WO2005102681A1 - 高温薬液及び/又はガス搬送用積層ホース - Google Patents
高温薬液及び/又はガス搬送用積層ホース Download PDFInfo
- Publication number
- WO2005102681A1 WO2005102681A1 PCT/JP2005/008397 JP2005008397W WO2005102681A1 WO 2005102681 A1 WO2005102681 A1 WO 2005102681A1 JP 2005008397 W JP2005008397 W JP 2005008397W WO 2005102681 A1 WO2005102681 A1 WO 2005102681A1
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- Prior art keywords
- polyamide
- hose
- acid
- layer
- gas
- Prior art date
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- 239000000126 substance Substances 0.000 title claims abstract description 104
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims abstract description 52
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000004953 Aliphatic polyamide Substances 0.000 claims abstract description 36
- 229920003231 aliphatic polyamide Polymers 0.000 claims abstract description 36
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims abstract description 21
- 125000004427 diamine group Chemical group 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical group C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 polyhexamethylene Polymers 0.000 claims description 96
- 229920002647 polyamide Polymers 0.000 claims description 82
- 239000004952 Polyamide Substances 0.000 claims description 77
- 229920001577 copolymer Polymers 0.000 claims description 48
- 229920000299 Nylon 12 Polymers 0.000 claims description 24
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 23
- 229920002292 Nylon 6 Polymers 0.000 claims description 17
- 150000001408 amides Chemical class 0.000 claims description 15
- 239000003502 gasoline Substances 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 239000004202 carbamide Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 239000002826 coolant Substances 0.000 claims description 10
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 229920000571 Nylon 11 Polymers 0.000 claims description 8
- 229920001519 homopolymer Polymers 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005553 drilling Methods 0.000 claims description 5
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims description 5
- GAGWMWLBYJPFDD-UHFFFAOYSA-N 2-methyloctane-1,8-diamine Chemical group NCC(C)CCCCCCN GAGWMWLBYJPFDD-UHFFFAOYSA-N 0.000 claims description 4
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical group NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims description 4
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical group C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 4
- 239000010410 layer Substances 0.000 abstract description 123
- 239000007789 gas Substances 0.000 abstract description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 239000011229 interlayer Substances 0.000 abstract description 8
- 230000004888 barrier function Effects 0.000 abstract 2
- 229920005989 resin Polymers 0.000 description 47
- 239000011347 resin Substances 0.000 description 47
- 239000000243 solution Substances 0.000 description 43
- 229920000642 polymer Polymers 0.000 description 34
- 239000002253 acid Substances 0.000 description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 23
- 239000005977 Ethylene Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 23
- 238000004519 manufacturing process Methods 0.000 description 22
- 239000011342 resin composition Substances 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- 238000001125 extrusion Methods 0.000 description 17
- 229920006122 polyamide resin Polymers 0.000 description 15
- 239000004609 Impact Modifier Substances 0.000 description 14
- 239000004734 Polyphenylene sulfide Substances 0.000 description 14
- 230000000704 physical effect Effects 0.000 description 14
- 229920000069 polyphenylene sulfide Polymers 0.000 description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 238000005259 measurement Methods 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- 238000012546 transfer Methods 0.000 description 13
- 229920002554 vinyl polymer Polymers 0.000 description 12
- 229920001400 block copolymer Polymers 0.000 description 11
- 229920000098 polyolefin Polymers 0.000 description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000012530 fluid Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 10
- 230000002265 prevention Effects 0.000 description 10
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 9
- 239000001110 calcium chloride Substances 0.000 description 9
- 229910001628 calcium chloride Inorganic materials 0.000 description 9
- 239000006229 carbon black Substances 0.000 description 9
- 235000019241 carbon black Nutrition 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 9
- 229920005992 thermoplastic resin Polymers 0.000 description 9
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 8
- 238000004898 kneading Methods 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 229920005672 polyolefin resin Polymers 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 239000005749 Copper compound Substances 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 239000011231 conductive filler Substances 0.000 description 7
- 150000001880 copper compounds Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 7
- 239000004926 polymethyl methacrylate Substances 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 6
- 150000001733 carboxylic acid esters Chemical class 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 229920002492 poly(sulfone) Polymers 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
- 229920000459 Nitrile rubber Polymers 0.000 description 5
- 239000004840 adhesive resin Substances 0.000 description 5
- 229920006223 adhesive resin Polymers 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000002981 blocking agent Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000004696 Poly ether ether ketone Substances 0.000 description 4
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
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- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- CHSILQAFIZTLJN-UHFFFAOYSA-N heptadecane-1,17-diamine Chemical compound NCCCCCCCCCCCCCCCCCN CHSILQAFIZTLJN-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- ATJCASULPHYKHT-UHFFFAOYSA-N hexadecane-1,16-diamine Chemical compound NCCCCCCCCCCCCCCCCN ATJCASULPHYKHT-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- POIZGMCHYSVWDU-UHFFFAOYSA-N icosane-1,20-diamine Chemical compound NCCCCCCCCCCCCCCCCCCCCN POIZGMCHYSVWDU-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical compound NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese 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
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- OETHQSJEHLVLGH-UHFFFAOYSA-N metformin hydrochloride Chemical compound Cl.CN(C)C(=N)N=C(N)N OETHQSJEHLVLGH-UHFFFAOYSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- FJXWKBZRTWEWBJ-UHFFFAOYSA-N nonanediamide Chemical compound NC(=O)CCCCCCCC(N)=O FJXWKBZRTWEWBJ-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- JFNLZVQOOSMTJK-UHFFFAOYSA-N norbornene Chemical compound C1C2CCC1C=C2 JFNLZVQOOSMTJK-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Chemical class 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- TXRPLFBVYIKTSU-UHFFFAOYSA-N pentadecane-1,15-diamine Chemical compound NCCCCCCCCCCCCCCCN TXRPLFBVYIKTSU-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000008177 pharmaceutical agent Substances 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920006110 poly(m-benzoyl4,4'-methylenebis(cyclohexylamine)) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 229920005554 polynitrile Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- WRHZVMBBRYBTKZ-UHFFFAOYSA-N pyrrole-2-carboxylic acid Chemical compound OC(=O)C1=CC=CN1 WRHZVMBBRYBTKZ-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- JWHOQZUREKYPBY-UHFFFAOYSA-N rubonic acid Natural products CC1(C)CCC2(CCC3(C)C(=CCC4C5(C)CCC(=O)C(C)(C)C5CC(=O)C34C)C2C1)C(=O)O JWHOQZUREKYPBY-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- MSVPBWBOFXVAJF-UHFFFAOYSA-N tetradecane-1,14-diamine Chemical compound NCCCCCCCCCCCCCCN MSVPBWBOFXVAJF-UHFFFAOYSA-N 0.000 description 1
- DJZKNOVUNYPPEE-UHFFFAOYSA-N tetradecane-1,4,11,14-tetracarboxamide Chemical group NC(=O)CCCC(C(N)=O)CCCCCCC(C(N)=O)CCCC(N)=O DJZKNOVUNYPPEE-UHFFFAOYSA-N 0.000 description 1
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- XWVHBWQEYOROBE-UHFFFAOYSA-N tridec-2-ene Chemical compound CCCCCCCCCCC=CC XWVHBWQEYOROBE-UHFFFAOYSA-N 0.000 description 1
- DUXYWXYOBMKGIN-UHFFFAOYSA-N trimyristin Chemical class CCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCC DUXYWXYOBMKGIN-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
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2597/00—Tubular articles, e.g. hoses, pipes
-
- 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
- F16L2011/047—Hoses, i.e. flexible pipes made of rubber or flexible plastics with a diffusion barrier layer
Definitions
- the present invention provides a multilayer hose for conveying a high-temperature chemical solution and / or gas, which comprises a layer made of an aliphatic polyamide and a layer made of a semi-aromatic polyamide having a specific structure. Chemical resistance, durability
- the present invention relates to a high-temperature chemical solution and a laminated hose for carrying z or gas, which are excellent in chemical permeation, Z or gas permeation prevention properties, and interlayer adhesion.
- hoses used in engine rooms have been subject to factors such as higher engine cooling water (LLC) temperature due to higher engine performance and higher output, and higher temperatures in the engine room. It has become harsh.
- LLC engine cooling water
- diesel gasoline is generally used for reasons such as improved fuel economy due to reduced fuel consumption.However, for the reasons described above, diesel gasoline transfer hoses are also more commonly used. Used in harsh environments.
- the removal and reduction of harmful substances that may cause environmental destruction, such as nitrogen oxides and suspended particulate matter emitted from diesel engines are urgent issues from the viewpoint of environmental protection.
- a urea solution has been attracting attention as a catalyst for removing nitrogen oxides, but it is expected that a hose that transports the solution will be used in a harsh environment. For these reasons, there is an increasing demand for highly durable materials and composite molded products even in harsh operating environments.
- Polyamide resins have excellent mechanical properties, heat resistance, chemical resistance, etc. As a result, it is widely used as a variety of automotive parts such as bottles, tanks, hoses, pipes, pots, and accessories such as packing flanges, pulp, and cocks.
- Polyamide 6-polyamide 66 which is widely used among polyamide-based resins, strongly interacts with water and halides of metals such as calcium and zinc. As a result, the polyamide 6 and the hose obtained by molding the polyamide 66 had a defect that a crack was generated when the hose was in contact with the metal halide. Therefore, studies have been conducted to improve the hot water resistance, zinc chloride resistance, calcium chloride resistance, etc. of polyamide 6 and polyamide 66, and a specific aromatic ring structure has been developed. A method using a polyamide-based resin and a method of adding a polyolefin-based resin have been proposed, but all of these methods are hot water-resistant, zinc chloride-resistant and calcium chloride-resistant of the polyamide resin. It did not essentially improve the chemical resistance, such as heat resistance, and the effect of chemical resistance at high temperatures was similarly inadequate.
- polyamide 11 and polyamide 12 have superior properties such as hot water resistance, zinc chloride resistance, and calcium chloride resistance when compared to polyamide 6 and polyamide 66.
- the durability was not sufficient when the ambient temperature of the operating environment was high.
- the circulating fluid is sealed as an engine coolant (LLC) mainly composed of ethylene glycol and diesel gasoline to prevent freezing in winter, and as a catalyst to remove NOX released from diesel engines.
- LLC engine coolant
- hoses for transporting chemicals such as urea solutions and / or gas
- single-layer hoses using polyamide 6, polyamide 66, polyamide 11 and polyamide 12 for general use In this case, the ambient temperature of the operating environment is extremely high, and the chemicals and Z or Has a large gas permeation through the hose partition. Therefore, it may be necessary to replenish these liquids in order to prevent a decrease in the amount of circulating fluid. It has been demanded.
- thermoplastic resin laminated tubular body consisting of an inner layer made of polyphenylene sulfide resin (PPS), which has excellent heat resistance, hot water resistance, and chemical resistance, and an outer layer made of a polyamide resin, is used. It has been proposed (see Japanese Patent Application Laid-Open No. 10-180911). Originally, even if a polyphenylene sulfide-based resin and a polyamide-based resin are simply laminated, delamination is likely to occur because there is no adhesion between the two materials.
- PPS polyphenylene sulfide resin
- thermoplastic resin-laminated tubular body is prepared by mixing a specific olefin copolymer and a specific amount of a polyamide resin with a polyolefin sulfide resin.
- a laminated tubular body in which a layer composed of a resin composition, a layer composed of a polyphenylene sulfide resin, and a layer composed of a polyamide resin are laminated is disclosed.
- the laminated tubular body also has a disadvantage that the layer indirect adhesion is insufficient depending on the use environment and temperature.
- An object of the present invention is to solve the above-mentioned problems, and to have excellent hot water resistance, chemical resistance, durability, interlayer adhesion, chemical liquid and / or gas permeation prevention properties, and particularly excellent in chemical liquid and Z or gas permeation prevention properties at high temperatures.
- Another object of the present invention is to provide a laminated hose for carrying high temperature chemicals and / or gas. Summary of the Invention
- the present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, they have obtained a laminate of a layer made of a semi-aromatic polyamide having a specific structure and a layer made of an aliphatic polyamide.
- High temperature chemical solution and / or gas transfer laminated hose is hot water resistant, chemical resistant, durable, chemical solution and / or gas 2005/008397 We found that it had excellent permeation prevention and interlayer adhesion.
- the present invention provides the following.
- (B) layer composed of semi-aromatic polyamide consisting of dicarboxylic acid units containing 50 mol% or more
- a laminated hose for carrying high-temperature chemicals and Z or gas comprising at least two layers.
- a layer (b) consisting of a semi-aromatic polyamide consisting of terephthalic acid and a dicarboxylic acid unit containing 50 mol% or more of Z or naphthalenedicarboxylic acid unit is disposed in the innermost layer;
- the laminated hose for conveying a high-temperature chemical and a gas or gas according to the above (1), wherein the (a) layer made of an amide is arranged outside the (b) layer.
- the aliphatic polyamide is polypromide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polyhexamethylene dodecamide (polyamide).
- polyamide 612 polydecaneamide
- polyamide 11 polydecaneamide
- polyamide 12 at least one homopolymer selected from the group consisting of polydodecane amide (polyamide 12), or raw materials for forming these
- the semi-aromatic polyamide is against JP2005 / 008,397 all Jiamin units, 1, 9 Nonanjiami emissions and / or 2-methyl-1, 8-Okutanjiami down units, or 1, 1 Jiami emissions containing 2-dodecane diamine
- the emission unit 6 0 mole 0/0 or more From (1) above, which is a polyamide comprising terephthalic acid and Z or 2,6-naphthalenedicarboxylic acid unit in total dicarboxylic acid unit and 50 mol% or more of dicarboxylic acid unit.
- the laminated hose for conveying a high-temperature chemical solution and a gas or gas according to any one of (3) to (4).
- the laminated hose is any one of an engine coolant (LLC) hose, a diesel gas hose, an oil drilling hose, a hose containing alcoholic gasoline, and a hose carrying urea solution.
- LLC engine coolant
- hose for transporting a high-temperature chemical and Z or gas according to any one of the above.
- the multilayer hose for conveying a high-temperature chemical and / or gas according to any one of (1) to (6), wherein the layer (a) and the layer (b) are adjacent to each other in the multilayer hose.
- the laminated hose for conveying a high-temperature chemical and / or gas according to the present invention has hot water resistance, chemical resistance, durability, interlayer adhesion, chemical and / or gas permeation prevention properties, and particularly, high-temperature chemical and / or gas permeation prevention properties. Excellent. Therefore, even when it comes into direct contact with chemicals and / or gases under high temperature conditions, it can be used for a long time, and its utility value is extremely large.
- FIG. 1 and FIG. 2 are cross-sectional views showing examples of a laminated hose for transporting a high-temperature chemical and Z or gas according to the present invention.
- the (A) aliphatic polyamide used in the present invention contains an amide bond (one NHCO—) in the main chain and is composed of an aliphatic polyamide forming unit.
- Aliphatic polyamides are prepared by melt polymerization, solution polymerization, solid-state polymerization, etc. using ratatam, aminocarboxylic acid, or a nylon salt composed of aliphatic diamine and aliphatic dicarboxylic acid as a raw material. It can be obtained by polymerization or copolymerization by a known method described in US Pat.
- ratatams examples include caprolactam, enantholactam, pendecanratatum, dodecaneratatum, ⁇ -pyrrolidone, ⁇ -piperidone, and the like.
- examples include noheptanoic acid, 91-aminoaminonananoic acid, 111-aminoundecanoic acid, and 12-aminododecanoic acid. This can be used alone or in combination of two or more.
- Aliphatic diamines composing nitrate salts include ethylenediamine, 1,3-propylenediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and 1-hexanediamine.
- Aliphatic dicarboxylic acids that constitute the nickel salt include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, pendene dicarboxylic acid, dodecane dicarboxylic acid, and tridecane dicarboxylic acid. Acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, eicosandicarboxylic acid and the like. One or more of these can be used.
- (A) aliphatic polyamides include polyproamide (polyamide 6), polyundecane amide (polyamide 11), polydodecane amide (polyamide 12) ), Polyethylene adipamide (polyamide 26), polytetramethylene adipamide (polyamide 46), polyhexamethylene adipamide (polyamide 66), polyhexamethylene Azeramide (polyamide 69), polyhexamethylene cepacamide (polyamide 610), polyhexamethylenediene decamide (polyamide 611), polyhexamethylene dodecamide (polyamide) Polyamide 612), Polynonamethylene adipamide (Polyamide 96), Polynonamethyleneazeramide (Polyamide 99), Polynonamethylenesepacamide (Polyamide) 910), polynonamethylene decamide (polyamide 911), polynonamethylene dodecamide (polyamide 912), polydecamethylene adipamide (polyamide 106
- polyproamide polyamide 6
- polyhexamethylene adipamide polyamide 66
- polydecaneamide polyproamide
- polyproamide polyamide 6
- polyhexamethylene adipamide polyamide
- the homopolymer of 6 6) is more preferable, and in consideration of hot water resistance, zinc chloride resistance, and calcium chloride resistance, polydecaneamide (polyamide 11) and polydodecaneamide are preferred.
- Homopolymers of (polyamide 12) and polyhexamethylene decamid (polyamide 612) are more preferred.
- the aliphatic polyamide used in the present invention may be a mixture of the above-mentioned homopolymer, a mixture of the above-mentioned copolymers, or a mixture of a homopolymer and a copolymer, Alternatively, it may be a mixture with another polyamide resin or another thermoplastic resin.
- the content of the aliphatic polyamide (A) in the mixture is preferably 60% by weight or more, more preferably 80% by weight or more.
- polyamide resins include polymethaxylylene adipamide
- Polyamide MXD 6 polymethaxylylene velamide (polyamide MXD 8), polymethaxylylene azelamide (polyamide MXD9), polymethaxylylene sepakamide (polyamide MXD10), polymethaxylylene decamide (Polyamide MXD12), polymethaxylene terephthalamide (polyamide MXD T), polymethaxylylene isophthalamide (polyamide MXD I), polymethoxy PT / JP2005 / 008397 Rirennaphthalamide (polyamide MXDN), polybis (4-aminohexyl hexyl) methane dodecamid (polyamide PA CM12), polybis (4-aminophenol) (Rohexyl) methane terephthalamide (polyamide PA CMT), polybis (41-aminohexyl) methaneisophthalamide (polyamide PACMI), polybis (3-
- thermoplastic resins include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ultra-high molecular weight.
- Polyethylene UHMWP E
- Polypropylene PP
- Ethylene propylene copolymer EPR
- Ethylene Z-butene copolymer EBR
- Ethylene vinyl acetate copolymer Ethylene JP2005 / 008397 Z-vinyl acetate copolymer copolymer (E VOH)
- EMA ethylene / methyl acrylate
- Polyolefin-based resins such as copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate
- an impact modifier to the aliphatic polyamide (A) used in the present invention.
- the impact modifier include rubbery polymers, and those having a flexural modulus of 50 OMPa or less measured according to ASTM D-790 are preferred. If the flexural modulus exceeds this value, it may be insufficient as an impact modifier.
- the impact modifier examples include: (ethylene and Z or propylene) / polyolefin copolymer, (ethylene and _ or propylene) / (a, j8—unsaturated carboxylic acid and / or unsaturated Carboxylic acid ester) -based copolymers, ionomer polymers, aromatic vinyl compound / co-genated compound-based block copolymers, and one or more of these can be used.
- the above (ethylene and / or propylene) / polyolefin copolymer is a copolymer of ethylene and Z or propylene with carbon atoms of 3 or more. It is a polymer obtained by copolymerizing olefins.
- the olefins having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-otaten, and 1-one.
- the above-mentioned (ethylene and / or propylene) Z (a,] 3-unsaturated rubonic acid and z or unsaturated carboxylic acid ester) -based copolymer is obtained by mixing ⁇ -unsaturated with ethylene and propylene or propylene.
- carboxylic acids and ⁇ or a polymer obtained by copolymerizing an unsaturated carboxylic acid ester monomer, alpha,) 3- unsaturated carboxylic acid monomer, accession acrylic acid, include Metaku acrylic acid, alpha
- the monounsaturated carboxylic acid ester monomers include methyl ester, ethyl ester, propynoleestenol, butynoleestenol, pentyl ester, hexinolester, heptinoleestenol, and octyl ester of these unsaturated carboxylic acids. Nolestenore, noninoestenoles, decyl esters and the like. One or more of these can be used.
- 8-unsaturated 'carboxylic acid copolymer is ionized by neutralization of metal ion.
- Ethylene is preferably used as the olefin, and acrylic acid and methacrylic acid are preferably used as the ⁇ , j3-unsaturated carboxylic acid, but are not limited to those exemplified herein.
- an unsaturated carboxylic acid ester monomer may be copolymerized.
- Metal ions are L i, N a,
- Alkali metals such as K, Mg, Ca, Sr, Ba, alkaline earth metals, Al, Sn, Sb, Ti, Mn, Fe, Ni, Cu , Z n,
- C d and the like. One or more of these can be used.
- the aromatic vinyl compound conjugated gen-based block copolymer is a block copolymer comprising an aromatic vinyl compound-based polymer block and a conjugated gen-based polymer block. At least one vinyl compound-based polymer block and a conjugated gen-based polymer block A block copolymer having at least one is used. In the above block copolymer, the unsaturated bond in the conjugated gen-based polymer block may be hydrogenated.
- An aromatic vinyl compound polymer block is a polymer block mainly composed of structural units derived from an aromatic vinyl compound.
- the aromatic vinyl compounds include styrene, ⁇ -methylstyrene, ⁇ —methylinstyrene, m—methylstyrene, p, methylstyrene, 2,4-dimethylinolestyrene, vinylinolephthalene, and vinylanine.
- Examples include tracerene, 4-propynolestyrene, 4-cyclohexynolestyrene, 4-dodecyl / restyrene, 2-ethyl-4-benzinolestyrene, 4- (phenylbutyl) styrene, and one of these. Alternatively, two or more types can be used.
- the aromatic butyl compound-based polymer block may have a structural unit composed of a small amount of another unsaturated monomer in some cases.
- Conjugated gen-based polymer blocks are 1,3-butadiene, co-prene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 4-methinole 1,3-pentadiene , 1,3—a polymer block formed from one or more conjugated compounds such as hexadene, and hydrogenated aromatic vinyl compounds.
- conjugated compounds such as hexadene, and hydrogenated aromatic vinyl compounds.
- the molecular structure of the aromatic vinyl compound Z-conjugated gen compound-based block copolymer and its hydrogenated product may be any of linear, branched, radial, or any combination thereof.
- Triblock copolymers in which three polymer blocks are linked linearly, and one or two or more hydrogenated products thereof are preferably used, and are unhydrogenated or hydrogenated.
- (ethylene and / or propylene) / ⁇ -olefin copolymer, (ethylene and / or propylene) ⁇ (a,] 3-unsaturated carboxylic acid and / or (Unsaturated carboxylic acid ester) -based copolymer, ionomer polymer, aromatic vinyl compound / conjugated gen compound-based block copolymer, etc. are preferably polymers modified with carboxylic acid and Z or a derivative thereof. Is done. By being modified with such a component, the molecule contains a functional group having an affinity for the polyamide resin.
- Functional groups having an affinity for polyamide resin include carboxyl groups, acid anhydride groups, carboxylic acid ester groups, carboxylic acid metal salts, carboxylic acid imido groups, carboxylic acid amide groups, Examples include an epoxy group.
- Examples of compounds containing these functional groups include acrylic acid, metaacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, and glutaconic acid.
- the compounding amount of the impact modifier is 1 to 35 parts by weight based on 100 parts by weight of the aliphatic polyamide component (A). More preferably, it is 5 to 25 parts by weight. If the amount of the impact modifier exceeds the above-mentioned value, the original mechanical properties of the high-temperature chemical and the laminated hose for conveying Z or gas may be impaired.
- the aliphatic polyamide (A) used in the present invention has a carbon number per amide group in a polyamide repeating unit such as polyamide 6, polyamide 66, etc.
- a polyamide containing aliphatic diamin and terephthalic acid and / or isophthalic acid as a polyamide-forming unit in order to improve calcium chloride resistance.
- 1,6-hexanediamine is preferably selected in consideration of the compatibility with polyamide 6 and polyamide 66.
- the polyamide having aliphatic polyamide, terephthalic acid and di- or isophthalic acid as polyamide-forming units may be a polymer in which the above-mentioned polyamide-forming units are 100% by weight. 85% by weight or more of the polyamide-forming unit, and other components such as the polyamide-forming unit introduced by diamine and dicarboxylic acid other than ratatam, aminocarboxylic acid, terephthalic acid and isophtalic acid, and 1
- the copolymer may be 5% by weight or less.
- As the other copolymerized unit it is particularly preferable to use a polyamide composed of a hexamethylene adipamide unit and a Z or force proamide unit.
- (A) aliphatic polyamides may contain, if necessary, antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, lubricants, inorganic fillers, antistatic agents, flame retardants, crystallization Accelerators, coloring agents, plasticizers and the like may be added.
- Production equipment used in the production of aliphatic polyamides includes a patch-type reaction vessel, a single- or multi-tank intermittent reaction apparatus, a tubular continuous reaction apparatus, a single-screw kneading extruder, Known polyamide manufacturing equipment such as a kneading reaction extruder such as a twin-screw kneading extruder can be used.
- a polymerization method a known method such as melt polymerization, solution polymerization, or solid phase polymerization can be used, and normal pressure, reduced pressure, and pressurized operations can be repeated. These polymerization methods can be used alone or in an appropriate combination.
- the relative viscosity of the aliphatic polyamide measured in accordance with JISK-6920 is preferably 1.5 to 5.0, and more preferably 2.0 to 4.5. Is more preferred.
- the relative viscosity of the aliphatic polyamide is less than the above-mentioned value, the mechanical properties of the obtained high-temperature chemical solution and / or the laminated hose for gas transfer may be insufficient, and if it exceeds the above-mentioned value. , Extrusion pressure and torque may be too high, making it difficult to manufacture high-temperature chemicals and laminated hoses for Z or gas transfer.
- the (B) semi-aromatic polyamide used in the present invention refers to a diamine unit containing 60 to mol% or more of aliphatic diamine units having 9 to 13 carbon atoms, based on all diamine units.
- a polyamide comprising dicarboxylic acid units containing 50 moles 0 / o or more of terephthalic acid and / or naphthalenedicarboxylic acid units with respect to all dicarboxylic acid units (hereinafter sometimes referred to as semi-aromatic polyamide). is there) .
- (B) in the semi-aromatic polyamide-de it is the content of units consisting of terephthalic acid and Z or naphthalate dicarboxylic acid, relative to the total dicarboxylic acid units is 5 0 mole 0/0 or more, 6 is preferably 0 mole 0/0 or more, 7 Ri preferably good that 5 is mol% or more, preferably in the is et at 9 0 mol% or more.
- the content of terephthalic acid and / or naphthalenedicarboxylic acid unit is less than 50 mol%, the heat resistance, chemical resistance, chemical liquid and / or gas permeation resistance of the obtained high-temperature chemical liquid and / or gas carrying laminated hose is obtained.
- naphthalenedicarboxylic acid units that tend to have reduced physical properties such as 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and '1 , 5 — Units derived from naphthalenedicarboxylic acid. One or more of these can be used. Among the above naphthalenedicarboxylic acid units, a unit derived from 2,6-naphthalene dicarboxylic acid is preferred.
- the dicarboxylic acid unit in the semi-aromatic polyamide is terephthalic acid and / or naphthalene as long as it does not impair the excellent properties of the high-temperature chemical solution and / or the gas-transporting laminated hose of the present invention. It may contain another dicarboxylic acid unit other than the unit derived from dicarboxylic acid.
- Examples of the other dicarboxylic acid unit include malonic acid and dimethyl malo 8397 acid, succinic acid, gnoletalic acid, adipic acid, 2-methyladipic acid, 2, 2, 4/2, 4, 4-trimethyladipic acid, pimelic acid, 2,2-dimethyldaltal Acids, aliphatic dicarboxylic acids such as 2,2-getylsuccinic acid, suberic acid, azelaic acid, sebacic acid, pendecanedicarboxylic acid, dodecanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1, 3/1 Alicyclic dicarboxylic acids such as 2,4-cyclohexanedicarboxylic acid, isophthalic acid, 1,3Z1,4-phenylenedioxydiacetic acid, diphenic acid, 4,4, -oxydibenzoic acid, diphenylmethane-1,4,4, Dicarboxylic acid, dipheninoleethane
- Ru can be used alone or in combination of two or more of these.
- a unit derived from an aromatic dicarboxylic acid is preferred.
- the content of these other dicarboxylic acid units is 50 mol% or less, preferably 40 mol% or less, more preferably 25 mol% or less, and more preferably 10 mol% or less. It is even more preferred.
- polyvalent carboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid and the like can be used as long as melt molding is possible.
- (B) in the semi-aromatic polyamide-de it is the content of carbon number 9-1 3 aliphatic Jiami emission units, the total Jiami down units, at 6 0 molar 0/0 or more And it is preferably at least 75 mol%, more preferably at least 90 mol%.
- the content of the aliphatic diamine unit having 9 to 13 carbon atoms is less than 60 mol%, the heat resistance, chemical resistance, and impact resistance of the high-temperature chemical solution and the laminated hose for transporting Z or gas are reduced. Tend.
- 1,9-nonane Units derived from diamine, 1,10-decanediamine, 1,11-ndecandiamine, 1,12-dodecanediamine, 1,13-tridecanediamine.
- aliphatic diamine units having 9 to 13 carbon atoms units derived from 1,9-nonandiamine and / or 2-methyl-1,8-octanediamin are preferable from the viewpoint of chemical solution and Z or gas permeation prevention. From the viewpoint of low-temperature impact resistance, a unit derived from 1,12-dodecanediamine is preferred. Furthermore, the molar ratio of the 1,9-nonandiamine unit to the 2-methyl-1,8-octanediamin unit is 30:70 to 9 from the viewpoint of moldability, impact resistance, and balance of coextrusion moldability. 8: is preferably 2 mol 0/0, 4 0: 6 0-9 5: it is preferred Ri yo is 5 mol 0/0.
- the diamine unit in the semi-aromatic polyamide has a carbon number of 9 to 13 as long as it does not impair the excellent properties of the high-temperature chemical and / or gas carrying laminated hose of the present invention. And other diamine units other than the units derived from aliphatic diamines.
- the other diamine units include, for example, ethylenediamine, 1,3-propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1, Aliphatic diamines such as 8-octanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5_pentanediamine, 1, 3/1, 4-six mouth hexanediamine, 1, 3/1, 4-cyclohexanehexanedimethylamine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, bis (3-methyl-14-aminocyclohexyl) me Tan, bis (3-methyl-1-aminocyclohexyl) propane, 5- ⁇ , 1,2,4,4-trimethyl-1-1-cyclopi-tantanmethylamine, 51-amino No 1, 3, 3
- Alicyclic diamines such as piperazine, bis (aminoethyl) piperazine, norpolnandimethylamine, tricyclopentadecanedimethylamine, paraffin diene diamine, metafujiren diamine, paraxylylene diamine , Methaxylene ranger, 1, 4/1, 5 Z 2,
- units derived from an aromatic diamine such as 4,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl ether, and these may be used alone or in combination of two or more.
- the content of these other diamine units is 40 mol. /. Or less, preferably 25 mol% or less, more preferably 10 mol% or less.
- the relative viscosity of the semi-aromatic polyamide measured according to JISK-6920 is preferably 1.5 to 4.0, and more preferably 1.8 to 3.5. More preferably, it is more preferably 2.0 to 3.0. If the value is less than the above value, the mechanical properties of the obtained high-temperature chemical solution and / or the gas-transporting laminated hose may be insufficient, and if the value exceeds the value, the extrusion pressure or the torque becomes too high. In some cases, it may be difficult to manufacture multi-layer hoses for transporting high-temperature chemicals and water or gas. is there.
- the terminal of the molecular chain of (B) the semi-aromatic polyamide is preferably sealed with a terminal blocking agent, and more preferably 40% or more of the terminal groups are blocked. More preferably, 60% or more of the terminal groups are sealed.
- the terminal capping agent is not particularly limited as long as it is a monofunctional compound having a reactivity with an amino group or a carboxyl group at the terminal of the polyamide.
- monocarboxylic acids or monoamines are preferred, and monocarboxylic acids are more preferred from the viewpoint of easy handling.
- acid anhydrides, monoisocyanates, monoacid halides, monoesters, monoalcohols, etc. can also be used.
- a monocarboxylic acid used as a terminal blocking agent is reactive with an amino group.
- acetic acid propionic acid, butyric acid, valeric acid, cabronic acid, caprylic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, steariic acid
- Alicyclic monocarboxylic acids such as cyclohexane carboxylic acid, benzoic acid, toluic acid, ⁇ -naphthalene carboxylic acid, and ⁇ -naphthalene carboxylic acid
- aromatic monocarboxylic acids such as acid, methylnaphthalenecarboxylic acid and phenylacetic acid.
- aromatic monocarboxylic acids such as acid, methylnaphthalenecarboxylic acid and phenylacetic acid.
- acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecyl acid, myristin Acids, palmitic, stearic, and benzoic acids are more preferred.
- the monoamine used as the terminal blocking agent is not particularly limited as long as it has reactivity with a carboxyl group.
- Aliphatic monoamines such as tilamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, getylamine, dipropylamine, dibutylamine, and cyclobutylamine.
- Alicyclic monoamines such as hexylamine and dicyclohexinoleamine; and aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine. One or more of these can be used.
- butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, butylamine, hexylamine, octylamine, decylamine, and the like from the viewpoints of reactivity, boiling point, stability of the sealed terminal, and price.
- aniline are more preferred.
- the amount of the terminal blocking agent used in producing the semi-aromatic polyamide is determined based on the relative viscosity of the finally obtained polyamide and the blocking rate of the terminal groups.
- the specific amount used varies depending on the reactivity of the terminal blocking agent used, the boiling point, the reaction apparatus, the reaction conditions, and the like, but it is usually 0.3 to the total number of moles of the raw materials, dicarboxylic acid and diamine. It is used in the range of ⁇ 10 mol%.
- (B) semi-aromatic polyamide production equipment includes a patch-type reactor, a single- or multi-chamber continuous reactor, a tubular continuous reactor, a single-screw kneading extruder, and a twin-screw kneading extruder.
- Known polyamide production equipment such as a kneading reaction extruder such as the above.
- a polymerization method a known method such as melt polymerization, solution polymerization, or solid phase polymerization can be used, and normal pressure, reduced pressure, and pressurized operations can be repeated for polymerization. These polymerization methods can be used alone or in combination as appropriate.
- the semi-aromatic polyamide may be a mixture with another polyamide-based resin or another thermoplastic resin. Further, it may be a mixture with (A) an aliphatic polyamide used in the present invention.
- the content of (B) semi-aromatic polyamide in the mixture was 80%. It is preferable that the content be not less than weight%.
- Copper compounds include cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cupric sulfate, cupric nitrate, and copper nitrate.
- the compounding amount of the copper compound is preferably 0.01 to 3 parts by weight, more preferably 0.02 to 1 part by weight, based on 100 parts by weight of the semiaromatic polyamide component (B). Is more preferred. If the amount of the copper compound is less than the above-mentioned value, the heat resistance of the obtained high-temperature chemical solution and the laminated hose for gas transfer may not be sufficient. If the amount exceeds the above-mentioned value, the high-temperature chemical solution and / or During the melt-molding of a laminated gas transfer hose, metal salts may be liberated, and coloring may impair the value of the product.
- a metal halide compound may be added in combination with the copper compound.
- the halogenated alkali metal compounds include lithium chloride, lithium bromide, lithium iodide, lithium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium chloride, and potassium bromide. Lithium, potassium iodide, potassium fluoride, and the like. One or more of these can be used. Among these, potassium iodide is more preferred.
- the compounding amount of these alkali metal halide compounds is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the semiaromatic polyamide component (B), and is preferably 0.01 to 10 parts by weight. 2-3 parts by weight And more preferably 100 to 100 parts by weight based on 100 parts by weight of the copper compound.
- aliphatic polyamide (A) When the aliphatic polyamide has a relatively small number of carbon atoms per amide group in the polyamide repeating unit such as polyamide 6 and polyamide 66, the calcium chloride resistance is lowered.
- a semi-aromatic polyamide may be blended.
- (B) semi-aromatic polyamides may contain, if necessary, antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, lubricants, inorganic fillers, antistatic agents, Flame retardants, crystallization accelerators, plasticizers, coloring agents, lubricants, impact modifiers and the like may be added.
- a rubbery polymer having a flexural modulus measured according to D-790 of 500 MPa or less is added.
- the laminated hose for transporting a high-temperature chemical solution and / or gas according to the present invention comprises: (A) a layer (a) composed of an aliphatic polyamide; and (B) a carbon number of 9 to 13 with respect to all diamine units. and Jiami emission units containing aliphatic Jiami down unit 6 0 mol% or more, relative to the total dicarboxylic acid unit, 5 0 mole 0 / terephthalic acid and Z or naphthalene dicarboxylic acid units. It is composed of at least two or more layers, including the (b) layer made of a semi-aromatic polyamide composed of the dicarboxylic acid units contained above.
- the (b) layer is disposed on the innermost layer, and the (a) layer composed of (A) an aliphatic polyamide is disposed on the outer side of the (b) layer.
- (B) semi-aromatic poly 8397 amide layer (b) was placed on the innermost layer, and (A) layer consisting of aliphatic polyamide (a) layer was placed on the outermost layer in terms of balance of hose properties including low-temperature impact resistance.
- the structure is more preferable.
- (B) layer consisting of semi-aromatic polyamide (b) is the innermost layer and outermost layer
- (A) layer consisting of aliphatic polyamide (a) May be a structure of three or more layers arranged in the intermediate layer.
- 1 and 2 are cross-sectional views showing examples of such a high-temperature chemical and / or gas carrying laminated hose according to the present invention.
- Figure 1 shows a two-layer hose
- Figure 3 shows a three-layer hose.
- reference numeral 1 denotes a (a) layer as an outer layer
- 2 denotes a (b) layer as an inner layer
- reference numeral 5 denotes a (b) layer as an outermost layer
- 6 ′ denotes a (b) layer as an innermost layer
- 7 denotes a (a) layer as an intermediate layer.
- the high-temperature chemical solution and the laminated hose for conveying Z or gas of the present invention it is essential to include a layer (b) composed of (B) a semi-aromatic polyamide, and (B) a layer composed of a semi-aromatic polyamide (b) )
- a layer (b) composed of (B) a semi-aromatic polyamide
- B) a layer composed of a semi-aromatic polyamide
- the thickness of each layer is not particularly limited, and the type of polymer constituting each layer, the number of layers in the laminated hose for conveying high-temperature chemical and z or gas, etc.
- the thickness of each layer is determined in consideration of the properties such as low-temperature impact resistance and flexibility of the high-temperature chemical solution and the laminated hose for carrying Z or gas, and generally the thickness of the (a) layer
- the thickness of the (b) layer is preferably 3 to 97% with respect to the total thickness of the high-temperature chemical solution and the total thickness of the laminated hose for carrying Z or gas.
- the thickness of the layer (b) is more preferably 5 to 80% with respect to the thickness of the high-temperature chemical solution and / or gas. At 10-50% More preferably, there is.
- a layer made of a resin composition containing a conductive filler is preferably disposed as the innermost layer. This makes it possible to prevent explosion due to static electricity generated when a fluid such as a chemical solution is transported. In that case, the non-conductive layer is disposed outside the conductive layer, so that both low-temperature impact resistance and conductivity can be achieved, and it is economically advantageous. is there.
- 'Conductive fillers include all fillers added for imparting conductive properties to resins, and include granular, flaky and fibrous fillers.
- Examples of the granular filler include carbon black and graphite.
- As the flaky filler aluminum flakes, nickel flakes, nickel-coated my strength, and the like can be suitably used.
- Examples of the fibrous filler include carbon fibers, carbon-coated ceramic fibers, carbon whiskers, carbon nanotubes, aluminum fibers, and copper fibers.
- Carbon nanotubes and carbon black are preferred.
- Carbon nanotubes are referred to as hollow carbon fibrils, which have an outer region consisting of an essentially continuous multi-layer of regularly arranged carbon atoms and an inner hollow region.
- An essentially cylindrical fibril wherein each layer and the hollow region are substantially concentrically arranged around the cylindrical axis of the fipril.
- the regularly arranged carbon atoms in the outer region are graphite-like, and the diameter of the hollow region is 2 to 20 nm.
- Carbon nano tube The outer diameter of the bulb is preferably from 3.5 to 70 nm, more preferably from 4 to 60 nm.
- the aspect ratio (meaning the ratio of the length and outer diameter) of the carbon nanotube is preferably 5 or more, more preferably 100 or more, and even more preferably 500 or more. . By satisfying the aspect ratio, a conductive network can be easily formed, and excellent conductivity can be exhibited by adding a small amount.
- Carbon black includes all carbon blacks generally used for imparting conductivity.
- Preferred carbon blacks include acetylene black obtained by incomplete combustion of acetylene gas and crude oil as raw material. Ketjen black, oil black, naphthalene black, thermal black, lamp black, channeroreb's rack, mouth black, disk black, etc. However, it is not limited to these. Of these, acetylene black and furnace black (Ketchen Black) are more preferred.
- carbon black various carbon powders having different properties such as particle diameter, surface area, DBP oil absorption, and ash content can be produced.
- the carbon black that can be used in the present invention is not particularly limited in these properties, but preferably has a good chain structure and a large aggregation density.
- a large amount of carbon black is not preferred in terms of impact resistance, and from the viewpoint of obtaining excellent electrical conductivity with a smaller amount, the average particle size is preferably 50 O nm or less, and 5 to 100 nm.
- the surface area (BET method) is more preferably 10 m 2 / g or more, and the surface area (BET method) is more preferably 10 m 2 / g or more.
- DBP dibutyl phthalate
- the ash content is preferably 0.5% by weight or less, more preferably 0.3% by weight or less.
- the DBP oil absorption here is a value measured by the method specified in ASTM D-2414. More preferably, the carbon black has a volatile content of less than 1.0% by weight.
- These conductive films may be surface-treated with a surface treatment agent such as a titanate, aluminum, or silane. It is also possible to use those granulated to improve the workability of the melt-kneading.
- a surface treatment agent such as a titanate, aluminum, or silane. It is also possible to use those granulated to improve the workability of the melt-kneading.
- the resin component 100 In general, it is preferably 3 to 30 parts by weight based on parts by weight.
- the surface resistivity of the molten extrudate is less than 1 0 8 ⁇ / square, or less 1 0 6 Q / square It is more preferred.
- the compounding of the above-mentioned conductive filler tends to cause deterioration in strength and fluidity. Therefore, if a target conductivity level is obtained, it is desirable that the amount of the conductive filler is as small as possible.
- the total number of layers in the high-temperature chemical solution and / or gas-transporting laminated hose of the present invention is not particularly limited, and (A) is composed of an aliphatic polyamide.
- any number of layers may be used as long as there are at least two layers, including (a) a layer and (B) a layer made of a semi-aromatic polyamide (b).
- the high-temperature chemical solution of the present invention and the multi-layer hose for conveying Z or gas have additional functions.
- it may have one or more layers made of another thermoplastic resin.
- thermoplastic resins in the layer made of other thermoplastic resins include high-density polyethylene (HD PE), medium-density polyethylene (MD PE), low-density polyethylene (LDPE), and linear low-density polyethylene.
- LLDPE ultra-high molecular weight polyethylene
- PP polypropylene
- EPR ethylene / propylene copolymer
- EBR ethylene knobene copolymer
- EVA ethylene Z-butyl acetate copolymer
- EAA ethylene Z vinyl acetate copolymer
- EAA ethylene Z acrylic acid copolymer
- EAA ethylene / methacrylic acid copolymer
- EAA ethylene Z acryl Polyolefin resins such as methyl acrylate copolymer (EMA), ethylene methyl methacrylate copolymer (EMMA), ethylene Z ethyl acrylate copolymer (EEA), and their polyolefin resins Resin is acrylic Acids,
- Polymers such as meta- lonitrile Z-styrene copolymer, acrylonitrile-trinobutadiene Z-styrene copolymer (ABS), meta- lonitrile / / Polynitrile resins such as styrene / butadiene copolymer (MBS), and polymethacrylates such as polymethyl methacrylate (PMMA) and polymethyl methacrylate (PEMA) Resin, Polyvinyl ester resin such as polyvinyl acetate (PVAc), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinylino chloride vinylidene chloride copolymer, vinylidene chloride vinylidene chloride copolymer Polychlorinated vinyl resins such as polymers, cellulose resins such as cellulose acetate and cellulose butyrate, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF),
- polyamide PACM I (4-aminocyclohexyl) methaneisophthalamide
- polyamide PACM II polybis (3-methyl_4-aminocyclohexyl) methane dodecamide
- Polyamide dimethyl PACM12 Polyisophorone adipamide
- polyamide IPD 6 polyisophorone terephthalamide
- polyamide IPDT polyhexamethylene terephthalamide
- polyamide 6T polyhexamethylene isophthalamide
- polyamide 6I polynonamethyleneisophthalamide
- polyamide 9T polynonamethylenehexahydrodoterephthalamide
- polydecamethyleneisophthalamide polyamide 101
- Polydecamethylene hexadroterephthalamide Polyamide 10 T (H)
- Polydecamethylene ethylenephthalate De poly A Mi de 1 1 I
- Kisahi Doroterefutarami de to poly Undekamechiren
- Polyamide 12 I polydodecamethylenehexahydroterephthalate
- A aliphatic polyamides defined in the present invention, such as amides (polyamide 12 T (H)) and copolymers using several kinds of polyamide starting monomers.
- B Polyamide resins other than semi-aromatic polyamides.
- polyolefin resins polyester resins, polyamide resins, polyetherether resins, and fluorine resins are preferable, and polyolefin resins, polyester resins, polyamide resins, and fluorine resins. Resins are more preferable, and polyamide resins and fluorine resins are more preferable.
- thermoplastic resin such as paper, metal-based material, non-stretched, uniaxially or biaxially stretched plastic film or sheet, woven fabric, non-woven fabric, metal cotton, wood, etc.
- Metallic materials include metals such as aluminum, iron, copper, nickel, gold, silver, titanium, molybdenum, magnesium, manganese, lead, tin, chromium, beryllium, tungsten, and cobalt.
- metal compounds and alloy steels such as stainless steels composed of two or more of these, aluminum alloys, copper alloys such as brass and bronze, and alloys such as nickel alloys.
- the number of layers of the high-temperature chemical and / or gas transport laminated hose of the present invention is 2 or more, it is preferable that the number is 7 or less as judged from the mechanism of the high-temperature chemical and / or gas transport laminated hose manufacturing apparatus. More preferably, it is 2 to 5 layers, and more preferably, 2 to 4 layers. Further, in the laminated hose for transporting a high-temperature chemical solution and / or gas of the present invention, it is preferable that the layer (a) and the layer (b) are adjacent to each other from the viewpoint of improving the adhesion between the layers.
- melt extrusion is performed using an extruder corresponding to the number of layers or the number of materials, and lamination is performed simultaneously inside or outside a die (co-extrusion method).
- a single-layer hose or a high-temperature chemical once produced by the above method JP2005 / 008397
- a method (coating method) in which a laminated hose for liquid and / or gas transport is manufactured in advance, and a resin is integrated and laminated successively on the outside using an adhesive as necessary.
- the laminated hose for conveying a high-temperature chemical solution and / or gas of the present invention (A) an aliphatic polyamide and (B) a semi-aromatic polyamide are co-extruded in a molten state, and both are heat-sealed ( It is preferable that the hose is manufactured by a co-extrusion method in which a hose having a laminated structure is manufactured in one step by performing a melt bonding.
- the above-mentioned method is used to remove residual distortion of the molded product.
- heat-treat for 0.01 to 10 hours at a temperature lower than the lowest melting point of the resin constituting the hose to obtain the desired molded article. It is also possible to get.
- the laminated hose for conveying high-temperature chemicals and / or gas may have a corrugated region.
- the waveform region is a region formed in a waveform shape, a bellows shape, an accordion shape, a corrugated shape, or the like.
- the corrugated region may not only be provided over the entire length of the high-temperature chemical and / or gas-conveying laminated hose, but may be partially provided in an appropriate region along the way.
- the corrugated region can be easily formed by first forming a straight tubular hose and then molding it to form a predetermined corrugated shape. By having such a corrugated area, it has a shock absorbing property and the mounting property becomes easy. Furthermore, it is possible to add necessary parts and to make L-shape and U-shape by bending.
- epichlorohydrin rubber ECO
- Li Roni Tril Z Tajen rubber NBR
- a mixture of NBR and polyvinyl chloride chlorosulfonated polyethylene rubber, chlorinated polyethylene rubber, acryl rubber (ACM), chloroprene rubber (CR), ethylene / propylene rubber (EPR ), Ethylene propylene Z-gen rubber (EPDM), a rubber mixture of NBR and EPDM
- a thermoplastic elastomer such as vinyl chloride, olefin, ester, amide, etc.
- a sponge-like protection member can be provided.
- the protection member may be a sponge-like porous body by a known method.
- a porous material By using a porous material, a protective portion that is lightweight and has excellent heat insulating properties can be formed. Also, material costs can be reduced. Alternatively, glass fibers or the like may be added to improve the strength.
- the shape of the protective member is not particularly limited, it is usually a tubular member or a block-shaped member having a concave portion for receiving the laminated hose. In the case of a tubular member, a laminated hose can be inserted later into a previously produced tubular member, or the tubular member can be covered and extruded onto the laminated hose to make them close together.
- the outer diameter of the high-temperature chemical and Z or gas-transporting laminated hose is determined in consideration of the flow rate of the circulating chemical and / or gas (for example, engine coolant). Designed to be thick enough to maintain the normal hose breaking pressure, and flexible enough to ensure easy hose assembly and good vibration resistance during use. But not limited to.
- the outer diameter is preferably 4 to 200 mm
- the inner diameter is 2 to 160 mm
- the wall thickness is preferably 0.5 to 20 mm.
- PT / JP2005 / 008397 The laminated hose according to the present invention is excellent as a chemical and / or gas permeation prevention property and a heat resistance under high temperature, and thus is useful as a hose for transporting a high temperature chemical and / or gas.
- the high-temperature chemical and the gas or gas refer to a chemical and / or gas at a temperature of 50 ° C. or more, and a chemical which flows and circulates instantaneously or continuously in the laminated hose at these temperatures or more. And / or gas.
- Chemicals include, for example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, methanol, ethanol, propanol, butanol, pentanole, ethylene glycol, propylene glycol, diethylene glycol.
- aromatic hydrocarbon solvents such as benzene, toluene and xylene
- methanol ethanol
- propanol butanol
- pentanole ethylene glycol
- propylene glycol diethylene glycol
- Athenole solvents chloroform, methylene chloride, trichloroethylene, dichlorinated styrene, phenol 0 , chloronoethylene, monochloronoethane, dichloronoethane, tetrachloronoleethane, nonoguchi Halogen-based solvents such as ethane and chloronobenzene, ketone-based solvents such as acetone, methylethylketone, jetinoletone, and acetophenone, urea solution, gasoline, kerosene, diesel gasoline, and alcohol-containing gasoline , Oxygen-containing gasoline, Amines gasoline, Sourgasoline, Castor oil-based brake fluid, Glycol ether brake fluid, Borate ester brake fluid, Brake fluid for extreme cold regions, Silicone oil brake fluid, Mineral oil system Examples include brake fluid, power steering oil, hydrogen sulfide-containing oil, engine coolant, window washer fluid, pharmaceutical agents, ink, and paint. Further, in the
- Fluorine-1 2 Fluorine 1 14 3 A, Fluorine 1 4 1b, Fluorine 1 4 2b, Fluorine 2 2 5, Fluorine 1 C 3 1 8, fin-50
- Methyl chloride chlorinated ethyl, air, oxygen, hydrogen, nitrogen, carbon oxide, methane, propane, isobutane, n-butane, argon, rubber, xenon, and the like.
- the laminated hose for transporting a high-temperature chemical and / or gas according to the present invention may be a feed hose, a return hose, an epapo hose, a fuel hose, or a fuel hose.
- It can be used as a floor heating hose, an infrastructure supply hose, a fire extinguisher and a fire extinguisher hose, a medical cooling equipment hose, an ink, a paint spraying hose, and other chemical and gas hoses.
- LLC engine coolant
- diesel gasoline hoses diesel gasoline hoses
- oil drilling hoses oil drilling hoses
- alcohol-containing gasoline hoses alcohol-containing gasoline hoses
- urea solution transfer hoses heater hoses
- reservoir tank hoses which are expected to be used under severe conditions Useful as a road heating hose and a floor heating hose.
- the measurement was carried out in 96% sulfuric acid, at a polyamide concentration of 1%, and at a temperature of 25 ° C. in accordance with JISK-690.
- a hose cut to 200 mm was further halved in the vertical direction to produce a test piece.
- a 180 ° C peel test was performed at a tensile speed of 50 mmZ. The peel strength was read from the maximum point of the S-S curve, and the interlayer adhesion was evaluated.
- Polyamide 12 (UBE TA 300 U, manufactured by Ube Industries, Ltd., relative viscosity 2.27) was used as an impact modifier to improve maleic anhydride-modified ethylene Z propylene.
- the combined JSR Co., Ltd., JSRT 7712 SP
- JSR Co., Ltd., JSRT 7712 SP is mixed in advance and supplied to a twin-screw kneader (manufactured by Nippon Steel Works, Model: TEX44) while the twin-screw kneader is mixed.
- Butyl benzenesulfonate as a plasticizer was injected by a metering pump from the middle of the cylinder of the machine, and was melt-kneaded at a cylinder temperature of 180 to 260 ° C to melt the molten resin. After being extruded into a strand, it is introduced into a water tank, cooled, cut, and vacuum-dried.
- Polyamide 12 resin 85% by weight, impact modifier 10% by weight, plasticizer 5% by weight % Of a polyamide 12 resin composition (hereinafter, this polyamide resin composition is referred to as (A-1)). U).
- Polyamide 66 (UBENylon 206 B, manufactured by Ube Industries, Ltd., relative viscosity 3.36) was used as an impact modifier to improve maleic anhydride-modified ethylene propylene copolymer ( JSRT 7712 SP, manufactured by JSR Corporation), Hexamethyle as a calcium chloride resistance improving material N-terephthalamide Z hexamethylene isofphthalamide copolymer (polyamide 6T / 6I) (Ems' Showa Denko KK, Grivory
- polyamide 66 resin product In the production of polyamide 66 resin product, polyamide 66 (UBEN ylon 206 B, relative viscosity 3.36) manufactured by Ube Industries, Ltd.) was used. Polyamide 6 (manufactured by Ube Industries, Ltd., UBENy 1 on 130 B, relative viscosity 4.08), except for melt kneading at a cylinder temperature of 200 to 260 ° C (A-3) Polyamide 6 resin 65% by weight, impact modifier 15% by weight, calcium chloride resistance modifier 20% by the same method as in the production of polyamide 6 resin composition Thus, a pellet of the polyamide 6 resin composition was obtained (hereinafter, this polyamide resin composition is referred to as (A-3)).
- Terephthalic acid 32 927 g (199.2 mol), 1,9-nonanediamine 158 929 g (100 mol), 2-methyl-1,8-otatandiamine 15 8 2 9 g (100 mol), benzoic acid 4 39.6 g
- Adipic acid 229 230 g (200 moles), metaxidiresamine 27 73 6 g (201 mol), benzoic acid 122.1 g (1.0 mol), sodium hypophosphite monohydrate 57 g (0.1 1% by weight) and 40 L of distilled water were placed in an autoclave and purged with nitrogen.
- D-1 Toray ( TORELINA A670X011), an ethylene Z dalicydyl methacrylate copolymer (letterspar: RA3150, manufactured by Nippon Polyolefin Co., Ltd.) are mixed in advance, and
- (A) / (b) 0.75 / 0.25mm when the (b) layer (inner layer) is composed of a metal (B-1) and the inner diameter is 6mm and the outer diameter is 8mm Was obtained.
- Table 1 shows the measurement results of the physical properties of the laminated hose.
- Example 1 was repeated except that (B) the semi-aromatic polyamide (B-1) was changed to (B-2) and (B) was melted at an extrusion temperature of 320 ° C.
- B the semi-aromatic polyamide
- B-2 the semi-aromatic polyamide
- B-2 was changed to (B-2) and (B) was melted at an extrusion temperature of 320 ° C.
- Table 1 shows the measurement results of the physical properties of the laminated hose.
- Example 1 Example 1 was repeated except that (B) the semi-aromatic polyamide (B-1) was changed to (B-3) and (B) was melted at an extrusion temperature of 310 ° C.
- a laminated hose having the layer configuration shown in Table 1 was obtained in the same manner as described above. Table 1 shows the measurement results of the physical properties of the laminated hose.
- Example 4 Example 1 was repeated except that (A) the aliphatic polyamide (A_l) was changed to (A-2) and (A) was melted at an extrusion temperature of 280 ° C. In the same manner, a laminated hose having a layer configuration shown in Table 1 was obtained. Table 1 shows the measurement results of the physical properties of the laminated hose.
- Example 1 Example 1 was repeated except that (A) the aliphatic polyamide (A-1) was changed to (A-3) and (A) was melted at an extrusion temperature of 260 ° C.
- a laminated hose having the layer configuration shown in Table 1 was obtained in the same manner as described above. Table 1 shows the measurement results of the physical properties of the laminated hose.
- a single-layer hose having a layer configuration shown in Table 1 was obtained in the same manner as in Example 1 except that (B) semiaromatic polyamide (B_1) was not used.
- Table 1 shows the measurement results of the physical properties of the single-layer hose.
- Comparative Example 2 A single-layer hose having the layer configuration shown in Table 1 was obtained in the same manner as in Example 1 except that (A) the polyamide 12 resin composition (A-1) was not used. Table 1 shows the measurement results of the physical properties of the single-layer hose. Comparative Example 3
- (B) the semi-aromatic polyamide (B-1) was changed to (B-14) in Example 5.
- Got. Table 1 shows the physical property measurement results of the laminated hose.
- Table 1 shows the measurement results of the physical properties of the laminated hose.
- Example 1 A-1 0.75--B-1 0.25 203 193 (95) 0/10 0/10 9.2 9.8 45 25 29
- Example 2 A -1 0.75--B-2 0.25 208 204 (98) 0/10 0/10 9.0 9.5
- Non-peelable 46 35
- Example 3 A-1 0.75--B-3 0.25 198 190 (96) 0/10 0/10 9.5 10.2 43 23 7
- Example 4 A-2 0.75--B-1 0.25 210 195 (93) 0/10 0/10 11.2 11.4 42 24 42
- Example 5 A-3 0.75--B-1 0.25 205 187 ( 91) 0/10 0/10 10.8 11.0 46 22 44
- Example 6 B-1 0.125 A-1 0.75 B-1 0.125 195 187 (96) 0/10 0/10 9.3 9.9
- Comparative Example 1 A-1 1.00----241 166 (69) 0/10 7/10 8.3 10.1--150 Comparative example 2-one-one B-1 1
- the laminated hose according to the present invention is useful as a hose for transporting a high-temperature chemical solution and / or gas, since it has excellent properties for preventing the permeation of a chemical solution and gas or gas at high temperatures and heat resistance.
- the laminated hose for carrying high-temperature chemicals and / or gas according to the present invention is particularly suitable for use under severe conditions, such as engine coolant (LL.C) hose, diesel gasoline hose, oil drilling hose, Useful as alcohol-containing gasoline hoses, urea solution transfer hoses, heater hoses, lizano tank hoses, load heating hoses, and floor heating hoses.
- LLC engine coolant
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
- Laminated Bodies (AREA)
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006512669A JP4480718B2 (ja) | 2004-04-27 | 2005-04-26 | 高温薬液及び/又はガス搬送用積層ホース |
CA2564762A CA2564762C (en) | 2004-04-27 | 2005-04-26 | Multilayer hose for the transportation of high-temperature liquid and/or gas chemical |
BRPI0510373A BRPI0510373B1 (pt) | 2004-04-27 | 2005-04-26 | "mangueira em multicamadas, que atua em alta temperatura, pelo menos igual e superior a 50ºc, para o transporte de uma substância química líquida e/ou gasosa". |
EP05736572.8A EP1741549B1 (en) | 2004-04-27 | 2005-04-26 | Multilayer hose for transporting high-temperature chemical and/or gas |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004-132128 | 2004-04-27 | ||
JP2004132128 | 2004-04-27 |
Publications (1)
Publication Number | Publication Date |
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WO2005102681A1 true WO2005102681A1 (ja) | 2005-11-03 |
Family
ID=35196822
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2005/008397 WO2005102681A1 (ja) | 2004-04-27 | 2005-04-26 | 高温薬液及び/又はガス搬送用積層ホース |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP1741549B1 (ja) |
JP (1) | JP4480718B2 (ja) |
CN (1) | CN100519167C (ja) |
BR (1) | BRPI0510373B1 (ja) |
CA (1) | CA2564762C (ja) |
WO (1) | WO2005102681A1 (ja) |
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- 2005-04-26 CA CA2564762A patent/CA2564762C/en not_active Expired - Fee Related
- 2005-04-26 BR BRPI0510373A patent/BRPI0510373B1/pt active IP Right Grant
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Also Published As
Publication number | Publication date |
---|---|
BRPI0510373B1 (pt) | 2016-07-05 |
CN100519167C (zh) | 2009-07-29 |
JP4480718B2 (ja) | 2010-06-16 |
BRPI0510373A (pt) | 2007-11-06 |
CN1946547A (zh) | 2007-04-11 |
JPWO2005102681A1 (ja) | 2008-03-13 |
EP1741549A4 (en) | 2009-11-11 |
EP1741549A1 (en) | 2007-01-10 |
CA2564762A1 (en) | 2005-11-03 |
EP1741549B1 (en) | 2016-09-07 |
CA2564762C (en) | 2013-10-29 |
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