CN102666091B - 橡胶金属积层体 - Google Patents
橡胶金属积层体 Download PDFInfo
- Publication number
- CN102666091B CN102666091B CN201080051592.XA CN201080051592A CN102666091B CN 102666091 B CN102666091 B CN 102666091B CN 201080051592 A CN201080051592 A CN 201080051592A CN 102666091 B CN102666091 B CN 102666091B
- Authority
- CN
- China
- Prior art keywords
- nbr
- rubber
- adhesive
- weight portions
- metal
- 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.)
- Expired - Fee Related
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 70
- 239000005060 rubber Substances 0.000 title claims abstract description 70
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 48
- 239000000853 adhesive Substances 0.000 claims abstract description 68
- 230000001070 adhesive effect Effects 0.000 claims abstract description 68
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 39
- 239000005011 phenolic resin Substances 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000007822 coupling agent Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims description 21
- 229910000077 silane Inorganic materials 0.000 claims description 20
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 11
- 230000007797 corrosion Effects 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 9
- 239000004615 ingredient Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000003973 paint Substances 0.000 claims description 7
- 230000037452 priming Effects 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 238000002156 mixing Methods 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000013329 compounding Methods 0.000 abstract description 4
- 238000007654 immersion Methods 0.000 abstract description 3
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 2
- 229920003987 resole Polymers 0.000 abstract description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract 1
- 230000002528 anti-freeze Effects 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 230000007423 decrease Effects 0.000 abstract 1
- 229920003986 novolac Polymers 0.000 abstract 1
- 229920000459 Nitrile rubber Polymers 0.000 description 52
- 239000000243 solution Substances 0.000 description 32
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000000576 coating method Methods 0.000 description 14
- 239000000377 silicon dioxide Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- -1 age resister Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 150000004756 silanes Chemical class 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000033001 locomotion Effects 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- 150000002902 organometallic compounds Chemical class 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 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 3
- WGRZHLPEQDVPET-UHFFFAOYSA-N 2-methoxyethoxysilane Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008393 encapsulating agent Substances 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
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229940100630 metacresol Drugs 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000013500 performance material Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000008247 solid mixture Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 210000001138 tear Anatomy 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- XMTYMJRPVFGBIM-UHFFFAOYSA-N 2-ethoxyethoxysilane Chemical compound CCOCCO[SiH3] XMTYMJRPVFGBIM-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 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
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical class CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000012669 compression test Methods 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 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
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 210000000713 mesentery Anatomy 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010074 rubber mixing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical class CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- REGMWDPZVFOJLY-UHFFFAOYSA-N 1,4-bis(2-hydroperoxypropan-2-yl)benzene Chemical compound OOC(C)(C)C1=CC=C(C(C)(C)OO)C=C1 REGMWDPZVFOJLY-UHFFFAOYSA-N 0.000 description 1
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- AGUIILSGLFUTKG-UHFFFAOYSA-N CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] Chemical compound CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] AGUIILSGLFUTKG-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- GQVCNZBQZKXBMX-UHFFFAOYSA-N butan-2-one;toluene Chemical compound CCC(C)=O.CC1=CC=CC=C1 GQVCNZBQZKXBMX-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000010073 coating (rubber) Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical class CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- LCDFWRDNEPDQBV-UHFFFAOYSA-N formaldehyde;phenol;urea Chemical compound O=C.NC(N)=O.OC1=CC=CC=C1 LCDFWRDNEPDQBV-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000004379 membrane Anatomy 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical class CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- MTZWHHIREPJPTG-UHFFFAOYSA-N phorone Chemical compound CC(C)=CC(=O)C=C(C)C MTZWHHIREPJPTG-UHFFFAOYSA-N 0.000 description 1
- 229930193351 phorone Natural products 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HCOKJWUULRTBRS-UHFFFAOYSA-N propan-2-yloxysilane Chemical compound CC(C)O[SiH3] HCOKJWUULRTBRS-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 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 1
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/06—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
- C08J5/128—Adhesives without diluent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09J109/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/14—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/14—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
Abstract
橡胶金属积层体,其是用含有线型和可熔型酚醛树脂、NBR、白碳以及具有碳数2以上的烷氧基的乙烯基三烷氧基硅烷偶联剂的粘合剂将NBR与金属粘合而成的。作为粘合剂,具体使用橡胶糊与酚醛树脂系粘合剂溶液的混合物溶液,所述橡胶糊是在NBR中配合有白碳和硅烷偶联剂的NBR复合物的有机溶剂溶液。该橡胶金属积层体在高温下的耐摩擦、磨损特性优异,并且用水或防冻液浸渍后粘合强度的降低少,由此能够有效防止剥离等。
Description
技术领域
本发明涉及橡胶金属积层体。更详细地说,涉及为NBR与金属的积层体的橡胶金属积层体。
背景技术
在发动机密封垫部分等温度变化变大的部分,因其温度变化而在发动机与密封垫的接合面之间发生损坏(磨损)。用作密封垫的橡胶金属积层体例如因这种损坏而产生大的剪切应力,进而因橡胶与金属之间的摩擦而发生橡胶的剥离或磨损,结果会出现橡胶层自金属剥离的问题。
此处,通过增加通常用于提高橡胶的耐摩擦、磨损特性的碳黑的的比例,难以防止橡胶金属积层体中所用橡胶的磨损或者剥离。另外,也采用了在橡胶表面涂布PTFE或聚乙烯树脂的溶液来降低摩擦系数、降低橡胶的磨损的方法,但当发生由这些溶液形成的涂膜剥离或磨损时,橡胶可能出现瞬时磨损的情况,课题是改善橡胶自身的耐摩擦、磨损特性。
而且,若粘合性不良,即使在摩擦、磨损时橡胶不磨损的情况下橡胶的剥离也无法避免;反之,即使粘合性优异,如果橡胶的耐磨损性不良,由于橡胶磨损,为了提高橡胶金属积层体中橡胶的耐磨损性,需要提高橡胶自身的耐磨损性,还需要提高与金属的粘合性。
为了形成需要对水或LLC(长效冷却液)具有耐性的橡胶与金属的复合体,金属大多使用不锈钢,但在不锈钢上直接应用硫化粘合剂而与橡胶硫化粘合的不锈钢-橡胶复合体的耐水性、耐LLC性差,对它们实施浸渍试验,会发生粘合剂层剥离。
作为解决上述问题的对策,提出了在金属板上使用作为底漆(primer)的硅烷系底涂剂和作为粘合剂的酚醛树脂系面涂剂,由此来提高耐液体性的各种提案,但这类方法无法获得与实施了含环境对策上不优选的六价铬离子的涂布式铬酸盐处理的不锈钢同等程度的附着性,近年的发动机或防冻液有发生橡胶剥离的问题。另外,酚醛树脂系面涂粘合剂受不了LLC或高温时的磨损,因高面压的压缩而在粘合剂层发生剥离。
本申请人就橡胶金属积层体提出了各种提案,例如有如下提案:
·专利文献1~2中记载了经由底漆层和酚醛树脂系粘合剂层在不锈钢板上层合橡胶的橡胶金属积层体,该积层体作为底漆层设置了含有有机金属化合物和二氧化硅的表面处理剂层;或者设置了含有硅烷偶联剂、有机金属化合物以及二氧化硅的基底处理层。
·专利文献3中记载了在未进行涂布式铬酸盐处理的金属板上涂布粘合剂,向其上涂布含有NBR的水性胶乳和碳黑粒子的水性分散液的水系橡胶涂布液,干燥后进行加压硫化来制备金属/橡胶复合材料的方法,其中指出作为粘合剂使用酚系粘合剂、硅烷系或者钛酸酯系偶联剂的至少一种,作为硅烷系偶联剂,举出了具有乙烯基、氨基、巯基等官能团的甲氧基硅烷类和乙氧基硅烷类作为代表性的例子。
·专利文献4中记载了在基板的规定部位涂布粘合剂来粘合密封材料时,由喷墨头的喷嘴吐出粘合剂进行涂布的密封垫的制备方法,密封材料使用丁腈橡胶等,在任意涂布适当的底漆后进行粘合剂的涂布。该文献指出,作为粘合剂,使用乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、乙烯基三(2-乙氧基乙氧基)硅烷等硅烷系粘合剂;或者向线型或可熔型酚醛树脂中加入六亚甲基四胺等固化剂和填充剂,用溶剂制成的溶液等。
现有技术文献
专利文献
专利文献1:日本特开2005-180682号公报
专利文献2:日本特开2005-249031号公报
专利文献3:日本专利第3933017号公报
专利文献4:日本特开2007-292274号公报
发明内容
发明要解决的课题
本发明的目的在于:提供用酚醛树脂系粘合剂使NBR与金属粘合的橡胶金属积层体,该积层体在高温下的耐摩擦、磨损特性优异,并且用水或防冻液浸渍后粘合强度的降低少,由此有效防止了剥离等。
解决课题的手段
上述本发明的目的由下述橡胶金属积层体实现:用含有线型和可熔型酚醛树脂、NBR、白碳以及具有碳数2以上的烷氧基的乙烯基三烷氧基硅烷偶联剂的粘合剂使NBR与金属粘合的橡胶金属积层体。
发明效果
本发明涉及的橡胶金属积层体在高温下的耐摩擦、磨损特性优异,并且用水或防冻液浸渍后粘合强度的降低少,由此能够有效防止剥离等。
另外,本发明中用作粘合剂成分的橡胶糊(NBR复合物溶液)具有下述优选的性质:与由刚混炼的NBR复合物制备有机溶剂溶液的情况相比,即使在考虑量产时的状况,将经混炼的NBR复合物例如放置10天后制备有机溶剂溶液的情况下,其粒度的增大也很小。
再者,通过在酚醛树脂系粘合剂中混合一定量的橡胶糊,步骤数的削减、粘合剂成本的削减成为可能,优选在粘合剂中使用与形成橡胶层所用NBR相同的NBR的情况下,可以形成与橡胶层的粘合性优异的粘合剂层。
这种粘合剂中,NBR可以提高与橡胶层的粘合性,还提高粘合剂层的柔软性;白碳可以提高与橡胶层和底漆层的粘合性,同时谋求提高粘合剂自身的强度,提高耐水性;硅烷偶联剂可以提高与橡胶层和底漆层的粘合性,同时谋求提高粘合剂自身的强度,提高耐水性。由于所述各成分的作用,可以提高对水或LLC的耐性,同时谋求提高高温下的耐磨损性,并有效防止高面压下的压缩引起的剥离。
需要说明的是,若将含有白碳的NBR复合物长期放置,则二氧化硅凝集,若使用含有该凝集二氧化硅的粘合剂,则粘合剂涂布表面会粗糙不平,粘合力、耐磨损性恶化,但通过采用在预先制备的橡胶糊中混合酚醛树脂系粘合剂成分的方法,可以克服所述难题。制备橡胶糊中所用的NBR复合物随着时间的经过是稳定的。
具体实施方式
本发明涉及的橡胶金属积层体是用含有线型和可熔型酚醛树脂、NBR、白碳以及具有碳数2以上的烷氧基的乙烯基三烷氧基硅烷偶联剂的粘合剂使NBR与金属层合而制作的。
作为与金属粘合的NBR和作为粘合剂成分的NBR,使用结合丙烯腈含量(AN含量)为18~48%,优选31~42%,门尼粘度ML1+4(100℃)为30~85,优选40~70的丙烯腈-丁二烯共聚橡胶,实际上可以原样使用显示这种性状的商品。
为与金属粘合的NBR的情况下,若AN含量小于上述范围,则与层合橡胶层时所用粘合剂的粘合性降低,另一方面,若AN含量大于上述范围,则耐寒性受损。若门尼粘度低于上述值,则耐摩擦、磨损特性变差,另一方面,若大于上述值,则混炼加工性受损。
与用作粘合剂成分的NBR的情况同样,优选在形成橡胶层的该NBR中添加白碳和特定性状的硅烷偶联剂后使用。还适宜配合使用碳黑等填充剂、氧化锌等吸酸剂、硬脂酸等加工助剂、抗老化剂、石蜡系或聚酯系等增塑剂、有机过氧化物、硫等硫化剂等橡胶工业中通常使用的各种配合剂。需要说明的是,作为填充剂,从耐磨损性的观点来看,优选使用粒径小、补强性高的无机填充剂,另外,在使用有机过氧化物交联剂的情况下,优选将三烯丙基异氰尿酸酯代表的多官能性不饱和化合物作为共交联剂联用。
有机过氧化物的商品例如有日本油脂制品Perbutyl Z、Perhexa Z、Perbutyl P、Percumyl D、Perhexa 25B、Perbutyl C、Perbutyl D、PercumylP等,作为硫系化合物,除硫之外,例如有二硫化四甲基秋兰姆、二硫化四乙基秋兰姆、一硫化四甲基秋兰姆等秋兰姆类化合物;2-巯基苯并噻唑、二硫化二苯并噻唑等噻唑类化合物;二甲基二硫代氨基甲酸锌、二乙基二硫代氨基甲酸锌、二丁基二硫代氨基甲酸锌等二硫代氨基甲酸盐类等。
作为用于粘合NBR与金属的粘合剂,使用在线型和可熔型酚醛树脂粘合剂中添加了上述NBR、白碳以及特定性状的硅烷偶联剂的试剂。所述粘合剂如下制备:使用肖氏密炼机(Intermix)、捏和机、班伯里密炼机等混炼机或者开放式炼胶机(open roll)将各种配合剂配合在NBR中形成NBR复合物,将NBR复合物溶解在酮类、酯类、醚类、芳族烃类或它们的混合溶剂中成为有机溶剂溶液(即橡胶糊),将橡胶糊与制备成溶液的酚醛树脂系粘合剂成分混合。也可以不对NBR进行混炼,通过将上述各成分溶解在溶剂中,用三辊研磨机、球磨机、均化机等进行湿式精密分散来制备粘合剂。
作为酚醛树脂,将线型酚醛树脂与可熔型酚醛树脂两者联用。作为线型酚醛树脂,使用在草酸、盐酸、马来酸等酸催化剂的存在下,使苯酚、对甲酚、间甲酚、对叔丁基苯酚等在酚羟基的邻位和/或对位具有2个或3个可取代的环氢原子的酚类或者它们的混合物与甲醛发生缩合反应而得到的、融点80~150℃的树脂,优选由间甲酚与甲醛制备的、融点120℃以上的树脂。
作为可熔型酚醛树脂,使用在氨、碱金属氢氧化物、氢氧化镁等碱性催化剂的存在下,使苯酚、对甲酚、间甲酚、对叔丁基苯酚等在酚羟基的邻位和/或对位具有2个或3个可取代的环氢原子的酚类或者它们的混合物与甲醛发生缩合反应而得到的树脂。
这2种酚醛树脂以相对于100重量份线型酚醛树脂,可熔型酚醛树脂约为10~1000重量份、优选约60~400重量份的比例使用。上述各成分通过加入有机溶剂使成分总浓度约为3~10重量%,并进行混合、搅拌,制成酚醛树脂系粘合剂。若可熔型酚醛树脂以小于上述范围的比例使用,则与金属面的粘合性降低;另一方面,若以大于上述范围的比例使用,则与橡胶层的粘合性降低,在仅使用可熔型酚醛树脂的情况下,压缩试验中发生橡胶面剥离。也可以与这些酚醛树脂一起使用其固化剂即六亚甲基四胺等。
作为NBR用酚醛树脂系粘合剂,实际上可以使用例如东洋化学研究所制品Metaloc N31、Rohm and Haas公司制品Thixon 715(由酚醛树脂系粘合剂溶液Thixon 715A与含有六亚甲基四胺的固化剂Thixon 715B形成)、LORD Far East公司制品TS1677-13、LORD FarEast公司制品Chemlok 205等商品,优选使用线型酚醛树脂和可熔型酚醛树脂按9∶1~1∶9的比例配合而成的粘合剂,通常作为甲醇、乙醇、异丙醇等醇系有机溶剂或者丙酮、丁酮、甲基异丁基酮等酮系有机溶剂的单溶剂溶液或者混合溶剂溶液使用。
这些酚醛树脂按每100重量份NBR约100~900重量份、优选约240~900重量份的比例使用。若使用比例少于上述范围,则与金属的粘合性变差;另一方面,若以多于上述范围的使用比例使用,则与橡胶层的粘合性变差。
白碳(二氧化硅)可以是用卤化硅酸或有机硅化合物的热分解法、或者加热还原硅砂、空气氧化经气化的SiO的方法等制备的干法白碳;用硅酸钠的热分解法等制备的湿法白碳等,可以使用非晶质二氧化硅,其粒径为0.01~0.1μm。若二氧化硅的粒径大于该范围,则耐磨损性恶化;另一方面,若二氧化硅的粒径小于该范围,则使二氧化硅在橡胶中分散时粒子凝集而变大,耐磨损性仍会恶化。所述二氧化硅可以将例如日本Silica工业制品Nipsil等商品原样使用。另外,通常使用其比表面积(BET法)约20~300m2/g优选约50~250m2/g左右的二氧化硅。与通常用作填充剂的碳黑相比,白碳虽然耐磨损性差,但由于其价格、处理性以及耐磨损性良好,故可提高粘合剂的粘合性,并防止高温高面压下橡胶的流动。
白碳按每100重量份NBR约15~100重量份、优选约30~80重量份的比例使用。若白碳以小于该范围的比例使用,则无法获得作为目标的与金属的粘合性,摩擦、磨损时发生橡胶的剥离;另一方面,若以大于该范围的比例使用,则橡胶硬度升高,且橡胶弹性也丧失。此外,若使用粒径大于该范围的白碳,则耐摩擦、磨损特性会受损,不优选。
硅烷偶联剂可举出:具有碳数2以上、优选碳数2~4的烷氧基的乙烯基三烷氧基硅烷CH2=CHSi(OR)3,例如乙烯基三乙氧基硅烷、乙烯基三异丙氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、乙烯基三(2-乙氧基乙氧基)硅烷等,可以使用其中至少一种。与无机填充剂白碳反应的烷氧基的碳原子为1的乙烯基三甲氧基硅烷,没有防止凝集的效果。
碳数2以上的烷氧基中,优选为分子量更大的烷氧基,因此烷氧基可以为上述例示的烷氧基烷氧基。另外,乙烯基通过与聚合物反应,更有效地防止无机填充剂白碳的凝集。
硅烷偶联剂相对于100重量份NBR以约2~10重量份、且相对于白碳以约3~30重量%、优选约5~20重量%的比例使用。若硅烷偶联剂的使用比例小于该范围,则白碳凝集,涂布表面发生粗糙不平或者耐磨损性受损。另一方面,若以大于该范围的比例使用,则橡胶的交联密度升高,密封性恶化,因热劣化后的弯曲而产生裂纹、热劣化后的耐磨损性恶化等。
作为形成粘合剂溶液的有机溶剂,使用例如丙酮、丁酮、甲基异丁基酮、二丙基酮、环己酮、佛尔酮、异佛尔酮等酮类,乙酸乙酯、乙酸丁酯等酯类,甲基溶纤剂、乙基溶纤剂等多元醇单醚类,甲苯、二甲苯等芳族烃类。
粘合剂的制备如下进行:将在NBR中配合了各种配合剂的NBR复合物在制备后放置0~15天左右,切断后使其溶解在例如丁酮-甲苯(重量比1∶9)混合溶剂中,制备固形成分(NBR复合物)浓度约10~30重量%的橡胶糊,之后向其中添加酚醛树脂系粘合剂溶液和丁酮等有机溶剂。相对于橡胶糊中的NBR,酚醛树脂系粘合剂溶液中酚醛树脂的比例按上述比例使用,另外粘合剂中的固形成分浓度(由NBR复合物和酚醛树脂构成的固形成分的浓度)为约2~15重量%,优选为约3~10重量%左右。
粘合剂溶液的稀释浓度根据涂布厚度、涂布方法等适当选择。粘合剂的涂布厚度通常为约1~10μm,优选约2~6μm。涂布厚度比上述范围薄时,无法将金属的凹凸表面全部覆盖,粘合性降低。另一方面,若涂布厚度比上述范围厚,则柔软性可能受损。粘合剂溶液的涂布方法使用浸渍、喷雾、辊涂、流涂、喷射等任意的方法。
作为用这些粘合剂与NBR层合的金属,通常使用金属板,金属板使用不锈钢板、软钢板、镀锌钢板、SPCC板(冷轧钢板)、钢板、铜板、镁板、铝板、铝压铸板等,优选使用SUS301、SUS301H、SUS304、SUS430等不锈钢板。这些板通常以脱脂的状态使用,必要时通过喷砂、Scotch-Brite、细线(hairline)、消光等将金属表面粗化。另外,其板厚在用作密封材料的情况下,通常使用约0.1~1mm左右的厚度。
在这些金属板上优选形成底漆层。希望底漆层大幅提高橡胶金属积层体的耐热性和耐水性,特别是将橡胶金属积层体用作密封材料时,希望形成底漆层。
作为底漆层,可以原样使用磷酸锌膜,磷酸铁膜,钒、锆、钛、钼、钨、锰、锌、铈等金属的化合物,特别是这些金属的氧化物等的无机系膜;硅烷、酚醛树脂、环氧树脂、聚氨酯等有机系膜等通常市售的药液或者公知技术,优选使用包含具有至少1个以上的螯合环和烷氧基的有机金属化合物的底漆层、或者进一步向其中添加了金属氧化物或二氧化硅的底漆层,更优选使用向这些形成底漆层的成分中加入了含氨基的烷氧基硅烷与含乙烯基的烷氧基硅烷的水解缩合产物的底漆层。该水解缩合产物单独也可用作底漆。
将这些底漆成分制成醇类或酮类的有机溶剂溶液,使其固形成分浓度为约0.2~5重量%左右,在保持其溶液稳定性的限度内,也可以向其中混合20重量%以下的水使用。通过浸渍、喷雾、刷涂或使用辊涂机等,将获得的底漆溶液按约50~300mg/m2左右的单位面积重量涂布在金属板上,室温或温风干燥后,在约100~250℃下烘烤处理约0.5~20分钟,形成底漆层。
在金属板上形成粘合剂层优选如下进行:在形成有底漆层的金属板上涂布粘合剂溶液,在室温条件下风干后,在约100~250℃下加热约5~30分钟左右。粘合剂层可以仅为一层或多层的构成,例如,也可以在底漆层上形成含有机金属化合物的酚醛树脂系粘合剂层,再在其上设置含上述NBR复合物的酚醛树脂系粘合剂层,经该多次涂布后,设置橡胶层。通过采用这种构成,虽然粘合剂的涂布步骤增加,但底漆层和橡胶层的粘合性可能更加牢固。
将由NBR复合物溶液构成的橡胶糊涂布在粘合剂层上,使作为未硫化橡胶层的厚度约10~200μm左右,干燥后在约150~230℃进行约0.5~30分钟左右的硫化。获得的橡胶金属积层体中,必要时,为了防止与橡胶粘着,也可以将树脂系、石墨系等抗粘剂涂布在橡胶层上。
实施例
下面,参考实施例来说明本发明。
实施例1
(1)NBR(JSR制品N235S;CN含量36%):100重量份
SRF碳黑(I2吸附量29g/kg,DBP吸油量72ml/100g):60重量份
白碳(日本Silica制品Nipsil LP;比表面积200m2/g,粒径0.02μm):40重量份
氧化锌:5重量份
硬脂酸:2重量份
抗老化剂(大内新兴化学制品,Nocrac 224):2重量份
三烯丙基异氰尿酸酯(日本化成制品,TAIC):1.2重量份
1,3-双(叔丁基过氧异丙基)苯(三建化工制品,Sunperox TY-13):6重量份
乙烯基三(2-甲氧基乙氧基)硅烷(Momentive PerformanceMaterials公司制品,A-172):3重量份
(合计)219.2重量份
对于以上各配合成分,用捏和机将聚合物捏和后,首先加入碳黑、氧化锌、硬脂酸以及抗老化剂进行混炼,接着一起加入白碳和硅烷偶联剂,在最大温度为130℃的条件下进行混炼。之后,用开放式炼胶机加入有机过氧化物和交联助剂进行混炼,得到NBR复合物。
(2)将250重量份制备后放置10天的该NBR复合物、75重量份丁酮以及675重量份甲苯搅拌混合,制备固形成分(NBR复合物)浓度25重量%的橡胶糊。
(3)在碱法脱脂的厚0.2mm的不锈钢板(日新制钢制品SUS301)表面,通过浸渍法涂布由1.0重量%四(乙酰丙酮)合钛、2.5重量%烷氧基硅烷水解缩合物、10.0重量%水以及86.5重量%甲醇构成的硅烷系底漆,用热空气干燥后,在约200℃下烘烤处理约5分钟,形成底漆层(单位面积重量250mg/m2)。
此处使用的烷氧基硅烷水解缩合物如下制备:向带有搅拌机、加热套以及滴液漏斗的三口烧瓶中加入40重量份γ-氨基丙基三乙氧基硅烷以及20重量份水,加入乙酸调整pH至4~5,搅拌数分钟。继续进行搅拌,同时使用滴液漏斗缓慢滴加40重量份乙烯基三乙氧基硅烷,滴加结束后在约60℃进行5小时加热回流,冷却至室温,得到烷氧基硅烷水解缩合物。
(4)酚醛树脂系粘合剂溶液(Rohm and Haas公司制品,Thixon715A;有机溶剂溶液中可熔酚醛树脂、线型酚醛树脂的固形成分浓度为38重量%,相当于每100重量份NBR,酚醛树脂量为217重量份):97重量份
含六亚甲基四胺的固化剂(Rohm and Haas公司制品,Thixon715-B):3重量份
上述(2)中获得的橡胶糊(固形成分浓度25重量%):68重量份
丁酮:969重量份
将由以上各成分构成的粘合剂组合物溶液(固形成分浓度5重量%)浸渍涂布在上述(3)得到的形成有底漆层的不锈钢板上,室温条件下风干后,在约200℃下加热约5分钟,形成厚度约2μm的粘合剂层。
(5)将上述(2)中获得的橡胶糊用刮涂机涂布在形成有底漆层和粘合剂层的不锈钢板上,干燥,形成厚度约20μm的未硫化橡胶层,接着在180℃进行6分钟的加压硫化,形成NBR橡胶层。
(6)异氰酸酯改性1,2-聚丁二烯(日本曹达制品TP1001;50重量%乙酸丁酯溶液):25重量份
含羟基1,2-聚丁二烯(日本曹达制品GQ-1000;45重量%二甲苯溶液):25重量份
聚乙烯蜡(分子量2000、融点110℃、粒径1μm、15重量%甲苯溶液):125重量份
聚四氟乙烯(粒径1μm、15重量%甲苯分散液):125重量份
甲苯:950重量份
将具有上述组成的表面涂布剂浸渍涂布在上述(5)中获得的形成有硫化橡胶层的不锈钢表面,在200℃、通过空气加热进行5分钟加热处理,形成厚度5μm的防粘层,制作橡胶金属积层体。
对如此获得的橡胶金属积层体进行下述各项测定。
橡胶糊的粒度:按照对应于ASTM D1210的JIS K5400,将刚混炼或者在25℃放置10天后的NBR复合物切断后溶解在溶剂中,测定未溶解粒子的粒度
高温摩擦磨损试验:对使用用混炼后在25℃放置10天的NBR复合物制备的橡胶糊制作的橡胶金属积层体,按照对应于ASTMD1894的JIS K7125、P8147测定
使用新东科学制表面性测试机,通过在下述条件下的往复运动试验进行摩擦磨损试验,测定直至橡胶磨损、粘合剂层露出的次数
配偶材料:硬质镀Cr钢球(直径10mm)
移动速度:400mm/分
往复运动幅度:30mm
温度:150℃
负荷:2.5kg
压缩试验:目测评价在橡胶金属积层体的橡胶面上以150℃、2吨f/cm2(98MPa)、5分钟的条件压缩不锈钢制凸状体时橡胶的状态(有无剥离)
粘合强度:按照对应于ASTM D1002的JIS K6850(使用万能材料测试机,在环境温度:常温、拉伸速度50mm/分、卡盘间距:50mm的设定条件下测定),测定初期、水浸渍后(95℃、浸渍120小时)以及防冻液(Toyota纯正LLC与水的体积比为1∶1的混合液)浸渍后(100℃、浸渍120小时)的粘合强度
实施例2
实施例1(1)中,用等量的乙烯基三(异丙氧基)硅烷(Toray DowCorning制品,Z-6550)作为硅烷系偶联剂。
实施例3
实施例1(1)中,用等量的乙烯基三乙氧基硅烷(MomentivePerformance Materials公司制品,A-151)作为硅烷系偶联剂。
比较例1
实施例1(1)中,用等量的3-甲基丙烯酰氧基丙基三甲氧基硅烷CH2=C(CH3)COOC3H6Si(OCH3)3(Toray Dow Corning制品,Z-6030)作为硅烷系偶联剂。
比较例2
实施例1(1)中,用等量的正辛基三乙氧基硅烷CH3(CH2)7Si(OC2H5)3(Momentive Performance Materials公司制品,A-137)作为硅烷系偶联剂。
比较例3
实施例1(1)中,不使用硅烷系偶联剂,获得NBR复合物。
比较例4
实施例1(1)中,不使用白碳和硅烷系偶联剂,获得NBR复合物。
比较例5
实施例1(4)中,使用由以下各成分构成的粘合剂组合物溶液。
酚醛树脂系粘合剂溶液(大日本INK化学制品,Phenolite PN树脂;甲醇溶剂溶液中的线型酚醛树脂的固形成分浓度为38重量%):97重量份
含六亚甲基四胺的固化剂(Thixon 715-B):3重量份
丁酮:967重量份
比较例6
实施例1(4)中,将依次添加以下各成分
未硫化NBR(JSR制品N-237,中高丁腈):2重量份
可熔型酚醛树脂(LORD Far East公司制品,Chemlok TS1677):5重量份
氯化聚乙烯(Daiso制品,SE-200Z):3重量份
丁酮:90重量份
制备的粘合剂组合物溶液涂布在形成有底漆层的不锈钢板上,在室温条件下风干后,在约200℃加热约5分钟,形成厚度约2μm的粘合剂层。
比较例7
实施例1(1)中,用等量的乙烯基三甲氧基硅烷(Momentive公司制品,A171)作为硅烷系偶联剂。
比较例8
实施例1(1)中,用等量的乙烯基三乙酰氧基硅烷(Toray DowCorning制品,Z-6075)作为硅烷系偶联剂。
比较例9
实施例1(4)中,将依次添加以下各成分
可熔型酚醛树脂(LORD Far East社制品,Chemlok TS1677):5重量份
丁酮:95重量份
制备的粘合剂组合物溶液涂布在形成有底漆层的不锈钢板上,在室温条件下风干后,在约150℃加热约5分钟,形成厚度约2μm的粘合剂层。
实施例2~3和比较例1~9中记载的步骤以外的其他步骤以及测定与实施例1同样进行。包括实施例1在内的各实施例以及比较例所得结果示于下表中。
表
Claims (2)
1.橡胶金属积层体,其是用粘合剂使NBR与金属粘合而成的橡胶金属积层体,
其中,使用橡胶糊与酚醛树脂系粘合剂溶液的混合物溶液作为粘合剂,所述橡胶糊是在NBR中配合有白碳和具有碳数2以上的烷氧基的乙烯基三烷氧基硅烷偶联剂的NBR复合物的有机溶剂溶液,
相对于100重量份NBR,以100~900重量份的比例使用酚醛树脂,15~100重量份的比例使用白碳,2~10重量份的比例使用硅烷偶联剂。
2.权利要求1记载的橡胶金属积层体,其中金属为不锈钢。
3. 权利要求2记载的橡胶金属积层体,其中金属为涂布了底漆的不锈钢板。
4. 权利要求1记载的橡胶金属积层体,其中使用与粘合剂成分中所用NBR相同的NBR作为与金属层合的NBR。
5. 用于层合NBR与金属的粘合剂,其是橡胶糊与酚醛树脂系粘合剂溶液的混合物溶液,所述橡胶糊是在NBR中配合有白碳和具有碳数2以上的烷氧基的乙烯基三烷氧基硅烷偶联剂的NBR复合物的有机溶剂溶液,
其中,相对于100重量份NBR,以100~900重量份的比例使用酚醛树脂,15~100重量份的比例使用白碳,2~10重量份的比例使用硅烷偶联剂。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009-255845 | 2009-11-09 | ||
JP2009255845A JP4877380B2 (ja) | 2009-11-09 | 2009-11-09 | ゴム金属積層体 |
PCT/JP2010/069552 WO2011055735A1 (ja) | 2009-11-09 | 2010-11-04 | ゴム金属積層体 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102666091A CN102666091A (zh) | 2012-09-12 |
CN102666091B true CN102666091B (zh) | 2014-11-26 |
Family
ID=43969973
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201080051592.XA Expired - Fee Related CN102666091B (zh) | 2009-11-09 | 2010-11-04 | 橡胶金属积层体 |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP2500168B1 (zh) |
JP (1) | JP4877380B2 (zh) |
CN (1) | CN102666091B (zh) |
WO (1) | WO2011055735A1 (zh) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013147020A1 (ja) * | 2012-03-30 | 2013-10-03 | 東海ゴム工業株式会社 | ゴム組成物および燃料電池シール体 |
WO2014132997A1 (ja) * | 2013-02-27 | 2014-09-04 | 三菱電線工業株式会社 | 積層体およびその製造方法 |
WO2015093261A1 (ja) * | 2013-12-20 | 2015-06-25 | 住友ベークライト株式会社 | 熱硬化性樹脂組成物および金属樹脂複合体 |
CN105829452B (zh) * | 2013-12-20 | 2019-06-18 | 住友电木株式会社 | 热固化性树脂组合物及金属树脂复合体 |
CN105202183A (zh) * | 2015-10-08 | 2015-12-30 | 蚌埠冠宜型材科技有限公司 | 一种铸造用的耐高温密封垫 |
JP6934312B2 (ja) * | 2017-04-04 | 2021-09-15 | Nok株式会社 | ゴム金属積層体およびガスケット |
CN110637073B (zh) * | 2017-05-25 | 2020-09-18 | Nok株式会社 | 硫化粘接剂组合物 |
JP7284379B2 (ja) * | 2019-02-07 | 2023-05-31 | 日本製鉄株式会社 | 複合体およびその製造方法、ならびに塗装金属板 |
CN109830485B (zh) * | 2019-02-27 | 2020-10-30 | 武汉天马微电子有限公司 | 一种显示面板、其制备方法及显示装置 |
IT202100010424A1 (it) | 2021-04-23 | 2022-10-23 | M E Rin S R L | “struttura di tessuto stratificato con materiale elastomerico e metodo di produzione dello stesso” |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003334885A (ja) * | 2002-05-21 | 2003-11-25 | Nok Corp | ゴム金属積層ガスケット |
JP2007038533A (ja) * | 2005-08-03 | 2007-02-15 | Nok Corp | ゴム金属積層体 |
WO2009016922A1 (ja) * | 2007-08-01 | 2009-02-05 | Nok Corporation | ニトリルゴム金属積層体の製造方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3933017B2 (ja) | 2002-09-11 | 2007-06-20 | Nok株式会社 | 金属・ゴム複合材料の製造法 |
JP4617737B2 (ja) | 2003-11-27 | 2011-01-26 | Nok株式会社 | ニトリルゴム−金属積層ガスケット素材 |
JP4736332B2 (ja) | 2004-03-03 | 2011-07-27 | Nok株式会社 | ゴム−金属積層ガスケット素材 |
JP2005299823A (ja) * | 2004-04-13 | 2005-10-27 | Nok Corp | ゴム−金属積層ガスケット素材 |
US7772305B2 (en) * | 2006-02-17 | 2010-08-10 | Nok Corporation | Hydrogenated NBR composition |
JP2007292274A (ja) | 2006-03-31 | 2007-11-08 | Nok Corp | ガスケットの製造方法及びインクジェット塗布装置 |
JP5012074B2 (ja) * | 2007-02-15 | 2012-08-29 | Nok株式会社 | 水素化nbr組成物 |
-
2009
- 2009-11-09 JP JP2009255845A patent/JP4877380B2/ja active Active
-
2010
- 2010-11-04 CN CN201080051592.XA patent/CN102666091B/zh not_active Expired - Fee Related
- 2010-11-04 WO PCT/JP2010/069552 patent/WO2011055735A1/ja active Application Filing
- 2010-11-04 EP EP10828295.5A patent/EP2500168B1/en not_active Not-in-force
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003334885A (ja) * | 2002-05-21 | 2003-11-25 | Nok Corp | ゴム金属積層ガスケット |
JP2007038533A (ja) * | 2005-08-03 | 2007-02-15 | Nok Corp | ゴム金属積層体 |
WO2009016922A1 (ja) * | 2007-08-01 | 2009-02-05 | Nok Corporation | ニトリルゴム金属積層体の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP2500168B1 (en) | 2017-09-27 |
CN102666091A (zh) | 2012-09-12 |
JP4877380B2 (ja) | 2012-02-15 |
JP2011098541A (ja) | 2011-05-19 |
EP2500168A4 (en) | 2014-05-07 |
EP2500168A1 (en) | 2012-09-19 |
WO2011055735A1 (ja) | 2011-05-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102666091B (zh) | 橡胶金属积层体 | |
CN104289408B (zh) | 丁腈橡胶金属层压体的制备方法 | |
KR101090091B1 (ko) | 고무 금속 적층체 | |
CN103517942B (zh) | Nbr组合物及橡胶金属层叠体 | |
JP5971247B2 (ja) | ガスケット材料 | |
JP2008018707A5 (zh) | ||
US6350799B1 (en) | Coolant resistant and thermally stable primer composition | |
WO2005023949A1 (ja) | 加硫接着用プライマー | |
JP4577140B2 (ja) | ゴム金属積層体 | |
JP5125052B2 (ja) | Nbr組成物 | |
JP2005226064A (ja) | 加硫接着剤組成物 | |
JP5152287B2 (ja) | 加硫接着剤組成物 | |
JP2005299823A (ja) | ゴム−金属積層ガスケット素材 | |
JP4736332B2 (ja) | ゴム−金属積層ガスケット素材 | |
JP4947823B2 (ja) | 被覆金属成形品および被覆金属成形品の製造方法 | |
JP2008213354A (ja) | ゴム金属複合体 | |
JP2004076699A (ja) | エンジン用シリンダヘッドガスケット素材 | |
CN101472739A (zh) | 橡胶金属层压体 | |
JP5716508B2 (ja) | ニトリルゴム組成物 | |
KR20150091300A (ko) | 금속 표면 처리제 | |
JP2007196690A (ja) | ゴム金属積層ガスケット |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141126 |