CN111601995B - 层叠管 - Google Patents
层叠管 Download PDFInfo
- Publication number
- CN111601995B CN111601995B CN201980008723.7A CN201980008723A CN111601995B CN 111601995 B CN111601995 B CN 111601995B CN 201980008723 A CN201980008723 A CN 201980008723A CN 111601995 B CN111601995 B CN 111601995B
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- CN
- China
- Prior art keywords
- polyamide
- laminated tube
- layer
- hfc
- acid
- Prior art date
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- 239000000203 mixture Substances 0.000 claims abstract description 175
- 239000004953 Aliphatic polyamide Substances 0.000 claims abstract description 172
- 229920003231 aliphatic polyamide Polymers 0.000 claims abstract description 172
- 229920000098 polyolefin Polymers 0.000 claims abstract description 87
- 229920000642 polymer Polymers 0.000 claims abstract description 63
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 29
- 238000002844 melting Methods 0.000 claims abstract description 24
- 230000008018 melting Effects 0.000 claims abstract description 24
- 125000003368 amide group Chemical group 0.000 claims abstract description 15
- 125000004018 acid anhydride group Chemical group 0.000 claims abstract description 12
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims abstract description 10
- 239000004952 Polyamide Substances 0.000 claims description 233
- 229920002647 polyamide Polymers 0.000 claims description 233
- -1 alkyl aliphatic alcohol Chemical compound 0.000 claims description 164
- 229920001577 copolymer Polymers 0.000 claims description 87
- 239000004014 plasticizer Substances 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 46
- 239000000178 monomer Substances 0.000 claims description 40
- 239000004711 α-olefin Substances 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- 229920000299 Nylon 12 Polymers 0.000 claims description 25
- 125000003277 amino group Chemical group 0.000 claims description 21
- 125000000524 functional group Chemical group 0.000 claims description 21
- 239000004743 Polypropylene Substances 0.000 claims description 19
- 229920001155 polypropylene Polymers 0.000 claims description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 14
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 13
- 229920001519 homopolymer Polymers 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 12
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 10
- 239000002826 coolant Substances 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 125000004434 sulfur atom Chemical group 0.000 claims description 7
- 229920005992 thermoplastic resin Polymers 0.000 claims description 7
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 6
- 229920000571 Nylon 11 Polymers 0.000 claims description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 6
- 229920006152 PA1010 Polymers 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229920006396 polyamide 1012 Polymers 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 125000005462 imide group Chemical group 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 125000002560 nitrile group Chemical group 0.000 claims description 4
- 238000004378 air conditioning Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 52
- 238000010828 elution Methods 0.000 abstract description 15
- 239000010410 layer Substances 0.000 description 189
- 230000000704 physical effect Effects 0.000 description 55
- 239000000243 solution Substances 0.000 description 50
- 238000004519 manufacturing process Methods 0.000 description 45
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 32
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 28
- 238000006116 polymerization reaction Methods 0.000 description 24
- 229920001971 elastomer Polymers 0.000 description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 22
- 239000005977 Ethylene Substances 0.000 description 22
- 239000000806 elastomer Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 239000008188 pellet Substances 0.000 description 18
- 239000003963 antioxidant agent Substances 0.000 description 17
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 17
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 230000003078 antioxidant effect Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 14
- 229910052698 phosphorus Inorganic materials 0.000 description 14
- 239000011574 phosphorus Substances 0.000 description 14
- 238000012545 processing Methods 0.000 description 14
- 239000003381 stabilizer Substances 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 12
- AWTUIOQHXHBRDW-UHFFFAOYSA-N 2-hexyldecyl 4-hydroxybenzoate Chemical compound CCCCCCCCC(CCCCCC)COC(=O)C1=CC=C(O)C=C1 AWTUIOQHXHBRDW-UHFFFAOYSA-N 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 12
- 150000002148 esters Chemical group 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 11
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 11
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 11
- 230000007774 longterm Effects 0.000 description 11
- 239000003507 refrigerant Substances 0.000 description 11
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 10
- 230000004888 barrier function Effects 0.000 description 10
- 239000012530 fluid Substances 0.000 description 10
- 229920001748 polybutylene Polymers 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 235000019198 oils Nutrition 0.000 description 9
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229920005604 random copolymer Polymers 0.000 description 8
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 150000001735 carboxylic acids Chemical class 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000000379 polymerizing effect Effects 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 229920000459 Nitrile rubber Polymers 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 239000003502 gasoline Substances 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 5
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 description 5
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000004702 methyl esters Chemical class 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 5
- 229920000768 polyamine Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 5
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 4
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 4
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-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
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- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 4
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 4
- IPOPWGGDRWYTLB-UHFFFAOYSA-N 4-[(4,4-diaminocyclohexyl)methyl]cyclohexane-1,1-diamine Chemical compound C1CC(N)(N)CCC1CC1CCC(N)(N)CC1 IPOPWGGDRWYTLB-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
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- 239000004696 Poly ether ether ketone Substances 0.000 description 4
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 4
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- 238000011955 best available control technology Methods 0.000 description 4
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- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 4
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- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 4
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- 230000000694 effects Effects 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 description 4
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- JJOJFIHJIRWASH-UHFFFAOYSA-N icosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCC(O)=O JJOJFIHJIRWASH-UHFFFAOYSA-N 0.000 description 4
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical compound NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
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- COWHOTSOONQDCJ-UHFFFAOYSA-N naphthalene-2,6-dicarboxamide Chemical compound C1=C(C(N)=O)C=CC2=CC(C(=O)N)=CC=C21 COWHOTSOONQDCJ-UHFFFAOYSA-N 0.000 description 4
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- 229920002530 polyetherether ketone Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
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- 239000002904 solvent Substances 0.000 description 4
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- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 3
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VTIMKVIDORQQFA-UHFFFAOYSA-N 2-Ethylhexyl-4-hydroxybenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(O)C=C1 VTIMKVIDORQQFA-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 3
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 3
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Abstract
本发明提供一种低温耐冲击性、高温时的破坏压强度、柔软性、尺寸稳定性、以及低分子量物、离子成分的耐溶出性优异的层叠管。本发明所述的层叠管具有包含脂肪族聚酰胺组合物的层和包含改性聚烯烃的层,且包含脂肪族聚酰胺组合物的层的厚度在管的总壁厚之中占特定的比例以上,所述脂肪族聚酰胺组合物通过含有脂肪族聚酰胺和弹性体聚合物,且根据需要含有具有特定结构的增塑剂,从而使弯曲弹性模量处于特定范围,所述脂肪族聚酰胺的亚甲基数相对于酰胺基数的比值为规定范围,所述弹性体聚合物含有由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元,所述改性聚烯烃的熔点为特定的熔点以上。
Description
技术领域
本发明涉及层叠管。
背景技术
在油压管、水压管等各种压力管、真空管和汽车所使用的燃料配管管路、制动器管、冷却液用软管、空调配管管路、SCR(柴油发动机尾气去除装置)管、控制电缆套筒等中使用大量的软管(hose)/管(tube)类。在这些软管/管中运输冷却液(醇和水)、制冷剂、油、尿素溶液等化学溶液。对于在汽车工业领域中使用的各种软管/管等而言,要求在高温下的高破坏压强度、长期维持的耐热性、耐化学品性、水蒸气和/或化学溶液阻隔性、柔软性等极高的性能。
尤其,循环流体是用于防止冬季的冻结而以乙二醇作为主体的冷却液(LLC)、作为用于去除从柴油发动机释放的NOx的催化剂而封入的尿素溶液、空调/散热器等所使用的二氧化碳、氟利昂、氟利昂替代物、丙烷、水等制冷剂等时,若对这些化学溶液的阻隔性不充分,则在实际使用时无法充分地发挥冷却效果、催化作用效果。另外,随着臭氧层破坏气体的蒸散管控的加强,对于汽车等中使用的制冷剂运输用管的制冷剂阻隔性的要求变得严苛。
另一方面,随着臭氧层破坏气体的蒸散管控的加强,近年来汽车等中使用的制冷剂的品质也得以改良。例如,作为HFC-134a制冷剂的替代制冷剂而开发了R-1234yf制冷剂,其与HFC-134a制冷剂相比臭氧破坏系数和全球变暖潜能值低,是对于地球环境而言极其友善的制冷剂。然而,尤其是R-1234yf制冷剂在高温环境下因与水接触而容易发生水解并产生酸(甲酸等),主要由于该酸的因素,视与化学溶液接触的材料而异,容易发生水解、劣化,最差的情况下,存在产生裂纹、流体泄漏而无法实现流体运输目的这样的问题。或者,化学溶液、水有时也透过管主体而对接触的部件造成不良影响。
以往使用的、单独使用聚酰胺系树脂、尤其是强度、韧性、耐化学药品性、柔软性等优异的聚酰胺11或聚酰胺12得到的单层管对于前述化学溶液的长期耐久性和阻隔性不充分。
乙烯/四氟乙烯共聚物(ETFE)等氟系树脂对于各种化学溶液的耐性极其优异,可以认为其是对于水蒸气具有阻隔性能的材料部件之一。近年来,具有与聚酰胺的粘接性的氟系树脂的开发变得活跃(参照专利文献1~3)。然而,在环保方面避免使用含卤素材料的同时,存在比重高、成本高的问题,正在寻求开发出使用无卤素材料、对化学溶液的阻隔性优异且对各种化学溶液具有耐性的配管***。
另一方面,聚烯烃的价格低廉,抗化学溶液透过性、化学溶液长期耐性优异。例如,提出了一种由包含聚酰胺的外层、包含交联聚乙烯的内层构成的冷却用配管(参照专利文献4)。另外,提出了一种由包含聚酰胺的外层、具有一定以上的厚度且包含含有特定添加剂的聚丙烯的内层构成的冷却用配管(参照专利文献5)。同样地,提出了一种冷却用配管,其特征在于,其对冷却剂为非活性且不能溶胀,外层包含聚酰胺,内层由卤代或非卤代的均聚聚烯烃或共聚烯烃构成,该冷却用配管通过挤出吹塑成形来制造,在导管的整个长度上,层的壁厚不同,且内层和外层的聚合物的挠性明显不同(参照专利文献6)。另外,提出了一种多层管,其从内侧朝向外侧包含聚烯烃的内层、以粘接剂为基础的第一中间层、乙烯/乙烯醇共聚物的第二中间层、聚酰胺的第三中间层和外侧的保护层(参照专利文献7)。进而,还提出了一种燃料电池用配管,其用以聚酰胺系树脂和苯乙烯/异丁烯嵌段共聚物作为必需成分的外层用材料制成外层,且内层用材料以聚烯烃系树脂和苯乙烯/异丁烯嵌段共聚物作为必需成分(参照专利文献8)。
现有技术文献
专利文献
专利文献1:国际公开2001-058686号
专利文献2:国际公开2001-060606号
专利文献3:日本特开2004-301247号公报
专利文献4:日本特开平9-29869号公报
专利文献5:日本特表2008-507436号公报
专利文献6:日本特开平7-214647号公报
专利文献7:日本特开2006-116966号公报
专利文献8:日本特开2005-216725号公报
发明内容
发明要解决的问题
然而,专利文献4所公开的配管在使用聚乙烯作为内层的情况下,高温下的长期耐性、管物性差。
另外,对于化学溶液运输用管等,担心因硫成分对内部流通的化学溶液造成的污染所导致的催化剂污染、由低分子量物的溶出导致的管内堵塞,但专利文献5~7没有具体的技术数据、技术启示。
专利文献8中,外层材料中含有的苯乙烯/异丁烯嵌段共聚物的柔软性改良效果不充分,寻求进一步的改良。另一方面,配管的可施工空间日益变窄,对于电动汽车等而言,为了提高冷却效率,配管设计也逐渐变得更为复杂。在这种状况下,从部件的施工性、设计自由度的观点出发,寻求层叠管的柔软性,进而要求兼顾在高温气氛下可耐受化学溶液内压的高耐压性。
本发明的目的在于,解决前述问题点,提供低温耐冲击性、高温时的破坏压强度、柔软性、尺寸稳定性和低分子量物、离子成分的耐溶出性优异的层叠管。
用于解决问题的方案
本发明人等为了解决前述问题点而进行了深入研究,结果发现:通过具有包含脂肪族聚酰胺组合物的层和包含改性聚烯烃的层的层叠管,且包含脂肪族聚酰胺组合物的层的厚度在管的总壁厚之中具有特定的比例以上,从而低温耐冲击性、高温时的破坏压强度、柔软性、尺寸稳定性和低分子量物、离子成分的耐溶出性优异,所述脂肪族聚酰胺组合物含有脂肪族聚酰胺和弹性体聚合物,且根据需要而含有具有特定结构的增塑剂,从而使弯曲弹性模量处于特定范围,所述脂肪族聚酰胺的亚甲基数相对于酰胺基数的比值为规定范围,所述弹性体聚合物含有由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元,所述改性聚烯烃的熔点为特定的熔点以上。
即,本发明是一种层叠管,其为包含(a)层、(b)层的2层以上的层叠管,
前述(a)层包含脂肪族聚酰胺组合物(A),
前述(b)层包含改性聚烯烃(B),
前述脂肪族聚酰胺组合物(A)包含聚酰胺(A1)和弹性体聚合物(A2),
前述聚酰胺(A1)是亚甲基数相对于酰胺基数的比值为7.0以上的脂肪族聚酰胺,在前述脂肪族聚酰胺组合物(A)中包含55质量%以上且95质量%以下的前述聚酰胺(A1),
前述弹性体聚合物(A2)含有由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元,在前述脂肪族聚酰胺组合物(A)中包含5质量%以上且30质量%以下的前述弹性体聚合物(A2),
另外,前述脂肪族聚酰胺组合物(A)任选包含增塑剂(A3),
前述增塑剂(A3)不含硫原子,且含有对羟基苯甲酸和/或邻羟基苯甲酸与碳原子数为12以上且24以下的直链状和/或支链状烷基脂肪族醇形成的酯结构,前述脂肪族聚酰胺组合物(A)中的前述增塑剂(A3)的含量为0质量%以上且15质量%以下,
前述脂肪族聚酰胺组合物(A)的按照ISO 178而测得的弯曲弹性模量为400MPa以上且1000MPa以下,
前述改性聚烯烃(B)具有由基于碳原子数为2以上且10以下的α-烯烃的单体衍生的单元,且按照ISO 11357-3而测得的熔点为130℃以上,
在前述层叠管中,从外侧朝向内侧按照(a)层、(b)层的顺序配置,
前述(a)层的厚度占据管的总壁厚的60%以上。
以下示出层叠管的优选方式。优选的方式可以组合多种。
[1]一种层叠管,其中,前述聚酰胺(A1)为选自由聚十一酰胺(聚酰胺11)、聚十二酰胺(聚酰胺12)、聚癸二酰己二胺(聚酰胺610)、聚十二烷二酰己二胺(聚酰胺612)、聚癸二酰癸二胺(聚酰胺1010)、聚十二烷二酰癸二胺(聚酰胺1012)和聚十二烷二酰十二烷二胺(聚酰胺1212)组成的组中的至少1种均聚物;和或使用多种形成它们的原料单体得到的共聚物。
[2]一种层叠管,其中,将每1g前述聚酰胺(A1)的末端氨基浓度记作[A](μeq/g),并将末端羧基浓度记作[B](μeq/g)时,[A]>[B]+5。
[3]一种层叠管,其中,前述改性聚烯烃(B)含有由不饱和化合物衍生的单元,所述不饱和化合物具有选自由羧基或其衍生物、羟基、环氧基、氨基、酰胺基、酰亚胺基、腈基、硫醇基和异氰酸酯基组成的组中的至少1种官能团。
[4]一种层叠管,其中,前述改性聚烯烃(B)通过使改性前的聚烯烃发生熔融,并添加具有前述官能团的不饱和化合物,使其接枝共聚的方法来制造。
[5]一种层叠管,其中,前述改性聚烯烃(B)在230℃/2160g的条件下按照ISO 1133而测得的MFR值为1.0g/10min以上且10.0g/10min以下。
[6]一种层叠管,其中,前述改性聚烯烃(B)的按照ISO 1183-3而测得的密度为0.85g/cm3以上。
[7]一种层叠管,其中,前述改性聚烯烃(B)为马来酸酐改性聚丙烯,聚丙烯的含量为50质量%以上。
[8]一种层叠管,其还包含(c)层,前述(c)层包含聚烯烃(C),前述聚烯烃(C)具有由基于碳原子数为2以上且10以下的α-烯烃的单体衍生的单元,且按照ISO 11357-3而测得的熔点为120℃以上,按照ISO 527而测得的拉伸屈服应力为20MPa以上,按照ISO 179/1eA而测得的23℃下的夏比冲击强度(带缺口)为40kJ/m2以上。
[9]一种层叠管,其中,前述(c)层配置在前述(b)层的内侧。
[10]一种层叠管,其通过共挤出成形法来制造。
[11]一种层叠管,其为冷却液(LLC)冷却器管、尿素溶液运输管、电池冷却加热用管和空调用管中的任一者。
发明的效果
根据本发明,可提供低温耐冲击性、高温时的破坏压强度、柔软性、尺寸稳定性、以及低分子量物或离子成分的耐溶出性优异的层叠管。
具体实施方式
本发明的层叠管是包含(a)层、(b)层的2层以上的层叠管,前述(a)层包含脂肪族聚酰胺组合物(A),前述(b)层包含改性聚烯烃(B),前述脂肪族聚酰胺组合物(A)包含聚酰胺(A1)和弹性体聚合物(A2),前述聚酰胺(A1)是亚甲基数相对于酰胺基数的比值为7.0以上的脂肪族聚酰胺,在前述脂肪族聚酰胺组合物(A)中包含55质量%以上且95质量%以下的前述聚酰胺(A1),前述弹性体聚合物(A2)含有由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元,在前述脂肪族聚酰胺组合物(A)中包含5质量%以上且30质量%以下的前述弹性体聚合物(A2),另外,前述脂肪族聚酰胺组合物(A)任选包含增塑剂(A3),前述增塑剂(A3)不含硫原子,且含有对羟基苯甲酸和/或邻羟基苯甲酸与碳原子数为12以上且24以下的直链状和/或支链状烷基脂肪族醇形成的酯结构,前述脂肪族聚酰胺组合物(A)中的前述增塑剂(A3)的含量为0质量%以上且15质量%以下,前述脂肪族聚酰胺组合物(A)的按照ISO 178而测得的弯曲弹性模量が400MPa以上且1000MPa以下,前述改性聚烯烃(B)具有由基于碳原子数为2以上且10以下的α-烯烃的单体衍生的单元,且按照ISO 11357-3而测得的熔点为130℃以上,在前述层叠管中,从外侧朝向内侧按照(a)层、(b)层的顺序配置,前述(a)层的厚度占据管的总壁厚的60%以上。
1.(a)层
本发明的层叠管的(a)层包含脂肪族聚酰胺组合物(A)。
<脂肪族聚酰胺组合物(A)>
脂肪族聚酰胺组合物(A)包含聚酰胺(A1)和弹性体聚合物(A2),聚酰胺(A1)是亚甲基数相对于酰胺基数的比值为7.0以上的脂肪族聚酰胺,在脂肪族聚酰胺组合物(A)中包含55质量%以上且95质量%以下的聚酰胺(A1),弹性体聚合物(A2)含有由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元,在脂肪族聚酰胺组合物(A)中包含5质量%以上且30质量%以下的弹性体聚合物(A2),任选根据需要而包含增塑剂(A3),增塑剂(A3)不含硫原子,且含有对羟基苯甲酸和/或邻羟基苯甲酸与碳原子数为12以上且24以下的直链状和/或支链状烷基脂肪族醇形成的酯结构,脂肪族聚酰胺组合物(A)中的前述增塑剂(A3)的含量为0质量%以上且15质量%以下,脂肪族聚酰胺组合物(A)的按照ISO 178而测得的弯曲弹性模量为400MPa以上且1000MPa以下(以下有时称为脂肪族聚酰胺组合物(A))。
[聚酰胺(A1)]
聚酰胺(A1)是亚甲基数相对于酰胺基数的比值(以下有时称为[CH2]/[NHCO])为7.0以上的脂肪族聚酰胺(以下有时称为聚酰胺(A1))。通过使用[CH2]/[NHCO]为7.0以上的脂肪族聚酰胺,能够使所得层叠管的机械特性等各物性优异。
聚酰胺(A1)在主链中具有酰胺键(-CONH-),可通过以脂肪族内酰胺、脂肪族氨基羧酸、或者脂肪族二胺和脂肪族二羧酸作为原料,利用熔融聚合、溶液聚合、固相聚合等公知方法进行聚合或共聚来获得。
作为脂肪族内酰胺,可列举出己内酰胺、庚内酰胺、十一内酰胺、十二内酰胺、α-吡咯烷酮、α-哌啶酮等,作为脂肪族氨基羧酸,可列举出6-氨基己酸、7-氨基庚酸、9-氨基壬酸、11-氨基十一烷酸、12-氨基十二烷酸等。它们可以使用1种或2种以上。
作为脂肪族二胺,可以使用1,4-丁二胺、1,5-戊二胺、1,6-己二胺、1,7-庚二胺、1,8-辛二胺、1,9-壬二胺、1,10-癸二胺、1,11-十一烷二胺、1,12-十二烷二胺、1,13-十三烷二胺、1,14-十四烷二胺、1,15-十五烷二胺、1,16-十六烷二胺、1,17-十七烷二胺、1,18-十八烷二胺、1,19-十九烷二胺、1,20-二十烷二胺、2-甲基-1,5-戊二胺、3-甲基-1,5-戊二胺、2-甲基-1,8-辛二胺、2,2,4-三甲基-1,6-己二胺、2,4,4-三甲基-1,6-己二胺、5-甲基-1,9-壬二胺等。它们可以使用1种或2种以上。
作为脂肪族二羧酸,可列举出戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸、十三烷二酸、十四烷二酸、十五烷二酸、十六烷二酸、十八烷二酸、二十烷二酸等。它们可以使用1种或2种以上。
作为聚酰胺(A1),可列举出例如聚十一酰胺(聚酰胺11)、聚十二酰胺(聚酰胺12)、聚十二烷二酰丁二胺(聚酰胺412)、聚十二烷二酰戊二胺(聚酰胺512)、聚十二烷二酰己二胺(聚酰胺612)、聚十四烷二酰己二胺(聚酰胺614)、聚十六烷二酰己二胺(聚酰胺616)、聚十八烷二酰己二胺(聚酰胺618)、聚己二酰壬二胺(聚酰胺96)、聚辛二酰壬二胺(聚酰胺98)、聚壬二酰壬二胺(聚酰胺99)、聚癸二酰壬二胺(聚酰胺910)、聚十二烷二酰壬二胺(聚酰胺912)、聚己二酰癸二胺(聚酰胺106)、聚辛二酰癸二胺(聚酰胺108)、聚壬二酰癸二胺(聚酰胺109)、聚癸二酰癸二胺(聚酰胺1010)、聚十二烷二酰癸二胺(聚酰胺1012)、聚己二酰十二烷二胺(聚酰胺126)、聚辛二酰十二烷二胺(聚酰胺128)、聚壬二酰十二烷二胺(聚酰胺129)、聚癸二酰十二烷二胺(聚酰胺1210)、聚十二烷二酰十二烷二胺(聚酰胺1212)等均聚物、使用多种形成它们的原料单体得到的共聚物等。
这些之中,作为聚酰胺(A1),从能够充分确保所得层叠管的机械特性、耐热性等各物性的观点、经济性、获取容易度的观点等出发,优选使用选自由聚十一酰胺(聚酰胺11)、聚十二酰胺(聚酰胺12)、聚癸二酰己二胺(聚酰胺610)、聚十二烷二酰己二胺(聚酰胺612)、聚癸二酰癸二胺(聚酰胺1010)、聚十二烷二酰癸二胺(聚酰胺1012)和聚十二烷二酰十二烷二胺(聚酰胺1212)组成的组中的至少1种均聚物、和/或使用多种形成它们的原料单体得到的共聚物。
例如,在聚十一酰胺(聚酰胺11)的情况下,[CH2]/[NHCO]=10.0;在聚十二酰胺(聚酰胺12)的情况下,[CH2]/[NHCO]=11.0;在聚癸二酰己二胺(聚酰胺610)的情况下,[CH2]/[NHCO]=7.0;在聚十二烷二酰己二胺(聚酰胺612)的情况下,[CH2]/[NHCO]=8.0;在聚癸二酰癸二胺(聚酰胺1010)的情况下,[CH2]/[NHCO]=9.0;在聚十二烷二酰癸二胺(聚酰胺1012)的情况下,[CH2]/[NHCO]=10.0;在聚十二烷二酰十二烷二胺(聚酰胺1212)的情况下,[CH2]/[NHCO]=11.0,是亚甲基数相对于酰胺基数的比值为7.0以上的脂肪族聚酰胺。
作为聚酰胺(A1)的制造装置,可列举出间歇式反应釜、单槽式~多槽式的连续反应装置、管状连续反应装置、单螺杆型混炼挤出机、双螺杆型混炼挤出机等混炼反应挤出机等公知的聚酰胺制造装置。作为聚合方法,可以使用熔融聚合、溶液聚合、固相聚合等公知方法,反复进行常压、减压、加压操作来进行聚合。这些聚合方法可以单独使用或适当组合使用。
另外,从确保所得层叠管的机械性质、以及将熔融时的粘度设为适当范围而确保层叠管的期望成形性的观点出发,按照JIS K-6920在96%硫酸、聚合物浓度为1%、25℃的条件下测得的聚酰胺(A1)的相对粘度优选为1.5以上且5.0以下、更优选为2.0以上且4.5以下。
将每1g聚酰胺(A1)的末端氨基浓度记作[A](μeq/g),并将末端羧基浓度记作[B](μeq/g)时,从充分确保层叠管的层间粘接性的观点出发,优选为[A]>[B]+5、更优选为[A]>[B]+10、进一步优选为[A]>[B]+15。进而,从聚酰胺的熔融稳定性、抑制凝胶状物的产生的观点出发,优选为[A]>20、更优选为30<[A]<120。
另外,末端氨基浓度[A](μeq/g)可通过将该聚酰胺溶解于苯酚/甲醇混合溶液,并利用0.05N的盐酸进行滴定来测定。末端羧基浓度[B](μeq/g)可通过将该聚酰胺溶解于苄醇,并利用0.05N的氢氧化钠溶液进行滴定来测定。
聚酰胺(A1)可通过将前述聚酰胺原料在胺类的存在下利用熔融聚合、溶液聚合、固相聚合等公知方法进行聚合或共聚来制造。或者,通过在聚合后在胺类的存在下进行熔融混炼来制造。像这样,胺类可以在聚合时的任意阶段或者聚合后在熔融混炼时的任意阶段中添加,考虑到层叠管的层间粘接性时,优选在聚合时的阶段进行添加。
作为上述胺类,可列举出单胺、二胺、三胺、四胺和多胺。另外,除了胺类之外,只要不偏离上述末端基团浓度条件的范围,则可根据需要而添加单羧酸、二羧酸、三羧酸等羧酸类。这些胺类、羧酸类可以同时添加,也可以分别添加。另外,下述例示的胺类、羧酸类可以使用1种或2种以上。
作为所添加的单胺的具体例,可列举出甲胺、乙胺、丙胺、丁胺、戊胺、己胺、庚胺、辛胺、2-乙基己胺、壬胺、癸胺、十一烷基胺、十二烷基胺、十三烷基胺、十四烷基胺、十五烷基胺、十六烷基胺、十八烷基胺、十八烯基胺、二十烷基胺、二十二烷基胺等脂肪族单胺;环己胺、甲基环己胺等脂环式单胺;苄胺、β-苯基甲胺等芳香族单胺;N,N-二甲胺、N,N-二乙胺、N,N-二丙胺、N,N-二丁胺、N,N-二己胺、N,N-二辛胺等对称仲胺;N-甲基-N-乙胺、N-甲基-N-丁胺、N-甲基-N-十二烷基胺、N-甲基-N-十八烷基胺、N-乙基-N-十六烷基胺、N-乙基-N-十八烷基胺、N-丙基-N-十六烷基胺、N-丙基-N-苄胺等混合仲胺。它们可以使用1种或2种以上。
作为所添加的二胺的具体例,可列举出1,2-乙二胺、1,3-丙二胺、1,4-丁二胺、1,5-戊二胺、1,6-己二胺、1,7-庚二胺、1,8-辛二胺、1,9-壬二胺、1,10-癸二胺、1,11-十一烷二胺、1,12-十二烷二胺、1,13-十三烷二胺、1,14-十四烷二胺、1,15-十五烷二胺、1,16-十六烷二胺、1,17-十七烷二胺、1,18-十八烷二胺、2-甲基-1,5-戊二胺、3-甲基-1,5-戊二胺、2-甲基-1,8-辛二胺、2,2,4-三甲基-1,6-己二胺、2,4,4-三甲基-1,6-己二胺、5-甲基-1,9-壬二胺等脂肪族二胺;1,3-双(氨基甲基)环己烷、1,4-双(氨基甲基)环己烷、双(4-氨基环己基)甲烷、2,2-双(4-氨基环己基)丙烷、双(3-甲基-4-氨基环己基)甲烷、2,2-双(3-甲基-4-氨基环己基)丙烷、5-氨基-2,2,4-三甲基-1-环戊烷甲胺、5-氨基-1,3,3-三甲基环己烷甲胺、双(氨基丙基)哌嗪、双(氨基乙基)哌嗪、2,5-双(氨基甲基)降冰片烷、2,6-双(氨基甲基)降冰片烷、3,8-双(氨基甲基)三环癸烷、4,9-双(氨基甲基)三环癸烷等脂环式二胺;间苯二甲胺、对苯二甲胺等芳香族二胺。它们可以使用1种或2种以上。
作为所添加的三胺、四胺的具体例,可列举出1,2,3-三氨基丙烷、1,2,3-三氨基-2-甲基丙烷、1,2,4-三氨基丁烷、1,2,3,4-四氨基丁烷、1,3,5-三氨基环己烷、1,2,4-三氨基环己烷、1,2,3-三氨基环己烷、1,2,4,5-四氨基环己烷、1,3,5-三氨基苯、1,2,4-三氨基苯、1,2,3-三氨基苯、1,2,4,5-四氨基苯、1,2,4-三氨基萘、2,5,7-三氨基萘、2,4,6-三氨基吡啶、1,2,7,8-四氨基萘、1,4,5,8-四氨基萘。它们可以使用1种或2种以上。
所添加的多胺只要是具有多个伯氨基(-NH2)和/或仲氨基(-NH-)的化合物即可,可列举出例如聚亚烷基亚胺、聚亚烷基多胺、聚乙烯胺、聚烯丙胺等。具备活性氢的氨基是多胺的反应位点。
聚亚烷基亚胺通过使亚乙基亚胺、亚丙基亚胺等亚烷基亚胺发生离子聚合的方法或者使烷基噁唑啉聚合后再使该聚合物发生部分水解或完全水解的方法等来制造。作为聚亚烷基多胺,可列举出例如二亚乙基三胺、三亚乙基四胺、五亚乙基六胺、或者乙二胺与多官能化合物的反应物等。聚乙烯胺可通过例如使N-乙烯基甲酰胺发生聚合而制成聚(N-乙烯基甲酰胺)后,将该聚合物用盐酸等酸进行部分水解或完全水解来获得。聚烯丙胺通常通过使烯丙胺单体的盐酸盐发生聚合后,去除盐酸来获得。它们可以使用1种或2种以上。这些之中,优选为聚亚烷基亚胺。
作为聚亚烷基亚胺,可列举出通过常规方法将亚乙基亚胺、亚丙基亚胺、1,2-亚丁基亚胺、2,3-亚丁基亚胺、1,1-二甲基亚乙基亚胺等碳原子数为2以上且8以下的亚烷基亚胺中的1种或2种以上进行聚合而得到的均聚物、共聚物。这些之中,更优选为聚亚乙基亚胺。聚亚烷基亚胺可以是以亚烷基亚胺作为原料并使其开环聚合而得到的包含伯胺、仲胺和叔胺的支链型聚亚烷基亚胺;或者以烷基噁唑啉作为原料并使其聚合而得到的仅包含伯胺和仲胺的直链型聚亚烷基亚胺;交联成三维状的结构中的任一者。进而,可以为使乙二胺、丙二胺、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、二亚丙基三胺、三亚丙基四胺、二(六亚甲基)三胺、氨基丙基乙二胺、双氨基丙基乙二胺的单体发生共聚而得的物质。由于所包含的氮原子上的活性氢原子的反应性,聚亚烷基亚胺通常除了具有叔氨基之外,还具有包含活性氢原子的伯氨基、仲氨基(亚氨基)。
聚亚烷基亚胺中的氮原子数没有特别限定,优选为4以上且3000以下、更优选为8以上且1500以下、进一步优选为11以上且500以下。另外,聚亚烷基亚胺的数均分子量优选为100以上且20000以下、更优选为200以上且10000以下、进一步优选为500以上且8000以下。
另一方面,作为所添加的羧酸类,可列举出乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、癸酸、壬酸、十一烷酸、月桂酸、十三烷酸、肉豆蔻酸、肉豆寇烯酸、棕榈酸、硬脂酸、油酸、亚油酸、花生酸、山嵛酸、芥酸等脂肪族单羧酸;环己烷羧酸、甲基环己烷羧酸等脂环式单羧酸;苯甲酸、甲苯甲酸、乙基苯甲酸、苯基乙酸等芳香族单羧酸;丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸、十六烷二酸、十六碳烯二酸、十八烷二酸、十八碳烯二酸、二十烷二酸、二十碳烯二酸、二十二烷二酸、二甘醇酸、2,2,4-三甲基己二酸、2,4,4-三甲基己二酸等脂肪族二羧酸;1,3-环己烷二羧酸、1,4-环己烷二羧酸、降冰片烷二羧酸等脂环式二羧酸;对苯二甲酸、间苯二甲酸、邻苯二甲酸、间苯二亚甲基二羧酸、对苯二亚甲基二羧酸、1,4-萘二甲酸、2,6-萘二甲酸、2,7-萘二甲酸等芳香族二羧酸;1,2,4-丁烷三羧酸、1,3,5-戊烷三羧酸、1,2,6-己烷三羧酸、1,3,6-己烷三羧酸、1,3,5-环己烷三羧酸、均苯三酸等三羧酸。它们可以使用1种或2种以上。
所添加的胺类的用量考虑想要制造的聚酰胺(A1)的末端氨基浓度、末端羧基浓度和相对粘度,通过公知的方法来适当决定。通常,从获得充分的反应性、容易制造具有期望粘度的聚酰胺的观点出发,相对于聚酰胺原料1摩尔(构成重复单元的单体或单体单元1摩尔),胺类的添加量优选为0.5meq/摩尔以上且20meq/摩尔以下、更优选为1.0meq/摩尔以上且10meq/摩尔以下(关于氨基的当量(eq),将与羧基以1:1发生反应而形成酰胺基的氨基量作为1当量。)。
对于聚酰胺(A1)而言,在上述例示的胺类之中,为了满足末端基团浓度的条件,优选在聚合时添加二胺和/或多胺,从抑制凝胶的产生的观点出发,更优选在聚合时添加选自由脂肪族二胺、脂环式二胺和聚亚烷基亚胺组成的组中的至少1种。
另外,聚酰胺(A1)只要在满足上述末端基团浓度的范围内,则还优选为包含末端基团浓度不同的2种以上脂肪族聚酰胺的脂肪族聚酰胺混合物。在该情况下,脂肪族聚酰胺混合物的末端氨基浓度、末端羧基浓度根据构成混合物的脂肪族聚酰胺的末端氨基浓度、末端羧基浓度及其配混比例来决定。
[弹性体聚合物(A2)]
脂肪族聚酰胺组合物(A)含有弹性体聚合物(A2),所述弹性体聚合物(A2)包含由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元(以下有时称为弹性体聚合物(A2))。
作为弹性体聚合物(A2),可列举出(乙烯和/或丙烯)/α-烯烃系共聚物、(乙烯和/或丙烯)/(α,β-不饱和羧酸酯)系共聚物等,它们可以使用1种或2种以上。
前述(乙烯和/或丙烯)/α-烯烃系共聚物是将乙烯和/或丙烯与碳原子数为3以上的α-烯烃共聚得到的聚合物,作为碳原子数为3以上的α-烯烃,可列举出丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯、1-十一碳烯、1-十二碳烯、1-十三碳烯、1-十四碳烯、1-十五碳烯、1-十六碳烯、1-十七碳烯、1-十八碳烯、1-十九碳烯、1-二十碳烯、3-甲基-1-丁烯、3-甲基-1-戊烯、3-乙基-1-戊烯、4-甲基-1-戊烯、4-甲基-1-己烯、4,4-二甲基-1-己烯、4,4-二甲基-1-戊烯、4-乙基-1-己烯、3-乙基-1-己烯、9-甲基-1-癸烯、11-甲基-1-十二碳烯、12-乙基-1-十四碳烯等。它们可以使用1种或2种以上。另外,可以共聚有1,3-丁二烯、1,4-戊二烯、1,4-己二烯、1,5-己二烯、1,4-辛二烯、1,5-辛二烯、1,6-辛二烯、1,7-辛二烯、2-甲基-1,5-己二烯、6-甲基-1,5-庚二烯、7-甲基-1,6-辛二烯、4-乙叉基-8-甲基-1,7-壬二烯、4,8-二甲基-1,4,8-癸三烯(DMDT)、二环戊二烯、环己二烯、环辛二烯、5-乙烯基降冰片烯、5-乙叉基-2-降冰片烯、5-亚甲基-2-降冰片烯、5-异丙叉基-2-降冰片烯、6-氯甲基-5-异丙烯基-2-降冰片烯、2,3-二异丙叉基-5-降冰片烯、2-乙叉基-3-异丙叉基-5-降冰片烯、2-丙烯基-2,5-降冰片二烯等非共轭二烯的多烯。它们可以使用1种或2种以上。
前述(乙烯和/或丙烯)/(α,β-不饱和羧酸酯)系共聚物是将乙烯和/或丙烯与α,β-不饱和羧酸酯单体进行共聚而得的聚合物,作为α,β-不饱和羧酸酯单体,可列举出丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸戊酯、甲基丙烯酸戊酯、丙烯酸己酯、甲基丙烯酸己酯、丙烯酸庚酯、甲基丙烯酸庚酯、丙烯酸辛酯、甲基丙烯酸辛酯、丙烯酸壬酯、甲基丙烯酸壬酯、丙烯酸癸酯、甲基丙烯酸癸酯、丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯、丙烯酸羟基乙酯、甲基丙烯酸羟基乙酯、马来酸单甲酯、衣康酸单甲酯、马来酸二甲酯、衣康酸二甲酯等。它们可以使用1种或2种以上。
作为弹性体聚合物(A2)中的具有羧基的不饱和化合物,可列举出丙烯酸、甲基丙烯酸、马来酸、富马酸、衣康酸、巴豆酸、中康酸、柠康酸、戊烯二酸、顺式-4-环己烯-1,2-二羧酸、内双环-[2.2.1]-5-庚烯-2,3-二羧酸、以及这些羧酸的金属盐等α,β-不饱和羧酸。作为具有酸酐基的不饱和化合物,可列举出马来酸酐、衣康酸酐、柠康酸酐、内双环-[2.2.1]-5-庚烯-2,3-二羧酸酐等具有α,β-不饱和键的二羧酸酐。它们可以使用1种或2种以上。这些之中,优选为具有α,β-不饱和键的二羧酸酐,更优选为马来酸酐、衣康酸酐。
从表现出与前述聚酰胺(A1)的良好相容性、以及所得脂肪族聚酰胺组合物(A)的流动性的观点出发,弹性体聚合物(A2)中的羧基和/或酸酐基浓度优选为25μeq/g以上且200μeq/g以下、更优选为50μeq/g以上且150μeq/g以下。
另外,弹性体聚合物(A2)中的羧基和/或酸酐基浓度可通过使用将该弹性体聚合物溶解于甲苯溶液,进而添加乙醇而制备的试样溶液,并以酚酞作为指示剂,利用0.1N的KOH乙醇溶液进行滴定来测定。
[增塑剂(A3)]
从对所得层叠管赋予柔软性的观点出发,脂肪族聚酰胺组合物(A)还优选包含增塑剂(A3)。
增塑剂(A3)不含硫原子,且含有对羟基苯甲酸和/或邻羟基苯甲酸与碳原子数为12以上且24以下的直链状和/或支链状烷基脂肪族醇形成的酯结构(以下有时称为增塑剂(A3))。
作为增塑剂(A3),包含对羟基苯甲酸和/或邻羟基苯甲酸与具有直链或支链的碳原子数为12以上且24以下的脂肪族醇形成的酯。作为酯的原料的脂肪族醇可以具有直链或支链中的任一者。另外,脂肪族醇的碳原子数优选为12以上且22以下。如果碳原子数为12以上且22以下,则饱和醇、不饱和醇均可使用。所述醇与羟基苯甲酸形成的酯与聚酰胺树脂的相容性良好,造成表面粘腻的情况少,且挥发性低,增塑化效果也变得充分。
作为增塑剂(A3),可列举出例如邻羟基苯甲酸十二烷基酯、对羟基苯甲酸十二烷基酯、邻羟基苯甲酸十三烷基酯、对羟基苯甲酸十三烷基酯、邻羟基苯甲酸十四烷基酯、对羟基苯甲酸十四烷基酯、邻羟基苯甲酸十五烷基酯、对羟基苯甲酸十五烷基酯、邻羟基苯甲酸十六烷基酯、对羟基苯甲酸十六烷基酯、邻羟基苯甲酸十七烷基酯、对羟基苯甲酸十七烷基酯、邻羟基苯甲酸十八烷基酯、对羟基苯甲酸十八烷基酯、邻羟基苯甲酸十九烷基酯、对羟基苯甲酸十九烷基酯、邻羟基苯甲酸二十烷基酯、对羟基苯甲酸二十烷基酯、邻羟基苯甲酸二十一烷基酯、对羟基苯甲酸二十一烷基酯、邻羟基苯甲酸二十二烷基酯、对羟基苯甲酸二十二烷基酯、邻羟基苯甲酸二十三烷基酯、对羟基苯甲酸二十三烷基酯、邻羟基苯甲酸二十四烷基酯、对羟基苯甲酸二十四烷基酯、邻羟基苯甲酸己基癸酯、对羟基苯甲酸己基癸酯、邻羟基苯甲酸乙基癸酯、对羟基苯甲酸乙基癸酯、邻羟基苯甲酸乙基十二烷基酯、对羟基苯甲酸乙基十二烷基酯、邻羟基苯甲酸辛基辛酯、对羟基苯甲酸辛基辛酯、邻羟基苯甲酸辛基十二烷基酯、对羟基苯甲酸辛基十二烷基酯、邻羟基苯甲酸癸基癸酯、对羟基苯甲酸癸基癸酯、邻羟基苯甲酸癸基十二烷基酯、对羟基苯甲酸癸基十二烷基酯等。它们可以使用1种或2种以上。这些之中,优选为对羟基苯甲酸2-己基癸酯(HDPB)、对羟基苯甲酸十六烷基酯(CEPB)。
脂肪族聚酰胺组合物(A)中的聚酰胺(A1)的含量相对于脂肪族聚酰胺组合物(A)100质量%为55质量%以上且95质量%以下,优选为60质量%以上且95质量%以下,更优选含有70质量%以上且89质量%以下。通过使聚酰胺(A1)的含量在前述范围内,能够使所得层叠管在高温时的破坏压强度等特性充分优异。与此相对,若聚酰胺(A1)的含量小于前述下限值,则无法充分获得层叠管在高温时的破坏压强度。另一方面,若聚酰胺(A1)的含量超过前述上限值,则无法充分获得层叠管的柔软性、低温冲击性。
脂肪族聚酰胺组合物(A)中的弹性体聚合物(A2)的含量相对于脂肪族聚酰胺组合物(A)100质量%为5质量%以上且30质量%以下,优选为7质量%以上且25质量%以下,更优选为10质量%以上且20质量%以下。通过使弹性体聚合物(A2)的含量在前述范围内,能够维持所得层叠管的机械特性,且使柔软性、低温耐冲击性优异。与此相对,若弹性体聚合物(A2)的含量小于前述下限值,则无法充分获得层叠管的柔软性、低温耐冲击性。另一方面,若弹性体聚合物(A2)的含量超过前述上限值,则无法充分获得层叠管在高温时的破坏压强度、其它机械特性。
脂肪族聚酰胺组合物(A)中的增塑剂(A3)的含量相对于脂肪族聚酰胺组合物(A)100质量%为0质量%以上且15质量%以下,优选为1质量%以上且10质量%以下。通过使增塑剂(A3)的含量处于前述适当范围内,能够维持所得层叠管的高温破坏压强度,且使层叠管的柔软性优异。与此相对,若增塑剂(A3)的含量超过前述上限值,则有时无法充分获得层叠管在高温时的破坏压强度。
脂肪族聚酰胺组合物(A)的按照ISO 178而测得的弯曲弹性模量为400MPa以上且1000MPa以下,优选为450MPa以上且950MPa以下,更优选为500MPa以上且900MPa以下。通过使脂肪族聚酰胺组合物(A)的弯曲弹性模量处于前述范围内,能够维持所得层叠管的高温破坏压强度,且使层叠管的柔软性优异。脂肪族聚酰胺组合物(A)的弯曲弹性模量可通过适当变更弹性体聚合物(A2)、根据需要的增塑剂(A3)的添加量来调整。
脂肪族聚酰胺组合物(A)的制造方法没有特别限定,可根据需要配混各种添加剂,并采用以往已知的各种方法。例如,可以通过下述方法等来制造:使用转鼓、混合器,将聚酰胺(A1)、弹性体聚合物(A2)和增塑剂(A3)与根据需要而添加的其它成分一同,以使粒料彼此成为前述混合比例的方式均匀地干混的方法;将聚酰胺(A1)、弹性体聚合物(A2)和增塑剂(A3)与根据需要而添加的其它成分一同预先干混,并进行熔融混炼的方法;将聚酰胺(A1)、弹性体聚合物(A2)和增塑剂(A3)与根据需要而添加的其它成分一同预先干混,并分别将它们各自进行喂料,进行熔融混炼的方法等。熔融混炼可以使用单螺杆挤出机、双螺杆挤出机、捏合机、班伯里密炼机等混炼机来进行。
进而,可根据需要向脂肪族聚酰胺组合物(A)中添加抗氧化剂、热稳定剂、紫外线吸收剂、光稳定化剂、润滑剂、无机填充剂、抗静电剂、阻燃剂、结晶促进剂、着色剂等。
2.(b)层
本发明的层叠管的(b)层包含改性聚烯烃(B)。
改性聚烯烃(B)具有由基于碳原子数为2以上且10以下的α-烯烃的单体衍生的单元,且按照ISO 11357-3而测得的熔点为130℃以上(以下有时称为改性聚烯烃(B))。
构成改性聚烯烃(B)的聚烯烃(B1)是以由基于碳原子数为2以上且10以下的α-烯烃的单体衍生的单元作为主成分的聚合物,优选为以由基于碳原子数为2以上且8以下的α-烯烃的单体衍生的单元作为主成分的聚合物。通过使改性聚烯烃(B)中的由基于α-聚烯烃的单体衍生的单元的碳原子数在前述范围内,能够使所得层叠管的低分子量物、离子成分的耐溶出性特别优异。
在共聚物的情况下,成为主成分的由基于碳原子数为2以上且10以下的α-聚烯烃的单体衍生的单元的含量相对于全部聚合单元100摩尔%优选为60摩尔%以上、更优选为70摩尔%以上、进一步优选为90摩尔%以上。通过使由基于碳原子数为2以上且10以下的α-聚烯烃的单体衍生的单元的含量为前述值以上,从而使所得层叠管的柔软性充分,且使低分子量物、离子成分的耐溶出性更优异。
作为基于碳原子数为2以上且10以下的α-烯烃的单体,可列举出乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯、2-丁烯、3-甲基-1-丁烯、3-甲基-1-戊烯、3-乙基-1-戊烯、4-甲基-1-戊烯、4,4-二甲基-1-戊烯、4-甲基-1-己烯、4,4-二甲基-1-己烯、4,4-二甲基-1-戊烯、4-乙基-1-己烯、3-乙基-1-己烯等。它们可以使用1种或2种以上。这些之中,优选为基于碳原子数为2以上且8以下的α-烯烃的单体。
只要在不损害所得层叠管的各个优异特性的范围内,则可以包含除了基于碳原子数为2以上且10以下的α-烯烃的单体之外的例如苯乙烯类、非共轭二烯类、环状烯烃类、含氧原子的烯烃类等其它单体。作为苯乙烯类,可列举出苯乙烯、邻甲基苯乙烯、间甲基苯乙烯、对甲基苯乙烯、1,5-二甲基苯乙烯、2,4-二甲基苯乙烯、乙烯基萘、乙烯基蒽、4-丙基苯乙烯、4-环己基苯乙烯、4-十二烷基苯乙烯、2-乙基-4-苄基苯乙烯、4-(苯基丁基)苯乙烯等。作为非共轭二烯类,可列举出1,3-丁二烯、1,4-戊二烯、1,4-己二烯、1,5-己二烯、1,4-辛二烯、1,5-辛二烯、1,6-辛二烯、1,7-辛二烯、2-甲基-1,5-己二烯、6-甲基-1,5-庚二烯、7-甲基-1,6-辛二烯、4-乙叉基-8-甲基-1,7-壬二烯、4,8-二甲基-1,4,8-癸三烯(DMDT)等。作为环状烯烃类,可列举出二环戊二烯、环己二烯、环辛二烯、5-乙烯基降冰片烯、5-乙叉基-2-降冰片烯、5-亚甲基-2-降冰片烯、5-异丙叉基-2-降冰片烯、6-氯甲基-5-异丙烯基-2-降冰片烯、2,3-二异丙叉基-5-降冰片烯、2-乙叉基-3-异丙叉基-5-降冰片烯、2-丙烯基-2,5-降冰片二烯等。作为含氧原子的烯烃类,可列举出己烯醇、己烯酸、辛烯酸甲酯等。由其它单体衍生的单元的含量相对于全部聚合单元100摩尔%优选小于40摩尔%、更优选小于30摩尔%、进一步优选小于10摩尔%。
作为这些聚烯烃(B1),优选为聚乙烯、聚丙烯、聚丁烯-1、聚(4-甲基戊烯-1);乙烯、丙烯、1-丁烯或4-甲基戊烯-1与能够共聚的单体形成的α-烯烃共聚物等结晶性聚烯烃。它们可以使用1种或2种以上。这些之中,更优选为聚丙烯均聚物、丙烯与20摩尔%以下的其它α-烯烃形成的无规共聚物、丙烯与30摩尔%以下的其它α-烯烃形成的嵌段共聚物。
聚烯烃(B1)的制造也可通过以往公知的任意方法来进行,可以使用例如钛系催化剂、钒系催化剂、茂金属催化剂等来进行聚合。另外,聚烯烃(B1)可以是树脂和弹性体中的任意形态,全同立构结构、间同立构结构这两者均可使用,针对立构规整性没有特别限定。在聚烯烃(B1)为共聚物的情况下,可以为交替共聚、无规共聚、嵌段共聚中的任一者。
另外,改性聚烯烃(B)的按照ISO 11357-3而测得的熔点为130℃以上,优选为145℃以上。通过使改性聚烯烃(B)的熔点为前述值以上,所得层叠管在高温时的破坏压强度、对化学溶液的长期耐性优异。
改性聚烯烃(B)优选含有由不饱和化合物衍生的单元,所述不饱和化合物具有选自由羧基或其衍生物、羟基、环氧基、氨基、酰胺基、酰亚胺基、腈基、硫醇基和异氰酸酯基组成的组中的至少1种官能团。通过使改性聚烯烃(B)含有由具有前述官能团的不饱和化合物衍生的单元,能够使所得层叠管中的(a)层与(b)层的层间粘接性提高。
作为具有羧基的不饱和化合物,可列举出例如丙烯酸、甲基丙烯酸、马来酸、富马酸、四氢邻苯二甲酸、衣康酸、柠康酸、巴豆酸、异巴豆酸、降冰片烯二羧酸、双环[2,2,1]庚-2-烯-5,6-二羧酸等不饱和羧酸或其衍生物(例如酸酐、酰卤、酰胺、酰亚胺、酯等)。它们可以使用1种或2种以上。
作为具有羧基的不饱和化合物的衍生物,可列举出例如马来酰氯、马来酰亚胺、马来酸酐、衣康酸酐、柠康酸酐、四氢邻苯二甲酸酐、双环[2,2,1]庚-2-烯-5,6-二羧酸酐、马来酸二甲酯、马来酸单甲酯、马来酸二乙酯、富马酸二乙酯、衣康酸二甲酯、柠康酸二乙酯、四氢邻苯二甲酸二甲酯、双环[2,2,1]庚-2-烯-5,6-二羧酸二甲酯等。它们可以使用1种或2种以上。
作为具有羟基的不饱和化合物,可列举出例如丙烯酸羟基乙酯、甲基丙烯酸羟基乙酯、丙烯酸羟基丙酯、甲基丙烯酸羟基丙酯、甘油单(甲基)丙烯酸酯、季戊四醇单(甲基)丙烯酸酯等含有羟基的(甲基)丙烯酸酯;10-十一碳烯-1-醇、1-辛烯-3-醇、甘油单烯丙醚、烯丙醇、2-丁烯-1,4-二醇、甘油单醇等。它们可以使用1种或2种以上。
作为具有环氧基的不饱和化合物,可列举出例如丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯等不饱和羧酸的缩水甘油酯;或者马来酸、富马酸等不饱和二羧酸的单缩水甘油酯(单缩水甘油酯情况下的烷基的碳原子数为1以上且12以下)、对苯乙烯羧酸的烷基缩水甘油酯、2-甲基烯丙基缩水甘油醚、3,4-环氧-1-丁烯、3,4-环氧-3-甲基-1-丁烯、3,4-环氧-1-戊烯、3,4-环氧-3-甲基-1-戊烯、5,6-环氧-1-己烯、乙烯基环己烯单氧化物等。它们可以使用1种或2种以上。
作为具有氨基的不饱和化合物,可列举出例如丙烯酸氨基甲酯、甲基丙烯酸氨基甲酯、甲基丙烯酸二甲基氨基乙酯、丙烯酸氨基丙酯、甲基丙烯酸氨基丙酯、甲基丙烯酸环己基氨基乙酯等丙烯酸或甲基丙烯酸的氨基烷基酯系衍生物类;N-乙烯基二乙胺、N-乙酰基乙烯基胺等乙烯基胺系衍生物类。它们可以使用1种或2种以上。
作为具有酰胺基的不饱和化合物,可列举出例如丙烯酰胺、甲基丙烯酰胺、N-甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N,N-二甲基氨基丙基丙烯酰胺等丙烯酰胺系衍生物。它们可以使用1种或2种以上。
作为具有酰亚胺基的不饱和化合物,可列举出例如N-丙烯酰氧基乙基-1,2,3,6-四氢邻苯二甲酰亚胺(东亚合成株式会社制,商品名:ARONIX TO-1428)、N-丙烯酰氧基乙基六氢邻苯二甲酰亚胺(东亚合成株式会社制、商品名:ARONIX TO-1429)、N-丙烯酰氧基乙基-3,4,5,6-四氢邻苯二甲酰亚胺(东亚合成株式会社制、商品名:ARONIX TO-1534)等。它们可以使用1种或2种以上。
作为具有腈基的不饱和化合物,可列举出例如丙烯腈、甲基丙烯腈、5-己烯腈、5-甲基-5-己烯腈、甲基-2-氰基丙烯酸酯、乙基-2-氰基丙烯酸酯、丁基-2-氰基丙烯酸酯、环己基-2-氰基丙烯酸酯、2-乙基己基-2-氰基丙烯酸酯、乙氧基乙基-2-氰基丙烯酸酯等。它们可以使用1种或2种以上。
作为具有硫醇基的不饱和化合物,可列举出例如2-巯基乙醇、乙二硫醇、1,2-丙二硫醇、1,3-丙二硫醇、对羟基苯硫酚、3-巯基-1,2-丙二硫醇、1,4-丁二硫醇、2-巯基***、2-巯基乙硫醚等脂肪族或芳香族的巯基醇或二硫醇等含硫醇基的化合物与丙烯酸或甲基丙烯酸形成的酯类等。它们可以使用1种或2种以上。
作为具有异氰酸酯基的不饱和化合物,可列举出例如2-甲基丙烯酰氧基乙基异氰酸酯(昭和电工株式会社制、商品名:Karenz MOI)、2-丙烯酰氧基乙基异氰酸酯(昭和电工株式会社制、商品名:Karenz AOI)等。它们可以使用1种或2种以上。
这些之中,优选为马来酸酐、衣康酸酐、柠康酸酐、四氢邻苯二甲酸酐、内双环-[2.2.1]-5-庚烯-2,3-二羧酸酐、丙烯酸、甲基丙烯酸、丙烯酸羟基乙酯、甲基丙烯酸羟基乙酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸氨基丙酯,更优选为马来酸酐、衣康酸酐、柠康酸酐、四氢邻苯二甲酸酐、内双环-[2.2.1]-5-庚烯-2,3-二羧酸酐这些二羧酸酐,进一步优选为马来酸酐。
作为向聚烯烃中导入由具有前述官能团的不饱和化合物衍生的单元的方法,可以采用公知的方法。可例示出例如对聚烯烃(B1)接枝共聚具有前述官能团的不饱和化合物的方法;将烯烃单体与具有前述官能团的不饱和化合物进行自由基共聚的方法等,优选为对聚烯烃(B1)接枝共聚具有前述官能团的不饱和化合物的方法。
关于这种改性聚烯烃(B),为了利用具有前述官能团的不饱和化合物使聚烯烃(B1)进行接枝改性,可以采用公知的各种方法。例如有下述方法等:使改性前的聚烯烃熔融,添加具有前述官能团的不饱和化合物并使其接枝共聚的方法;或者使其溶解于溶剂,添加接枝单体并使其接枝共聚的方法等。在任意情况下,为了高效地接枝聚合具有前述官能团的不饱和化合物,优选在自由基聚合引发剂的存在下实施反应。
所使用的自由基聚合引发剂只要促进聚烯烃主链与具有前述官能团的不饱和化合物的反应,就没有特别限定,优选为有机过氧化物、有机过酸酯。具体而言,可列举出过氧化苯甲酰、过氧化二氯苯甲酰、过氧化二异丙苯、二叔丁基过氧化物、2,5-二甲基-2,5-二(过氧化苯甲酸酯)己炔-3、1,4-双(叔丁基过氧化异丙基)苯、过氧化月桂酰、过氧乙酸叔丁酯、2,5-二甲基-2,5-二(叔丁基过氧化)己炔-3、2,5-二甲基-2,5-二(叔丁基过氧化)己烷、苯甲酸叔丁酯、过氧苯基乙酸叔丁酯、过氧异丁酸叔丁酯、过氧仲辛酸叔丁酯、过氧特戊酸叔丁酯、过氧特戊酸枯基酯、过氧二乙基乙酸叔丁酯等,其它偶氮化合物可列举出例如偶氮双异丁腈、二甲基偶氮异丁腈等。它们可以使用1种或2种以上。这些之中,更优选为过氧化二异丙苯、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、2,5-二甲基-2,5-二(叔丁基过氧化)己烷、1,4-双(叔丁基过氧化异丙基)苯等二烷基过氧化物。
自由基聚合引发剂优选以相对于聚烯烃(B1)100质量份为0.001~10质量份左右的量来使用。
具有前述官能团的不饱和化合物的接枝量相对于聚烯烃(B1)100质量%优选为0.05质量%以上且20质量%以下、更优选为0.05质量%以上且10质量%以下、进一步优选为0.05质量%以上且5质量%以下、特别优选为0.05质量%以上且3质量%以下。另外,聚烯烃(B1)的接枝量是从聚烯烃(B1)中去除具有前述官能团的不饱和化合物后测得的净重接枝量。另外,接枝量可通过13C-NMR、1H-NMR测定等公知手段来进行。作为具有前述官能团的不饱和化合物,在使用不饱和羧酸及其酸酐等具有酸性官能团的单体的情况下,作为成为向聚烯烃(B1)导入的官能团量的基准的量,也可以使用例如酸值。另外,作为具有前述官能团的不饱和化合物而使用马来酸酐时,也可以使用红外分光光度计,基于通常在1780~1790cm-1附近检测到的马来酸酐的羰基的吸收光谱来求出接枝量。
从获得具有良好的机械特性、对化学溶液的长期耐性和层间粘接性的层叠管的观点出发,改性聚烯烃(B)优选为马来酸酐改性聚丙烯。马来酸酐改性聚丙烯中的聚丙烯的含量相对于马来酸酐改性聚丙烯100质量%优选为50质量%以上且99.5质量%以下、更优选为60质量%以上且97质量%以下、进一步优选为70质量%以上且95质量%以下。通过使马来酸酐改性聚丙烯中的聚丙烯含量为前述值以上,能够使所得层叠管的柔软性充分,且使低分子量物、离子成分的耐溶出性更优异。
改性聚烯烃(B)在230℃/2160g的条件下按照ISO 1133而测得的MFR值优选为1.0g/10min以上且10.0g/10min以下、更优选为1.5g/10min以上且7.0g/10min以下。通过使改性聚烯烃(B)的MFR值在前述范围内,能够使所得层叠管的成形稳定性更高。
另外,改性聚烯烃(B)的按照ISO 1183-3而测得的密度优选为0.85g/cm3以上、更优选为0.85m3以上0.95m3以下。通过使改性聚烯烃(B)的密度在前述范围内,能够使所得层叠管的柔软性、破坏压强度充分优异。
改性聚烯烃(B)也可根据需要而含有各种添加剂。作为这种添加剂的例子,可列举出导电性填料、抗氧化剂、热稳定剂、紫外线吸收剂、光稳定化剂、润滑剂、无机质填充材料、抗静电剂、阻燃剂、结晶促进剂、增塑剂、着色剂、润滑剂和其它热塑性树脂等。
3.(c)层
层叠管优选还具有(c)层。
层叠管的(c)层包含聚烯烃(C)。
聚烯烃(C)具有由基于碳原子数为2以上且10以下的α-烯烃的单体衍生的单元,且按照ISO 11357-3而测得的熔点为120℃以上,按照ISO 527而测得的拉伸屈服应力为20MPa以上,按照ISO 179/1eA而测得的23℃下的夏比冲击强度(带缺口)为40kJ/m2以上(以下有时称为聚烯烃(C))。
聚烯烃(C)是以由基于碳原子数为2以上且10以下的α-烯烃的单体衍生的单元作为主成分的聚合物,优选为以由基于碳原子数为2以上且8以下的α-烯烃的单体衍生的单元作为主成分的聚合物。通过使聚烯烃(C)中的由基于α-聚烯烃的单体衍生的单元的碳原子数处于前述范围内,能够使所得层叠管的柔软性充分,且使抗化学溶液透过性、化学溶液长期耐性更优异。
作为聚烯烃(C),可列举出改性聚烯烃(B)的说明中记载的聚烯烃(B1)。这些之中,从获得具有良好的机械特性、对化学溶液的长期耐性的层叠管的观点出发,优选为(1)乙烯均聚物(制法可以是低压法、高压法中的任一者);(2)乙烯99摩尔%以下且80摩尔%以上与丙烯1摩尔%以上且20摩尔%以下的乙烯/丙烯共聚物、优选为乙烯95摩尔%以下且85摩尔%以上与丙烯5摩尔%以上且15摩尔%以下的乙烯/丙烯共聚物;(3)乙烯99摩尔%以下且80摩尔%以下与1-丁烯1摩尔%以上且20摩尔%以下的乙烯/1-丁烯共聚物、优选为乙烯95摩尔%以下且85摩尔%以上与1-丁烯5摩尔%以上且15摩尔%以下的乙烯/1-丁烯共聚物;(4)乙烯99摩尔%以下且80摩尔%以上与1-辛烯1摩尔%以上且20摩尔%以下的乙烯/1-辛烯共聚物、优选为乙烯97摩尔%以下且85摩尔%以上与1-辛烯3摩尔%以上且15摩尔%以下的乙烯/1-辛烯共聚物;(5)乙烯与10摩尔%以下的其它α-烯烃(不包括丙烯、1-丁烯、1-辛烯)或乙烯基单体(例如乙酸乙烯酯、丙烯酸乙酯等)的共聚物等乙烯系共聚物;(6)丙烯均聚物;(7)丙烯与30摩尔%以下的其它α-烯烃的无规共聚物、优选为丙烯与20摩尔%以下的其它α-烯烃的无规共聚物;(8)丙烯与40摩尔%以下的其它α-烯烃的嵌段共聚物;(9)1-丁烯均聚物、(10)1-丁烯与10摩尔%以下的其它α-烯烃的无规共聚物;(11)4-甲基-1-戊烯均聚物;(12)4-甲基-1-戊烯与20摩尔%以下的其它α-烯烃的无规共聚物等均聚物或共聚物,更优选为(6)丙烯均聚物;(7)丙烯与20摩尔%以下的其它α-烯烃的无规共聚物;(8)丙烯与40摩尔%以下的其它α-烯烃的嵌段共聚物;(9)1-丁烯均聚物;(10)1-丁烯与10摩尔%以下的其它α-烯烃的无规共聚物;(11)4-甲基-1-戊烯均聚物;(12)4-甲基-1-戊烯与20摩尔%以下的其它α-烯烃的无规共聚物等均聚物或共聚物。
聚烯烃(C)的按照ISO 11357-3而测得的熔点为120℃以上,优选为125℃以上。通过使聚烯烃(C)的熔点为前述值以上,能够使所得层叠管在高温时的破坏压强度、对化学溶液的长期耐性更优异。
另外,聚烯烃(C)的按照ISO 527而测得的拉伸屈服应力为20MPa以上,优选为25MPa以上。
进而,聚烯烃(C)的按照ISO 179/1eA而测得的23℃下的夏比冲击强度(带缺口)为40kJ/m2以上,优选为45kJ/m2以上。通过使聚烯烃(C)的拉伸屈服应力、23℃下的夏比冲击强度(带缺口)为前述值以上,能够使所得层叠管的低温耐冲击性、高温时的破坏压强度更优异。
聚烯烃(C)的制造也可通过以往公知的任意方法来进行,可使用例如钛系催化剂、钒系催化剂、茂金属催化剂等来进行聚合。另外,聚烯烃(C)可以是树脂和弹性体中的任意形态,全同立构结构、间同立构结构这两者均可使用,针对立构规整性没有特别限定。在聚烯烃(C)为共聚物的情况下,可以是交替共聚、无规共聚、嵌段共聚中的任一者。
聚烯烃(C)也可根据需要而含有各种添加剂。作为这种添加剂的例子,可列举出导电性填料、抗氧化剂、热稳定剂、紫外线吸收剂、光稳定化剂、润滑剂、无机填充材料、抗静电剂、阻燃剂、结晶化促进剂、增塑剂、着色剂、润滑剂和其它热塑性树脂等。
[层叠管]
层叠管的第一方式包含(a)层和(b)层的2层以上,从外侧朝向内侧按照(a)层、(b)层的顺序进行配置,前述(a)层的厚度占据管的总壁厚的60%以上。
在第一方式的层叠管中,必须包含(a)层,能够获得机械物性、耐化学药品性和柔软性优异的层叠管。还必须包含(b)层,层叠管的化学溶液阻隔性、尤其是对于水蒸气、冷却液(LLC)和尿素溶液的阻隔性、长期化学溶液耐性变得良好。
层叠管中的(a)层的厚度占据管的总壁厚的60%以上且95%以下,优选为65%以上且90%以下、更优选为70%以上且85%以下。通过使(a)层的层厚度处于前述范围内,能够有效地发挥出前述的各特性。
层叠管中的(b)层的厚度占据管的总壁厚的超过5%且小于40%,优选超过10%且小于35%、更优选超过15%且小于30%。通过使(b)层的层厚度处于前述范围内,能够有效地发挥出前述的各特性。
作为优选的实施方式,(a)层与(b)层邻接配置。由此,能够获得层间粘接性优异的层叠管。
作为更优选的实施方式,(a)层配置于层叠管的最外层。通过使(a)层配置于最外层,能够获得高温时的破坏压强度优异的层叠管。(b)层配置于层叠管的最内层。通过使(b)层配置于最内层,能够抑制因与化学溶液接触而导致的低分子量物的溶出。
关于第一方式的层叠管中的整体的层数,只要是具有(a)层和(b)层的至少2层,就没有特别限定。进而,第一方式的层叠管除了具有(a)层和(b)层这2层之外,为了赋予进一步的功能或者获得经济方面有利的层叠管,也可以具有1层或2层以上的包含其它热塑性树脂的层。第一方式的层叠管的层数为2层以上,但从制管装置的机理判断,优选为8层以下、更优选为2层以上且7层以下。
层叠管的第二方式是在第一方式中进一步具有(c)层,包含3层以上。
在第二方式的层叠管中,必须包含(a)层,能够获得机械物性、耐化学药品性和柔软性优异的层叠管。还必须包含(b)层,层叠管的化学溶液阻隔性、尤其是对水蒸气、冷却液(LLC)和尿素溶液的阻隔性变得良好。另外,还必须包含(c)层,能够获得所得层叠管的低温耐冲击性、高温时的破坏压强度和长期化学溶液耐性优异的层叠管。
层叠管中的(a)层的厚度占据管的总壁厚的60%以上且95%以下,优选为65%以上且90%以下、更优选为70%以上且85%以下。通过使(a)层的层厚度处于前述范围内,能够有效地发挥出前述的各特性。
层叠管中的(b)层与(c)层的合计厚度占据管的总壁厚的超过5%且小于40%,优选超过10%且小于35%,更优选超过15%且小于30%。通过使(b)层与(c)层的合计厚度处于前述范围内,能够有效地发挥出前述的各特性。
作为优选的实施方式,(c)层配置在(b)层的内侧。即,优选从外侧朝向内侧按照(a)层、(b)层、(c)层的顺序进行配置。通过按照这样的顺序来配置层,能够使所得层叠管的防化学溶液透过性、化学溶液长期耐性更优异。
作为更优选的实施方式,(b)层与(c)层邻接配置。即,在层叠管中,(a)层配置于最外层,(b)层配置于中间层,(c)层配置于最内层。通过使(a)层配置于最外层,能够获得高温时的破坏压强度优异的层叠管。通过使(b)层配置于中间层,能够获得层间粘接性优异的层叠管。通过使(c)层配置于最内层,能够抑制因与化学溶液接触而导致的低分子量物的溶出。
关于第二方式的层叠管中的整体的层数,只要是具有(a)层、(b)层和(c)层的至少3层,就没有特别限定。进而,第二方式的层叠管除了具有(a)层、(b)层和(c)层这3层之外,为了赋予进一步的功能或者获得经济方面有利的层叠管,也可以具有1层或2层以上的包含其它热塑性树脂的层。第二方式的层叠管的层数为3层以上,但从制管装置的机理判断,优选为8层以下、更优选为3层以上且7层以下。
作为第一方式和第二方式的层叠管中的其它热塑性树脂,可列举出除聚酰胺(A1)、改性聚烯烃(B)、聚烯烃(C)之外的聚己酰胺(聚酰胺6)、聚己二酰乙二胺(聚酰胺26)、聚丁二酰丁二胺(聚酰胺44)、聚戊二酰丁二胺(聚酰胺45)、聚己二酰丁二胺(聚酰胺46)、聚辛二酰丁二胺(聚酰胺48)、聚壬二酰丁二胺(聚酰胺49)、聚癸二酰丁二胺(聚酰胺410)、聚丁二酰戊二胺(聚酰胺54)、聚戊二酰戊二胺(聚酰胺55)、聚己二酰戊二胺(聚酰胺56)、聚辛二酰戊二胺(聚酰胺58)、聚壬二酰戊二胺(聚酰胺59)、聚癸二酰戊二胺(聚酰胺510)、聚丁二酰己二胺(聚酰胺64)、聚戊二酰己二胺(聚酰胺65)、聚己二酰己二胺(聚酰胺66)、聚辛二酰己二胺(聚酰胺68)、聚壬二酰己二胺(聚酰胺69)、聚己二酰壬二胺(聚酰胺96)、聚丁二酰间苯二甲胺(聚酰胺MXD4)、聚戊二酰间苯二甲胺(聚酰胺MXD5)、聚己二酰间苯二甲胺(聚酰胺MXD6)、聚辛二酰间苯二甲胺(聚酰胺MXD8)、聚壬二酰间苯二甲胺(聚酰胺MXD9)、聚癸二酰间苯二甲胺(聚酰胺MXD10)、聚十二烷二酰间苯二甲胺(聚酰胺MXD12)、聚对苯二甲酰间苯二甲胺(聚酰胺MXDT)、聚间苯二甲酰间苯二甲胺(聚酰胺MXDI)、聚六氢对苯二甲酰间苯二甲胺(聚酰胺MXDT(H))、聚萘二甲酰间苯二甲胺(聚酰胺MXDN)、聚丁二酰对苯二甲胺(聚酰胺PXD4)、聚戊二酰对苯二甲胺(聚酰胺PXD5)、聚己二酰对苯二甲胺(聚酰胺PXD6)、聚辛二酰对苯二甲胺(聚酰胺PXD8)、聚壬二酰对苯二甲胺(聚酰胺PXD9)、聚癸二酰对苯二甲胺(聚酰胺PXD10)、聚十二烷二酰对苯二甲胺(聚酰胺PXD12)、聚对苯二甲酰对苯二甲胺(聚酰胺PXDT)、聚间苯二甲酰对苯二甲胺(聚酰胺PXDI)、聚六氢对苯二甲酰对苯二甲胺(聚酰胺PXDT(H))、聚萘二甲酰对苯二甲胺(聚酰胺PXDN)、聚对苯二甲酰对苯二胺(PPTA)、聚间苯二甲酰对苯二胺(PPIA)、聚对苯二甲酰间苯二胺(PMTA)、聚间苯二甲酰间苯二胺(PMIA)、聚(丁二酰2,6-萘二甲胺)(聚酰胺2,6-BAN4)、聚(戊二酰2,6-萘二甲胺)(聚酰胺2,6-BAN5)、聚(己二酰2,6-萘二甲胺)(聚酰胺2,6-BAN6)、聚(辛二酰2,6-萘二甲胺)(聚酰胺2,6-BAN8)、聚(壬二酰2,6-萘二甲胺)(聚酰胺2,6-BAN9)、聚(癸二酰2,6-萘二甲胺)(聚酰胺2,6-BAN10)、聚(十二烷二酰2,6-萘二甲胺)(聚酰胺2,6-BAN12)、聚(对苯二甲酰2,6-萘二甲胺)(聚酰胺2,6-BANT)、聚(间苯二甲酰2,6-萘二甲胺)(聚酰胺2,6-BANI)、聚(六氢对苯二甲酰2,6-萘二甲胺)(聚酰胺2,6-BANT(H))、聚(萘二甲酰2,6-萘二甲胺)(聚酰胺2,6-BANN)、聚(丁二酰1,3-环己烷二甲胺)(聚酰胺1,3-BAC4)、聚(戊二酰1,3-环己烷二甲胺)(聚酰胺1,3-BAC5)、聚(己二酰1,3-环己烷二甲胺)(聚酰胺1,3-BAC6)、聚(辛二酰1,3-环己烷二甲胺(聚酰胺1,3-BAC8)、聚(壬二酰1,3-环己烷二甲胺)(聚酰胺1,3-BAC9)、聚(癸二酰1,3-环己烷二甲胺)(聚酰胺1,3-BAC10)、聚(十二烷二酰1,3-环己烷二甲胺)(聚酰胺1,3-BAC12)、聚(对苯二甲酰1,3-环己烷二甲胺)(聚酰胺1,3-BACT)、聚(间苯二甲酰1,3-环己烷二甲胺)(聚酰胺1,3-BACI)、聚(六氢对苯二甲酰1,3-环己烷二甲胺)(聚酰胺1,3-BACT(H))、聚(萘二甲酰1,3-环己烷二甲胺)(聚酰胺1,3-BACN)、聚(丁二酰1,4-环己烷二甲胺)(聚酰胺1,4-BAC4)、聚(戊二酰1,4-环己烷二甲胺)(聚酰胺1,4-BAC5)、聚(己二酰1,4-环己烷二甲胺)(聚酰胺1,4-BAC6)、聚(辛二酰1,4-环己烷二甲胺)(聚酰胺1,4-BAC8)、聚(壬二酰1,4-环己烷二甲胺)(聚酰胺1,4-BAC9)、聚(癸二酰1,4-环己烷二甲胺)(聚酰胺1,4-BAC10)、聚(十二烷二酰1,4-环己烷二甲胺)(聚酰胺1,4-BAC12)、聚(对苯二甲酰1,4-环己烷二甲胺)(聚酰胺1,4-BACT)、聚(间苯二甲酰1,4-环己烷二甲胺)(聚酰胺1,4-BACI)、聚(六氢对苯二甲酰1,4-环己烷二甲胺)(聚酰胺1,4-BACT(H))、聚(萘二甲酰1,4-环己烷二甲胺)(聚酰胺1,4-BACN)、聚(丁二酰4,4’-亚甲基双环己二胺)(聚酰胺PACM4)、聚(戊二酰4,4’-亚甲基双环己二胺)(聚酰胺PACM5)、聚(己二酰4,4’-亚甲基双环己二胺)(聚酰胺PACM6)、聚(辛二酰4,4’-亚甲基双环己二胺)(聚酰胺PACM8)、聚(壬二酰4,4’-亚甲基双环己二胺)(聚酰胺PACM9)、聚(癸二酰4,4’-亚甲基双环己二胺)(聚酰胺PACM10)、聚(十二烷二酰4,4’-亚甲基双环己二胺)(聚酰胺PACM12)、聚(十四烷二酰4,4’-亚甲基双环己二胺)(聚酰胺PACM14)、聚(十六烷二酰4,4’-亚甲基双环己二胺)(聚酰胺PACM16)、聚(十八烷二酰4,4’-亚甲基双环己二胺)(聚酰胺PACM18)、聚(对苯二甲酰4,4’-亚甲基双环己二胺)(聚酰胺PACMT)、聚(间苯二甲酰4,4’-亚甲基双环己二胺)(聚酰胺PACMI)、聚(六氢对苯二甲酰4,4’-亚甲基双环己二胺)(聚酰胺PACMT(H))、聚(萘二甲酰4,4’-亚甲基双环己二胺)(聚酰胺PACMN)、聚(丁二酰4,4’-亚甲基双(2-甲基-环己二胺))(聚酰胺MACM4)、聚(戊二酰4,4’-亚甲基双(2-甲基-环己二胺))(聚酰胺MACM5)、聚(己二酰4,4’-亚甲基双(2-甲基-环己二胺))(聚酰胺MACM6)、聚(辛二酰4,4’-亚甲基双(2-甲基-环己二胺))(聚酰胺MACM8)、聚(壬二酰4,4’-亚甲基双(2-甲基-环己二胺))(聚酰胺MACM9)、聚(癸二酰4,4’-亚甲基双(2-甲基-环己二胺))(聚酰胺MACM10)、聚(十二烷二酰4,4’-亚甲基双(2-甲基-环己二胺))(聚酰胺MACM12)、聚(十四烷二酰4,4’-亚甲基双(2-甲基-环己二胺))(聚酰胺MACM14)、聚(十六烷二酰4,4’-亚甲基双(2-甲基-环己二胺))(聚酰胺MACM16)、聚(十八烷二酰4,4’-亚甲基双(2-甲基-环己二胺))(聚酰胺MACM18)、聚(对苯二甲酰4,4’-亚甲基双(2-甲基-环己二胺))(聚酰胺MACMT)、聚(间苯二甲酰4,4’-亚甲基双(2-甲基-环己二胺))(聚酰胺MACMI)、聚(六氢对苯二甲酰4,4’-亚甲基双(2-甲基-环己二胺))(聚酰胺MACMT(H))、聚(萘二甲酰4,4’-亚甲基双(2-甲基-环己二胺))(聚酰胺MACMN)、聚(丁二酰4,4’-亚丙基双环己二胺)(聚酰胺PACP4)、聚(戊二酰4,4’-亚丙基双环己二胺)(聚酰胺PACP5)、聚(己二酰4,4’-亚丙基双环己二胺)(聚酰胺PACP6)、聚(辛二酰4,4’-亚丙基双环己二胺)(聚酰胺PACP8)、聚(壬二酰4,4’-亚丙基双环己二胺)(聚酰胺PACP9)、聚(癸二酰4,4’-亚丙基双环己二胺)(聚酰胺PACP10)、聚(十二烷二酰4,4’-亚丙基双环己二胺)(聚酰胺PACP12)、聚(十四烷二酰4,4’-亚丙基双环己二胺)(聚酰胺PACP14)、聚(十六烷二酰4,4’-亚丙基双环己二胺)(聚酰胺PACP16)、聚(十八烷二酰4,4’-亚丙基双环己二胺)(聚酰胺PACP18)、聚(对苯二甲酰4,4’-亚丙基双环己二胺)(聚酰胺PACPT)、聚(间苯二甲酰4,4’-亚丙基双环己二胺)(聚酰胺PACPI)、聚(六氢对苯二甲酰4,4’-亚丙基双环己二胺)(聚酰胺PACPT(H))、聚(萘二甲酰4,4’-亚丙基双环己二胺)(聚酰胺PACPN)、聚丁二酰异佛尔酮二胺(聚酰胺IPD4)、聚戊二酰异佛尔酮二胺(聚酰胺IPD5)、聚己二酰异佛尔酮二胺(聚酰胺IPD6)、聚辛二酰异佛尔酮二胺(聚酰胺IPD8)、聚壬二酰异佛尔酮二胺(聚酰胺IPD9)、聚癸二酰异佛尔酮二胺(聚酰胺IPD10)、聚十二烷二酰异佛尔酮二胺(聚酰胺IPD12)、聚对苯二甲酰异佛尔酮二胺(聚酰胺IPDT)、聚间苯二甲酰异佛尔酮二胺(聚酰胺IPDI)、聚六氢对苯二甲酰异佛尔酮二胺(聚酰胺IPDT(H))、聚萘二甲酰异佛尔酮二胺(聚酰胺IPDN)、聚对苯二甲酰丁二胺(聚酰胺4T)、聚间苯二甲酰丁二胺(聚酰胺4I)、聚六氢对苯二甲酰丁二胺(聚酰胺4T(H))、聚萘二甲酰丁二胺(聚酰胺4N)、聚对苯二甲酰戊二胺(聚酰胺5T)、聚间苯二甲酰戊二胺(聚酰胺5I)、聚六氢对苯二甲酰戊二胺(聚酰胺5T(H))、聚萘二甲酰戊二胺(聚酰胺5N)、聚对苯二甲酰己二胺(聚酰胺6T)、聚间苯二甲酰己二胺(聚酰胺6I)、聚六氢对苯二甲酰己二胺(聚酰胺6T(H))、聚萘二甲酰己二胺(聚酰胺6N)、聚(对苯二甲酰2-甲基戊二胺)(聚酰胺M5T)、聚(间苯二甲酰2-甲基戊二胺)(聚酰胺M5I)、聚(六氢对苯二甲酰2-甲基戊二胺)(聚酰胺M5T(H))、聚(萘二甲酰2-甲基戊二胺(聚酰胺M5N)、聚对苯二甲酰壬二胺(聚酰胺9T)、聚间苯二甲酰壬二胺(聚酰胺9I)、聚六氢对苯二甲酰壬二胺(聚酰胺9T(H))、聚萘二甲酰壬二胺(聚酰胺9N)、聚(对苯二甲酰2-甲基辛二胺)(聚酰胺M8T)、聚(间苯二甲酰2-甲基辛二胺)(聚酰胺M8I)、聚(六氢对苯二甲酰2-甲基辛二胺)(聚酰胺M8T(H))、聚(萘二甲酰2-甲基辛二胺)(聚酰胺M8N)、聚对苯二甲酰三甲基己二胺(聚酰胺TMHT)、聚间苯二甲酰三甲基己二胺(聚酰胺TMHI)、聚六氢对苯二甲酰三甲基己二胺(聚酰胺TMHT(H))、聚萘二甲酰三甲基己二胺(聚酰胺TMHN)、聚对苯二甲酰癸二胺(聚酰胺10T)、聚间苯二甲酰癸二胺(聚酰胺10I)、聚六氢对苯二甲酰癸二胺(聚酰胺10T(H))、聚萘二甲酰癸二胺(聚酰胺10N)、聚对苯二甲酰十一烷二胺(聚酰胺11T)、聚间苯二甲酰十一烷二胺(聚酰胺11I)、聚六氢对苯二甲酰十一烷二胺(聚酰胺11T(H))、聚萘二甲酰十一烷二胺(聚酰胺11N)、聚对苯二甲酰十二烷二胺(聚酰胺12T)、聚间苯二甲酰十二烷二胺(聚酰胺12I)、聚六氢对苯二甲酰十二烷二胺(聚酰胺12T(H))、聚萘二甲酰十二烷二胺(聚酰胺12N)等均聚物、和/或使用多种这些聚酰胺的原料单体和/或前述聚酰胺(A1)的原料单体得到的共聚物等聚酰胺系树脂。
另外,可列举出聚偏二氟乙烯(PVDF)、聚氟乙烯(PVF)、聚四氟乙烯(PTFE)、聚三氟氯乙烯(PCTFE)、四氟乙烯/全氟(烷基乙烯基醚)共聚物(PFA)、四氟乙烯/六氟丙烯共聚物(FEP)、四氟乙烯/全氟(烷基乙烯基醚)/六氟丙烯共聚物、乙烯/四氟乙烯共聚物(ETFE)、乙烯/四氟乙烯/六氟丙烯共聚物(EFEP)、偏二氟乙烯/四氟乙烯共聚物、偏二氟乙烯/六氟丙烯共聚物、偏二氟乙烯/全氟(烷基乙烯基醚)共聚物、四氟乙烯/六氟丙烯/偏二氟乙烯共聚物(THV)、偏二氟乙烯/全氟(烷基乙烯基醚)/四氟乙烯共聚物、四氟乙烯/六氟丙烯/偏二氟乙烯/全氟(烷基乙烯基醚)共聚物、乙烯/三氟氯乙烯共聚物(ECTFE)、三氟氯乙烯/四氟乙烯共聚物、偏二氟乙烯/三氟氯乙烯共聚物、三氟氯乙烯/全氟(烷基乙烯基醚)共聚物、三氟氯乙烯/六氟丙烯共聚物、三氟氯乙烯/四氟乙烯/六氟丙烯共聚物、三氟氯乙烯/四氟乙烯/偏二氟乙烯共聚物、三氟氯乙烯/全氟(烷基乙烯基醚)/四氟乙烯共聚物(CPT)、三氟氯乙烯/全氟(烷基乙烯基醚)/六氟丙烯共聚物、三氟氯乙烯/四氟乙烯/六氟丙烯/全氟(烷基乙烯基醚)共聚物、三氟氯乙烯/四氟乙烯/偏二氟乙烯/全氟(烷基乙烯基醚)共聚物、三氟氯乙烯/四氟乙烯/偏二氟乙烯/六氟丙烯共聚物、三氟氯乙烯/四氟乙烯/偏二氟乙烯/全氟(烷基乙烯基醚)/六氟丙烯共聚物等含氟系聚合物、和/或含有对氨基具有反应性的官能团的前述含氟系聚合物。
进而,可列举出聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸乙二醇酯(PET)、聚间苯二甲酸乙二醇酯(PEI)、聚(对苯二甲酸乙二醇酯/间苯二甲酸乙二醇酯)共聚物(PET/PEI)、聚对苯二甲酸1,3-丙二醇酯(PTT)、聚对苯二甲酸环己烷二甲醇酯(PCT)、聚萘二甲酸乙二醇酯(PEN)、聚萘二甲酸丁二醇酯(PBN)、聚芳酯(PAR)、液晶聚酯(LCP)、聚乳酸(PLA)、聚乙醇酸(PGA)等聚酯系树脂;聚缩醛(POM)、聚苯醚(PPO)等聚醚系树脂;聚砜(PSU)、聚醚砜(PESU)、聚苯砜(PPSU)等聚砜系树脂;聚苯硫醚(PPS)、聚硫醚砜(PTES)等聚硫醚系树脂;脂肪族聚酮、聚醚酮(PEK)、聚醚醚酮(PEEK)、聚醚酮酮(PEKK)、聚醚醚醚酮(PEEEK)、聚醚醚酮酮(PEEKK)、聚醚酮酮酮(PEKKK)、聚醚酮醚酮酮(PEKEKK)等聚酮系树脂;聚丙烯腈(PAN)、聚甲基丙烯腈、丙烯腈/苯乙烯共聚物(AS)、甲基丙烯腈/苯乙烯共聚物、丙烯腈/丁二烯/苯乙烯共聚物(ABS)、丙烯腈/丁二烯共聚物(NBR)等聚腈系树脂;聚甲基丙烯酸甲酯(PMMA)、聚甲基丙烯酸乙酯(PEMA)等聚甲基丙烯酸酯系树脂;聚乙酸乙烯酯(PVAc)等聚乙烯酯系树脂;聚偏二氯乙烯(PVDC)、聚氯乙烯(PVC)、氯乙烯/偏二氯乙烯共聚物、偏二氯乙烯/丙烯酸甲酯共聚物等聚氯乙烯系树脂;乙酸纤维素、丁酸纤维素等纤维素系树脂;聚碳酸酯(PC)等聚碳酸酯系树脂;热塑性聚酰亚胺(TPI)、聚醚酰亚胺、聚酯酰亚胺、聚酰胺酰亚胺(PAI)、聚酯酰胺酰亚胺等聚酰亚胺系树脂;热塑性聚氨酯系树脂;乙烯/乙酸乙烯酯共聚物皂化物(EVOH)、聚酰胺弹性体、聚氨酯弹性体、聚酯弹性体等。
另外,也可以层叠除了热塑性树脂之外的任意基材,例如纸、金属系材料、未拉伸、单轴或双轴拉伸塑料薄膜或片、织布、无纺布、金属棉、木材等。作为金属系材料,可列举出铝、铁、铜、镍、金、银、钛、钼、镁、锰、铅、锡、铬、铍、钨、钴等金属和/或其金属化合物、以及由它们中的2种以上形成的不锈钢等合金钢、铝合金、黄铜、青铜等铜合金、镍合金等合金类等。
作为层叠管制造方法,可列举出:使用与层数或材料数对应的挤出机进行熔融挤出,在模具内或模具外同时层叠的方法(共挤出成形法);或者,暂且预先制造单层管或者通过上述方法制造的层叠管,根据需要使用粘接剂,在外侧依次使树脂一体化并层叠的方法(涂布法)。本发明的层叠管优选通过下述共挤出法来制造:将各种材料在熔融状态下共挤出,使两者热融接(熔融粘接),从而通过一个阶段来制造层叠结构的管。
另外,所得层叠管为复杂形状的情况下、在成形后实施加热弯曲加工而制成成形品的情况下,为了去除成形品的残留应变,也可以在形成上述层叠管后,以低于构成前述管的树脂的熔点之中最低的熔点的温度进行0.01小时以上且10小时以下的热处理,从而得到目标成形品。
层叠管中可以具有波形区域。波形区域是指形成为波形形状、蛇腹形状、手风琴形状或波纹形状等的区域。不仅可以遍及层叠管全长地具有波形区域,也可以在中途的适当区域局部具有波形区域。波形区域可以通过首先成形为直管状的管后,接着进行模具成形,制成特定的波形形状等来容易地形成。通过具有该波形区域,从而具有冲击吸收性,安装性变得容易。进而,例如通过附加连接器等必要的部件或者进行弯曲加工,能够制成L字、U字的形状等。
对于这样成形的层叠管的外周的全部或一部而言,考虑到飞石、与其他部件的磨耗、以及耐火性,可以配设由天然橡胶(NR)、丁二烯橡胶(BR)、异戊二烯橡胶(IR)、丁基橡胶(IIR)、氯丁橡胶(CR)、羧基化丁二烯橡胶(XBR)、羧基化氯丁橡胶(XCR)、环氧氯丙烷橡胶(ECO)、丙烯腈丁二烯橡胶(NBR)、氢化丙烯腈丁二烯橡胶(HNBR)、羧基化丙烯腈丁二烯橡胶(XNBR)、NBR与聚氯乙烯的混合物、丙烯腈异戊二烯橡胶(NIR)、氯化聚乙烯橡胶(CM)、氯砜化聚乙烯橡胶(CSM)、乙烯丙烯橡胶(EPR)、乙烯丙烯二烯橡胶(EPDM)、乙烯乙酸乙烯酯橡胶(EVM)、NBR与EPDM的混合物橡胶、丙烯酸类橡胶(ACM)、乙烯丙烯酸类橡胶(AEM)、丙烯酸酯丁二烯橡胶(ABR)、苯乙烯丁二烯橡胶(SBR)、羧基化苯乙烯丁二烯橡胶(XSBR)、苯乙烯异戊二烯橡胶(SIR)、苯乙烯异戊二烯丁二烯橡胶(SIBR)、氨基甲酸酯橡胶、硅橡胶(MQ,VMQ)、氟橡胶(FKM,FFKM)、氟硅橡胶(FVMQ)、氯化乙烯基系、烯烃系、酯系、氨基甲酸酯系、酰胺系等热塑性弹性体等构成的固体或海绵状的保护构件(保护件)。保护构件可以通过已知手法制成海绵状的多孔体。通过制成多孔体,能够形成轻量且绝热性优异的保护部。另外,也可以降低材料成本。或者,也可以添加玻璃纤维等来改善其强度。保护构件的形状没有特别限定,通常为筒状构件或具有用于容纳层叠管的凹部的块状构件。为筒状构件时,可以在预先制作的筒状构件中随后***层叠管,或者在层叠管上覆盖挤出筒状构件并使两者密合而制作。为了使两者粘接,根据需要在保护构件内面或前述凹面上涂布粘接剂,并将层叠管***或镶嵌于其中,使两者密合,由此形成层叠管与保护构件一体化而成的结构体。另外,也可以用金属等进行增强。
关于层叠管的外径,考虑到循环化学溶液和/或气体(例如发动机冷却液)等的流量,壁厚被设计成化学溶液的透过性不会增大、且能够维持通常的管的破坏压力的厚度,并且,该厚度能够维持管的安装作业容易性和使用时的耐振动性良好这一程度的柔软性,但没有限定。优选的是:外径为4mm以上且300mm以下、内径为3mm以上且250mm以下、壁厚为0.5mm以上且25mm以下。
本发明的层叠管可以用于以汽车部件、内燃机用途、电动工具外壳类的机械部件为代表的工业材料、产业资材、电气/电子部件、医疗、食品、家庭/办公用品、建材相关部件、家具用部件等各种用途。
另外,本发明的层叠管因抗化学溶液透过性优异而适宜用作化学溶液运输管。作为化学溶液,例如可列举出苯、甲苯、二甲苯、烷基苯类等芳香族烃溶剂;甲醇、乙醇、丙醇、丁醇、戊醇、乙二醇、丙二醇、二乙二醇、苯酚、甲酚、聚乙二醇、聚丙二醇、聚亚烷基二醇等醇;酚溶剂;二甲醚、二丙醚、甲基-叔丁基醚、乙基-叔丁基醚、二噁烷、四氢呋喃、多元醇酯类、聚乙烯基醚类等醚溶剂;HFC-23(三氟甲烷)、HFC-32(二氟甲烷)、HFC-41(氟甲烷)、HFC-123(2,2-二氯-1,1,1-三氟乙烷)、HFC-125(1,1,1,2,2-五氟乙烷)、HFC-134(1,1,2,2-四氟乙烷)、HFC-134a(1,1,1,2-四氟乙烷)、HFC-143(1,1,2-三氟乙烷)、HFC-143a(1,1,1-三氟乙烷)、HFC-152(1,2-二氟乙烷)、HFC-152a(1,1-二氟乙烷)、HFC-161(氟乙烷)、HFC-227ea(1,1,1,2,3,3,3-七氟丙烷)、HFC-227ca(1,1,2,2,3,3,3-七氟丙烷)、HFC-236fa(1,1,1,3,3,3-六氟丙烷)、HFC-236ea(1,1,1,2,3,3-六氟丙烷)、HFC-236cb(1,1,1,2,2,3-六氟丙烷)、
HFC-236ca(1,1,2,2,3,3-六氟丙烷)、HFC-245ca(1,1,2,2,3-五氟丙烷)、HFC-245ea(1,1,2,3,3-五氟丙烷)、HFC-245eb(1,1,1,2,3-五氟丙烷)、HFC-245fa(1,1,1,3,3-五氟丙烷)、HFC-245cb(1,1,1,2,2-五氟丙烷)、HFC-254eb(1,1,1,2-四氟丙烷)、HFC-254cb(1,1,2,2-四氟丙烷)、HFC-254ca(1,2,2,3-四氟丙烷)、HFC-263fb(1,1,1-三氟丙烷)、HFC-263ca(1,2,2-三氟丙烷)、HFC-272fb(1,1-二氟丙烷)、HFC-272ea(1,2-二氟丙烷)、HFC-272fa(1,3-二氟丙烷)、HFC-272ca(2,2-二氟丙烷)、HFC-281fa(1-氟丙烷)、HFC-281ea(2-氟丙烷)、HFC-329p(1,1,1,2,2,3,3,4,4-九氟丁烷)、
HFC-329mmz(1,1,1,3,3,3-六氟-2-(三氟)丙烷)、HFC-338mf(1,1,1,3,3,4,4,4-八氟丁烷)、HFC-338mcc(1,1,1,2,2,3,4,4-八氟丁烷)、HFC-338pcc(1,1,2,2,3,3,4,4-八氟丁烷)、HFC-347s(1,1,1,2,2,3,3-七氟丁烷)、HFC-365mfc(1,1,1,3,3-五氟丁烷)、HFC-4310mee(1,1,1,2,3,4,4,5,5,5-十氟戊烷)、HFC-1123(三氟乙烯)、HFC-1132a(1,2-二氟乙烯)、FC-1216(六氟-1-丙烯)、HFC-1223(3,3,3-三氟-1-丙烯)、HFC-1225zc(1,1,3,3,3-五氟-1-丙烯)、HFC-1225ye(1,2,3,3,3-五氟-1-丙烯)、HFC-1225yc(1,1,2,3,3-五氟-1-丙烯)、HFC-1232xf(3,3-二氟-1-丙烯)、HFC-1234ye(1,2,3,3-四氟-1-丙烯)、HFC-1234ze(1,3,3,3-四氟-1-丙烯)、HFC-1234yf(2,3,3,3-四氟-1-丙烯)、HFC-1234yc(1,1,2,3-四氟-1-丙烯)、HFC-1234zc(1,1,3,3-四氟-1-丙烯)、HFC-1243yf(2,3,3-三氟-1-丙烯)、HFC-1243zc(1,1,3-三氟-1-丙烯)、HFC-1243ye(1,2,3-三氟-1-丙烯)、HFC-1243ze(1,3,3-三氟-1-丙烯)、HFC-1243zf(3,3,3-三氟-1-丙烯)、HFC-1243yc(1,1,2-三氟-1-丙烯)、HFC-1261yf(2-氟丙烯)、FC-1318my(1,1,1,2,3,4,4,4-八氟-2-丁烯)、
FC-1318cy(1,1,2,3,3,4,4,4-八氟-1-丁烯)、HFC-1327my(1,1,1,2,4,4,4-七氟-2-丁烯)、HFC-1327ye(1,2,3,3,4,4,4-七氟-1-丁烯)、HFC-1327py(1,1,1,2,3,4,4-七氟-2-丁烯)、HFC-1327et(1,3,3,3-四氟-2-(三氟甲基)-1-丙烯)、HFC-1327cz(1,1,3,3,4,4,4-七氟-1-丁烯)、HFC-1327cye(1,1,2,3,4,4,4-七氟-1-丁烯)、HFC-1327cyc(1,1,2,3,3,4,4-七氟-1-丁烯)、HFC-1336yf(2,3,3,4,4,4-六氟-1-丁烯)、HFC-1336ze(1,3,3,4,4,4-六氟-1-丁烯)、HFC-1336eye(1,2,3,4,4,4-六氟-1-丁烯)、HFC-1336eyc(1,2,3,3,4,4-六氟-1-丁烯)、HFC-1336pyy(1,1,2,3,4,4-六氟-2-丁烯)、HFC-1336pz(1,1,1,2,4,4-六氟-2-丁烯)、HFC-1336mzy(1,1,1,3,4,4-六氟-2-丁烯)、HFC-1336mzz(1,1,1,4,4,4-六氟-2-丁烯)、HFC-1336qc(1,1,2,3,3,4-六氟-1-丁烯)、HFC-1336pe(1,1,2,3,4,4-六氟-1-丁烯)、
HFC-1336ft(3,3,3-三氟-2-(三氟甲基)-1-丙烯)、HFC-1345qz(1,1,1,2,4-五氟-2-丁烯)、HFC-1345mzy(1,1,1,3,4-五氟-2-丁烯)、HFC-1345fz(3,3,4,4,4-五氟-1-丁烯)、HFC-1345mzz(1,1,1,4,4-五氟-2-丁烯)、HFC-1345sy(1,1,1,2,3-五氟-2-丁烯)、HFC-1345fyc(2,3,3,4,4-五氟-1-丁烯)、HFC-1345pyz(1,1,2,4,4-五氟-2-丁烯)、HFC-1345cyc(1,1,2,3,3-五氟-1-丁烯)、HFC-1345pyy(1,1,2,3,4-五氟-2-丁烯)、HFC-1345eyc(1,2,3,3,4-五氟-1-丁烯)、HFC-1345ctm(1,1,3,3,3-五氟-2-甲基-1-丙烯)、HFC-1345ftp(2-(二氟甲基)-3,3,3-三氟-1-丙烯)、HFC1345fye(2,3,4,4,4-五氟-1-丁烯)、HFC-1345eyf(1,2,4,4,4-五氟-1-丁烯)、HFC-1345eze(1,3,4,4,4-五氟-1-丁烯)、HFC-1345ezc(1,3,3,4,4-五氟-1-丁烯)、
HFC-1345eye(1,2,3,4,4-五氟-1-丁烯)、HFC-1354fzc(3,3,4,4-四氟-1-丁烯)、HFC-1354ctp(1,1,3,3-四氟-2-甲基-1-丙烯)、HFC-1354etm(1,3,3,3-四氟-2-甲基-1-丙烯)、HFC-1354tfp(2-(二氟甲基)-3,3-二氟-1-丙烯)、HFC-1354my(1,1,1,2-四氟-2-丁烯)、HFC-1354mzy(1,1,1,3-四氟-2-丁烯)、FC-141-10myy(1,1,1,2,3,4,4,5,5,5-十氟-2-戊烯)、FC-141-10cy(1,1,2,3,3,4,4,5,5,5-十氟-1-戊烯)HFC-1429mzt(1,1,1,4,4,4-六氟-2-(三氟甲基)-2-丁烯)、HFC-1429myz(1,1,1,2,4,4,5,5,5-九氟-2-戊烯)、HFC-1429mzy(1,1,1,3,4,4,5,5,5-九氟-2-戊烯)、HFC-1429eyc(1,2,3,3,4,4,5,5,5-九氟-1-戊烯)、HFC-1429czc(1,1,3,3,4,4,5,5,5-九氟-1-戊烯)、HFC-1429cycc(1,1,2,3,3,4,4,5,5-九氟-1-戊烯)、HFC-1429pyy(1,1,2,3,4,4,5,5,5-九氟-2-戊烯)、HFC-1429myyc(1,1,1,2,3,4,4,5,5-九氟-2-戊烯)、HFC-1429myye(1,1,1,2,3,4,5,5,5-九氟-2-戊烯)、HFC-1429eyym(1,2,3,4,4,4-六氟-3-(三氟甲基)-1-丁烯)、
HFC-1429cyzm(1,1,2,4,4,4-六氟-3-(三氟甲基)-1-丁烯)、HFC-1429mzt(1,1,1,4,4,4-六氟-2-(三氟甲基)-2-丁烯)、HFC-1429czym(1,1,3,4,4,4-六氟-3-(三氟甲基)-1-丁烯)、HFC-1438fy(2,3,3,4,4,5,5,5-八氟-1-戊烯)、HFC-1438eycc(1,2,3,3,4,4,5,5-八氟-1-戊烯)、HFC-1438ftmc(3,3,4,4,4-五氟-2-(三氟甲基)-1-丁烯)、HFC-1438czzm(1,1,4,4,4-五氟-3-(三氟甲基)-1-丁烯)、HFC-1438ezym(1,3,4,4,4-五氟-3-(三氟甲基)-1-丁烯)、HFC-1438ctmf(1,1,4,4,4-五氟-2-(三氟甲基)-1-丁烯)、HFC-1447fzy(3,4,4,4-四氟-3-(三氟甲基)-1-丁烯)、HFC-1447fz(3,3,4,4,5,5,5-七氟-1-戊烯)、HFC-1447fycc(2,3,3,4,4,5,5-七氟-1-戊烯)、
HFC-1447cz(1,1,3,3,5,5,5-七氟-1-戊烯)、HFC-1447mytm(1,1,1,2,4,4,4七氟-3-甲基-2-丁烯)、HFC-1447fyz(2,4,4,4-四氟-3-(三氟甲基)-1-丁烯)、HFC-1447ezz(1,4,4,4-四氟-3-(三氟甲基)-1-丁烯)、HFC-1447qzt(1,4,4,4-四氟-2-(三氟甲基)-2-丁烯)、HFC-1447syt(2,4,4,4-四氟-2-(三氟甲基)-2-丁烯)、HFC-1456szt(3-(三氟甲基)-4,4,4-三氟-2-丁烯)、HFC-1456szy(3,4,4,5,5,5六氟-2-戊烯)、HFC-1456mstz(1,1,1,4,4,4-六氟-2-甲基-2-丁烯)、HFC-1456fzce(3,3,4,5,5,5-六氟-1-戊烯)、HFC-1456ftmf(4,4,4-三氟-2-(三氟甲基)-1-丁烯)、FC-151-12c(1,1,2,3,3,4,4,5,5,6,6,6-十二-1-己烯、全氟-1-己烯)、FC-151-12mcy(1,1,1,2,2,3,4,5,5,6,6,6-十二-3-己烯、全氟-3-己烯)、FC-151-12mmtt(1,1,1,4,4,4-六氟-2,3-双(三氟甲基)-2-丁烯)、FC-151-12mmzz(1,1,1,2,3,4,5,5,5-九氟-4-(三氟甲基)-2-戊烯)、HFC-152-11mmtz(1,1,1,4,4,5,5,5-八氟-2-(三氟甲基)-2-戊烯)、
HFC-152-11mmyyz(1,1,1,3,4,5,5,5-八氟-4-(三氟甲基)-2-戊烯)、HFC-152-11mmyyz(1,1,1,3,4,5,5,5-八氟-4-(三氟甲基)-2-戊烯)、HFC-1549fz(PFBE)(3,3,4,4,5,5,6,6,6-九氟-1-己烯、全氟丁基)、HFC-1549fztmm(4,4,4-三氟-3,3-双(三氟甲基)-1-丁烯)、HFC-1549mmtts(1,1,1,4,4,4-六氟-3-甲基-2-(三氟甲基)-2-丁烯)、HFC-1549fycz(2,3,3,5,5,5-六氟-4-(三氟甲基)-1-戊烯)、HFC-1549myts(1,1,1,2,4,4,5,5,5-九氟-3-甲基-2-戊烯)、HFC-1549mzzz(1,1,1,5,5,5-六氟-4-(三氟甲基)-2-戊烯)、HFC-1558szy(3,4,4,5,5,6,6,6-八氟-2-己烯)、HFC-1558fzccc(3,3,4,4,5,5,6,6-八氟-2-己烯)、HFC-1558mmtzc(1,1,1,4,4-五氟-2-(三氟甲基)-2-戊烯)、HFC-1558ftmf(4,4,5,5,5-五氟-2-(三氟甲基)-1-戊烯)、HFC-1567fts(3,3,4,4,5,5,5-七氟-2-甲基-1-戊烯)、HFC-1567szz(4,4,5,5,6,6,6-七氟-2-己烯)、HFC-1567fzfc(4,4,5,5,6,6,6-七氟-1-己烯)、
HFC-1567sfyy(1,1,1,2,2,3,4-七氟-3-己烯)、HFC-1567fzfy(4,5,5,5-四氟-4-(三氟甲基)-1-戊烯)、HFC-1567myzzm(1,1,1,2,5,5,5-七氟-4-甲基-2-戊烯)、HFC-1567mmtyf(1,1,1,3-四氟-2-(三氟甲基)-2-戊烯)、FC-161-14myy(1,1,1,2,3,4,4,5,5,6,6,7,7,7-十四氟-2-庚烯)、FC-161-14mcyy(1,1,1,2,2,3,4,5,5,6,6,7,7,7-十四氟-2-庚烯)、HFC-162-13mzy(1,1,1,3,4,4,5,5,6,6,7,7,7-十三氟-2-庚烯)、HFC162-13myz(1,1,1,2,4,4,5,5,6,6,7,7,7-十三氟-2-庚烯)、HFC-162-13mczy(1,1,1,2,2,4,5,5,6,6,7,7,7-十三氟-3-庚烯)、HFC-162-13mcyz(1,1,1,2,2,3,5,5,6,6,7,7,7-十三氟-3-庚烯)、CFC-11(氟三氯甲烷)、CFC-12(二氯二氟甲烷)、CFC-114(1,1,2,2-四氟-1,2-二氯乙烷)、CFC-114a(1,1,1,2-四氟-2,2-二氯乙烷)、CFC-115(1,1,1,2,2-五氟-2-二氯乙烷)、HCFC-21(二氯氟甲烷)、HCFC-22(氯二氟甲烷)、HCFC-122(1,1,2-三氯-2,2-二氟乙烷)、
HCFC-123(1,1,1-三氟-2,2-二氯乙烷)、HCFC-124(1,1,1,2-四氟-2-氯乙烷)、HCFC-124a(1,1,2,2-四氟-2-氯乙烷)、HCFC-132(二氯二氟乙烷)、HCFC-133a(1,1,1-三氟-2-氯乙烷)、HCFC-141b(1,1-二氯-1-氟乙烷)、HCFC-142(1,1-二氟-2-氯乙烷)、HCFC-142b(1,1-二氟-1-氯乙烷)、HCFC-225ca(3,3-二氯-1,1,1,2,2-五氟丙烷)、HCFC-225cb(1,3-二氯-1,1,2,2,3-五氟丙烷)、HCFC-240db(1,1,1,2,3-五氯丙烷)、HCFC-243db(1,1,1-三氟-2,3-二氯丙烷)、
HCFC-243ab(1,1,1-三氟-2,2-二氯丙烷)、HCFC-244eb(1,1,1,2-四氟-3-氯丙烷)、HCFC-244bb(1,1,1,2-四氟-2-氯丙烷)、HCFC-244db(1,1,1,3-四氟-2-氯丙烷)、HCFC-1111(1,1,2-三氯-2-氟乙烯)、HCFC-1113(1,1,2-三氟-2-氯乙烯)、HCFC-1223xd(3,3,3-三氟-1,2-二氯丙烯)、HCFC-1224xe(1,3,3,3-四氟-2-氯丙烯)、HCFC-1232xf(3,3-二氟-1,3-二氯丙烯)、HCFC-1233xf(3,3,3-三氟-2-氯丙烯)、HCFC-1233zd(3,3,3-三氟-1-氯丙烯)、
以及它们的混合物等卤代烯烃类;丙酮、甲乙酮、二乙酮、苯乙酮等酮溶剂;矿物油类、硅油类、天然石蜡类、环烷类、合成石蜡类、聚α-烯烃类等、汽油、煤油、柴油、菜籽油甲酯、大豆油甲酯、棕榈油甲酯、椰子油甲酯、天然气液化油(Gas To Liquid:GTL)、煤液化油(Coal To Liquid:CTL)、生物质液化油(Biomass To Liquid:BTL)、含醇汽油、乙基叔丁醚共混含氧汽油、含胺汽油、酸性汽油、压缩天然气(CNG)、液化石油气(LPG)、液化烃气体(LHG)、液化天然气(LNG)、燃料用二甲醚(DME)、蓖麻油基制动液、二醇醚系制动液、硼酸酯系制动液、极地用制动液、硅油系制动液、矿物油系制动液、动力转向装置油、含硫化氢油、风窗洗涤液、发动机冷却液、尿素溶液、药剂、墨、涂料等。
层叠管适宜作为运输前述化学溶液的管,具体而言,优选用作进料管、回流管、蒸发器管、燃料供给管、ORVR管、贮存管、通风管等燃料管;油管、石油挖掘管、空压管、油压管、离合器管、制动器管、制动器负压管、悬架管、空气管、涡轮空气管、风管、漏气管、EGR阀控制管、风窗洗涤液用管、冷却液(LLC)冷却器管、储罐管、尿素溶液运输管、电池冷却加热用管、燃料电池用管、空调用管、加热器管、散热管、路面加热器管、地暖管、基础设施供给用管、灭火器和灭火设备用管、医疗用冷却机材料用管、油墨散布管、涂料散布管、其它化学溶液管,更优选用作冷却液(LLC)冷却器管、尿素溶液运输管、电池冷却加热用管和空调用管。
实施例
以下示出实施例和比较例,具体地说明本发明,但本发明不限定于此。
首先,示出实施例和比较例中的分析和物性的测定方法、以及实施例和比较例中使用的材料。
1.聚酰胺的特性利用下述方法进行测定。
[相对粘度]
按照JIS K-6920,在96%的硫酸中,在聚合物浓度为1%、温度为25℃的条件下进行测定。
[弯曲弹性模量]
按照ISO 178,测定弯曲弹性模量。
[末端氨基浓度]
向附带活塞的锥形瓶中投入规定量的聚酰胺试样,添加预先制备的溶剂苯酚/甲醇(体积比为9/1)40mL后,利用磁力搅拌器进行搅拌溶解,指示剂使用百里酚蓝,用0.05N的盐酸进行滴定,求出末端氨基浓度。
[末端羧基浓度]
向三口茄型烧瓶中投入规定量的聚酰胺试样,添加苄醇40mL后,在氮气气流下浸渍于设定为180℃的油浴中。利用安装在上部的搅拌发动机进行搅拌溶解,指示剂使用酚酞,用0.05N的氢氧化钠溶液进行滴定,求出末端羧基浓度。
2.聚烯烃的特性利用下述方法进行测定。
[熔点]
按照ISO11357-3,测定熔点。
[MFR]
按照ISO1133,在230℃、2160g的条件下测定MFR。
[密度]
按照ISO 1183-3,测定密度。
3.层叠管的各物性利用下述方法进行测定。
[低温耐冲击性]
利用SAE J 2260 7.5中记载的方法,以-40℃实施冲击试验。
[高温破坏压强度]
利用SAE J 2260 7.2中记载的方法,以115℃实施破坏压强度试验。
[弯曲刚性(柔软性)]
将切割成280mm的管用110℃的热风循环烘箱处理72小时后,利用SAE J 844 9.8中记载的方法,使用规定的试验机,以23℃测定试验片前端移动50mm时的载荷。测定载荷为30N以下时,判断为柔软性优异。
[重量减少量(尺寸稳定性)]
将切割成0.3m的管用100℃的热风循环烘箱处理72小时后,评价重量变化。
[低分子量物(增塑剂)的耐溶出性]
将切割成0.5m的管的单个端部密封,向内部投入水50%、乙二醇50%的混合物的LLC,将另一个端部也密封。其后,将试验管投入至135℃的烘箱中,处理96小时。其后,利用气相色谱仪对取出的管内溶液进行增塑剂的定量分析,测定溶出至LLC内的增塑剂含量。将溶出至LLC内的增塑剂含量除以管的内表面积,算出增塑剂的溶出量(g/m2)。溶出量为2.0g/m2以下时,判断为耐溶出性优异。
[是否检测到硫原子]
进行通过前述“低分子量物(增塑剂)的耐溶出性”试验而得到的管内溶液的元素分析,确认是否检测到硫原子。
4.实施例和比较例中使用的材料
(1)脂肪族聚酰胺(A1)
[聚酰胺12(A1-1)的制造]
向内容积为70升且附带搅拌机的耐压力反应容器中投入十二内酰胺19.73kg(100.0摩尔)、5-氨基-1,3,3-三甲基环己烷甲胺45.0g(0.264摩尔)和蒸馏水0.5L,将聚合槽内进行氮气置换后,加热至180℃为止,在该温度下搅拌以使得反应体系内成为均匀状态。接着,使聚合槽内温度升温至270℃为止,一边将槽内压力调整至3.5MPa,一边在搅拌下聚合2小时。其后,耗用约2小时释放压力至常压,接着减压至53kPa为止,在减压下进行5小时的聚合。接着,将氮气导入至高压釜内,恢复压力至常压后,从反应容器的下部喷嘴以股线的形式排出,进行切割而得到粒料。将该粒料进行减压干燥,得到相对粘度为2.20、末端氨基浓度为48μeq/g、末端羧基浓度为24μeq/g的聚酰胺12(以下将该聚酰胺12称为(A1-1))。聚酰胺12(A1-1)的亚甲基数相对于酰胺基数的比值[CH2]/[NHCO]为11.0,满足7.0以上。另外,聚酰胺12(A1-1)的末端氨基浓度[A](μeq/g)、末端羧基浓度[B](μeq/g)满足[A]>[B]+5。
[聚酰胺612(A1-2)的制造]
向内容积为70升且附带搅拌机的耐压力反应容器中投入1,6-己二胺与十二烷二酸的等摩尔盐16.42kg(50.0摩尔)、1,6-己二胺16.3g(0.14摩尔)和蒸馏水5.0L,将聚合槽内进行氮气置换后,加热至220℃为止,在该温度下搅拌以使得反应体系内成为均匀状态。接着,使聚合槽内温度升温至270℃为止,一边将槽内压力调整至1.7MPa,一边在搅拌下聚合2小时。其后,耗用约2小时释放压力至常压,接着减压至53kPa为止,在减压下进行4小时的聚合。接着,将氮气导入至高压釜内,恢复压力至常压后,从反应容器的下部喷嘴以股线的形式排出,进行切割而得到粒料。将该粒料进行减压干燥,得到相对粘度为2.48、末端氨基浓度为50μeq/g、末端羧基浓度为35μeq/g的聚酰胺612(以下将该聚酰胺612称为(A1-2))。聚酰胺612(A1-2)的亚甲基数相对于酰胺基数的比值[CH2]/[NHCO]为8.0,满足7.0以上。另外,聚酰胺612(A1-2)的末端氨基浓度[A](μeq/g)、末端羧基浓度[B](μeq/g)满足[A]>[B]+5。
(2)弹性体聚合物(A2)
马来酸酐改性乙烯/1-丁烯共聚物(A2-1)(三井化学株式会社制、Tafmer MH5010、酸酐基浓度:50μeq/g)
马来酸酐改性乙烯/1-丁烯共聚物(A2-2)(三井化学株式会社制、Tafmer MH5020、酸酐基浓度:100μeq/g)
(3)增塑剂(A3)
对羟基苯甲酸2-己基癸酯(A3-1)(花王株式会社制、EXEPARL HDPB)
对羟基苯甲酸十六烷基酯(A3-2)(上野制药株式会社制、CEPB)
N-丁基苯磺酰胺(A3-3)(Proviron公司制、Proviplast 024)
对羟基苯甲酸2-乙基己酯(A3-4)(上野制药株式会社制、EHPB)
(4)脂肪族聚酰胺组合物(A)
[脂肪族聚酰胺组合物(A-1)的制造]
向聚酰胺12(A1-1)中预先混合作为弹性体聚合物的马来酸酐改性乙烯/1-丁烯共聚物(A2-1)、作为增塑剂的对羟基苯甲酸2-己基癸酯(A3-1)、作为抗氧化剂的三乙二醇双[3-(3-叔丁基-5-甲基-4-羟基苯基)丙酸酯](BASFJAPAN公司制、IRGANOX245)和作为磷系加工稳定剂的三(2,4-二叔丁基苯基)亚磷酸酯(BASF JAPAN公司制、IRGAFOS168),供给至双螺杆熔融混炼机(株式会社日本制钢所制、型号:TEX44)中,以180℃~270℃的料筒温度进行熔融混炼,将熔融树脂挤出成股线状后,将其导入至水槽中,进行冷却、切割、真空干燥,得到相对于聚酰胺12(A1-1)/弹性体聚合物(A2-1)/增塑剂(A3-1)=85.0/10.0/5.0(质量%)的合计100质量份包含抗氧化剂0.8质量份、磷系加工稳定剂0.2质量份的脂肪族聚酰胺组合物(A-1)的粒料。脂肪族聚酰胺组合物(A-1)的弯曲弹性模量为600MPa。
[脂肪族聚酰胺组合物(A-2)的制造]
在脂肪族聚酰胺组合物(A-1)的制造中,变更弹性体聚合物和增塑剂的添加量,除此之外,利用与脂肪族聚酰胺组合物(A-1)的制造相同的方法,得到相对于聚酰胺12(A1-1)/弹性体聚合物(A2-1)/增塑剂(A3-1)=87.5/10.0/2.5(质量%)的合计100质量份包含抗氧化剂0.8质量份、磷系加工稳定剂0.2质量份的脂肪族聚酰胺组合物(A-2)的粒料。脂肪族聚酰胺组合物(A-2)的按照ISO 178而测得的弯曲弹性模量为850MPa。
[脂肪族聚酰胺组合物(A-3)的制造]
在脂肪族聚酰胺组合物(A-1)的制造中,变更弹性体聚合物和增塑剂的添加量,除此之外,利用与脂肪族聚酰胺组合物(A-1)的制造相同的方法,得到相对于聚酰胺12(A1-1)/弹性体聚合物(A2-1)/增塑剂(A3-1)=85.0/5.0/10.0(质量%)的合计100质量份包含抗氧化剂0.8质量份、磷系加工稳定剂0.2质量份的脂肪族聚酰胺组合物(A-3)的粒料。脂肪族聚酰胺组合物(A-3)的按照ISO 178而测得的弯曲弹性模量为490MPa。
[脂肪族聚酰胺组合物(A-4)的制造]
在脂肪族聚酰胺组合物(A-1)的制造中,将对羟基苯甲酸2-己基癸酯(A3-1)变更为对羟基苯甲酸十六烷基酯(A3-2),除此之外,利用与脂肪族聚酰胺组合物(A-1)的制造相同的方法,得到相对于聚酰胺12(A1-1)/弹性体聚合物(A2-1)/增塑剂(A3-2)=85.0/10.0/5.0(质量%)的合计100质量份包含抗氧化剂0.8质量份、磷系加工稳定剂0.2质量份的脂肪族聚酰胺组合物(A-4)的粒料。脂肪族聚酰胺组合物(A-4)的按照ISO 178而测得的弯曲弹性模量为620MPa。
[脂肪族聚酰胺组合物(A-5)的制造]
在脂肪族聚酰胺组合物(A-1)的制造中,将马来酸酐改性乙烯/1-丁烯共聚物(A2-1)变更为(A2-2),除此之外,利用与脂肪族聚酰胺组合物(A-1)的制造相同的方法,得到相对于聚酰胺12(A1-1)/弹性体聚合物(A2-2)/增塑剂(A3-1)=85.0/10.0/5.0(质量%)的合计100质量份包含抗氧化剂0.8质量份、磷系加工稳定剂0.2质量份的脂肪族聚酰胺组合物(A-5)的粒料。脂肪族聚酰胺组合物(A-5)的按照ISO 178而测得的弯曲弹性模量为620MPa。
[脂肪族聚酰胺组合物(A-6)的制造]
在脂肪族聚酰胺组合物(A-1)的制造中,将聚酰胺12(A1-1)变更为聚酰胺612(A1-2),除此之外,利用与脂肪族聚酰胺组合物(A-1)的制造相同的方法,得到相对于聚酰胺612(A1-2)/弹性体聚合物(A2-1)/增塑剂(A3-1)=85.0/10.0/5.0(质量%)的合计100质量份包含抗氧化剂0.8质量份、磷系加工稳定剂0.2质量份的脂肪族聚酰胺组合物(A-6)的粒料。脂肪族聚酰胺组合物(A-6)的按照ISO 178而测得的弯曲弹性模量为890MPa。
[脂肪族聚酰胺组合物(A-7)的制造]
在脂肪族聚酰胺组合物(A-1)的制造中,不添加对羟基苯甲酸2-己基癸酯(A3-1),变更马来酸酐改性乙烯/1-丁烯共聚物(A2-1)的添加量,除此之外,利用与脂肪族聚酰胺组合物(A-1)的制造相同的方法,得到相对于聚酰胺12(A1-1)/弹性体聚合物(A2-1)=70.0/30.0(质量%)的合计100质量份包含抗氧化剂0.8质量份、磷系加工稳定剂0.2质量份的脂肪族聚酰胺组合物(A-7)的粒料。脂肪族聚酰胺组合物(A-7)的按照ISO 178而测得的弯曲弹性模量为800MPa。
[脂肪族聚酰胺组合物(A-8)的制造]
在脂肪族聚酰胺组合物(A-7)的制造中,变更马来酸酐改性乙烯/1-丁烯共聚物(A2-1)的添加量,除此之外,利用与脂肪族聚酰胺组合物(A-7)的制造相同的方法,得到相对于聚酰胺12(A1-1)/弹性体聚合物(A2-1)=80.0/20.0(质量%)的合计100质量份包含抗氧化剂0.8质量份、磷系加工稳定剂0.2质量份的脂肪族聚酰胺组合物(A-8)的粒料。脂肪族聚酰胺组合物(A-8)的按照ISO 178而测得的弯曲弹性模量为1100MPa。
[脂肪族聚酰胺组合物(A-9)的制造]
在脂肪族聚酰胺组合物(A-7)的制造中,变更马来酸酐改性乙烯/1-丁烯共聚物(A2-1)的添加量,除此之外,利用与脂肪族聚酰胺组合物(A-7)的制造相同的方法,得到相对于聚酰胺12(A1-1)/弹性体聚合物(A2-1)=60.0/40.0(质量%)的合计100质量份包含抗氧化剂0.8质量份、磷系加工稳定剂0.2质量份的脂肪族聚酰胺组合物(A-9)的粒料。脂肪族聚酰胺组合物(A-9)的按照ISO 178而测得的弯曲弹性模量为650MPa。
[脂肪族聚酰胺组合物(A-10)的制造]
在脂肪族聚酰胺组合物(A-7)的制造中,将聚酰胺12(A1-1)变更为聚酰胺612(A1-2),除此之外,利用与脂肪族聚酰胺组合物(A-7)的制造相同的方法,得到相对于聚酰胺612(A1-2)/弹性体聚合物(A2-1)=70.0/30.0(质量%)的合计100质量份包含抗氧化剂0.8质量份、磷系加工稳定剂0.2质量份的脂肪族聚酰胺组合物(A-10)的粒料。脂肪族聚酰胺组合物(A-10)的按照ISO 178而测得的弯曲弹性模量为1150MPa。
[脂肪族聚酰胺组合物(A-11)的制造]
在脂肪族聚酰胺组合物(A-1)的制造中,变更马来酸酐改性乙烯/1-丁烯共聚物(A2-1)和对羟基苯甲酸2-己基癸酯(A3-1)的添加量,除此之外,利用与脂肪族聚酰胺组合物(A-1)的制造相同的方法,得到相对于聚酰胺12(A1-1)/弹性体聚合物(A2-1)/增塑剂(A3-1)=75.0/5.0/20.0(质量%)的合计100质量份包含抗氧化剂0.8质量份、磷系加工稳定剂0.2质量份的脂肪族聚酰胺组合物(A-11)的粒料。脂肪族聚酰胺组合物(A-11)的按照ISO 178而测得的弯曲弹性模量为260MPa。
[脂肪族聚酰胺组合物(A-12)的制造]
在脂肪族聚酰胺组合物(A-1)的制造中,将对羟基苯甲酸2-己基癸酯(A3-1)变更为N-丁基苯磺酰胺(A3-3),除此之外,利用与脂肪族聚酰胺组合物(A-1)的制造相同的方法,得到相对于聚酰胺12(A1-1)/弹性体聚合物(A2-1)/增塑剂(A3-3)=85.0/10.0/5.0(质量%)的合计100质量份包含抗氧化剂0.8质量份、磷系加工稳定剂0.2质量份的脂肪族聚酰胺组合物(A-12)的粒料。脂肪族聚酰胺组合物(A-12)的按照ISO 178而测得的弯曲弹性模量为500MPa。
[脂肪族聚酰胺组合物(A-13)的制造]
在脂肪族聚酰胺组合物(A-1)的制造中,将对羟基苯甲酸2-己基癸酯(A3-1)变更为对羟基苯甲酸2-乙基己酯(A3-4),除此之外,利用与脂肪族聚酰胺组合物(A-1)的制造相同的方法,得到相对于聚酰胺12(A1-1)/弹性体聚合物(A2-1)/增塑剂(A3-4)=85.0/10.0/5.0(质量%)的合计100质量份包含抗氧化剂0.8质量份、磷系加工稳定剂0.2质量份的脂肪族聚酰胺组合物(A-13)的粒料。脂肪族聚酰胺组合物(A-13)的按照ISO 178而测得的弯曲弹性模量为610MPa。
(5)改性聚烯烃(B)
改性聚丙烯(B-1)(三井化学株式会社制、Admer QB520E、熔点:160℃、MFR(230℃/2160g):1.8g/10min、密度:0.90g/cm3)
(6)聚烯烃(C)
聚丙烯(C-1)(Prime Polymer公司制、Prime Polypro E-702MG、熔点:162℃、拉伸屈服应力:30MPa、夏比冲击强度(带缺口、23℃):58kJ/m2)
聚丁烯-1(C-2)(三井化学株式会社制、BEAULON P5050、熔点:128℃、拉伸屈服应力:27MPa、夏比冲击强度(带缺口、23℃):49kJ/m2)
5.层叠管的制造
(实施例1)
使用前述示出的脂肪族聚酰胺组合物(A-1)、改性聚丙烯(B-1),利用Plabor(塑料工学研究所株式会社制)双层管成形机,使(A-1)以270℃的挤出温度、使(B-1)以220℃的挤出温度分别进行熔融,利用合流器使排出的熔融树脂合流,并成形为层叠管状体。接着,通过用于尺寸控制的定型模进行冷却并脱除,制成由(A-1)形成的(a)层(最外层)、由(B-1)形成的(b)层(最内层)时,得到层构成为(a)/(b)=0.75/0.25mm且内径6.0mm、外径8.0mm的层叠管。将该层叠管的物性测定结果示于表1。
(实施例2)
在实施例1中,变更层厚度,除此之外,利用与实施例1相同的方法,得到层构成为(a)/(b)=0.65/0.35mm且内径6.0mm、外径8.0mm的层叠管。将该层叠管的物性测定结果示于表1。
(实施例3)
在实施例1中,变更层厚度,除此之外,利用与实施例1相同的方法,得到层构成为(a)/(b)=0.80/0.20mm且内径6.0mm、外径8.0mm的层叠管。将该层叠管的物性测定结果示于表1。
(实施例4)
在实施例1中,将脂肪族聚酰胺组合物(A-1)变更为(A-2),除此之外,利用与实施例1相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(实施例5)
在实施例2中,将脂肪族聚酰胺组合物(A-1)变更为(A-2),除此之外,利用与实施例2相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(实施例6)
在实施例3中,将脂肪族聚酰胺组合物(A-1)变更为(A-2),除此之外,利用与实施例3相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(实施例7)
在实施例1中,将脂肪族聚酰胺组合物(A-1)变更为(A-3),除此之外,利用与实施例1相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(实施例8)
在实施例2中,将脂肪族聚酰胺组合物(A-1)变更为(A-3),除此之外,利用与实施例2相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(实施例9)
在实施例3中,将脂肪族聚酰胺组合物(A-1)变更为(A-3),除此之外,利用与实施例3相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(实施例10)
在实施例1中,将脂肪族聚酰胺组合物(A-1)变更为(A-4),除此之外,利用与实施例1相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(实施例11)
在实施例2中,将脂肪族聚酰胺组合物(A-1)变更为(A-4),除此之外,利用与实施例2相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(实施例12)
在实施例3中,将脂肪族聚酰胺组合物(A-1)变更为(A-4),除此之外,利用与实施例3相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(实施例13)
在实施例1中,将脂肪族聚酰胺组合物(A-1)变更为(A-5),除此之外,利用与实施例1相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(实施例14)
在实施例2中,将脂肪族聚酰胺组合物(A-1)变更为(A-5),除此之外,利用与实施例2相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(实施例15)
在实施例3中,将脂肪族聚酰胺组合物(A-1)变更为(A-5),除此之外,利用与实施例3相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(实施例16)
在实施例1中,将脂肪族聚酰胺组合物(A-1)变更为(A-6),除此之外,利用与实施例1相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(实施例17)
在实施例2中,将脂肪族聚酰胺组合物(A-1)变更为(A-6),除此之外,利用与实施例2相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(实施例18)
在实施例3中,将脂肪族聚酰胺组合物(A-1)变更为(A-6),除此之外,利用与实施例3相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(实施例19)
在实施例1中,将脂肪族聚酰胺组合物(A-1)变更为(A-7),除此之外,利用与实施例1相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(实施例20)
在实施例2中,将脂肪族聚酰胺组合物(A-1)变更为(A-7),除此之外,利用与实施例2相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(实施例21)
在实施例3中,将脂肪族聚酰胺组合物(A-1)变更为(A-7),除此之外,利用与实施例3相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(实施例22)
使用前述示出的脂肪族聚酰胺组合物(A-1)、改性聚丙烯(B-1)、聚丙烯(C-1),利用Plabor(塑料工学研究所株式会社制)三层管成形机,使(A-1)以270℃的挤出温度、使(B-1)以220℃的挤出温度、使(C-1)以220℃的挤出温度分别进行熔融,利用合流器使排出的熔融树脂合流,并成形为层叠管状体。接着,通过用于尺寸控制的定型模进行冷却并脱除,制成由(A-1)形成的(a)层(最外层)、由(B-1)形成的(b)层(中间层)、由(C-1)形成的(c)层(最内层)时,得到层构成为(a)/(b)/(c)=0.75/0.10/0.15mm且内径6.0mm、外径8.0mm的层叠管。将该层叠管的物性测定结果示于表2。
(实施例23)
在实施例22中,变更层厚度,除此之外,利用与实施例22相同的方法,得到层构成为(a)/(b)/(c)=0.65/0.10/0.25mm且内径6.0mm、外径8.0mm的层叠管。将该层叠管的物性测定结果示于表2。
(实施例24)
在实施例22中,变更层厚度,除此之外,利用与实施例22相同的方法,得到层构成为(a)/(b)/(c)=0.80/0.10/0.10mm且内径6.0mm、外径8.0mm的层叠管。将该层叠管的物性测定结果示于表2。
(实施例25)
在实施例22中,将脂肪族聚酰胺组合物(A-1)变更为(A-2),除此之外,利用与实施例22相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表2。
(实施例26)
在实施例23中,将脂肪族聚酰胺组合物(A-1)变更为(A-2),除此之外,利用与实施例23相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表2。
(实施例27)
在实施例22中,将脂肪族聚酰胺组合物(A-1)变更为(A-3),除此之外,利用与实施例22相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表2。
(实施例28)
在实施例23中,将脂肪族聚酰胺组合物(A-1)变更为(A-3),除此之外,利用与实施例23相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表2。
(实施例29)
在实施例22中,将脂肪族聚酰胺组合物(A-1)变更为(A-4),除此之外,利用与实施例22相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表2。
(实施例30)
在实施例23中,将脂肪族聚酰胺组合物(A-1)变更为(A-4),除此之外,利用与实施例23相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表2。
(实施例31)
在实施例22中,将脂肪族聚酰胺组合物(A-1)变更为(A-5),除此之外,利用与实施例22相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表2。
(实施例32)
在实施例23中,将脂肪族聚酰胺组合物(A-1)变更为(A-5),除此之外,利用与实施例23相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表2。
(实施例33)
在实施例22中,将脂肪族聚酰胺组合物(A-1)变更为(A-6),除此之外,利用与实施例22相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表2。
(实施例34)
在实施例23中,将脂肪族聚酰胺组合物(A-1)变更为(A-6),除此之外,利用与实施例23相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表2。
(实施例35)
在实施例22中,将脂肪族聚酰胺组合物(A-1)变更为(A-7),除此之外,利用与实施例22相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表2。
(实施例36)
在实施例23中,将脂肪族聚酰胺组合物(A-1)变更为(A-7),除此之外,利用与实施例23相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表2。
(实施例37)
在实施例22中,将聚丙烯(C-1)变更为聚丁烯-1(C-2),除此之外,利用与实施例22相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表2。
(比较例1)
在实施例1中,将脂肪族聚酰胺组合物(A-1)变更为(A-8),除此之外,利用与实施例1相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(比较例2)
在实施例1中,将脂肪族聚酰胺组合物(A-1)变更为(A-9),除此之外,利用与实施例1相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(比较例3)
在实施例1中,将脂肪族聚酰胺组合物(A-1)变更为(A-10),除此之外,利用与实施例1相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(比较例4)
在实施例1中,将脂肪族聚酰胺组合物(A-1)变更为(A-11),除此之外,利用与实施例1相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(比较例5)
在实施例1中,将脂肪族聚酰胺组合物(A-1)变更为(A-12),除此之外,利用与实施例1相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(比较例6)
在实施例1中,将脂肪族聚酰胺组合物(A-1)变更为(A-13),除此之外,利用与实施例1相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表1。
(比较例7)
在实施例1中,变更各层厚度,除此之外,利用与实施例1相同的方法,得到层构成为(a)/(b)=0.50/0.50mm且内径6.0mm、外径8.0mm的层叠管。将该层叠管的物性测定结果示于表1。
(比较例8)
在实施例22中,将脂肪族聚酰胺组合物(A-1)变更为(A-8),除此之外,利用与实施例22相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表2。
(比较例9)
在实施例22中,将脂肪族聚酰胺组合物(A-1)变更为(A-9),除此之外,利用与实施例22相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表2。
(比较例10)
在实施例22中,将脂肪族聚酰胺组合物(A-1)变更为(A-10),除此之外,利用与实施例22相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表2。
(比较例11)
在实施例22中,将脂肪族聚酰胺组合物(A-1)变更为(A-11),除此之外,利用与实施例22相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表2。
(比较例12)
在实施例22中,将脂肪族聚酰胺组合物(A-1)变更为(A-12),除此之外,利用与实施例22相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表2。
(比较例13)
在实施例22中,将脂肪族聚酰胺组合物(A-1)变更为(A-13),除此之外,利用与实施例22相同的方法,得到表1所示的层构成的层叠管。将该层叠管的物性测定结果示于表2。
(比较例14)
在实施例22中,变更层厚度,除此之外,利用与实施例22相同的方法,得到层构成为(a)/(b)/(c)=0.50/0.10/0.40mm且内径6.0mm、外径8.0mm的层叠管。将该层叠管的物性测定结果示于表2。
[表1]
表1
[表2]
表2
如上所述可知:各实施例的层叠管的低温耐冲击性、高温时的破坏压强度、柔软性、尺寸稳定性、以及低分子量物、离子成分的耐溶出性优异。
Claims (14)
1.一种层叠管,其为包含a层、b层的2层以上的层叠管,
所述a层包含脂肪族聚酰胺组合物A,
所述b层包含改性聚烯烃B,不包含其它热塑性树脂,
所述脂肪族聚酰胺组合物A包含聚酰胺A1和弹性体聚合物A2,
所述聚酰胺A1是亚甲基数相对于酰胺基数的比值为7.0以上的脂肪族聚酰胺,在所述脂肪族聚酰胺组合物A中包含70质量%以上且90质量%以下的所述聚酰胺A1,
所述弹性体聚合物A2含有由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元,在所述脂肪族聚酰胺组合物A中包含5质量%以上且30质量%以下的所述弹性体聚合物A2,
另外,所述脂肪族聚酰胺组合物A任选包含增塑剂A3,
所述增塑剂A3不含硫原子,且含有对羟基苯甲酸和/或邻羟基苯甲酸与碳原子数为12以上且24以下的直链状和/或支链状烷基脂肪族醇形成的酯结构,所述脂肪族聚酰胺组合物A中的所述增塑剂A3的含量为0质量%以上且15质量%以下,
所述脂肪族聚酰胺组合物A的按照ISO 178而测得的弯曲弹性模量为400MPa以上且1000MPa以下,
所述改性聚烯烃B具有由基于碳原子数为2以上且10以下的α-烯烃的单体衍生的单元,且按照ISO 11357-3而测得的熔点为130℃以上,
在所述层叠管中,从外侧朝向内侧按照a层、b层的顺序配置,
所述a层的厚度占据管的总壁厚的60%以上。
2.根据权利要求1所述的层叠管,其中,所述b层由改性聚烯烃B组成。
3.根据权利要求1所述的层叠管,其中,所述脂肪族聚酰胺组合物A中的所述增塑剂A3的含量为1质量%以上且15质量%以下。
4.根据权利要求1所述的层叠管,其中,所述聚酰胺A1为选自由聚十一酰胺(聚酰胺11)、聚十二酰胺(聚酰胺12)、聚癸二酰己二胺(聚酰胺610)、聚十二烷二酰己二胺(聚酰胺612)、聚癸二酰癸二胺(聚酰胺1010)、聚十二烷二酰癸二胺(聚酰胺1012)和聚十二烷二酰十二烷二胺(聚酰胺1212)组成的组中的至少1种均聚物;和/或使用多种形成它们的原料单体得到的共聚物。
5.根据权利要求1所述的层叠管,其中,将每1g所述聚酰胺A1的末端氨基浓度记作[A](μeq/g),并将末端羧基浓度记作[B](μeq/g)时,[A]>[B]+5。
6.根据权利要求1所述的层叠管,其中,所述改性聚烯烃B含有由不饱和化合物衍生的单元,所述不饱和化合物具有选自由羧基或其衍生物、羟基、环氧基、氨基、酰胺基、酰亚胺基、腈基、硫醇基和异氰酸酯基组成的组中的至少1种官能团。
7.根据权利要求6所述的层叠管,其中,所述改性聚烯烃B通过使改性前的聚烯烃发生熔融,并添加具有所述官能团的不饱和化合物,使其接枝共聚的方法来制造。
8.根据权利要求1所述的层叠管,其中,所述改性聚烯烃B在230℃/2160g的条件下按照ISO 1133而测得的MFR值为1.0g/10min以上且10.0g/10min以下。
9.根据权利要求1所述的层叠管,其中,所述改性聚烯烃B的按照ISO 1183-3而测得的密度为0.85g/cm3以上。
10.根据权利要求1所述的层叠管,其中,所述改性聚烯烃B为马来酸酐改性聚丙烯,聚丙烯的含量为50质量%以上。
11.根据权利要求1所述的层叠管,其还包含c层,
所述c层包含聚烯烃C,
所述聚烯烃C具有由基于碳原子数为2以上且10以下的α-烯烃的单体衍生的单元,且按照ISO 11357-3而测得的熔点为120℃以上,按照ISO 527而测得的拉伸屈服应力为20MPa以上,按照ISO 179/1eA而测得的23℃下的夏比冲击强度(带缺口)为40kJ/m2以上。
12.根据权利要求11所述的层叠管,其中,所述c层配置在所述b层的内侧。
13.根据权利要求1所述的层叠管,其通过共挤出成形法来制造。
14.根据权利要求1所述的层叠管,其为冷却液LLC冷却器管、尿素溶液运输管、电池冷却加热用管和空调用管中的任一者。
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WO2015029571A1 (ja) * | 2013-08-29 | 2015-03-05 | 三菱瓦斯化学株式会社 | 多層構造体 |
CN105517789B (zh) * | 2013-09-04 | 2017-10-17 | 宇部兴产株式会社 | 层叠管 |
US20170283556A1 (en) * | 2013-12-06 | 2017-10-05 | Mitsui Chemicals, Inc. | Polyamide-based thermoplastic elastomer composition and molded article thereof |
BR112018069437B8 (pt) | 2016-03-31 | 2023-05-16 | Ube Industries | Tubo multicamada |
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2019
- 2019-01-16 JP JP2019523887A patent/JP6610838B1/ja active Active
- 2019-01-16 US US16/961,421 patent/US10960635B1/en active Active
- 2019-01-16 WO PCT/JP2019/001033 patent/WO2019142808A1/ja unknown
- 2019-01-16 EP EP19741157.2A patent/EP3742033A4/en active Pending
- 2019-01-16 CN CN201980008723.7A patent/CN111601995B/zh active Active
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CN111601995A (zh) | 2020-08-28 |
EP3742033A4 (en) | 2021-10-13 |
US10960635B1 (en) | 2021-03-30 |
WO2019142808A1 (ja) | 2019-07-25 |
EP3742033A1 (en) | 2020-11-25 |
US20210078283A1 (en) | 2021-03-18 |
JPWO2019142808A1 (ja) | 2020-02-06 |
JP6610838B1 (ja) | 2019-11-27 |
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