 JP 5176267B2
- Authority
- JP
- Japan
- Prior art keywords
- chelating agent
- agent
- acid
- nitrile
- nitrile rubber
- 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.)
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- 229920000459 Nitrile rubber Polymers 0.000 title claims description 58
- 239000000203 mixture Substances 0.000 title claims description 46
- 239000002738 chelating agent Substances 0.000 claims description 65
- -1 hydroxylimino Chemical group 0.000 claims description 62
- 239000000178 monomer Substances 0.000 claims description 52
- 229920001971 elastomer Polymers 0.000 claims description 31
- 239000005060 rubber Substances 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 29
- 239000003431 cross linking reagent Substances 0.000 claims description 29
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 26
- 239000004593 Epoxy Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000004132 cross linking Methods 0.000 claims description 18
- 125000002560 nitrile group Chemical group 0.000 claims description 18
- 229920006395 saturated elastomer Polymers 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 150000002825 nitriles Chemical class 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 150000001993 dienes Chemical class 0.000 claims description 12
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 10
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- 239000004711 α-olefin Substances 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 239000011630 iodine Substances 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 150000001451 organic peroxides Chemical class 0.000 claims description 6
- 239000004471 Glycine Substances 0.000 claims description 5
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 claims description 5
- HJMZMZRCABDKKV-UHFFFAOYSA-N carbonocyanidic acid Chemical compound OC(=O)C#N HJMZMZRCABDKKV-UHFFFAOYSA-N 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 150000002923 oximes Chemical class 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- XYZGDYPGGXDMGG-QVTWQEFQSA-J [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC[C@H](NC(C([O-])=O)C([O-])=O)C([O-])=O Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC[C@H](NC(C([O-])=O)C([O-])=O)C([O-])=O XYZGDYPGGXDMGG-QVTWQEFQSA-J 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910001507 metal halide Inorganic materials 0.000 claims description 3
- 150000005309 metal halides Chemical class 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims 1
- 230000032683 aging Effects 0.000 description 15
- 238000007906 compression Methods 0.000 description 14
- 230000006835 compression Effects 0.000 description 14
- 239000002253 acid Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 7
- MZZYGYNZAOVRTG-UHFFFAOYSA-N 2-hydroxy-n-(1h-1,2,4-triazol-5-yl)benzamide Chemical compound OC1=CC=CC=C1C(=O)NC1=NC=NN1 MZZYGYNZAOVRTG-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 230000003712 anti-aging effect Effects 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- XSQHUYDRSDBCHN-UHFFFAOYSA-N 2,3-dimethyl-2-propan-2-ylbutanenitrile Chemical compound CC(C)C(C)(C#N)C(C)C XSQHUYDRSDBCHN-UHFFFAOYSA-N 0.000 description 3
- UPPKSXGVDOLHDL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole;potassium Chemical compound [K].CC1=CC=CC2=NNN=C12 UPPKSXGVDOLHDL-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-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
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 description 2
- VVAAYFMMXYRORI-UHFFFAOYSA-N 4-butoxy-2-methylidene-4-oxobutanoic acid Chemical compound CCCCOC(=O)CC(=C)C(O)=O VVAAYFMMXYRORI-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
- LVIMPTXYQLEPFS-UHFFFAOYSA-N 5-methyl-2h-benzotriazole;potassium Chemical compound [K].C1=C(C)C=CC2=NNN=C21 LVIMPTXYQLEPFS-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical class [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- APEJMQOBVMLION-UHFFFAOYSA-N cinnamamide Chemical compound NC(=O)C=CC1=CC=CC=C1 APEJMQOBVMLION-UHFFFAOYSA-N 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-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
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 2
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- HLWRUJAIJJEZDL-UHFFFAOYSA-M sodium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC([O-])=O HLWRUJAIJJEZDL-UHFFFAOYSA-M 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
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- 125000002723 alicyclic group Chemical group 0.000 description 1
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- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
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- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
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- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- FYGDTMLNYKFZSV-UHFFFAOYSA-N mannotriose Natural products OC1C(O)C(O)C(CO)OC1OC1C(CO)OC(OC2C(OC(O)C(O)C2O)CO)C(O)C1O FYGDTMLNYKFZSV-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- SINFYWWJOCXYFD-UHFFFAOYSA-N methoxymethyl prop-2-enoate Chemical compound COCOC(=O)C=C SINFYWWJOCXYFD-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- 229940074369 monoethyl fumarate Drugs 0.000 description 1
- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 1
- 229940005650 monomethyl fumarate Drugs 0.000 description 1
- GFSJJVJWCAMZEV-UHFFFAOYSA-N n-(4-anilinophenyl)-2-methylprop-2-enamide Chemical compound C1=CC(NC(=O)C(=C)C)=CC=C1NC1=CC=CC=C1 GFSJJVJWCAMZEV-UHFFFAOYSA-N 0.000 description 1
- HKLPOBRVSAUJSG-UHFFFAOYSA-N n-(4-anilinophenyl)prop-2-enamide Chemical compound C1=CC(NC(=O)C=C)=CC=C1NC1=CC=CC=C1 HKLPOBRVSAUJSG-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003004 phosphinoxides Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 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
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017454 sodium diacetate Nutrition 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- POCQWBKETUXWSC-UHFFFAOYSA-N sodium;benzotriazol-2-ide Chemical compound [Na+].C1=CC=C2[N-]N=NC2=C1 POCQWBKETUXWSC-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LESFYQKBUCDEQP-UHFFFAOYSA-N tetraazanium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound N.N.N.N.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O LESFYQKBUCDEQP-UHFFFAOYSA-N 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 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
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- IMTKRLUCQZWPRY-UHFFFAOYSA-N triazine-4-carbaldehyde Chemical compound O=CC1=CC=NN=N1 IMTKRLUCQZWPRY-UHFFFAOYSA-N 0.000 description 1
- OAHWWXAJFXEIPX-UHFFFAOYSA-M tributyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](CCCC)(CCCC)CCCC OAHWWXAJFXEIPX-UHFFFAOYSA-M 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- FYGDTMLNYKFZSV-BYLHFPJWSA-N β-1,4-galactotrioside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@H](CO)O[C@@H](O[C@@H]2[C@@H](O[C@@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-BYLHFPJWSA-N 0.000 description 1
Description
本発明は、耐熱老化性に優れ、かつ、圧縮永久ひずみの小さな架橋物を与えるニトリルゴム組成物に関する。 The present invention relates to a nitrile rubber composition which is excellent in heat aging resistance and gives a crosslinked product having a small compression set.
従来から、ニトリル基含有高飽和共重合体ゴム(高飽和ニトリルゴム)は、耐油性、耐熱老化性および耐オゾン性に優れるゴムとして知られており、その架橋物はベルト、ホース、ガスケット、パッキン、シールなど種々の工業用、自動車用等のゴム製品の材料として用いられている。しかし、さらなる寿命の延長、高温環境での使用適合性、などのニーズから、耐熱老化性に一層優れ、かつ、圧縮永久ひずみが小さいことが求められるようになった。
高飽和ニトリルゴム架橋物の耐熱老化性を一層向上する試みとしては、pHが8.5以上のシリカ系無機配合剤とビニルシラン系カップリング剤を配合する方法(特許文献1)、強塩基、強塩基と弱酸の塩、カルボジイミド、ポリカルボジイミドおよびそれらの混合物を包含する群から選択される添加剤を配合する方法(特許文献2)などが提案されている。しかしながら、これらによって耐熱老化性と同時に圧縮永久ひずみの改善をも期待することはできない。そのため、高飽和ニトリルゴム架橋物の耐熱老化性の一層の引き上げと圧縮永久ひずみの低減とを、共に改善する技術の開発が望まれている。
Conventionally, nitrile group-containing highly saturated copolymer rubber (highly saturated nitrile rubber) has been known as a rubber excellent in oil resistance, heat aging resistance and ozone resistance, and its cross-linked products are belts, hoses, gaskets, packings. It is used as a material for various industrial and automotive rubber products such as seals. However, due to needs such as further extension of life and suitability for use in high temperature environments, it has become necessary to have better heat aging resistance and lower compression set.
As an attempt to further improve the heat aging resistance of the highly saturated nitrile rubber cross-linked product, a method of blending a silica-based inorganic compounding agent with a pH of 8.5 or more and a vinylsilane coupling agent (Patent Document 1), a strong base, A method of blending an additive selected from the group including a salt of a base and a weak acid, carbodiimide, polycarbodiimide, and a mixture thereof (Patent Document 2) has been proposed. However, it is not possible to expect improvement in compression set as well as heat aging resistance. Therefore, it is desired to develop a technique for improving both the heat aging resistance of the highly saturated nitrile rubber cross-linked product and the reduction of compression set.
本発明の目的は、耐熱老化性に優れると共に圧縮永久ひずみが小さい架橋物を与える、ニトリル基含有高飽和共重合体ゴム組成物を提供することにある。 An object of the present invention is to provide a nitrile group-containing highly saturated copolymer rubber composition that provides a cross-linked product having excellent heat aging resistance and low compression set.
本発明者らは、前記課題を解決するために鋭意研究した結果、カルボキシル基を有するニトリル基含有高飽和共重合体ゴムとキレート化剤と架橋剤とを含有してなるニトリルゴム組成物により上記の目的が達成されることを見出し、本発明を完成するに到った。
かくして本発明によれば、α,β−エチレン性不飽和ニトリル単量体、ジエン単量体またはα−オレフィン単量体、およびカルボキシル基含有単量体と、必要に応じて共重合可能なその他の単量体とを乳化重合し、場合によっては、さらに水素添加反応を行う方法により得られた、α,β−エチレン性不飽和ニトリル単量体単位含有量が10〜60重量%でヨウ素価が100以下である、カルボキシル基を有するニトリル基含有高飽和共重合体ゴム(A)100重量部に対して、キレート化剤(B)0.3〜10重量部、架橋剤(C)0.3〜10重量部の割合で含有してなり、かつ、トリフェニルホスフィンを含まないニトリルゴム組成物であって、
(i)該キレート化剤(B)が、ヒドラジド系キレート化剤、ヒドラジン系キレート化剤、多価アミン酢酸系キレート化剤、ニトリロ酢酸系キレート化剤、ヒドロキシルイミノ系キレート化剤、オキサミド系キレート化剤、オキシム系キレート化剤、グリシン系キレート化剤、1,3−ジアミノ−2−ヒドロキシプロパン四酢酸ナトリウム塩、及びジカルボキシメチルグルタミン酸四ナトリウム塩からなる群より選ばれる少なくとも1種の、ドナー窒素原子を1個以上含有する化学構造を有し、かつ、含窒素複素環を含有しないキレート化剤であり、及び、
(ii)該架橋剤(C)が、有機過酸化物、硫黄系架橋剤、樹脂架橋剤、多価アミン化合物、多価エポキシ化合物、多価イソシアナート化合物、多価アルコール化合物、アジリジン化合物、塩基性金属酸化物、及び有機金属ハロゲン化物からなる群より選ばれる少なくとも1種の架橋剤であるニトリルゴム組成物が提供される。本発明の架橋性ニトリルゴム組成物において、好ましくは前記ニトリル基含有高飽和共重合体ゴム(A)の有するカルボキシル基の量が5×10−4〜5×10−1ephrである。
また別の本発明によれば、これらの架橋性ニトリルゴム組成物を架橋してなる架橋物が提供される。
As a result of diligent research to solve the above-mentioned problems, the present inventors have found that the above-described nitrile rubber composition containing a nitrile group-containing highly saturated copolymer rubber having a carboxyl group, a chelating agent, and a crosslinking agent. As a result, the present invention has been achieved.
Thus, according to the present invention, α, β-ethylenically unsaturated nitrile monomer, diene monomer or α-olefin monomer, and carboxyl group-containing monomer, and other copolymerizable if necessary In some cases, the content of α, β-ethylenically unsaturated nitrile monomer units obtained by a method of further hydrogenation reaction is 10 to 60% by weight and iodine value 100 parts by weight of the nitrile group-containing highly saturated copolymer rubber (A) having a carboxyl group of not more than 100, 0.3 to 10 parts by weight of the chelating agent (B), and 0. A nitrile rubber composition containing 3 to 10 parts by weight and containing no triphenylphosphine,
(I) The chelating agent (B) is a hydrazide chelating agent, a hydrazine chelating agent, a polyvalent amine acetic acid chelating agent, a nitriloacetic acid chelating agent, a hydroxylimino chelating agent, or an oxamide chelating agent. At least one donor selected from the group consisting of an agent, an oxime chelator, a glycine chelator, 1,3-diamino-2-hydroxypropanetetraacetic acid sodium salt, and dicarboxymethylglutamic acid tetrasodium salt A chelating agent having a chemical structure containing one or more nitrogen atoms and not containing a nitrogen-containing heterocycle; and
(Ii) The crosslinking agent (C) is an organic peroxide, a sulfur-based crosslinking agent, a resin crosslinking agent, a polyvalent amine compound, a polyvalent epoxy compound, a polyvalent isocyanate compound, a polyhydric alcohol compound, an aziridine compound, a base There is provided a nitrile rubber composition which is at least one crosslinking agent selected from the group consisting of a conductive metal oxide and an organometallic halide. In the crosslinkable nitrile rubber composition of the present invention, the amount of carboxyl groups of the nitrile group-containing highly saturated copolymer rubber (A) is preferably 5 × 10 −4 to 5 × 10 −1 ephr.
Moreover, according to another this invention, the crosslinked material formed by bridge | crosslinking these crosslinkable nitrile rubber compositions is provided.
本発明により、耐熱老化性に優れると共に圧縮永久ひずみが小さい架橋物を与える、ニトリル基含有高飽和共重合体ゴム組成物が提供される。 The present invention provides a nitrile group-containing highly saturated copolymer rubber composition that provides a cross-linked product that is excellent in heat aging resistance and has a low compression set.
本発明のニトリルゴム組成物は、α,β−エチレン性不飽和ニトリル単量体、ジエン単量体またはα−オレフィン単量体、およびカルボキシル基含有単量体と、必要に応じて共重合可能なその他の単量体とを乳化重合する方法により得られた、α,β−エチレン性不飽和ニトリル単量体単位含有量が10〜60重量%でヨウ素価が100以下である、カルボキシル基を有するニトリル基含有高飽和共重合体ゴム(A)100重量部に対して、キレート化剤(B)0.3〜10重量部、架橋剤(C)0.3〜10重量部の割合で含有してなり、かつ、トリフェニルホスフィンを含まないニトリルゴム組成物であって、
(i)該キレート化剤(B)が、ヒドラジド系キレート化剤、ヒドラジン系キレート化剤、多価アミン酢酸系キレート化剤、ニトリロ酢酸系キレート化剤、ヒドロキシルイミノ系キレート化剤、オキサミド系キレート化剤、オキシム系キレート化剤、グリシン系キレート化剤、1,3−ジアミノ−2−ヒドロキシプロパン四酢酸ナトリウム塩、及びジカルボキシメチルグルタミン酸四ナトリウム塩からなる群より選ばれる少なくとも1種の、ドナー窒素原子を1個以上含有する化学構造を有し、かつ、含窒素複素環を含有しないキレート化剤であり、及び、
(ii)該架橋剤(C)が、有機過酸化物、硫黄系架橋剤、樹脂架橋剤、多価アミン化合物、多価エポキシ化合物、多価イソシアナート化合物、多価アルコール化合物、アジリジン化合物、塩基性金属酸化物、及び有機金属ハロゲン化物からなる群より選ばれる少なくとも1種の架橋剤であるニトリルゴム組成物である。
The nitrile rubber composition of the present invention can be copolymerized with an α, β-ethylenically unsaturated nitrile monomer, a diene monomer or an α-olefin monomer, and a carboxyl group-containing monomer as necessary. Do the other monomer obtained by the method of emulsion polymerization, alpha, beta-ethylenically unsaturated nitrile monomer unit content of iodine value 10 to 60% by weight is 100 or less, a carboxyl group against the nitrile group-containing highly saturated copolymer rubber (a) 100 parts by weight of having, chelating agent (B) 0.3 to 10 parts by weight, a proportion of the crosslinking agent (C) 0.3 to 10 parts by weight Ri Na and and a nitrile rubber composition containing no triphenylphosphine,
(I) The chelating agent (B) is a hydrazide chelating agent, a hydrazine chelating agent, a polyvalent amine acetic acid chelating agent, a nitriloacetic acid chelating agent, a hydroxylimino chelating agent, or an oxamide chelating agent. At least one donor selected from the group consisting of an agent, an oxime chelator, a glycine chelator, 1,3-diamino-2-hydroxypropanetetraacetic acid sodium salt, and dicarboxymethylglutamic acid tetrasodium salt A chelating agent having a chemical structure containing one or more nitrogen atoms and not containing a nitrogen-containing heterocycle; and
(Ii) The crosslinking agent (C) is an organic peroxide, a sulfur-based crosslinking agent, a resin crosslinking agent, a polyvalent amine compound, a polyvalent epoxy compound, a polyvalent isocyanate compound, a polyhydric alcohol compound, an aziridine compound, a base A nitrile rubber composition which is at least one crosslinking agent selected from the group consisting of conductive metal oxides and organometallic halides .
カルボキシル基を有するニトリル基含有高飽和共重合体ゴム(A)(以下、「ニトリルゴム(A)」と記すことがある。)のα,β−エチレン性不飽和ニトリル単量体単位を形成するα,β−エチレン性不飽和ニトリル単量体は、ニトリル基を有するα,β−エチレン性不飽和化合物であれば限定されず、アクリロニトリル;α−クロロアクリロニトリル、α−ブロモアクリロニトリルなどのα−ハロゲノアクリロニトリル;メタクリロニトリルなどのα−アルキルアクリロニトリルなどが挙げられ、アクリロニトリルおよびメタクリロニトリルが好ましい。α,β−エチレン性不飽和ニトリル単量体はこれらの複数種を併用してもよい。 Forming α, β-ethylenically unsaturated nitrile monomer unit of nitrile group-containing highly saturated copolymer rubber (A) (hereinafter sometimes referred to as “nitrile rubber (A)”) having a carboxyl group The α, β-ethylenically unsaturated nitrile monomer is not limited as long as it is an α, β-ethylenically unsaturated compound having a nitrile group, and α-halogeno such as acrylonitrile; α-chloroacrylonitrile, α-bromoacrylonitrile, etc. Examples include acrylonitrile; α-alkylacrylonitrile such as methacrylonitrile, and acrylonitrile and methacrylonitrile are preferable. These α, β-ethylenically unsaturated nitrile monomers may be used in combination.
ニトリルゴム(A)におけるα,β−エチレン性不飽和ニトリル単量体単位の含有量は、10〜60重量%、好ましくは15〜55重量%、より好ましくは20〜50重量%である。α,β−エチレン性不飽和ニトリル単量体単位の含有量が少なすぎると架橋物は耐油性が低下するおそれがあり、逆に、多すぎると耐寒性が低下する可能性がある。 The content of the α, β-ethylenically unsaturated nitrile monomer unit in the nitrile rubber (A) is 10 to 60% by weight, preferably 15 to 55% by weight, more preferably 20 to 50% by weight. If the content of the α, β-ethylenically unsaturated nitrile monomer unit is too low, the cross-linked product may have low oil resistance, and conversely if too high, cold resistance may be reduced.
ニトリルゴム(A)は、架橋物がゴム弾性を保有するために、通常、ジエン単量体単位またはα−オレフィン単量体単位をも有する。 The nitrile rubber (A) usually has a diene monomer unit or an α-olefin monomer unit because the crosslinked product has rubber elasticity.
ジエン単量体としては、1,3−ブタジエン、イソプレン、2,3−ジメチル−1,3−ブタジエン、1,3−ペンタジエンなどの炭素数が4以上の共役ジエン;1,4−ペンタジエン、1,4−ヘキサジエンなどの好ましくは炭素数が4〜12の非共役ジエンが挙げられる。これらの中では共役ジエンが好ましく、1,3−ブタジエンがより好ましい。 Examples of the diene monomer include conjugated dienes having 4 or more carbon atoms such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene; 1,4-pentadiene, 1 Preferred examples include non-conjugated dienes having 4 to 12 carbon atoms, such as 1,4-hexadiene. Among these, conjugated dienes are preferable, and 1,3-butadiene is more preferable.
α−オレフィン単量体としては、好ましくは炭素数が2〜12のものであり、エチレン、プロピレン、1−ブテン、4−メチル−1−ペンテン、1−ヘキセン、1−オクテンなどが例示される。 The α-olefin monomer preferably has 2 to 12 carbon atoms, and examples thereof include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene. .
ニトリルゴム(A)におけるジエン単量体単位またはα−オレフィン単量体単位の含有量は、好ましくは25〜85重量%、より好ましくは35〜80重量%、特に好ましくは45〜75重量%である。これら単量体の単位が少なすぎると架橋物のゴム弾性が低下するおそれがあり、多すぎると耐油性が低下する可能性がある。 The content of the diene monomer unit or α-olefin monomer unit in the nitrile rubber (A) is preferably 25 to 85% by weight, more preferably 35 to 80% by weight, and particularly preferably 45 to 75% by weight. is there. If the number of these monomer units is too small, the rubber elasticity of the cross-linked product may be lowered, and if it is too much, the oil resistance may be lowered.
ニトリル基含有高飽和共重合体ゴム(A)にカルボキシル基を含有させる方法としては、α,β−エチレン性不飽和ニトリル単量体、ジエン単量体またはα−オレフィン単量体、およびカルボキシル基含有単量体とを共重合する方法が挙げられる。 Examples of the method for adding a carboxyl group to the nitrile group-containing highly saturated copolymer rubber (A) include an α 1 , β-ethylenically unsaturated nitrile monomer, a diene monomer or an α-olefin monomer, and a carboxyl group how copolymerizing containing monomers.
前記共重合法で用いられるカルボキシル基含有単量体としては、α,β−エチレン性不飽和ジカルボン酸モノアルキルエステル、α,β−エチレン性不飽和モノカルボン酸およびα,β−エチレン性不飽和多価カルボン酸が挙げられる。また、カルボキシル基含有単量体には、これらの単量体のカルボキシル基がカルボン酸塩を形成する単量体も含まれる。また、α,β−エチレン性不飽和多価カルボン酸無水物も、共重合後に酸無水物基を開裂させてカルボキシル基を形成するので、カルボキシル基含有単量体として用いることができる。 As the carboxyl group-containing monomer used in the copolymerization method, α, β-ethylenically unsaturated dicarboxylic acid monoalkyl ester, α, β-ethylenically unsaturated monocarboxylic acid and α, β-ethylenically unsaturated A polyvalent carboxylic acid is mentioned. In addition, the carboxyl group-containing monomer includes monomers in which the carboxyl group of these monomers forms a carboxylate. Further, α, β-ethylenically unsaturated polyvalent carboxylic acid anhydrides can also be used as carboxyl group-containing monomers because they form a carboxyl group by cleaving the acid anhydride group after copolymerization.
α,β−エチレン性不飽和ジカルボン酸モノアルキルエステルとしては、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノプロピル、マレイン酸モノn−ブチルなどのマレイン酸モノアルキルエステル;マレイン酸モノシクロペンチル、マレイン酸モノシクロヘキシル、マレイン酸モノシクロヘプチルなどのマレイン酸モノシクロアルキルエステル;フマル酸モノメチル、フマル酸モノエチル、フマル酸モノプロピル、フマル酸モノn−ブチルなどのフマル酸モノアルキルエステル;フマル酸モノシクロペンチル、フマル酸モノシクロヘキシル、フマル酸モノシクロヘプチルなどのフマル酸モノシクロアルキルエステル;イタコン酸モノメチル、イタコン酸モノエチル、イタコン酸モノプロピル、イタコン酸モノn−ブチルなどのイタコン酸モノアルキルエステル;イタコン酸モノシクロペンチル、イタコン酸モノシクロヘキシル、イタコン酸モノシクロヘプチルなどのイタコン酸モノシクロアルキルエステル;などが挙げられ、イタコン酸モノn−ブチル、フマル酸モノn−ブチルおよびマレイン酸モノn−ブチルが特に好ましい。 As the α, β-ethylenically unsaturated dicarboxylic acid monoalkyl ester, maleic acid monoalkyl ester such as monomethyl maleate, monoethyl maleate, monopropyl maleate, mono n-butyl maleate; monocyclopentyl maleate, maleic acid Monocyclohexyl maleate such as monocyclohexyl and monocycloheptyl maleate; monoalkyl fumarate such as monomethyl fumarate, monoethyl fumarate, monopropyl fumarate and mono n-butyl fumarate; monocyclopentyl fumarate, fumarate Monocyclohexyl esters of fumaric acid such as monocyclohexyl acid and monocycloheptyl fumarate; monomethyl itaconate, monoethyl itaconate, monopropyl itaconate, mono n-butyl itaconate, etc. Itaconic acid monoalkyl ester of itaconic acid monocyclopentyl, itaconic acid monocyclohexyl, itaconic acid monocycloheptyl etc. Itaconic acid monocycloalkyl ester; and the like, and itaconic acid mono n-butyl, fumarate mono n-butyl and Mono n-butyl maleate is particularly preferred.
また、α,β−エチレン性不飽和モノカルボン酸としては、アクリル酸、メタクリル酸などが挙げられる。α,β−エチレン性不飽和多価カルボン酸としては、イタコン酸、フマル酸、マレイン酸などが挙げられる。α,β−エチレン性不飽和多価カルボン酸無水物としては、無水マレイン酸などが挙げられる。 Examples of the α, β-ethylenically unsaturated monocarboxylic acid include acrylic acid and methacrylic acid. Examples of the α, β-ethylenically unsaturated polyvalent carboxylic acid include itaconic acid, fumaric acid and maleic acid. Examples of the α, β-ethylenically unsaturated polyvalent carboxylic acid anhydride include maleic anhydride.
ニトリルゴム(A)は、また、α,β−エチレン性不飽和ニトリル単量体、ジエン単量体またはα−オレフィン単量体およびカルボキシル基含有単量体と共重合可能なその他の単量体の単位を含有することができる。共重合可能なその他の単量体としては、α,β−エチレン性不飽和ジカルボン酸モノアルキルエステル以外のα,β−エチレン性不飽和カルボン酸エステル、芳香族ビニル化合物、フッ素含有ビニル化合物、共重合性老化防止剤などが例示される。 Nitrile rubber (A) is also an α, β-ethylenically unsaturated nitrile monomer, diene monomer or α-olefin monomer and other monomer copolymerizable with a carboxyl group-containing monomer. The unit can be contained. Other monomers that can be copolymerized include α, β-ethylenically unsaturated dicarboxylic acid monoalkyl esters other than α, β-ethylenically unsaturated dicarboxylic acid esters, aromatic vinyl compounds, fluorine-containing vinyl compounds, Examples thereof include a polymerizable antiaging agent.
α,β−エチレン性不飽和ジカルボン酸モノアルキルエステル以外のα,β−エチレン性不飽和カルボン酸エステルとしては、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸n−ドデシル、メタクリル酸メチル、メタクリル酸エチルなどのアクリル酸アルキルエステルおよびメタクリル酸アルキルエステルであって、アルキル基の炭素数が1〜18のもの;アクリル酸メトキシメチル、メタクリル酸メトキシエチルなどのアクリル酸アルコキシアルキルエステルおよびメタクリル酸アルコキシエステルであって、アルコキシアルキル基の炭素数が2〜12のもの;アクリル酸α−シアノエチル、アクリル酸β−シアノエチル、メタクリル酸シアノブチルなどのアクリル酸シアノアルキルエステルおよびメタクリル酸シアノアルキルエステルであって、シアノアルキル基の炭素数が2〜12のもの;アクリル酸2−ヒドロキシエチル、アクリル酸3−ヒドロキシプロピルなどのアクリル酸ヒドロキシアルキルエステルおよびメタクリル酸ヒドロキシアルキルエステルであって、ヒドロキシアルキル基の炭素数が1〜12のもの; マレイン酸ジメチル、フマル酸ジメチル、イタコン酸ジメチル、イタコン酸ジエチルなどの不飽和多価カルボン酸ポリアルキルエステル;アクリル酸ジメチルアミノメチル、アクリル酸ジエチルアミノエチルなどのアミノ基含有α,β−エチレン性不飽和カルボン酸エステル;アクリル酸トリフルオロエチル、メタクリル酸テトラフルオロプロピルなどのフルオロアルキル基含有アクリル酸エステルおよびフルオロアルキル基含有メタクリル酸エステル;アクリル酸フルオロベンジル、メタクリル酸フルオロベンジルなどのフッ素置換ベンジル基含有アクリル酸エステルおよびフッ素置換ベンジル基含有メタクリル酸エステル;などが挙げられる。 Examples of the α, β-ethylenically unsaturated carboxylic acid ester other than the α, β-ethylenically unsaturated dicarboxylic acid monoalkyl ester include methyl acrylate, ethyl acrylate, n-dodecyl acrylate, methyl methacrylate, and methacrylic acid. Acrylic acid alkyl esters and methacrylic acid alkyl esters such as ethyl acrylate, wherein the alkyl group has 1 to 18 carbon atoms; alkoxy alkoxy esters such as methoxymethyl acrylate and methoxyethyl acrylate, and methacrylic acid alkoxy esters An alkoxyalkyl group having 2 to 12 carbon atoms; acrylic acid cyanoalkyl ester such as α-cyanoethyl acrylate, β-cyanoethyl acrylate, cyanobutyl methacrylate and cyanoalkyl methacrylate; A cyanoalkyl group having 2 to 12 carbon atoms; acrylic acid hydroxyalkyl esters and methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate and 3-hydroxypropyl acrylate, Having 1 to 12 carbon atoms; unsaturated polycarboxylic acid polyalkyl ester such as dimethyl maleate, dimethyl fumarate, dimethyl itaconate, diethyl itaconate; dimethylaminomethyl acrylate, diethylaminoethyl acrylate, etc. Amino group-containing α, β-ethylenically unsaturated carboxylic acid ester; fluoroalkyl group-containing acrylic acid ester such as trifluoroethyl acrylate and tetrafluoropropyl methacrylate, and fluoroalkyl group-containing methacrylic acid ester Fluorine-substituted benzyl group-containing acrylic acid ester and fluorine-substituted benzyl group-containing methacrylic acid ester such as fluorobenzyl acrylate and fluorobenzyl methacrylate.
芳香族ビニル化合物としては、スチレン、α−メチルスチレン、ビニルピリジンなどが挙げられる。 Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyl pyridine and the like.
フッ素含有ビニル化合物としては、フルオロエチルビニルエーテル、フルオロプロピルビニルエーテル、o−トリフルオロメチルスチレン、ペンタフルオロ安息香酸ビニル、ジフルオロエチレン、テトラフルオロエチレンなどが挙げられる。 Examples of the fluorine-containing vinyl compound include fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-trifluoromethylstyrene, vinyl pentafluorobenzoate, difluoroethylene, and tetrafluoroethylene.
共重合性老化防止剤としては、N−(4−アニリノフェニル)アクリルアミド、N−(4−アニリノフェニル)メタクリルアミド、N−(4−アニリノフェニル)シンナムアミド、N−(4−アニリノフェニル)クロトンアミド、 N−フェニル−4−(3−ビニルベンジルオキシ)アニリン、N−フェニル−4−(4−ビニルベンジルオキシ)アニリンなどが例示される。 Examples of copolymerizable anti-aging agents include N- (4-anilinophenyl) acrylamide, N- (4-anilinophenyl) methacrylamide, N- (4-anilinophenyl) cinnamamide, N- (4-anilino). Examples include phenyl) crotonamide, N-phenyl-4- (3-vinylbenzyloxy) aniline, N-phenyl-4- (4-vinylbenzyloxy) aniline and the like.
これらの共重合可能な他の単量体は、複数種類を併用してもよい。ニトリルゴム(A)が有する、これらの他の単量体単位の含有量は、好ましくは80重量%以下、より好ましくは70重量%以下、特に好ましくは60重量%以下である。 These other copolymerizable monomers may be used in combination. The content of these other monomer units contained in the nitrile rubber (A) is preferably 80% by weight or less, more preferably 70% by weight or less, and particularly preferably 60% by weight or less.
本発明で使用するニトリルゴム(A)におけるカルボキシル基の含有量、すなわち、ニトリルゴム(A)100g当たりのカルボキシル基数は、5×10−4〜5×10−1ephr、好ましくは1×10−3〜1×10−1ephr、より好ましくは5×10−3〜6×10−2ephrである。ニトリルゴム(A)のカルボキシル基含有量が少なすぎると架橋物の機械的強度が低下するおそれがあり、多すぎると架橋物の耐寒性が低下する可能性がある。 The content of carboxyl groups in the nitrile rubber (A) used in the present invention, that is, the number of carboxyl groups per 100 g of the nitrile rubber (A) is 5 × 10 −4 to 5 × 10 −1 ephr, preferably 1 × 10 − 3 to 1 × 10 −1 ephr, more preferably 5 × 10 −3 to 6 × 10 −2 ephr. If the carboxyl group content of the nitrile rubber (A) is too small, the mechanical strength of the crosslinked product may be lowered, and if it is too large, the cold resistance of the crosslinked product may be lowered.
ニトリルゴム(A)は、そのヨウ素価が100以下、好ましくは30以下、より好ましくは20以下、特に好ましくは15以下のものである。ニトリルゴム(A)のヨウ素価が高すぎると、架橋物の耐オゾン性が低下するおそれがある。 The nitrile rubber (A) has an iodine value of 100 or less, preferably 30 or less, more preferably 20 or less, and particularly preferably 15 or less. If the iodine value of the nitrile rubber (A) is too high, the ozone resistance of the crosslinked product may be lowered.
また、ニトリルゴム(A)のムーニー粘度(ML1+4、100℃)は、好ましくは15〜200、より好ましくは30〜100、特に好ましくは45〜90である。ニトリルゴム(A)のムーニー粘度が低すぎると架橋物の強度特性が低下するおそれがあり、ムーニー粘度が高すぎるとニトリルゴム組成物の加工性が低下するおそれがある。 The Mooney viscosity (ML 1 + 4 , 100 ° C.) of the nitrile rubber (A) is preferably 15 to 200, more preferably 30 to 100, and particularly preferably 45 to 90. If the Mooney viscosity of the nitrile rubber (A) is too low, the strength properties of the cross-linked product may be reduced, and if the Mooney viscosity is too high, the processability of the nitrile rubber composition may be reduced.
ニトリルゴム(A)の製造方法は、α,β−エチレン性不飽和ニトリル単量体、ジエン単量体またはα−オレフィン単量体、カルボキシル基含有単量体、および必要に応じて加えられるこれらと共重合可能なその他の単量体を共重合する方法が簡便で好ましい。重合法としては、公知の乳化重合法、懸濁重合法、塊状重合法および溶液重合法のいずれをも用いることができるが、重合反応の制御の容易性等から、乳化重合法が好ましい。
共重合して得られた共重合体のヨウ素価が前記の範囲より高い場合は、共重合体の水素化(水素添加反応)を行うと良い。
水素化の方法は特に限定されず、公知の方法を採用すればよい。
The method for producing the nitrile rubber (A) includes an α, β-ethylenically unsaturated nitrile monomer, a diene monomer or an α-olefin monomer, a carboxyl group-containing monomer, and those added as necessary. A method of copolymerizing other monomers copolymerizable with the polymer is simple and preferred. As the polymerization method, any of the known emulsion polymerization method, suspension polymerization method, bulk polymerization method and solution polymerization method can be used, but the emulsion polymerization method is preferable from the viewpoint of easy control of the polymerization reaction.
When the iodine value of the copolymer obtained by copolymerization is higher than the above range, the copolymer may be hydrogenated (hydrogenation reaction).
The method for hydrogenation is not particularly limited, and a known method may be employed.
ニトリルゴム組成物が有するキレート化剤(B)は、金属に二座以上で配位して金属キレート(中心に金属を結合した環状の錯体)を形成する化合物であれば限定されないが、金属と配位結合しうるドナー窒素原子を1個以上含有するものが好ましい。また、キレート化剤(B)の炭素数は、好ましくは4〜50、より好ましくは6〜40である。
ニトリルゴム組成物で用いるキレート化剤(B)の例としては、3−(N−サリチロイル)アミノ−1,2,4−トリアゾール、1H−ベンゾトリアゾール、1H−ベンゾトリアゾールナトリウム塩、4−メチルベンゾトリアゾール、5−メチルベンゾトリアゾール、4−メチル−1H−ベンゾトリアゾールカリウム塩、5−メチル−1H−ベンゾトリアゾールカリウム塩、4−メチル−1H−ベンゾトリアゾールアミン塩、5−メチル−1H−ベンゾトリアゾールアミン塩などのトリアゾール系キレート化剤;デカメチレンカルボン酸ジサリチロイルヒドラジド、N,N’−ビス〔3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオニル〕ヒドラジンなどのヒドラジド系およびヒドラジン系キレート化剤;N−アルケニルプロピレンジアミン3酢酸、エチレンジアミン四酢酸、エチレンジアミン四酢酸アンモニウム塩、エチレンジアミン四酢酸アミン塩、エチレンジアミン四酢酸金属塩、ヒドロキシエチルエチレンジアミン三酢酸、ヒドロキシエチルエチレンジアミン三酢酸ナトリウム塩、ジヒドロキシエチルエチレンジアミン二酢酸、ジヒドロキシエチルエチレンジアミン二酢酸ナトリウム塩、1,3−プロパンジアミン四酢酸、ジエチレントリアミン五酢酸、ジエチレントリアミン五酢酸ナトリウム塩、トリエチレンテトラミン六酢酸などの多価アミン酢酸系キレート化剤;ニトリロ三酢酸、ニトリロ三酢酸ナトリウム塩、ニトリロ三酢酸アンモニウム塩などのニトリロ酢酸系キレート化剤;ヒドロキシエチルイミノ二酢酸、ヒドロキシエチルイミノ二酢酸ナトリウム塩などのヒドロキシルイミノ系キレート化剤;2,2’−オキサミドビス〔エチル−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート〕などのオキサミド系キレート化剤;2,3−ブタンジオンジオキシムなどのオキシム系キレート化剤;ジヒドロキシエチルグリシン、ジヒドロキシエチルグリシンナトリウム塩などのグリシン系キレート化剤;1,3−ジアミノ−2−ヒドロキシプロパン四酢酸ナトリウム塩、ジカルボキシメチルグルタミン酸四ナトリウム塩などが挙げられる。なかでも3−(N−サリチロイル)アミノ−1,2,4−トリアゾール、デカメチレンカルボン酸ジサリチロイルヒドラジド、4−メチル−1H−ベンゾトリアゾールカリウム塩、5−メチル−1H−ベンゾトリアゾールカリウム塩、エチレンジアミン四酢酸およびエチレンジアミン四酢酸ナトリウム塩が好ましい。また、これらのキレート化剤を複数併用してもよい。
本発明では、キレート化剤として、ヒドラジド系キレート化剤、ヒドラジン系キレート化剤、多価アミン酢酸系キレート化剤、ニトリロ酢酸系キレート化剤、ヒドロキシルイミノ系キレート化剤、オキサミド系キレート化剤、オキシム系キレート化剤、グリシン系キレート化剤、1,3−ジアミノ−2−ヒドロキシプロパン四酢酸ナトリウム塩、及びジカルボキシメチルグルタミン酸四ナトリウム塩からなる群より選ばれる少なくとも1種の、ドナー窒素原子を1個以上含有する化学構造を有し、かつ、含窒素複素環を含有しないキレート化剤を用いる。
Chelating agents nitrile rubber composition has (B) is not limited as long as it is a compound metal coordinated with bidentate or higher to form a metal chelate (cyclic complexes bound to metal center), and the metal Those containing one or more donor nitrogen atoms capable of coordination bonding are preferred. Moreover, carbon number of a chelating agent (B) becomes like this. Preferably it is 4-50, More preferably, it is 6-40.
Examples of chelating agent (B) used in the nitrile rubber composition, 3- (N-salicyloyl) amino-1,2,4-triazole, 1H-benzotriazole, 1H-benzotriazole sodium salt, 4-methylbenzo Triazole, 5-methylbenzotriazole, 4-methyl-1H-benzotriazole potassium salt, 5-methyl-1H-benzotriazole potassium salt, 4-methyl-1H-benzotriazoleamine salt, 5-methyl-1H-benzotriazoleamine Triazole chelating agents such as salts; hydrazides such as decamethylene carboxylic acid disalicyloyl hydrazide, N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine And hydrazine chelating agents; N-alkenyl groups Lopylenediamine triacetic acid, ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid ammonium salt, ethylenediaminetetraacetic acid amine salt, ethylenediaminetetraacetic acid metal salt, hydroxyethylethylenediaminetriacetic acid, hydroxyethylethylenediaminetriacetic acid sodium salt, dihydroxyethylethylenediaminediacetic acid, dihydroxyethylethylenediamine Polyacetic acid acetic acid chelating agents such as sodium diacetate, 1,3-propanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, diethylenetriaminepentaacetic acid sodium salt, triethylenetetraminehexaacetic acid; nitrilotriacetic acid, nitrilotriacetic acid sodium salt, Nitriloacetic acid chelating agents such as ammonium nitrilotriacetate; hydroxyethyliminodiacetic acid, hydroxyethyliminodiacetic acid Hydroxylimino chelating agents such as lithium salts; oxamide chelating agents such as 2,2′-oxamidobis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]; Oxime chelating agents such as 3-butanedione dioxime; glycine chelating agents such as dihydroxyethyl glycine and dihydroxyethyl glycine sodium salt; 1,3-diamino-2-hydroxypropanetetraacetic acid sodium salt, dicarboxymethyl glutamic acid Examples include tetrasodium salt. Among them, 3- (N-salicyloyl) amino-1,2,4-triazole, decamethylenecarboxylic acid disalicyloyl hydrazide, 4-methyl-1H-benzotriazole potassium salt, 5-methyl-1H-benzotriazole potassium salt Ethylenediaminetetraacetic acid and ethylenediaminetetraacetic acid sodium salt are preferred. A plurality of these chelating agents may be used in combination.
In the present invention, as a chelating agent, a hydrazide chelating agent, a hydrazine chelating agent, a polyvalent amine acetic acid chelating agent, a nitriloacetic acid chelating agent, a hydroxylimino chelating agent, an oxamide chelating agent, At least one donor nitrogen atom selected from the group consisting of an oxime chelating agent, a glycine chelating agent, 1,3-diamino-2-hydroxypropanetetraacetic acid sodium salt, and dicarboxymethylglutamic acid tetrasodium salt; A chelating agent having a chemical structure containing at least one and containing no nitrogen-containing heterocycle is used.
本発明のニトリルゴム組成物におけるキレート化剤(B)の含有量は、ニトリルゴム(A)100重量部に対して、好ましくは0.1〜15重量部、より好ましくは0.2〜13重量部、特に好ましくは0.3〜10重量部である。本発明では、0.3〜10重量部である。キレート化剤(B)の含有量が少なすぎると架橋物は圧縮永久ひずみが大きくなるおそれがあり、逆に多すぎると機械的強度が低下する可能性がある。 The content of the chelating agent (B) in the nitrile rubber composition of the present invention is preferably 0.1 to 15 parts by weight, more preferably 0.2 to 13 parts by weight with respect to 100 parts by weight of the nitrile rubber (A). Parts, particularly preferably 0.3 to 10 parts by weight. In this invention, it is 0.3-10 weight part. Crosslinked product content is too small chelating agent (B) there is a possibility that compression set is large, too large in the opposite potential to the mechanical strength is lowered Ru Oh.
本発明のニトリルゴム組成物は、架橋物を形成するための架橋剤(C)を含有する。架橋剤(C)としては、有機過酸化物、硫黄系架橋剤、樹脂架橋剤、多価アミン化合物、多価エポキシ化合物、多価イソシアナート化合物、多価アルコール化合物、アジリジン化合物、塩基性金属酸化物、有機金属ハロゲン化物などが挙げられる。また、これらの架橋剤を複数併用してもよい。 The nitrile rubber composition of the present invention contains a crosslinking agent (C) for forming a crosslinked product. As the crosslinking agent (C), organic peroxide, sulfur-based crosslinking agent, resin crosslinking agent, polyvalent amine compound, polyvalent epoxy compound, polyvalent isocyanate compound, polyhydric alcohol compound, aziridine compound, basic metal oxidation And organic metal halides. A plurality of these crosslinking agents may be used in combination.
有機過酸化物としては、ジアルキルパーオキサイド類、ジアシルパーオキサイド類、パーオキシエステル類などが挙げられる。
ジアルキルパーオキサイドとしては、ジクミルパーオキサイド、ジ−t−ブチルパーオキサイド、2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)−3−ヘキシン、2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)ヘキサン、1,3−ビス(t−ブチルパーオキシイソプロピル)ベンゼンなどが挙げられる。ジアシルパーオキサイドとして、ベンゾイルパーオキサイド、イソブチリルパーオキサイドなどが挙げられる。パーオキシエステルとして、2,5−ジメチル−2,5−ビス(ベンゾイルパーオキシ)ヘキサン、t−ブチルパーオキシイソプロピルカーボネートなど)などが挙げられる。
硫黄系架橋剤としては、粉末硫黄、沈降硫黄などの硫黄;4,4’−ジチオモルホリンやテトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、高分子多硫化物など有機硫黄化合物;などが挙げられる。
Examples of the organic peroxide include dialkyl peroxides, diacyl peroxides, and peroxyesters.
Dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2, Examples include 5-di (t-butylperoxy) hexane and 1,3-bis (t-butylperoxyisopropyl) benzene. Examples of the diacyl peroxide include benzoyl peroxide and isobutyryl peroxide. Examples of peroxyesters include 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyisopropyl carbonate, and the like.
Examples of the sulfur-based crosslinking agent include sulfur such as powdered sulfur and precipitated sulfur; organic sulfur compounds such as 4,4′-dithiomorpholine, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and polymer polysulfide;
樹脂架橋剤としては、アルキルフェノール・ホルムアルデヒド樹脂、メラミン−ホルムアルデヒド縮合物、トリアジン−ホルムアルデヒド縮合物、オクチルフェノール・ホルムアルデヒド樹脂、アルキルフェノール・スルフィド樹脂、ヘキサメトキシメチル・メラミン樹脂などが挙げられる。
多価アミン化合物としては、炭素数4〜30の多価アミン化合物が好ましい。かかる多価アミン化合物の例としては、脂肪族多価アミン化合物、芳香族多価アミン化合物などが挙げられ、グアニジン化合物のように非共役の窒素−炭素二重結合を有するものは含まれない。脂肪族多価アミン化合物としては、ヘキサメチレンジアミン、ヘキサメチレンジアミンカルバメ−ト、N,N’−ジシンナミリデン−1,6−ヘキサンジアミンなどが挙げられる。芳香族多価アミン化合物としては、4,4’−ジアミノジフェニルエーテル、3,4’−ジアミノジフェニルエーテル、4,4’−メチレンジアニリン、4,4’−(m−フェニレンジイソプロピリデン)ジアニリン、4,4’−(p−フェニレンジイソプロピリデン)ジアニリン、2,2’−ビス〔4−(4−アミノフェノキシ)フェニル〕プロパン、4,4’−ジアミノベンズアニリド、4,4’−ビス(4−アミノフェノキシ)ビフェニル、m−フェニレンジアミン、m−キシリレンジアミン、p−キシリレンジアミン、1,3,5−ベンゼントリアミンなどが挙げられる。
Examples of the resin crosslinking agent include alkylphenol-formaldehyde resins, melamine-formaldehyde condensates, triazine-formaldehyde condensates, octylphenol-formaldehyde resins, alkylphenol-sulfide resins, hexamethoxymethyl-melamine resins, and the like.
As the polyvalent amine compound, a polyvalent amine compound having 4 to 30 carbon atoms is preferable. Examples of such polyvalent amine compounds include aliphatic polyvalent amine compounds, aromatic polyvalent amine compounds, and the like, and those having non-conjugated nitrogen-carbon double bonds such as guanidine compounds are not included. Examples of the aliphatic polyvalent amine compound include hexamethylene diamine, hexamethylene diamine carbamate, N, N′-dicinnamylidene-1,6-hexane diamine and the like. Examples of the aromatic polyamine compound include 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-methylenedianiline, 4,4 ′-(m-phenylenediisopropylidene) dianiline, 4 , 4 ′-(p-phenylenediisopropylidene) dianiline, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-diaminobenzanilide, 4,4′-bis (4 -Aminophenoxy) biphenyl, m-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 1,3,5-benzenetriamine and the like.
多価エポキシ化合物としては、例えば、フェノールノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物、クレゾール型エポキシ化合物、ビスフェノールA型エポキシ化合物、ビスフェノールF型エポキシ化合物、臭素化ビスフェノールA型エポキシ化合物、臭素化ビスフェノールF型エポキシ化合物、水素添加ビスフェノールA型エポキシ化合物などのグリシジルエーテル型エポキシ化合物;脂環式エポキシ化合物、グリシジルエステル型エポキシ化合物、グリシジルアミン型エポキシ化合物、イソシアヌレート型エポキシ化合物などの多価エポキシ化合物;などの分子内に2以上のエポキシ基を有する化合物が挙げられる。 Examples of the polyvalent epoxy compound include a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, a cresol type epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a brominated bisphenol A type epoxy compound, and a brominated bisphenol F. Type epoxy compounds, glycidyl ether type epoxy compounds such as hydrogenated bisphenol A type epoxy compounds; polycyclic epoxy compounds such as alicyclic epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, isocyanurate type epoxy compounds; etc. And compounds having two or more epoxy groups in the molecule.
多価イソシアナート化合物としては、炭素数6〜24の、ジイソシアナート類及びトリイソシアナート類が好ましい。ジイソシアナート類の具体例としては、2,4−トリレンジイソシアナート(2,4−TDI)、2,6−トリレンジイソシアナート(2,6−TDI)、4,4’−ジフェニルメタンジイソシアナート(MDI)、ヘキサメチレンジイソシアナート、p−フェニレンジイソシアナート、m−フェニレンジイソシアナート、1,5−ナフチレンジイソシアナートなどが挙げられる。また、トリイソシアナート類の具体例としては、1,3,6−ヘキサメチレントリイソシアナート、1,6,11−ウンデカントリイソシアナート、ビシクロヘプタントリイソシアナートなどが挙げられる。 As the polyvalent isocyanate compound, diisocyanates and triisocyanates having 6 to 24 carbon atoms are preferable. Specific examples of the diisocyanates include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4′-diphenylmethane diisocyanate. Nert (MDI), hexamethylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 1,5-naphthylene diisocyanate and the like. Specific examples of the triisocyanates include 1,3,6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate, bicycloheptane triisocyanate, and the like.
多価アルコール化合物としては、エチレングリコール、プロピレングリコール、ブチレングリコール、ヘキシレングリコール、ヘキサメチレングリコール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、ポリエチレングリコール、ポリオキシプロピレングリコール、ポリオキシブチレングリコール、1,7−ヘプタンジオール、1,8−オクタンジオール、1,9−ノナンジオール、1,10−デカンジオール、ヒドロベンゾイン、ベンズピナコール、シクロペンタン−1,2−ジオール、シクロヘキサンジメタノール、グリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリト−ル、ヒドロキノンジヒドロキシエチルエーテル、トリメチロールエタン、トリメチロールヘキサン、トリメチロールオクタン、トリメチロールドデカン、ビスフェノールA等の低分子量ポリオール;ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、ブタンジオール、グリセリン等の低分子量ポリオールにアルキレンオキシドを付加重合させたポリオール;トリエタノールアミン、ジエタノールアミン、エチルアミン、プロピルアミン、エチレンジアミン、トリエチレンジアミン、ジエチレントリアミン等の低分子量アミンにアルキレンオキシドを付加重合させたポリオール;アルビトール、ソルビト−ル、ソルビタン、キシロース、アラビノース、グルコース、ガラクトース、ソルボース、フラクトース、パラチノース、マルトトリオ−ス、マレジトース、ソルビタンプロピルエステル等の多糖類;ポリグリセリンエステル、ポリビニルアルコール、水酸基を複数有するポリオレフィン系オリゴマー、エチレン−ヒドロキシエチル(メタ)アクリレート共重合体等の分子内に水酸基を複数有する重合体;末端に水酸基を有するスピログリコール、末端に水酸基を有するジオキサングリコール、末端に水酸基を有するトリシクロデカン−ジメタノール、末端に水酸基を有しポリスチレンを側鎖に持つマクロモノマー等の水酸基を複数有する環状化合物;等が挙げられる。 Polyhydric alcohol compounds include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, hexamethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, 1,7 -Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, hydrobenzoin, benzpinacol, cyclopentane-1,2-diol, cyclohexanedimethanol, glycerin, trimethylolethane, Trimethylolpropane, pentaerythritol, dipentaerythritol, hydroquinone dihydroxyethyl ether, trimethylolethane, trimethylol Low molecular weight polyols such as tyrolhexane, trimethyloloctane, trimethylol dodecane, bisphenol A; polyols obtained by addition polymerization of alkylene oxide to low molecular weight polyols such as diethylene glycol, propylene glycol, dipropylene glycol, butanediol, glycerin; triethanolamine , Diethanolamine, ethylamine, propylamine, ethylenediamine, triethylenediamine, diethylenetriamine and other low molecular weight amines, polyols obtained by addition polymerization of alkylene oxide; arbitol, sorbitol, sorbitan, xylose, arabinose, glucose, galactose, sorbose, fructose, palatinose , Maltotriose, marezitose, sorbitan propyl ester, etc. A polymer having a plurality of hydroxyl groups in a molecule such as polyglycerin ester, polyvinyl alcohol, a polyolefin oligomer having a plurality of hydroxyl groups, an ethylene-hydroxyethyl (meth) acrylate copolymer; a spiroglycol having a hydroxyl group at the terminal; Examples thereof include dioxane glycol having a hydroxyl group, tricyclodecane-dimethanol having a hydroxyl group at the terminal, a cyclic compound having a plurality of hydroxyl groups such as a macromonomer having a hydroxyl group at the terminal and polystyrene in the side chain.
アジリジン化合物としては、トリス−2,4,6−(1−アジリジニル)−1,3,5−トリアジン、トリス〔1−(2−メチル)アジリジニル〕ホスフィノキシド、ヘキサ〔1−(2−メチル)アジリジニル〕トリホスファトリアジンなどが挙げられる。
塩基性金属酸化物としては、酸化亜鉛、酸化鉛、酸化カルシウム、酸化マグネシウムなどが挙げられる。
有機金属ハロゲン化物としては、ジシクロペンタジエニル金属ジハロゲン化物が例示される。該金属としては、チタン、ジルコニウム、ハフニウムなどがある。
Examples of the aziridine compound include tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, tris [1- (2-methyl) aziridinyl] phosphinoxide, hexa [1- (2-methyl) aziridinyl. ] Triphosphatriazine and the like.
Examples of the basic metal oxide include zinc oxide, lead oxide, calcium oxide, and magnesium oxide.
Examples of the organic metal halide include dicyclopentadienyl metal dihalide. Examples of the metal include titanium, zirconium, and hafnium.
上記架橋剤は、1種単独でも、2種以上を混合して用いることができるが、中でも、有機過酸化物及び多価アミン化合物が好ましく、多価アミン化合物がより好ましい。多価アミン化合物の中ではヘキサメチレンジアミンカルバメートおよび2,2’−ビス〔4−(4−アミノフェノキシ)フェニル〕プロパンが好ましい。 The crosslinking agent can be used alone or in combination of two or more. Among them, an organic peroxide and a polyvalent amine compound are preferable, and a polyvalent amine compound is more preferable. Among the polyvalent amine compounds, hexamethylenediamine carbamate and 2,2'-bis [4- (4-aminophenoxy) phenyl] propane are preferred.
本発明のニトリルゴム組成物における架橋剤(C)の含有量は、ニトリルゴム(A)100重量部に対して、好ましくは0.1〜20重量部、より好ましくは0.2〜15重量部、特に好ましくは0.3〜10重量部である。本発明では、0.3〜10重量部である。架橋剤(C)の含有量が少なすぎるとニトリルゴム組成物の架橋が不足して架橋物の機械的強度の低下や圧縮永久ひずみが増大するおそれがあり、逆に多すぎると伸びが低下する可能性がある。 The content of the crosslinking agent (C) in the nitrile rubber composition of the present invention is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 15 parts by weight with respect to 100 parts by weight of the nitrile rubber (A). Particularly preferred is 0.3 to 10 parts by weight. In this invention, it is 0.3-10 weight part. If the content of the crosslinking agent (C) is too small, the crosslinking of the nitrile rubber composition may be insufficient and the mechanical strength of the crosslinked product may be reduced or the compression set may be increased. there is a possibility.
本発明のニトリルゴム組成物には、その他必要に応じて架橋促進剤、架橋助剤、架橋遅延剤、共架橋剤、老化防止剤、充填剤、補強剤、可塑剤、滑剤、粘着剤、潤滑剤、難燃剤、防黴剤、帯電防止剤、着色剤などの添加剤を配合してもよい。 The nitrile rubber composition of the present invention includes a crosslinking accelerator, a crosslinking assistant, a crosslinking retarder, a co-crosslinking agent, an anti-aging agent, a filler, a reinforcing agent, a plasticizer, a lubricant, an adhesive, and a lubrication as necessary. You may mix | blend additives, such as an agent, a flame retardant, an antifungal agent, an antistatic agent, and a coloring agent.
架橋促進剤に限定はないが、グアニジン化合物、イミダゾール化合物、第四級オニウム塩、多価第三級アミン化合物、第三級ホスフィン化合物、弱酸のアルカリ金属塩などが好ましい。
グアニジン化合物としては、1,3−ジ−o−トリルグアニジン、1,3−ジフェニルグアニジンなどが挙げられる。イミダゾール化合物としては、2−メチルイミダゾール、2−フェニルイミダゾールなどが挙げられる。第四級オニウム塩としては、テトラ−n−ブチルアンモニウムブロマイド、オクタデシルトリ−n−ブチルアンモニウムブロマイドなどが挙げられる。多価第三級アミン化合物としては、トリエチレンジアミン、1,8−ジアザビシクロ[5.4.0]ウンデセン−7などが挙げられる。第三級ホスフィン化合物としては、トリフェニルホスフィン、トリ−p−トリルホスフィンなどが挙げられる。弱酸のアルカリ金属塩としては、リン酸、炭酸など無機弱酸のナトリウムもしくはカリウム塩やステアリン酸、ラウリン酸など有機弱酸のナトリウムもしくはカリウム塩が挙げられる。
架橋遅延剤としては、モノ第一アミン化合物が好ましい。
The crosslinking accelerator is not limited, but guanidine compounds, imidazole compounds, quaternary onium salts, polyvalent tertiary amine compounds, tertiary phosphine compounds, weak acid alkali metal salts, and the like are preferable.
Examples of the guanidine compound include 1,3-di-o-tolylguanidine, 1,3-diphenylguanidine and the like. Examples of the imidazole compound include 2-methylimidazole and 2-phenylimidazole. Examples of the quaternary onium salt include tetra-n-butylammonium bromide and octadecyltri-n-butylammonium bromide. Examples of the polyvalent tertiary amine compound include triethylenediamine and 1,8-diazabicyclo [5.4.0] undecene-7. Examples of the tertiary phosphine compound include triphenylphosphine and tri-p-tolylphosphine. Examples of the alkali metal salt of a weak acid include sodium or potassium salts of inorganic weak acids such as phosphoric acid and carbonic acid, and sodium or potassium salts of organic weak acids such as stearic acid and lauric acid.
As a crosslinking retarder, a mono primary amine compound is preferable.
老化防止剤としては、フェノール系、アミン系、ベンズイミダゾール系、リン酸系などの老化防止剤を使用することができる。フェノール系では、2,2’−メチレンビス(4−メチル−6−t−ブチルフェノール)などが、アミン系では、4,4’−ビス(α、α−ジメチルベンジル)ジフェニルアミンなどが、ベンズイミダゾール系では2−メルカプトベンズイミダゾールなどが挙げられる。これらは1種単独でまたは2種以上併せて使用される。 As the anti-aging agent, an anti-aging agent such as phenol, amine, benzimidazole or phosphoric acid can be used. In the phenol system, 2,2′-methylenebis (4-methyl-6-t-butylphenol) is used, in the amine system, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine is used, and in the benzimidazole system. Examples include 2-mercaptobenzimidazole. These may be used alone or in combination of two or more.
充填剤としては、カーボンブラック、シリカ、炭酸カルシウム、炭酸マグネシウム、タルク、クレー等を使用することができる。これらにはシラン系カップリング剤などを配合することもできる。 As the filler, carbon black, silica, calcium carbonate, magnesium carbonate, talc, clay and the like can be used. These can be blended with a silane coupling agent or the like.
また、本発明の架橋性ニトリルゴム組成物には、ニトリルゴム(A)以外のゴムを配合してもよい。ニトリルゴム(A)以外のゴムには特に限定がない。しかし、一般的なアクリロニトリル−ブタジエン共重合体ゴムのように、不飽和度の高いニトリル基含有共重合体ゴムを配合する場合は、ニトリルゴム(A)100重量部当たり30重量部以下、好ましくは20重量部以下、より好ましくは10重量部以下の使用とすべきである。不飽和度の高いニトリル基含有共重合体ゴムの配合量が多すぎると、本発明の架橋物が有する後述の特性が発揮されない。 Moreover, you may mix | blend rubbers other than a nitrile rubber (A) with the crosslinkable nitrile rubber composition of this invention. There is no particular limitation on the rubber other than the nitrile rubber (A). However, when a highly unsaturated nitrile group-containing copolymer rubber is blended like a general acrylonitrile-butadiene copolymer rubber, it is preferably 30 parts by weight or less per 100 parts by weight of the nitrile rubber (A), preferably The use should be 20 parts by weight or less, more preferably 10 parts by weight or less. When the blending amount of the nitrile group-containing copolymer rubber having a high degree of unsaturation is too large, the following properties of the crosslinked product of the present invention cannot be exhibited.
本発明のニトリルゴム組成物を調製する方法に限定はないが、通常、架橋剤および熱に不安定な架橋助剤などを除いた成分を、バンバリーミキサ、インターミキサ、ニーダなどの混合機で一次混練した後、ロールなどに移して加硫剤等を加えて二次混練する。 The method for preparing the nitrile rubber composition of the present invention is not limited, but usually the components excluding the cross-linking agent and the heat-labile cross-linking aid are firstly mixed in a mixer such as a Banbury mixer, an intermixer, or a kneader. After kneading, the mixture is transferred to a roll or the like, and a vulcanizing agent or the like is added to perform secondary kneading.
調製されたニトリルゴム組成物を架橋して本発明の架橋物を得るには、所望の形状に対応した成形機、例えば押出機、射出成形機、圧縮機、ロールなどにより成形を行い、また、架橋反応により架橋物として形状を固定化する。予め成形した後に架橋しても、成形と同時に架橋を行ってもよい。成形温度は、通常、10〜200℃、好ましくは25〜120℃である。架橋温度は、通常、100〜200℃、好ましくは130〜190℃であり、架橋時間は、通常、1分〜24時間、好ましくは2分〜1時間である。 In order to obtain a crosslinked product of the present invention by crosslinking the prepared nitrile rubber composition, molding is performed by a molding machine corresponding to a desired shape, for example, an extruder, an injection molding machine, a compressor, a roll, etc. The shape is fixed as a crosslinked product by a crosslinking reaction. Crosslinking may be performed after molding in advance, or may be performed simultaneously with molding. The molding temperature is usually 10 to 200 ° C, preferably 25 to 120 ° C. The crosslinking temperature is usually 100 to 200 ° C., preferably 130 to 190 ° C., and the crosslinking time is usually 1 minute to 24 hours, preferably 2 minutes to 1 hour.
また、架橋物の形状、大きさなどによっては、表面が架橋していても内部まで十分に架橋していない場合があるので、さらに加熱して二次架橋を行ってもよい。
本発明の架橋物は、耐油性および耐オゾン性に優れるニトリル基含有高飽和共重合体ゴムの特性に加えて、耐熱老化性に優れ、圧縮永久ひずみが小さい特徴を有する。そのため本発明の架橋物は、ベルト、シール、ロール、ホース、チューブなどに好適に使用できる。
ベルトとしては、平ベルト、Vベルト、Vリブドベルト、丸ベルト、角ベルト、歯付ベルトなどが挙げられる。ホースとしては、単管ゴムホース、多層ゴムホース、編上式補強ホース、布巻式補強ホースなどが挙げ挙げられる。ダイアフラムとしては、平形ダイアフラム、転動形ダイアフラムなどが挙げられる。
シールとしては、回転用、揺動用、往復動用などの運動用シールと固定用シールが挙げられる。運動用シールとしては、オイルシール、ピストンシール、メカニカルシール、ブーツ、ダストカバー、ダイアフラム、アキュムレータプラダなどが挙げられる。固定用シールとしては、Oリング、各種ガスケットなどが挙げられる。
ロールとしては、印刷機器、コピー機器などのOA機器の部品であるロール;紡糸用延伸ロール、紡績用ドラフトロールなどの繊維加工用ロール;ブライドルロール、スナバロール、ステアリングロールなどの製鉄用ロール;などが挙げられる。
その他にもバルブおよびバブルシート、BOP(Blow Out Preventar)、プラターなどの油田用ゴム部品、クッション材、防振材などの減衰材ゴム部品や、自動車内装部材、靴底など幅広い用途に使用することができる。
Depending on the shape and size of the cross-linked product, even if the surface is cross-linked, it may not be sufficiently cross-linked to the inside. Therefore, secondary cross-linking may be performed by heating.
The crosslinked product of the present invention is characterized by excellent heat aging resistance and low compression set in addition to the characteristics of a nitrile group-containing highly saturated copolymer rubber excellent in oil resistance and ozone resistance. Therefore, the crosslinked product of the present invention can be suitably used for belts, seals, rolls, hoses, tubes and the like.
Examples of the belt include a flat belt, a V belt, a V-ribbed belt, a round belt, a square belt, and a toothed belt. Examples of the hose include a single tube rubber hose, a multilayer rubber hose, a braided reinforcement hose, and a cloth wound reinforcement hose. Examples of the diaphragm include a flat diaphragm and a rolling diaphragm.
Examples of the seal include a seal for movement and a seal for fixation such as for rotation, swing, and reciprocation. Examples of the exercise seal include an oil seal, a piston seal, a mechanical seal, a boot, a dust cover, a diaphragm, and an accumulator prada. Examples of the fixing seal include an O-ring and various gaskets.
As rolls, rolls that are parts of OA equipment such as printing equipment, copying equipment; rolls for fiber processing such as spinning rolls for spinning, draft rolls for spinning; iron-making rolls such as bridle rolls, snubber rolls, steering rolls, etc. Can be mentioned.
In addition, use in a wide range of applications such as rubber parts for oilfields such as valves and bubble seats, BOP (Blow Out Preventar), platers, damping rubber parts such as cushioning materials and anti-vibration materials, automobile interior parts, and shoe soles. Can do.
以下に製造例、実施例および比較例を挙げて、本発明を具体的に説明する。ただし本発明は、これらの実施例に限定されるものではない。以下の配合において〔部〕は、特に断わりのない限り重量基準である。
測定方法及び試験方法を下記に示す。
(1)カルボキシル基含有量
カルボキシル基含有量は、水酸化カリウムの0.02Nエタノール溶液を用いて、室温でチモールフタレインを指示薬とする滴定により、ゴム100グラムに対するカルボキシル基の当量数を求めた。単位はephrである。
(2)ムーニー粘度
JIS K 6300に従って測定した。
The present invention will be specifically described below with reference to production examples, examples and comparative examples. However, the present invention is not limited to these examples. In the following formulation, [part] is based on weight unless otherwise specified.
The measurement method and test method are shown below.
(1) Carboxyl group content The carboxyl group content was determined by titration with thymolphthalein as an indicator at room temperature using a 0.02N ethanol solution of potassium hydroxide, and the equivalent number of carboxyl groups with respect to 100 grams of rubber. . The unit is ephr.
(2) Mooney viscosity Measured according to JIS K 6300.
(3)常態物性(引張強さ、伸び)
ニトリルゴム組成物を縦15cm、横15cm、深さ0.2cmの金型に入れ、加圧しながら170℃で20分間プレス成形した後、170℃のオーブンに4時間置いてシート状架橋物を得た。得られたシート状架橋物を3号形ダンベルで打ち抜き、試験片を作製した。これらの試験片を用いて、JIS K 6251に従い、架橋物の引張強さおよび伸びを測定した。
(4)常態物性(硬さ)
上記(3)と同様にして得たシート状ゴム架橋物につき、JIS K 6253に従い、デュロメータ硬さ試験機タイプAを用いて架橋物の硬さを測定した。
(3) Normal physical properties (tensile strength, elongation)
The nitrile rubber composition is placed in a mold having a length of 15 cm, a width of 15 cm, and a depth of 0.2 cm, press-molded at 170 ° C. for 20 minutes under pressure, and then placed in an oven at 170 ° C. for 4 hours to obtain a sheet-like crosslinked product. It was. The obtained sheet-like crosslinked product was punched with a No. 3 dumbbell to prepare a test piece. Using these test pieces, the tensile strength and elongation of the cross-linked product were measured according to JIS K 6251.
(4) Normal physical properties (hardness)
About the sheet-like rubber cross-linked product obtained in the same manner as (3) above, the hardness of the cross-linked product was measured using a durometer hardness tester type A according to JIS K 6253.
(5)耐熱老化性(空気加熱老化試験)
上記(3)と同様にして得た試験片をJIS K 6257(ノーマルオーブン法)に従い、150℃に置いて168時間後の引張強さおよび伸びの変化率(%)並びに硬さの変化(ポイント)を求めた。
(5) Heat aging resistance (air heat aging test)
The test piece obtained in the same manner as in the above (3) was placed at 150 ° C. in accordance with JIS K 6257 (normal oven method) and the change rate (%) of tensile strength and elongation after 168 hours and change in hardness (points) )
(6)圧縮永久ひずみ(O−リング・セット試験)
内径30mm、リング径3mmの金型を用いて、各ニトリルゴム組成物を170℃で20分間、プレス圧10MPaで架橋した後、170℃で4時間二次架橋を行って圧縮永久ひずみ試験用O−リング試験片を得た。圧縮永久ひずみは、これらの試験片を用いて150℃にて25%圧縮状態で168時間保持した後、JIS K 6262に従って測定した。
(6) Compression set (O-ring set test)
Using a mold having an inner diameter of 30 mm and a ring diameter of 3 mm, each nitrile rubber composition was crosslinked at 170 ° C. for 20 minutes at a press pressure of 10 MPa, and then subjected to secondary crosslinking at 170 ° C. for 4 hours to obtain a compression set O -A ring specimen was obtained. The compression set was measured according to JIS K 6262 after being held at 150 ° C. in a 25% compressed state for 168 hours.
(製造例1)
金属製ボトルに、イオン交換水180部、濃度10重量%のドデシルベンゼンスルホン酸ナトリウム水溶液25部、アクリロニトリル37部、イタコン酸モノn-ブチル4部、t−ドデシルメルカプタン(分子量調整剤)0.5部の順に仕込み、内部の気体を窒素で3回置換した後、ブタジエン61部を仕込んだ。金属製ボトルを5℃に保ち、クメンハイドロパーオキサイド(重合開始剤)0.1部を仕込み、金属製ボトルを回転させながら16時間重合反応を行った。濃度10重量%のハイドドキノン水溶液(重合停止剤)0.1部を加えて重合反応を停止した後、水温60℃のロータリーエバポレータを用いて残留単量体を除去し、アクリロニトリル単位36重量%、ブタジエン単位60重量%およびイタコン酸モノn−ブチル単位4重量%を有するアクリロニトリル−ブタジエン−α,β−エチレン性不飽和ジカルボン酸モノアルキルエステル共重合体ゴムラテックス(固形分濃度約30重量%)を得た。
(Production Example 1)
In a metal bottle, 180 parts of ion-exchanged water, 25 parts of a 10% strength by weight aqueous solution of sodium dodecylbenzenesulfonate, 37 parts of acrylonitrile, 4 parts of mono-n-butyl itaconate, t-dodecyl mercaptan (molecular weight regulator) 0.5 In order of parts, the internal gas was replaced with nitrogen three times, and then 61 parts of butadiene was charged. The metal bottle was kept at 5 ° C., 0.1 part of cumene hydroperoxide (polymerization initiator) was charged, and the polymerization reaction was carried out for 16 hours while rotating the metal bottle. The polymerization reaction was stopped by adding 0.1 part of a 10% by weight aqueous solution of hydridoquinone (polymerization terminator), then the residual monomer was removed using a rotary evaporator at a water temperature of 60 ° C., and 36% by weight of acrylonitrile unit, butadiene Acrylonitrile-butadiene-α, β-ethylenically unsaturated dicarboxylic acid monoalkyl ester copolymer rubber latex (60% solid content concentration) having 60% by weight units and 4% by weight mono n-butyl itaconate units is obtained. It was.
該ラテックスに含有される乾燥ゴム重量に対してパラジウム含有量が1,000ppmになるようにオートクレーブにパラジウム触媒(1重量%酢酸パラジウムアセトン溶液に等重量のイオン交換水を混合した溶液)を添加して、水素圧3MPa、温度50℃で6時間水素添加反応を行い、ニトリル基含有高飽和共重合体ゴムラテックスを得た。
得られたニトリル基含有高飽和共重合体ゴムラテックスに2倍容量のメタノールを加えて、ニトリル基含有高飽和共重合体ゴムを凝固した後、60℃で12時間真空乾燥してニトリルゴム(a)を得た。ニトリルゴム(a)のヨウ素価は10、カルボキシル基含有量は2.2×10−2ephr、ムーニー粘度〔ML1+4、100℃〕 は85であった。
A palladium catalyst (a solution obtained by mixing an equal weight of ion exchange water with a 1 wt% palladium acetate / acetone solution) was added to an autoclave so that the palladium content was 1,000 ppm with respect to the dry rubber weight contained in the latex. Then, a hydrogenation reaction was performed at a hydrogen pressure of 3 MPa and a temperature of 50 ° C. for 6 hours to obtain a nitrile group-containing highly saturated copolymer rubber latex.
The obtained nitrile group-containing highly saturated copolymer rubber latex was added with twice the volume of methanol to coagulate the nitrile group-containing highly saturated copolymer rubber, and then vacuum-dried at 60 ° C. for 12 hours to obtain a nitrile rubber (a ) The iodine value of the nitrile rubber (a) was 10, the carboxyl group content was 2.2 × 10 −2 ephr, and the Mooney viscosity [ML 1 + 4 , 100 ° C.] was 85.
(参考例1)
バンバリーミキサを用いてニトリルゴム(a)100部に、ステアリン酸1部、FEFカーボンブラック(製品名「旭60」、旭カーボン社製、充填剤)40部、トリメリット酸メチル(製品名「アデカサイザーC−8」、旭電化工業社製、可塑剤)5部、置換ジフェニルアミン(製品名「ナウガード445」、ユニロイヤル社製、老化防止剤)1.5部、2−メルカプトベンズイミダゾール(製品名「ノクラックMB」、大内新興社製、老化防止剤)1.5部および3−(N−サリチロイル)アミノ−1,2,4−トリアゾール(製品名「アデカスタブCDA−1」、旭電化工業社製、キレート化剤)2部を添加して混合し、次いで、混合物をロールに移して1,3−ジ−o−トリルグアニジン(製品名「ノクセラーDT」、大内新興社製、架橋促進剤)2部、および、ヘキサメチレンジアミンカルバメート(製品名「Diak#1」、デュポン・ダウエラストマー社製、架橋剤)1.7部添加して混練し、ニトリルゴム組成物を調製した。この組成物を架橋して得た架橋物について常態物性の測定、空気加熱老化試験(耐熱老化性)およびO−リング・セット試験(圧縮永久ひずみ)を行い、評価した結果を表1に記す。
( Reference Example 1)
Using a Banbury mixer, 100 parts of nitrile rubber (a), 1 part of stearic acid, 40 parts of FEF carbon black (product name “Asahi 60”, manufactured by Asahi Carbon Co., Ltd., filler), methyl trimellitic acid (product name “ADEKA” Sizer C-8 ", manufactured by Asahi Denka Kogyo Co., Ltd., plasticizer), 5 parts of substituted diphenylamine (product name" Nauguard 445 ", manufactured by Uniroyal, anti-aging agent), 2-mercaptobenzimidazole (product name) “NOCRACK MB”, manufactured by Ouchi Shinsei Co., Ltd., anti-aging agent) and 3- (N-salicyloyl) amino-1,2,4-triazole (product name “ADK STAB CDA-1”, Asahi Denka Kogyo Co., Ltd.) Product, chelating agent) 2 parts are added and mixed, then the mixture is transferred to a roll and 1,3-di-o-tolylguanidine (product name “Noxeller DT”, manufactured by Ouchi Shinsei Co., Ltd.) Crosslinking accelerator) 2 parts, and, hexamethylenediamine carbamate (product name "Diak # 1", DuPont Dow Elastomers Co., crosslinking agent) 1.7 parts were added and kneaded to prepare a nitrile rubber composition. Table 1 shows the evaluation results of the cross-linked product obtained by cross-linking this composition, measurement of normal properties, air heat aging test (heat aging resistance) and O-ring set test (compression set).
(実施例1〜3、参考例2〜3、比較例1)
参考例1において、3−(N−サリチロイル)アミノ−1,2,4−トリアゾール2部に代えて表1に記すキレート化剤を表記量使用した他は参考例1と同様に行ってそれぞれニトリルゴム組成物を調製した(実施例1〜3、参考例2〜3)。また、比較例1ではキレート化剤を使用しなかった他は参考例1と同様にしてニトリルゴム組成物を調製した。各ニトリルゴム組成物について、参考例1と同様の測定及び試験を行い、評価した結果を表1に記す。ここで、表1にある(イ)〜(ホ)は以下の化合物を指す。
(イ):3−(N−サリチロイル)アミノ−1,2,4−トリアゾール(製品名「アデカスタブCDA−1」、旭電化工業社製)
(ロ):デカメチレンカルボン酸ジサリチロイルヒドラジド(製品名「アデカスタブCDA−6」、旭電化工業社製)
(ハ):4−メチル−1H−ベンゾトリアゾールカリウム塩および5−メチル−1H−ベンゾトリアゾールカリウム塩の混合物(製品名「シーテックTT−K」、シプロ化成社製)
(ニ):エチレンジアミン四酢酸(製品名「クレワット−TTA」、ナガセケムテックス社製)
(ホ):エチレンジアミン四酢酸ナトリウム塩(製品名「キレスト400」、キレスト社製)
(Examples 1-3, Reference Examples 2-3 , Comparative Example 1)
In Reference Example 1, each nitrile was prepared in the same manner as Reference Example 1 except that the indicated amount of the chelating agent shown in Table 1 was used instead of 2 parts of 3- (N-salicyloyl) amino-1,2,4-triazole. Rubber compositions were prepared (Examples 1 to 3, Reference Examples 2 to 3 ). In Comparative Example 1, a nitrile rubber composition was prepared in the same manner as in Reference Example 1 except that no chelating agent was used. Each nitrile rubber composition was subjected to the same measurements and tests as in Reference Example 1, and the evaluation results are shown in Table 1. Here, (i) to (e) in Table 1 indicate the following compounds.
(I): 3- (N-salicyloyl) amino-1,2,4-triazole (product name “ADK STAB CDA-1”, manufactured by Asahi Denka Kogyo Co., Ltd.)
(B): Decamethylene carboxylic acid disalicyloyl hydrazide (product name “ADK STAB CDA-6”, manufactured by Asahi Denka Kogyo Co., Ltd.)
(C): Mixture of 4-methyl-1H-benzotriazole potassium salt and 5-methyl-1H-benzotriazole potassium salt (product name “C-Tech TT-K”, manufactured by Sipro Kasei Co., Ltd.)
(D): Ethylenediaminetetraacetic acid (product name “Clewat-TTA”, manufactured by Nagase ChemteX Corporation)
(E): Ethylenediaminetetraacetic acid sodium salt (Product name “Cylest 400”, manufactured by Cylest)
表1が示すように、本発明のニトリルゴム組成物を架橋すると(実施例1〜3、参考例1〜3)、キレート化剤を配合しない従来のニトリルゴム組成物の架橋物(比較例1)と対比して、空気加熱老化試験で引張強さおよび伸びの変化率が大幅に減少し、かつ、硬さの変化の度合いも小さいことから耐熱老化性が改良された。また、O−リング・セット試験で数値が小さいことから圧縮永久ひずみも改良されたことも明らかである。 As Table 1 shows, when the nitrile rubber composition of the present invention is crosslinked (Examples 1 to 3, Reference Examples 1 to 3 ), a crosslinked product of a conventional nitrile rubber composition not containing a chelating agent (Comparative Example 1) In contrast, the heat aging resistance was improved because the rate of change in tensile strength and elongation was significantly reduced in the air heating aging test and the degree of change in hardness was small. It is also clear that the compression set was improved due to the small numerical value in the O-ring set test.
Claims (4)
(i)該キレート化剤(B)が、ヒドラジド系キレート化剤、ヒドラジン系キレート化剤、多価アミン酢酸系キレート化剤、ニトリロ酢酸系キレート化剤、ヒドロキシルイミノ系キレート化剤、オキサミド系キレート化剤、オキシム系キレート化剤、グリシン系キレート化剤、1,3−ジアミノ−2−ヒドロキシプロパン四酢酸ナトリウム塩、及びジカルボキシメチルグルタミン酸四ナトリウム塩からなる群より選ばれる少なくとも1種の、ドナー窒素原子を1個以上含有する化学構造を有し、かつ、含窒素複素環を含有しないキレート化剤であり、及び、
(ii)該架橋剤(C)が、有機過酸化物、硫黄系架橋剤、樹脂架橋剤、多価アミン化合物、多価エポキシ化合物、多価イソシアナート化合物、多価アルコール化合物、アジリジン化合物、塩基性金属酸化物、及び有機金属ハロゲン化物からなる群より選ばれる少なくとも1種の架橋剤であるニトリルゴム組成物。 Emulsifying α, β-ethylenically unsaturated nitrile monomer, diene monomer or α-olefin monomer, and carboxyl group-containing monomer, and other copolymerizable monomers as required Polymerized and optionally obtained by a method of performing a hydrogenation reaction , a carboxyl group having an α, β-ethylenically unsaturated nitrile monomer unit content of 10 to 60% by weight and an iodine value of 100 or less. Ratio of 0.3 to 10 parts by weight of chelating agent (B) and 0.3 to 10 parts by weight of crosslinking agent (C) with respect to 100 parts by weight of nitrile group-containing highly saturated copolymer rubber (A) having a group And a nitrile rubber composition containing no triphenylphosphine,
(I) The chelating agent (B) is a hydrazide chelating agent, a hydrazine chelating agent, a polyvalent amine acetic acid chelating agent, a nitriloacetic acid chelating agent, a hydroxylimino chelating agent, or an oxamide chelating agent. At least one donor selected from the group consisting of an agent, an oxime chelator, a glycine chelator, 1,3-diamino-2-hydroxypropanetetraacetic acid sodium salt, and dicarboxymethylglutamic acid tetrasodium salt A chelating agent having a chemical structure containing one or more nitrogen atoms and not containing a nitrogen-containing heterocycle; and
(Ii) The crosslinking agent (C) is an organic peroxide, a sulfur-based crosslinking agent, a resin crosslinking agent, a polyvalent amine compound, a polyvalent epoxy compound, a polyvalent isocyanate compound, a polyhydric alcohol compound, an aziridine compound, a base A nitrile rubber composition which is at least one crosslinking agent selected from the group consisting of conductive metal oxides and organic metal halides.
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US20100324226A1 (en) * | 2007-08-10 | 2010-12-23 | Daizo Hosotani | Highly saturated nitrile rubber for seal material and cross-linked rubber |
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