CN1403732A - 软管 - Google Patents
软管 Download PDFInfo
- Publication number
- CN1403732A CN1403732A CN02132288A CN02132288A CN1403732A CN 1403732 A CN1403732 A CN 1403732A CN 02132288 A CN02132288 A CN 02132288A CN 02132288 A CN02132288 A CN 02132288A CN 1403732 A CN1403732 A CN 1403732A
- Authority
- CN
- China
- Prior art keywords
- mentioned
- flexible pipe
- described flexible
- rubber
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001971 elastomer Polymers 0.000 claims abstract description 109
- 239000005060 rubber Substances 0.000 claims abstract description 109
- 239000000203 mixture Substances 0.000 claims abstract description 77
- GHMLBKRAJCXXBS-UHFFFAOYSA-N Resorcinol Natural products OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000011347 resin Substances 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000004640 Melamine resin Substances 0.000 claims abstract description 25
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 25
- 239000011888 foil Substances 0.000 claims abstract description 24
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 23
- 150000002978 peroxides Chemical class 0.000 claims abstract description 15
- -1 resorcinol compound Chemical class 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 31
- 229920006122 polyamide resin Polymers 0.000 claims description 12
- 239000004615 ingredient Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 238000010276 construction Methods 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910001021 Ferroalloy Inorganic materials 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 abstract description 18
- 229920002292 Nylon 6 Polymers 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 19
- 239000000446 fuel Substances 0.000 description 19
- 239000004952 Polyamide Substances 0.000 description 18
- 229920002647 polyamide Polymers 0.000 description 18
- 239000007789 gas Substances 0.000 description 17
- 239000005030 aluminium foil Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- 235000019241 carbon black Nutrition 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 238000002156 mixing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920005549 butyl rubber Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 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 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000005987 sulfurization reaction Methods 0.000 description 4
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 3
- ZPMCCZKDFLIVHD-UHFFFAOYSA-N 2-tert-butylperoxy-2-methylpropane;1,2-di(propan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C.CC(C)C1=CC=CC=C1C(C)C ZPMCCZKDFLIVHD-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 150000003951 lactams Chemical class 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- AVKNGPAMCBSNSO-UHFFFAOYSA-N cyclohexylmethanamine Chemical compound NCC1CCCCC1 AVKNGPAMCBSNSO-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 2
- 206010016766 flatulence Diseases 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000007591 painting process Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- HYBLFDUGSBOMPI-BQYQJAHWSA-N (4e)-octa-1,4-diene Chemical compound CCC\C=C\CC=C HYBLFDUGSBOMPI-BQYQJAHWSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- YEECOJZAMZEUBB-UHFFFAOYSA-N 2,2,3,3,6,6,7,7-octamethyloctane Chemical compound CC(C)(C)C(C)(C)CCC(C)(C)C(C)(C)C YEECOJZAMZEUBB-UHFFFAOYSA-N 0.000 description 1
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 1
- DSAYAFZWRDYBQY-UHFFFAOYSA-N 2,5-dimethylhexa-1,5-diene Chemical compound CC(=C)CCC(C)=C DSAYAFZWRDYBQY-UHFFFAOYSA-N 0.000 description 1
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical compound FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-UHFFFAOYSA-N 0.000 description 1
- LDQDHHWLNHBLLU-UHFFFAOYSA-N 2-tert-butylperoxy-2-methylpropane pentanoic acid Chemical compound C(C)(C)(C)OOC(C)(C)C.C(CCCC)(=O)O LDQDHHWLNHBLLU-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229920006020 amorphous polyamide Polymers 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 229920003233 aromatic nylon Polymers 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000004067 bulking agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 description 1
- UVJHQYIOXKWHFD-UHFFFAOYSA-N cyclohexa-1,4-diene Chemical compound C1C=CCC=C1 UVJHQYIOXKWHFD-UHFFFAOYSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 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
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- MAHNFPMIPQKPPI-UHFFFAOYSA-N disulfur Chemical compound S=S MAHNFPMIPQKPPI-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage 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
- 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
- 230000000007 visual effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- B32B15/08—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 synthetic resin
-
- 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
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
-
- 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
-
- 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
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
-
- 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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- 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
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
-
- 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
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/02—Noble metals
- B32B2311/08—Silver
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Abstract
本发明提供一种软管,它是具有由以下述(A)~(D)作为必需成分的橡胶组合物构成的橡胶层、及由金属箔和树脂构成的层压层的叠层结构的软管,该软管重量轻、成本低,气体阻隔性优良。(A)由乙烯-丙烯-二烯三元共聚物和乙烯-丙烯共聚物中的至少1种构成的橡胶;(B)过氧化物硫化剂;(C)间苯二酚系化合物;(D)蜜胺树脂。
Description
发明领域
本发明涉及一种软管,更详细地说,涉及一种燃料电池车用软管(甲醇燃料软管、氢燃料软管)和输送制冷剂用空调软管等汽车用软管。
背景技术
过去,几乎没有使用甲醇燃料(有时与一部分汽油混合使用)或氢燃料的车辆,尚未对这些专用软管进行具体的开发。然而,作为新一代的汽车***,随着装载使用甲醇燃料或氢燃料的燃料电池的研究开发活跃,用于该燃料电池车的甲醇燃料软管和氢燃料软管等燃料电池车用软管的开发需求也逐步提高。
发明内容
目前,作为汽车制造商的燃料电池试验车中的甲醇燃料管或氢燃料管等燃料电池车用软管,从耐气体性(耐气体劣化性)以及气体阻隔性(耐甲醇渗透性、耐氢渗透性等)的观点考虑,使用不锈钢(SUS)等的金属配管,可是,金属配管重量非常重,存在燃料费用高、成本也高的问题。
本发明就是鉴于这种情况而进行的,目的是提供一种气体阻隔性优良、重量轻、低成本的软管。
为了达到上述目的,本发明的软管具有以下构成:由以下述的(A)~(D)作为必需成分的橡胶组合物构成的橡胶层、和由金属箔和树脂构成的层压层的叠层结构,
(A)由乙烯-丙烯-二烯三元共聚物和乙烯-丙烯共聚物中的至少1种构成的橡胶;
(B)过氧化物硫化剂;
(C)间苯二酚系化合物;
(D)蜜胺树脂。
即,本发明人为了获得气体阻隔性优良、重量轻、低成本的软管,反复进行了精心的研究。首先,设想到:使用不是以往的金属配管的、具有橡胶层和金属箔层压层的叠层结构的软管,或许可谋求软管整体达到轻量化,于是注意到橡胶材料中价格比较便宜的乙烯-丙烯-二烯三元共聚物(以下简称为“EPDM”)和乙烯-丙烯共聚物(以下简称为“EPM”)。并且试制了用粘合剂将橡胶层与金属箔层压层粘接的软管,但由于粘合剂的涂布不匀等而使橡胶层与金属箔层压层的粘接力不足。另外,由于需要粘合剂的涂布工序,因此制造工序复杂、成本也提高,同时还需要注意粘合剂的贮存期和浓度调整等,存在着稳定生产性差的问题。而且,由于作为粘合剂的稀释溶剂使用甲苯等有机溶剂,故也有环境污染等问题。
因此,为了不必在橡胶层与金属箔层压层的界面上涂布粘合剂,而又能获得橡胶层与金属箔层压层的粘接性优良的软管,进行了反复研究。于是,考虑到在上述特定的橡胶中掺入粘合剂成分,并对与特定橡胶的粘接性优良的粘合剂成分进行研究开发,结果发现,如果在特定的橡胶中掺入特定的粘合剂成分(间苯二酚系化合物和蜜胺树脂),并用过氧化物硫化剂将其硫化,就可以获得与金属箔层压层的优良粘接力,从而完成本发明。
附图的简单说明
图1为表示本发明软管的一个例子的截面斜视图。
图2为用于评价气体阻隔性的抖动试验的说明图。
符号说明
1橡胶层
2层压层
发明的实施方案
以下详细地说明本发明的实施方案。
本发明的软管其构成例如图1所示,在由特殊的橡胶组合物构成的橡胶层1的外周面上形成层压层2,再在其外周面上形成由特殊的橡胶组合物构成的橡胶层3,层压层2含有至少1层的树脂层和金属箔。
作为上述橡胶层1用材料的特殊橡胶组合物可以使用特定的橡胶(A成分)、过氧化物硫化剂(B成分)、间苯二酚系化合物(C成分)和蜜胺树脂(D成分)来获得。
作为上述特定的橡胶(A成分),可以使用乙烯-丙烯-二烯三元共聚物(EPDM)和乙烯-丙烯共聚物(EPM)中的至少1种。上述EPDM只要是用作橡胶组合物的基材,就没有特别的限定,但优选碘值为6~30的范围、乙烯比率为48~70重量%的范围的EPDM,特别优选碘值为10~24的范围、乙烯比率为50~60重量%的范围的EPDM。
作为上述EPDM中含有的二烯系单体(第3种成分)没有特别的限定,优选碳原子数为5~20的二烯系单体,具体地可以举出1,4-戊二烯、1,4-己二烯、1,5-己二烯、2,5-二甲基-1,5-己二烯、1,4-辛二烯、1,4-环己二烯、环辛二烯、双环戊二烯(DCP)、5-亚乙基-2-降冰片烯(ENB)、5-亚丁基-2-降冰片烯、2-甲代烯丙基-5-降冰片烯、2-异丙烯基-5-降冰片烯等。这些二烯系单体(第3种成分)中,优选双环戊二烯(DCP)、5-亚乙基-2-降冰片烯(ENB)。
作为与上述特定的橡胶(A成分)同时使用的过氧化物硫化剂(B成分),例如可以举出过氧化2,4-二氯苯甲酰、过氧化苯甲酰、1,1-二叔丁基过氧化-3,3,5-三甲基环己烷、2,5-二甲基-2,5-二苯甲酰基过氧化己烷、正丁基-4,4′-二叔丁基过氧化戊酸酯、二枯烯基过氧化物、叔丁基过氧化苯甲酸酯、二叔丁基过氧化-二异丙苯、叔丁基枯烯基过氧化物、2,5-二甲基-2,5-二叔丁基过氧化己烷、二叔丁基过氧化物、2,5-二甲基-2,5-二叔丁基过氧化己炔-3等。它们可以单独使用,也可以2种以上合并使用。其中,从没有臭气方面考虑,优选使用二叔丁基过氧化-二异丙苯。
上述过氧化物硫化剂(B成分)的配合比例,相对于上述特定的橡胶(A成分)100重量份(以下简称为“份”),优选为1.5~20份的范围。这是由于如果B成分不足1.5份,则交联不充分,软管的强度差,而如果B成分超过20份,则软管变得过硬,柔软性差。
作为与上述A成分和B成分同时使用的间苯二酚系化合物(C成分),只要是主要起粘合剂作用的,就没有特别的限定,例如可以举出改性间苯二酚·甲醛树脂、间苯二酚、间苯二酚·甲醛(RF)树脂等。它们可以单独使用,或者2种以上合并使用。其中,从蒸发性、吸湿性、与橡胶的相溶性等方面考虑,优选使用改性间苯二酚·甲醛树脂。
[式中,n为正数。]
上述间苯二酚系化合物(C成分)的配合比例,相对于上述特定的橡胶(A成分)100份,优选为0.1~10份的范围,特别优选为0.5~5份。这是因为如果C成分不足0.1份,则与层压层的粘合性差,而如果C成分超过10份,则使成本提高。
作为与上述A~C成分同时使用的蜜胺树脂(D成分),只要是主要起粘接助剂作用的,就没有特别的限定,例如可以举出甲醛·蜜胺聚合物的甲基化物、六亚甲基四胺等。它们可以单独使用,也可以2种以上合并使用。其中,从蒸发性、吸湿性、与橡胶的相溶性等方面考虑,优选使用甲醛·蜜胺聚合物的甲基化物。
[式中,n为正数。]
上述蜜胺树脂(D成分)中,优选用上述通式(4)表示的化合物的混合物,特别优选n=1的化合物占43~44重量%、n=2的化合物占27~30重量%、n=3的化合物占26~30重量%的混合物。
另外,上述间苯二酚系化合物(C成分)与蜜胺树脂(D成分)的配合比,按重量比计,优选为C成分/D成分=1/0.5~1/2的范围,特别优选为C成分/D成分=1/0.77~1/1.5。这是因为如果D成分的重量比不足0.5,则橡胶层的拉伸强度(TB)和延伸率(EB)等常规物性有些变差的倾向,而如果D成分的重量比超过2,则粘接性饱和,粘接力稳定,即使进一步提高D成分的重量比,也只是使成本提高,而不能期待更高的效果。
再者,上述特殊的橡胶组合物中,除了上述A~D成分以外,还配合炭黑、操作油剂等为好。
另外,上述特殊的橡胶组合物中,除了上述各成分以外,也可根据需要适宜地配合抗老化剂、加工助剂、交联促进剂、白色填充剂、反应性单体、发泡剂等。
上述特殊的橡胶组合物可通过配合上述A~D成分和根据需要的其他成分,使用滚筒、捏合机、班伯里混炼机等混炼机将其混炼来制备。
作为用于上述层压层2的树脂没有特别的限定,可以举出聚酰胺树脂、乙烯-乙烯基醇共聚物(EVOH)等。它们可以单独使用或2种以上合并使用。
上述聚酰胺树脂只要是重复单元中具有聚酰胺键(-CONH-)的高分子化合物就没有特别的限定,例如可以举出聚合形式的以下聚合物。
(1)二胺与二元酸的缩聚物,例如由六亚甲基二胺、十亚甲基二胺、十二亚甲基二胺、2,2,4-或2,4,4-三甲基六亚甲基二胺、1,3-或1,4-二(氨基甲基)环己烷、二(对氨基环己基甲烷)、间-或对-苯二甲基二胺之类的脂肪族、脂环族或芳香族的二胺与己二酸、辛二酸、癸二酸、环己烷二羧酸、对苯二甲酸、间苯二甲酸之类的脂肪族、脂环族或芳香族的二元羧酸制造的聚酰胺树脂。
(2)氨基羧酸的缩聚物,例如由6-氨基己酸、11-氨基十一烷酸、1 2-氨基十二烷酸之类的氨基羧酸制造的结晶性或非结晶性的聚酰胺树脂。
(3)内酰胺的开环聚合物,例如由ε-己内酰胺、ω-十二内酰胺之类的内酰胺制造的聚酰胺树脂。
作为本发明中使用的聚酰胺树脂,除了上述聚酰胺树脂以外,还可以使用共聚聚酰胺树脂、聚酰胺树脂的混合物等。作为上述聚酰胺树脂的具体例子,可以举出尼龙6、尼龙66、尼龙610、尼龙612、尼龙11、尼龙12、芳香族尼龙、非晶尼龙等。其中,从刚性和耐热性特别优良的方面考虑,优选尼龙6、尼龙66。
作为上述EVOH没有特别的限定,通常使用在ASTM D 1238、190℃、2.16kg下的熔体流动速率(MFR)(日本名称:熔体指数)为1~10g/10分钟、优选为1~6g/10分钟的聚合物。
另外,作为用于上述层压层2的金属箔没有特别的限定,例如可以举出由铁、铁合金(SUS等)、铜、钛、银、镍、镍合金、铝等构成的金属箔。它们可以单独使用或2种以上合并使用。又,上述铝箔不仅仅是单一的铝,也可以是由铝合金构成的箔。其中,从耐气体性优良的方面考虑,适宜使用SUS箔和铝箔。
上述层压层2只要是用粘合剂等将金属箔和树脂薄膜叠层的层就没有特别的限定,例如可以举出金属箔与树脂薄膜的2层结构(金属箔/树脂薄膜)、以金属箔为芯材并将其两面用树脂薄膜夹住的3层结构(树脂薄膜/金属箔/树脂薄膜)等。又,作为上述粘合剂,只要是通常的层压法中采用的,就没有特别的限定。
作为上述层压层2的具体例子,可以举出以SUS箔为芯材,其两面用聚酰胺(PA)树脂薄膜夹住的3层结构(PA树脂薄膜/SUS箔/PA树脂薄膜)、以SUS箔为芯材,其两面用EVOH薄膜夹住的3层结构(EVOH薄膜/SUS箔/EVOH薄膜)、以SUS箔为芯材,其两面用EVOH薄膜夹住、再将其两面用PA树脂薄膜夹住的5层结构(PA树脂薄膜/EVOH薄膜/SUS箔/EVOH薄膜/PA树脂薄膜)等。
另外,作为上述层压层2的其他具体例子,可以举出以铝箔为芯材,其两面用聚酰胺(PA)树脂薄膜夹住的3层结构(PA树脂薄膜/铝箔/PA树脂薄膜)、以铝箔为芯材,其两面用EVOH薄膜夹住的3层结构(EVOH薄膜/铝箔/EVOH薄膜)、以铝箔为芯材,其两面用EVOH薄膜夹住、再将其两面用PA树脂薄膜夹住的5层结构(PA树脂薄膜/EVOH薄膜/铝箔/EVOH薄膜/PA树脂薄膜)等。
上述图1所示的软管可用以下方法制作。即,首先,将上述特殊的橡胶组合物在心轴上挤出成型之后,在其表面上卷绕上述金属箔和树脂薄膜,形成层压层2。接着,将上述特殊的橡胶组合物在上述层压层2的表面上挤出成型,将其整体硫化后,抽出心轴。这样就能够制成在橡胶层1的外周面上形成层压层2、再在其外周面上形成橡胶层3的软管(参照图1)。
这样制得的软管各层的厚度根据软管的用途不同而不同,橡胶层1及3的厚度通常为0.5~4mm,优选为1~3mm。另外,层压层2的总厚度通常为8μm~0.4mm,考虑到柔软性和气体阻隔性的平衡,优选为15μm~0.3mm。又,软管的内径根据用途不同而不同,通常为2~40mm,优选为4~35mm。
本发明的软管并不限定于图1所示的结构,只要是具有至少1层的橡胶层和层压层的叠层结构的,就可以是橡胶层与层压层的2层结构,也可以将橡胶层和层压层的任一层作为内层。
另外,本发明中,也可以在橡胶层3(外层)的外周面上形成增强层,再在其外周面上形成通用橡胶层。
作为上述的增强层用材料,例如可以举出聚乙烯基醇(维尼纶)丝、聚酰胺(尼龙)丝、芳族聚酰胺丝、聚对苯二甲酸乙二醇酯(PET)丝、金属丝等。
作为上述通用橡胶层用材料,例如可以举出EPDM、丁基橡胶(IIR)、卤化丁基橡胶(Cl-IIR、Br-IIR)、异戊二烯橡胶(IR)、聚氨酯橡胶、氯丁橡胶(CR)、表氯醇橡胶(ECO)、氟橡胶等通用橡胶。其中,从价格比较便宜的方面考虑,优选使用EPDM。
本发明的软管通过适宜地选择各层的构成,可适合作为燃料电池车用软管(甲醇燃料软管、氢燃料软管)、输送制冷剂用空调软管、汽车等车辆的发动机与散热器连接用的散热器软管和发动机与加热器中心连接用的加热器软管等发动机冷却***软管、汽油燃料软管等汽车用软管使用。又,EPDM由于耐汽油性差,所以作为汽油燃料软管使用时,希望由特殊的橡胶组合物构成的橡胶层用作内层以外的层(例如外层)。
下面和比较例一起说明实施例。
首先,在实施例和比较例之前,制备下述材料。橡胶(A成分)①
EPDM(住友化学工业公司制,エスプレン510A)(碘值:12,乙烯比率:50重量%,门尼粘度(ML 1+4 100℃):43)橡胶(A成分)②
EPM(住友化学工业公司制,エスプレン201)过氧化物硫化剂(B成分)
二叔丁基过氧化二异丙苯(日本油脂公司制,ペロキシモン F-40)间苯二酚系化合物(C成分)
用上述通式(1)表示的改性间苯二酚·甲醛树脂(住友化学工业公司制,スミカノ-ル620)蜜胺树脂(D成分)
甲醛·蜜胺聚合物的甲基化物(住友化学工业公司制,スミカノ-ル507A)炭黑
东海碳公司制,シ-ストSO操作油剂
出光兴产公司制,ダイアナプロセスPW-380硫化促进剂①
二硫化四甲基秋兰姆(三新化学公司制,サンセラ-TT)硫化促进剂②
二甲基二硫代氨基甲酸锌(三新化学公司制,サンセラ-PZ)硫化促进剂③
巯基苯并噻唑(三新化学公司制,サンセラ-M)硫化剂
硫黄
【实施例1】橡胶组合物的制备
配合EPDM 100份、过氧化物硫化剂4.2份、间苯二酚系化合物1份、蜜胺树脂0.77份、炭黑100份和操作油剂60份,将其用滚筒混炼,制备成橡胶组合物。软管的制作
首先,将上述橡胶组合物在心轴上挤出成型,形成未硫化橡胶层后,在其表面上卷绕总厚度为70μm的层压箔(PA6薄膜/SUS箔/PA6薄膜),形成层压层。接着,将上述橡胶组合物在上述层压层的表面上挤出成型,再将其整体在160℃下硫化45分钟后,抽出心轴。这样就制成在橡胶层(厚2mm)的外周面上形成层压层(厚70μm)、再在其外周面上形成橡胶层(厚2mm)的软管(参照图1)。
【实施例2~12、比较例1~4】
将橡胶层用材料或者层压层用材料变更为后述的表1~表3所示的材料,除此之外,与实施例1一样地制作软管。
【实施例13】橡胶组合物的制备
配合EPDM 100份、过氧化物硫化剂4.2份、间苯二酚系化合物1份、蜜胺树脂0.77份、炭黑100份及操作油剂60份,将其用滚筒混炼,制备成橡胶组合物。软管的制作
首先,将上述橡胶组合物在心轴上挤出成型,形成未硫化橡胶层后,在其表面上卷绕总厚度为70μm的层压箔(PA6薄膜/铝箔/PA6薄膜),形成层压层。接着,将上述橡胶组合物在上述层压层的表面上挤出成型,再将其整体在160℃下硫化45分钟后,抽出心轴。这样就制成在橡胶层(厚2mm)的外周面上形成层压层(厚70μm)、再在其外周面上形成橡胶层(厚2mm)的软管(参照图1)。
【实施例14~21、比较例5~8】
将橡胶层用材料或者层压层用材料变更为后述的表4~表6所示的材料,除此之外,与实施例13一样地制作软管。
用这样制得的实施例软管和比较例软管,按照下述标准,评价各种特性。将评价结果一并示于后述的表1~表6中。拉伸强度(TB)、延伸率(EB)
将上述橡胶组合物在160℃下加压硫化45分钟,制成厚2 mm的硫化橡胶片材。接着,冲压出JIS 5号哑铃形试样,以JIS K6251为基准,评价拉伸强度(TB)和延伸率(EB)。粘接性
从上述软管上切取粘接评价用试样(宽20mm,长100mm),将其安装到拉伸试验机(JIS B 7721)上,将内侧的橡胶层侧固定,以每分钟50mm的速度拉伸层压层的一侧,评价粘接力(kg/25mm)。另外,此时以目测观察橡胶层与层压层的剥离状态,橡胶层破坏的评价为○,界面剥离的评价为×。气体阻隔性
用上述软管进行抖动试验。即,如图2所示,将试样长(软管长)300mm的软管11的一端12固定,在振幅±5mm、压力3.5MPa、试验温度80℃的条件下,进行100小时的抖动试验。接着,将氦封入抖动试验后的软管中,将其在80℃的环境气氛中放置72小时后,测定软管的重量,将其与抖动试验前软管中封入氦时的初期状态的重量进行比较。评价时,重量不变的为○,抖动试验后的重量变轻的(氦渗透多的)为×。
表1 (重量份)
实 施 例 | |||||||
1 | 2 | 3 | 4 | 5 | 6 | ||
橡胶层 | EPDM | 100 | 100 | 100 | 100 | 100 | 100 |
EPM | - | - | - | - | - | - | |
过氧化物硫化剂 | 4.2 | 4.2 | 4.2 | 4.2 | 4.2 | 4.2 | |
间苯二酚系化合物 | 1 | 5 | 10 | 1 | 1 | 0.1 | |
蜜胺树脂 | 0.77 | 3.85 | 3.85 | 0.5 | 2 | 0.05 | |
炭黑 | 100 | 100 | 100 | 100 | 100 | 100 | |
操作油剂 | 60 | 60 | 60 | 60 | 60 | 60 | |
层压层 | *1 | *1 | *1 | *1 | *1 | *1 | |
TB(MPa) | 13.0 | 10.5 | 8.2 | 13.0 | 11.0 | 13.8 | |
EB(%) | 250 | 250 | 230 | 250 | 250 | 260 | |
粘接力(kg/25mm) | 8.8 | 8.6 | 9.2 | 7.8 | 8.4 | 6.4 | |
剥离状态 | ○ | ○ | ○ | ○ | ○ | ○ | |
气体阻隔性 | ○ | ○ | ○ | ○ | ○ | ○ |
*1:PA6薄膜/SUS箔/PA6薄膜(总厚度70μm)
表2 (重量份)
实 施 例 | |||||||
7 | 8 | 9 | 10 | 11 | 12 | ||
橡胶层 | EPDM | - | 100 | 100 | 100 | 100 | 100 |
EPM | 100 | - | - | - | - | - | |
过氧化物硫化剂 | 4.2 | 4.2 | 4.2 | 4.2 | 4.2 | 4.2 | |
间苯二酚系化合物 | 1 | 1 | 1 | 1 | 1 | 1 | |
蜜胺树脂 | 0.77 | 0.77 | 0.77 | 0.77 | 0.77 | 0.77 | |
炭黑 | 100 | 100 | 100 | 100 | 100 | 100 | |
操作油剂 | 60 | 60 | 60 | 60 | 60 | 60 | |
层压层 | *1 | *2 | *3 | *4 | *5 | *6 | |
TB(MPa) | 7.5 | 13.0 | 13.0 | 13.0 | 13.0 | 13.0 | |
EB(%) | 450 | 250 | 250 | 250 | 250 | 250 | |
粘接力(kg/25mm) | 8.5 | 7.5 | 8.8 | 8.8 | 9.0 | 9.0 | |
剥离状态 | ○ | ○ | ○ | ○ | ○ | ○ | |
气体阻隔性 | ○ | ○ | ○ | ○ | ○ | ○ |
*1:PA6薄膜/SUS箔/PA6薄膜(总厚度70μm)
*2:EVOH薄膜/SUS箔/EVOH薄膜(总厚度50μm)
*3:PA6薄膜/铜箔/PA6薄膜(总厚度70μm)
*4:PA6薄膜/钛箔/PA6薄膜(总厚度70μm)
*5:PA6薄膜/EVOH薄膜/SUS箔/EVOH薄膜/PA6薄膜(总厚度100μm)
*6:PA6薄膜/EVOH薄膜/铜箔/EVOH薄膜/PA6薄膜(总厚度100μm)
表3 (重量份)
比 较 例 | |||||
1 | 2 | 3 | 4 | ||
橡胶层 | EPDM | 100 | 100 | 100 | 100 |
过氧化物硫化剂 | 4.2 | 4.2 | 4.2 | - | |
间苯二酚系化合物 | - | 1 | - | 1 | |
蜜胺树脂 | - | - | 1 | 0.77 | |
炭黑 | 100 | 100 | 100 | 100 | |
操作油剂 | 60 | 60 | 60 | 60 | |
硫化促进剂① | - | - | - | 0.75 | |
硫化促进剂② | - | - | - | 0.75 | |
硫化促进剂③ | - | - | - | 0.5 | |
硫化剂(硫黄) | - | - | - | 1.5 | |
层压层 | *1 | *1 | *1 | *1 | |
TB(MPa) | 14.0 | 13.0 | 14.0 | 13.3 | |
EB(%) | 260 | 300 | 270 | 500 | |
粘接力(kg/25mm) | 0.2 | 1.2 | 1.0 | 1.8 | |
剥离状态 | × | × | × | × | |
气体阻隔性 | × | × | × | × |
*1:PA6薄膜/SUS箔/PA6薄膜(总厚度70μm)
表4 (重量份)
实 施 例 | |||||||
13 | 14 | 15 | 16 | 17 | 18 | ||
橡胶层 | EPDM | 100 | 100 | 100 | 100 | 100 | 100 |
EPM | - | - | - | - | - | - | |
过氧化物硫化剂 | 4.2 | 4.2 | 4.2 | 4.2 | 4.2 | 4.2 | |
间苯二酚系化合物 | 1 | 5 | 10 | 1 | 1 | 0.1 | |
蜜胺树脂 | 0.77 | 3.85 | 3.85 | 0.5 | 2 | 0.05 | |
炭黑 | 100 | 100 | 100 | 100 | 100 | 100 | |
操作油剂 | 60 | 60 | 60 | 60 | 60 | 60 | |
层压层 | *7 | *7 | *7 | *7 | *7 | *7 | |
TB(MPa) | 13.0 | 10.5 | 8.2 | 13.0 | 11.0 | 13.8 | |
EB(%) | 250 | 250 | 230 | 250 | 250 | 260 | |
粘接力(kg/25mm) | 8.8 | 8.6 | 9.2 | 7.8 | 8.4 | 6.4 | |
剥离状态 | ○ | ○ | ○ | ○ | ○ | ○ | |
气体阻隔性 | ○ | ○ | ○ | ○ | ○ | ○ |
*7:PA6薄膜/铝箔/PA6薄膜(总厚度70μm)
表5 (重量份)
实 施 例 | ||||
19 | 20 | 21 | ||
橡胶层 | EPDM | - | 100 | 100 |
EPM | 100 | - | - | |
过氧化物硫化剂 | 4.2 | 4.2 | 4.2 | |
间苯二酚系化合物 | 1 | 1 | 1 | |
蜜胺树脂 | 0.77 | 0.77 | 0.77 | |
炭黑 | 100 | 100 | 100 | |
操作油剂 | 60 | 60 | 60 | |
层压层 | *7 | *8 | *9 | |
TB(MPa) | 7.5 | 13.0 | 13.0 | |
EB(%) | 450 | 250 | 250 | |
粘接力(kg/25mm) | 8.5 | 7.5 | 9.0 | |
剥离状态 | ○ | ○ | ○ | |
气体阻隔性 | ○ | ○ | ○ |
*7:PA6薄膜/铝箔/PA6薄膜(总厚度70μm)
*8:EVOH薄膜/铝箔/EVOH薄膜(总厚度50μm)
*9:PA6薄膜/EVOH薄膜/铝箔/EVOH薄膜/PA6薄膜
(总厚度100μm)
表6 (重量份)
比 较 例 | |||||
5 | 6 | 7 | 8 | ||
橡胶层 | EPDM | 100 | 100 | 100 | 100 |
过氧化物硫化剂 | 4.2 | 4.2 | 4.2 | - | |
间苯二酚系化合物 | - | 1 | - | 1 | |
蜜胺树脂 | - | - | 1 | 0.77 | |
炭黑 | 100 | 100 | 100 | 100 | |
操作油剂 | 60 | 60 | 60 | 60 | |
硫化促进剂① | - | - | - | 0.75 | |
硫化促进剂② | - | - | - | 0.75 | |
硫化促进剂③ | - | - | - | 0.5 | |
硫化剂(硫黄) | - | - | - | 1.5 | |
层压层 | *7 | *7 | *7 | *7 | |
TB(MPa) | 14.0 | 13.0 | 14.0 | 13.3 | |
EB(%) | 260 | 300 | 270 | 500 | |
粘接力(kg/25mm) | 0.2 | 1.2 | 1.0 | 1.8 | |
剥离状态 | × | × | × | × | |
气体阻隔性 | × | × | × | × |
*7:PA6薄膜/铝箔/PA6薄膜(总厚度70μm)
从上述结果看出,所有的实施例软管,由于其橡胶层是由间苯二酚系化合物和蜜胺树脂所构成的特殊橡胶组合物来形成的,因此橡胶层与层压层的粘接力非常高。另外还看出,气体阻隔性优良。
与此相反,比较例1、5的软管,由于使用未配合间苯二酚系化合物和蜜胺树脂中任一种的橡胶组合物来形成橡胶层,橡胶层与层压层的粘接力极小,界面发生剥离,气体阻隔性差。比较例2、6的软管,由于使用只配合了间苯二酚系化合物而未配合蜜胺树脂的橡胶组合物来形成橡胶层,橡胶层与层压层的粘接力极小,界面发生剥离,气体阻隔性差。比较例3、7的软管,由于使用只配合了蜜胺树脂而未配合间苯二酚系化合物的橡胶组合物来形成橡胶层,橡胶层与层压层的粘接力极小,界面发生剥离,气体阻隔性差。比较例4、8的软管,由于使用含有粘合剂成分,但含有非过氧化物硫化剂的硫黄系硫化剂的橡胶组合物来形成橡胶层,因此橡胶层与层压层的粘接力极小,发生界面剥离,气体阻隔性差。其理由推测是,硫黄系硫化剂的硫化速度比过氧化物硫化剂的快,在与层压层粘接之前橡胶层本身就发生了硫化,因此粘接力差。
发明的效果
如上所述,本发明的软管由于具有由特殊的橡胶组合物构成的橡胶层和由金属箔与树脂构成的层压层的叠层结构,与以往的金属配管相比,可以减轻重量,降低成本。因此,将本发明的软管例如用于燃料电池车用软管等汽车用软管时,由于软管的重量轻,可以谋求节省燃料费,同时,通过使用橡胶层,还可以吸收车辆的振动。此外,由于橡胶层本身具有粘接性,即使不在橡胶层与层压层的界面处涂布粘合剂,橡胶层与层压层的粘接性也优良。另外,由于不需要粘合剂的涂布工序(所谓无粘合剂),故不需担心粘合剂贮存过期,也不需调配浓度,生产稳定性优良,同时由于也不使用作为粘合剂稀释溶剂的有机溶剂,故没有环境污染等问题。进而,由于不是使用以往的硫黄硫化体系,而是使用过氧化物硫化剂进行硫化,因此不需要配合氧化锌(无锌化),即使在例如将橡胶层用作软管内层的场合下,也可以解除软管堵塞和密封部位泄漏等的软管缺点。
另外,如果将上述间苯二酚系化合物(C)与蜜胺树脂(D)的配合比设定在规定范围内,则橡胶层与层压层的粘接力提高。
进而,如果将间苯二酚系化合物(C)对于特定的橡胶(A)的配合比例设定在一定范围内,则橡胶层与层压层的粘接力提高。
Claims (16)
1.一种软管,其特征在于,它具有由以下述的(A)~(D)作为必需成分的橡胶组合物构成的橡胶层、及由金属箔和树脂构成的层压层的叠层结构,
(A)由乙烯-丙烯-二烯三元共聚物和乙烯-丙烯共聚物中的至少一方构成的橡胶;
(B)过氧化物硫化剂;
(C)间苯二酚系化合物;
(D)蜜胺树脂。
2.权利要求1所述的软管,其中,上述层压层的树脂是聚酰胺树脂和乙烯-乙烯基醇共聚物中的至少一方。
3.权利要求1所述的软管,其中,上述金属箔是由选自铁、铁合金、铜、钛、银、镍和铝中的至少1种构成的金属箔。
4.权利要求2所述的软管,其中,上述金属箔是由选自铁、铁合金、铜、钛、银、镍和铝中的至少1种构成的金属箔。
5.权利要求1所述的软管,其中,上述(C)与(D)的重量混合比设定在(C)/(D)=1/0.5~1/2的范围。
6.权利要求2所述的软管,其中,上述(C)与(D)的重量混合比设定在(C)/(D)=1/0.5~1/2的范围。
7.权利要求3所述的软管,其中,上述(C)与(D)的重量混合比设定在(C)/(D)=1/0.5~1/2的范围。
8.权利要求4所述的软管,其中,上述(C)与(D)的重量混合比设定在(C)/(D)=1/0.5~1/2的范围。
9.权利要求1所述的软管,其中,上述(C)的配合比例,相对于上述(A)100重量份,设定在0.1~10重量份的范围。
10.权利要求2所述的软管,其中,上述(C)的配合比例,相对于上述(A)100重量份,设定在0.1~10重量份的范围。
11.权利要求3所述的软管,其中,上述(C)的配合比例,相对于上述(A)100重量份,设定在0.1~10重量份的范围。
12.权利要求4所述的软管,其中,上述(C)的配合比例,相对于上述(A)100重量份,设定在0.1~10重量份的范围。
13.权利要求5所述的软管,其中,上述(C)的配合比例,相对于上述(A)100重量份,设定在0.1~10重量份的范围。
14.权利要求6所述的软管,其中,上述(C)的配合比例,相对于上述(A)100重量份,设定在0.1~10重量份的范围。
15.权利要求7所述的软管,其中,上述(C)的配合比例,相对于上述(A)100重量份,设定在0.1~10重量份的范围。
16.权利要求8所述的软管,其中,上述(C)的配合比例,相对于上述(A)100重量份,设定在0.1~10重量份的范围。
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JP2001267703A JP3951651B2 (ja) | 2001-09-04 | 2001-09-04 | 自動車用ホース |
JP267704/2001 | 2001-09-04 | ||
JP2001267704A JP2003074759A (ja) | 2001-09-04 | 2001-09-04 | ホース |
JP267703/2001 | 2001-09-04 |
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EP (1) | EP1287981B1 (zh) |
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CN102504424A (zh) * | 2011-10-24 | 2012-06-20 | 天津鹏翎胶管股份有限公司 | 用于汽车空调软管的丁基橡胶组合物 |
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JP2003278958A (ja) * | 2002-03-25 | 2003-10-02 | Tokai Rubber Ind Ltd | 燃料電池車用水素燃料輸送ホース |
FR2858037B1 (fr) * | 2003-07-23 | 2006-11-03 | Nobel Plastiques | Conduite multicouche ayant une couche interne comportant une cyclo-olefine |
ITMI20040155A1 (it) * | 2004-02-02 | 2004-05-02 | Parker Hannifin S P A Fluid Co | Impianto di condizionamento aria o refrigerazione perfezionato e tubazione di collegamento relativa |
US7263975B2 (en) * | 2005-01-25 | 2007-09-04 | Dana Corporation | Plastic coated metal fuel rail |
US7624761B2 (en) * | 2005-10-04 | 2009-12-01 | Gm Global Technology Operations, Inc. | Tube shaped high pressure storage tank |
EP2232120B1 (en) * | 2007-11-07 | 2012-04-18 | Parker-Hannifin Corporation | Aluminum foil based hose |
EP2130669A1 (en) * | 2008-06-05 | 2009-12-09 | Novelis Inc. | Compound tubes |
DE202009019165U1 (de) * | 2009-12-22 | 2017-05-15 | Veritas Ag | Fluidleitung |
JP5885240B2 (ja) | 2011-11-21 | 2016-03-15 | ゲイツ・ユニッタ・アジア株式会社 | 伝動ベルト |
DE102011055752A1 (de) * | 2011-11-28 | 2013-05-29 | Contitech Mgw Gmbh | Extraktionsarmer Schlauch, insbesondere für Brennstoffzellen-Anwendungen, und Verfahren zu dessen Herstellung |
US12031658B2 (en) | 2016-07-15 | 2024-07-09 | Nordson Corporation | Adhesive transfer hose having a barrier layer and method of use |
EP3584075B1 (en) | 2017-02-20 | 2024-06-05 | Mitsui Chemicals, Inc. | Laminate |
JP2019085539A (ja) * | 2017-11-10 | 2019-06-06 | 横浜ゴム株式会社 | ゴム組成物及びホース |
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JPS5985041U (ja) | 1982-11-26 | 1984-06-08 | 古河電気工業株式会社 | 防水型熱収縮性被覆具 |
US4633912A (en) | 1985-05-31 | 1987-01-06 | The Goodyear Tire & Rubber Company | Hose construction |
US4758455A (en) * | 1985-07-10 | 1988-07-19 | Handy & Harman Automotive Group Inc. | Composite fuel and vapor tube having increased heat resistance |
US5271977A (en) * | 1989-02-10 | 1993-12-21 | Bridgestone Corporation | Low permeable rubber hose |
JPH04131581A (ja) * | 1990-09-25 | 1992-05-06 | Bridgestone Corp | 低透過性ゴムホース |
US6074717A (en) * | 1997-07-29 | 2000-06-13 | Dayco Products, Inc. | Flexible hose having an aluminum barrier layer to prevent ingestion of oxygen |
JP2000146034A (ja) * | 1998-11-06 | 2000-05-26 | Tokai Rubber Ind Ltd | 電動コンプレッサ用冷媒ホース |
JP2000146031A (ja) * | 1998-11-11 | 2000-05-26 | Tokai Rubber Ind Ltd | 非透過型複合ホース |
US6279615B1 (en) * | 1999-09-03 | 2001-08-28 | Tokai Rubber Industries, Ltd. | Fuel hose |
US6619329B2 (en) * | 2000-10-03 | 2003-09-16 | Tokai Rubber Industries, Ltd. | Hose |
JP3783564B2 (ja) | 2000-10-03 | 2006-06-07 | 東海ゴム工業株式会社 | 自動車用ホース |
JP3951611B2 (ja) | 2000-10-03 | 2007-08-01 | 東海ゴム工業株式会社 | 自動車用ホース |
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- 2002-08-28 EP EP20020019310 patent/EP1287981B1/en not_active Expired - Fee Related
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CN102504424A (zh) * | 2011-10-24 | 2012-06-20 | 天津鹏翎胶管股份有限公司 | 用于汽车空调软管的丁基橡胶组合物 |
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DE60206716D1 (de) | 2006-03-02 |
EP1287981B1 (en) | 2005-10-19 |
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US6838141B2 (en) | 2005-01-04 |
DE60206716T2 (de) | 2006-06-01 |
US20030124284A1 (en) | 2003-07-03 |
EP1287981A2 (en) | 2003-03-05 |
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