CN113226763B - 层叠体 - Google Patents
层叠体 Download PDFInfo
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- CN113226763B CN113226763B CN201980086288.XA CN201980086288A CN113226763B CN 113226763 B CN113226763 B CN 113226763B CN 201980086288 A CN201980086288 A CN 201980086288A CN 113226763 B CN113226763 B CN 113226763B
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- China
- Prior art keywords
- polyamide
- mass
- poly
- composition
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 claims abstract description 162
- 239000004953 Aliphatic polyamide Substances 0.000 claims abstract description 126
- 229920003231 aliphatic polyamide Polymers 0.000 claims abstract description 126
- 229920000642 polymer Polymers 0.000 claims abstract description 94
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims abstract description 55
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 52
- 125000003368 amide group Chemical group 0.000 claims abstract description 35
- 125000004018 acid anhydride group Chemical group 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 229920002647 polyamide Polymers 0.000 claims description 365
- 239000004952 Polyamide Substances 0.000 claims description 364
- -1 polyhexamethylene Polymers 0.000 claims description 127
- 229920001577 copolymer Polymers 0.000 claims description 108
- 229920000299 Nylon 12 Polymers 0.000 claims description 88
- 229920002292 Nylon 6 Polymers 0.000 claims description 51
- 229920001971 elastomer Polymers 0.000 claims description 47
- 239000000806 elastomer Substances 0.000 claims description 45
- 239000000178 monomer Substances 0.000 claims description 44
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 35
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 34
- 150000001408 amides Chemical class 0.000 claims description 29
- 125000003277 amino group Chemical group 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 24
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 21
- 229920000571 Nylon 11 Polymers 0.000 claims description 17
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 15
- 229920001519 homopolymer Polymers 0.000 claims description 15
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 claims description 13
- 229960002684 aminocaproic acid Drugs 0.000 claims description 13
- PBLZLIFKVPJDCO-UHFFFAOYSA-N omega-Aminododecanoic acid Natural products NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 claims description 13
- 150000004985 diamines Chemical class 0.000 claims description 11
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- QUBNFZFTFXTLKH-UHFFFAOYSA-N 2-aminododecanoic acid Chemical compound CCCCCCCCCCC(N)C(O)=O QUBNFZFTFXTLKH-UHFFFAOYSA-N 0.000 claims description 9
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 229920006152 PA1010 Polymers 0.000 claims description 6
- 229920006396 polyamide 1012 Polymers 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- FJXWKBZRTWEWBJ-UHFFFAOYSA-N nonanediamide Chemical compound NC(=O)CCCCCCCC(N)=O FJXWKBZRTWEWBJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 154
- 239000011229 interlayer Substances 0.000 abstract description 28
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 97
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 44
- 238000004519 manufacturing process Methods 0.000 description 35
- 238000000034 method Methods 0.000 description 34
- 229920005989 resin Polymers 0.000 description 29
- 239000011347 resin Substances 0.000 description 29
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 23
- 239000005977 Ethylene Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 19
- 230000000704 physical effect Effects 0.000 description 19
- 238000006116 polymerization reaction Methods 0.000 description 18
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 17
- 229920002554 vinyl polymer Polymers 0.000 description 17
- 239000000446 fuel Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 16
- ALBYIUDWACNRRB-UHFFFAOYSA-N hexanamide Chemical compound CCCCCC(N)=O ALBYIUDWACNRRB-UHFFFAOYSA-N 0.000 description 15
- 239000008188 pellet Substances 0.000 description 14
- 150000001412 amines Chemical class 0.000 description 13
- 239000003921 oil Substances 0.000 description 13
- 235000019198 oils Nutrition 0.000 description 13
- 239000004696 Poly ether ether ketone Substances 0.000 description 12
- XEXIPRQHXNUUAA-UHFFFAOYSA-N [5-(aminomethyl)oxolan-2-yl]methanamine Chemical compound NCC1CCC(CN)O1 XEXIPRQHXNUUAA-UHFFFAOYSA-N 0.000 description 12
- 229920001400 block copolymer Polymers 0.000 description 12
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 12
- 229920002530 polyetherether ketone Polymers 0.000 description 12
- NWYDEWXSKCTWMJ-UHFFFAOYSA-N 2-methylcyclohexane-1,1-diamine Chemical compound CC1CCCCC1(N)N NWYDEWXSKCTWMJ-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 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
- 229920005992 thermoplastic resin Polymers 0.000 description 11
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 10
- VKLGKDZCKSMSHG-UHFFFAOYSA-N [5-(aminomethyl)furan-2-yl]methanamine Chemical compound NCC1=CC=C(CN)O1 VKLGKDZCKSMSHG-UHFFFAOYSA-N 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 10
- 235000019241 carbon black Nutrition 0.000 description 10
- 239000012530 fluid Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003963 antioxidant agent Substances 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011231 conductive filler Substances 0.000 description 9
- YVORDIMCXSWNQQ-UHFFFAOYSA-N furan-2,5-dicarboxamide Chemical compound NC(=O)C1=CC=C(C(N)=O)O1 YVORDIMCXSWNQQ-UHFFFAOYSA-N 0.000 description 9
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 230000003078 antioxidant effect Effects 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
- 239000000835 fiber Substances 0.000 description 8
- 239000003502 gasoline Substances 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
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 229920000459 Nitrile rubber Polymers 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000012790 adhesive layer Substances 0.000 description 7
- VDBXLXRWMYNMHL-UHFFFAOYSA-N decanediamide Chemical compound NC(=O)CCCCCCCCC(N)=O VDBXLXRWMYNMHL-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 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 7
- 230000001681 protective effect Effects 0.000 description 7
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- 229920002492 poly(sulfone) Polymers 0.000 description 6
- 229920001748 polybutylene Polymers 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 229920001470 polyketone Polymers 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 229920003049 isoprene rubber Polymers 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 229920000768 polyamine Polymers 0.000 description 5
- 229920005672 polyolefin resin Polymers 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical compound FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 4
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-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
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 239000004695 Polyether sulfone Substances 0.000 description 4
- 229920000954 Polyglycolide Polymers 0.000 description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 description 4
- 229920000491 Polyphenylsulfone Polymers 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 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
- 239000007788 liquid Substances 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 229920001179 medium density polyethylene Polymers 0.000 description 4
- 239000004701 medium-density polyethylene Substances 0.000 description 4
- 150000004702 methyl esters Chemical class 0.000 description 4
- 229920001643 poly(ether ketone) Polymers 0.000 description 4
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 229920002490 poly(thioether-sulfone) polymer Polymers 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- 229920001230 polyarylate Polymers 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920006393 polyether sulfone Polymers 0.000 description 4
- 239000004633 polyglycolic acid Substances 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 229920006324 polyoxymethylene Polymers 0.000 description 4
- 229920006380 polyphenylene oxide Polymers 0.000 description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920005990 polystyrene resin Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 229920002620 polyvinyl fluoride Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 229920006132 styrene block copolymer Polymers 0.000 description 4
- DJZKNOVUNYPPEE-UHFFFAOYSA-N tetradecane-1,4,11,14-tetracarboxamide Chemical compound NC(=O)CCCC(C(N)=O)CCCCCCC(C(N)=O)CCCC(N)=O DJZKNOVUNYPPEE-UHFFFAOYSA-N 0.000 description 4
- 229920006259 thermoplastic polyimide Polymers 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- ZQTIKDIHRRLSRV-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluorobutane Chemical compound FC(F)C(F)(F)C(F)(F)C(F)(F)F ZQTIKDIHRRLSRV-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000011955 best available control technology Methods 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- ZWUNKULTLYLLTH-UHFFFAOYSA-N cyclohexane-1,4-dicarboxamide Chemical compound NC(=O)C1CCC(C(N)=O)CC1 ZWUNKULTLYLLTH-UHFFFAOYSA-N 0.000 description 3
- 229960003750 ethyl chloride Drugs 0.000 description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
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Abstract
本发明提供在维持低温耐冲击性、破坏抗压强度、柔软性之类的各种特性的同时,层间粘接性及其耐久性优异的层叠管。在具有至少两种层且该两层邻接的层叠管中,构成一层的脂肪族聚酰胺组合物包含脂肪族聚酰胺、共聚聚酰胺和弹性体聚合物,所述脂肪族聚酰胺中的亚甲基数与酰胺基数之比为特定值以上,所述共聚聚酰胺具有特定的单元,所述弹性体聚合物任选含有由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元。
Description
技术领域
本发明涉及层叠体。
背景技术
对于以面向一般产业用途的动力传导用油压管、汽车用空气制动器用等的空压管为首的汽车配管用化学溶液和/或气体输送管而言,从轻量化、作业性(组装性)的观点出发,其主要原材料逐渐从金属替换成防锈性优异且轻量的树脂。通常,作为化学溶液和/或气体输送管的材料,使用强度、韧性、耐化学药品性、柔软性等优异的聚酰胺11或聚酰胺12。
另一方面,作为化学溶液和/或气体输送管用材料,有时也使用热塑性聚氨酯。它们比聚酰胺11或聚酰胺12价格低,但机械强度和耐化学药品性差。
例如,聚酰胺612、聚酰胺11、聚酰胺12等长链脂肪族聚酰胺的破坏抗压强度、低温耐冲击性等机械特性良好,对于应力龟裂的形成具有抗性,且对于燃料、油和烃等化学品的耐性、耐水解性优异。为了将长链脂肪族聚酰胺的这些特性发挥至最大限度且降低成本,进行了各种将其与除长链脂肪族聚酰胺之外的其它廉价聚酰胺进行粘接、层叠化等的研究。
例如,提出了一种空气制动器用层叠管,其具有:由聚酰胺11或聚酰胺12形成的最外层、由改性聚烯烃或聚酰胺612形成的粘接层、由高温时的弯曲弹性模量为特定值以上的耐冲击性改良聚酰胺6形成的内层;以及,由聚酰胺11或聚酰胺12形成的最外层、由改性聚烯烃或聚酰胺612形成的粘接层、由高温时的弯曲弹性模量为特定值以上的耐冲击性改良聚酰胺6或聚酰胺66形成的中间层、由改性聚烯烃或聚酰胺612形成的粘接层、由聚酰胺11或聚酰胺12形成的最内层(参照专利文献1)。
另外,提出了一种压缩空气用层叠软管,其具有由聚酰胺11、聚酰胺12、脂肪族聚酰胺、聚酰胺11/12共聚物等长链脂肪族聚酰胺形成的最外层,所述脂肪族聚酰胺由碳原子数为6以上且12以下的脂肪族二胺和碳原子数为9以上且12以下的脂肪族二羧酸形成,并且该软管以聚酰胺、耐冲击性改良聚酰胺、聚酰胺弹性体、聚酰胺和聚酰胺弹性体的混合物作为内层,该软管具有由以改性聚烯烃或聚酰胺6/12共聚物为主体的聚酰胺共聚物形成的粘接层(参照专利文献2)。
进而,提出了一种空气制动器用层叠管,其由外层、中间层和内层构成,所述外层由单体单元的平均碳原子数为8以上的聚酰胺形成,所述中间层由未经耐冲击性改良的聚酰胺6、聚酰胺66、聚酰胺6/66共聚物形成,所述内层由单体单元的平均碳原子数为8以上的聚酰胺形成,中间层的厚度为特定范围的比率(参照专利文献3)。该技术公开了一种层叠管,其中,在作为外层材料而使用聚酰胺12作为单体单元的平均碳原子数为8以上的聚酰胺的情况下,在由未经耐冲击性改良的聚酰胺6、聚酰胺66、聚酰胺6/66共聚物形成的中间层之间,使用单体单元的平均碳原子数为9的聚酰胺612,从外侧朝向内侧依次配置有聚酰胺12、聚酰胺612、聚酰胺6、聚酰胺612、聚酰胺12。
现有技术文献
专利文献
专利文献1:美国专利第6670004号说明书
专利文献2:日本特开2004-34705号公报
专利文献3:日本特表2010-507501号公报
发明内容
发明要解决的问题
对于这些层叠管而言,不仅未公开长期接触/浸渍于燃料后、热处理后的层间粘接性(层间粘接性的耐久性),而且对于初始的层间粘接性也未公开具体的技术数据,如后所示已明确:专利文献1~3的层叠管虽然初始的层间粘接性在某种程度上是充分的,但在长期接触/浸渍于燃料后、热处理后等,其层间粘接性的耐久性尚有改善的余地。
因而,本发明的课题在于,提供即便不使用粘接层,其层间粘接性及其耐久性也优异的层叠体。
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:在具有至少两种层且该两层邻接的层叠体中,通过使构成一种层的脂肪族聚酰胺组合物包含亚甲基数与酰胺基数之比为特定值以上的脂肪族聚酰胺、作为由特定单体种类形成的共聚物的聚酰胺、以及任选含有由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元的弹性体聚合物,从而能够得到即便不使用粘接层,其层间粘接性及其耐久性也优异的层叠体。
即,本发明涉及一种层叠体,
其为包含(a)层和(b)层的两层以上的层叠体,
至少1组前述(a)层与前述(b)层邻接地配置,
前述(a)层包含脂肪族聚酰胺组合物(A),
前述(b)层包含脂肪族聚酰胺组合物(B),
前述脂肪族聚酰胺组合物(A)包含聚酰胺(A1)、聚酰胺(A2)和弹性体聚合物(A3),
前述聚酰胺(A1)是亚甲基数与酰胺基数之比为8.0以上的脂肪族聚酰胺,且该脂肪族聚酰胺不含如下共聚物,所述共聚物包含:由ε-己内酰胺或ε-氨基己酸衍生的单元a、以及由氨基十二烷酸或ω-月桂内酰胺衍生的单元b,前述脂肪族聚酰胺组合物(A)中包含30质量%以上且85质量%以下的前述聚酰胺(A1),
前述聚酰胺(A2)为包含如下共聚物的脂肪族聚酰胺,所述共聚物包含:由ε-己内酰胺或ε-氨基己酸衍生的单元a、以及由氨基十二烷酸或ω-月桂内酰胺衍生的单元b,前述脂肪族聚酰胺组合物(A)中包含10质量%以上且35质量%以下的前述聚酰胺(A2),
前述弹性体聚合物(A3)为任选含有由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元的弹性体聚合物,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(A3),
前述脂肪族聚酰胺组合物(B)包含聚酰胺(B1)和弹性体聚合物(B2),
前述聚酰胺(B1)是亚甲基数与酰胺基数之比小于8.0的脂肪族聚酰胺,前述脂肪族聚酰胺组合物(B)中包含55质量%以上且95质量%以下的前述聚酰胺(B1),
前述弹性体聚合物(B2)为含有由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元的弹性体聚合物,前述脂肪族聚酰胺组合物(B)中包含5质量%以上且30质量%以下的前述弹性体聚合物(B2)。
以下示出层叠体的优选方式。优选方式可以组合多个。
[1]一种层叠体,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、使用两种以上形成它们的原料单体而得的至少1种共聚物。
[2]一种层叠体,其中,前述聚酰胺(A2)为选自聚酰胺6/12、聚酰胺6/66/12中的共聚物。
[3]一种层叠体,其中,前述聚酰胺(A2)包含50质量%以上的由ε-己内酰胺或ε-氨基己酸衍生的单元a。
[4]一种层叠体,其中,前述弹性体聚合物(A3)包含在前述弹性体聚合物(A3)100质量%中为60质量%以上的如下弹性体聚合物,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。
[5]一种层叠体,其中,前述聚酰胺(B1)为选自由聚己酰胺(聚酰胺6)、聚己二酰己二胺(聚酰胺66)、聚壬二酰己二胺(聚酰胺69)和聚癸二酰己二胺(聚酰胺610)组成的组中的至少1种均聚物、和/或、使用两种以上形成它们的原料单体而得的至少1种共聚物。
[6]一种层叠体,其中,将每1g脂肪族聚酰胺组合物(A)中的聚酰胺(A1)和聚酰胺(A2)各自的末端氨基浓度(μeq/g)乘以其混合质量比而得的值进行求和而得到的末端氨基浓度记作[A](μeq/g),并将每1g脂肪族聚酰胺组合物(A)中的聚酰胺(A1)和聚酰胺(A2)各自的末端羧基浓度(μeq/g)乘以其混合质量比而得的值进行求和而得到的末端羧基浓度记作[B](μeq/g)时,[A]>[B]+5。
[7]一种层叠体,其中,前述(a)层包含40质量%以上且100质量%以下的前述脂肪族聚酰胺组合物(A),前述(b)层包含60质量%以上且100质量%以下的前述脂肪族聚酰胺组合物(B)。
[8]一种层叠体,其通过共挤出成形来制造。
[9]一种层叠体,其形状为中空体。
[10]一种层叠体,其用作化学溶液和/或气体输送管。
[11]一种层叠体,其具有与前述(a)层相比配置在内侧的至少1个前述(b)层。
[12]一种层叠体,其中,从外侧起依次层叠前述(a)层、前述(b)层、前述(a)层,且彼此邻接。
发明的效果
根据本发明,可提供即使不使用粘接层,其层间粘接性及其耐久性也优异的层叠体。
具体实施方式
层叠体包含至少1组的(a)层和(b)层,且为两层以上。
1.(a)层
层叠体的(a)层包含脂肪族聚酰胺组合物(A)。从耐热性、耐化学药品性、机械物性的观点出发,脂肪族聚酰胺组合物(A)在(a)层中优选包含40质量%以上且100质量%以下,更优选包含45质量%以上且100质量%以下。
[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)、聚酰胺(A2)和弹性体聚合物(A3),聚酰胺(A1)是亚甲基数与酰胺基数之比为8.0以上的脂肪族聚酰胺,且该脂肪族聚酰胺不含如下共聚物,所述共聚物包含:由ε-己内酰胺或ε-氨基己酸衍生的单元a、以及由氨基十二烷酸或ω-月桂内酰胺衍生的单元b,脂肪族聚酰胺组合物(A)中包含30质量%以上且85质量%以下的聚酰胺(A1),前述聚酰胺(A2)为包含如下共聚物的脂肪族聚酰胺,所述共聚物包含:由ε-己内酰胺或ε-氨基己酸衍生的单元a、以及由氨基十二烷酸或ω-月桂内酰胺衍生的单元b,前述脂肪族聚酰胺组合物(A)中包含10质量%以上且35质量%以下的前述聚酰胺(A2),弹性体聚合物(A3)为任选含有由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元的弹性体聚合物,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(A3)(以下,有时称为脂肪族聚酰胺组合物(A))。另外,从长期接触/浸渍于燃料后和/或短时间热处理后的层间粘接性的耐久性的观点出发,脂肪族聚酰胺组合物(A)优选不含增塑剂。
[聚酰胺(A1)]
聚酰胺(A1)是在结构重复单元中包含脂肪族基团,且主链中具有酰胺键(-CONH-),亚甲基数([CH2])与酰胺基数([NHCO])之比[CH2]/[NHCO](以下,有时将亚甲基数与酰胺基数之比称为[CH2]/[NHCO])为8.0以上的脂肪族聚酰胺,其是除了包含由ε-己内酰胺或ε-氨基己酸衍生的单元a、以及由氨基十二烷酸或ω-月桂内酰胺衍生的单元b的共聚物之外的脂肪族聚酰胺(以下,有时称为聚酰胺(A1))。聚酰胺(A1)的[CH2]/[NHCO]优选为9.0以上、更优选为9.5以上、进一步优选为10.0以上。若聚酰胺(A1)的亚甲基数([CH2])与酰胺基数([NHCO])之比小于前述值,则所得层叠体的机械特性和耐化学药品性差。
另外,聚酰胺(A1)优选为:亚甲基数与酰胺基数之比[CH2]/[NHCO]为8.0以上的脂肪族聚酰胺的均聚物;仅使用至少两种形成亚甲基数与酰胺基数之比[CH2]/[NHCO]为8.0以上的脂肪族聚酰胺的原料单体(结构重复单元)而得的聚酰胺共聚物;以及,将形成亚甲基数与酰胺基数之比[CH2]/[NHCO]为8.0以上的脂肪族聚酰胺的原料单体(结构重复单元)作为至少一种组分,且使用至少一种形成亚甲基数与酰胺基数之比[CH2]/[NHCO]小于8.0的脂肪族聚酰胺的原料单体(结构重复单元)而得的聚酰胺共聚物。聚酰胺(A1)不含如下共聚物,所述共聚物包含:由ε-己内酰胺或ε-氨基己酸衍生的单元a、以及由氨基十二烷酸或ω-月桂内酰胺衍生的单元b。
分成以下情况来说明优选的聚酰胺(A1)的例子:亚甲基数与酰胺基数之比[CH2]/[NHCO]为8.0以上的脂肪族聚酰胺均聚物(A1X)(以下,有时称为聚酰胺(A1X));仅使用两种以上的形成亚甲基数与酰胺基数之比[CH2]/[NHCO]为8.0以上的脂肪族聚酰胺的原料单体(结构重复单元)而得的聚酰胺共聚物(A1XX)(以下,有时称为聚酰胺(A1XX));以及,将形成亚甲基数与酰胺基数之比[CH2]/[NHCO]为8.0以上的脂肪族聚酰胺的原料单体(结构重复单元)作为至少一种组分,且使用至少一种形成亚甲基数与酰胺基数之比[CH2]/[NHCO]小于8.0的脂肪族聚酰胺的原料单体(结构重复单元)而得的聚酰胺共聚物(A1Y)(以下,有时称为聚酰胺(A1Y))。
作为亚甲基数与酰胺基数之比[CH2]/[NHCO]为8.0以上的聚酰胺(A1X),可列举出:聚十一酰胺(聚酰胺11):[CH2]/[NHCO]=10.0、聚十二酰胺(聚酰胺12):[CH2]/[NHCO]=11.0、聚十二烷二酰己二胺(聚酰胺612):[CH2]/[NHCO]=8.0、聚十四烷二酰己二胺(聚酰胺614):[CH2]/[NHCO]=9.0、聚十六烷二酰己二胺(聚酰胺616):[CH2]/[NHCO]=10.0、聚十八烷二酰己二胺(聚酰胺618):[CH2]/[NHCO]=11.0、聚癸二酰辛二胺(聚酰胺810):[CH2]/[NHCO]=8.0、聚十二烷二酰辛二胺(聚酰胺812):[CH2]/[NHCO]=9.0、聚壬二酰壬二胺(聚酰胺99):[CH2]/[NHCO]=8.0、聚癸二酰壬二胺(聚酰胺910):[CH2]/[NHCO]=8.5、聚十二烷二酰壬二胺(聚酰胺912):[CH2]/[NHCO]=9.5、聚辛二酰癸二胺(聚酰胺108):[CH2]/[NHCO]=8.0、聚壬二酰癸二胺(聚酰胺109):[CH2]/[NHCO]=8.5、聚癸二酰癸二胺(聚酰胺1010):[CH2]/[NHCO]=9.0、聚十二烷二酰癸二胺(聚酰胺1012):[CH2]/[NHCO]=10.0、聚己二酰十二烷二胺(聚酰胺126):[CH2]/[NHCO]=8.0、聚辛二酰十二烷二胺(聚酰胺128):[CH2]/[NHCO]=9.0、聚壬二酰十二烷二胺(聚酰胺129):[CH2]/[NHCO]=9.5、聚癸二酰十二烷二胺(聚酰胺1210):[CH2]/[NHCO]=10.0、聚十二烷二酰十二烷二胺(聚酰胺1212):[CH2]/[NHCO]=11.0。它们可以使用1种或两种以上。
另外,作为仅使用两种以上形成亚甲基数与酰胺基数之比[CH2]/[NHCO]为8.0以上的脂肪族聚酰胺的原料单体(结构重复单元)而得的聚酰胺共聚物(A1XX),可列举出使用两种以上形成前述聚酰胺(A1X)中的至少1种均聚物的原料单体而得的共聚物。它们可以使用1种或两种以上。
聚酰胺(A1)为共聚物时,其亚甲基数与酰胺基数之比[CH2]/[NHCO]可如下求出:将构成共聚物的结构重复单元的单体的均聚物中的亚甲基数与酰胺基数之比[CH2]/[NHCO]乘以该结构重复单元在共聚物中的摩尔比而得到数值,针对全部结构重复单元进行加合来求出。
作为仅使用两种以上形成亚甲基数与酰胺基数之比[CH2]/[NHCO]为8.0以上的脂肪族聚酰胺的原料单体(结构重复单元)而得的聚酰胺共聚物(A1XX),例如,由于聚十二酰胺(聚酰胺12)和聚十二烷二酰十二烷二胺(聚酰胺1212)的亚甲基数与酰胺基数之比[CH2]/[NHCO]为11.0,因此,无论结构重复单元的摩尔比如何,聚(十二酰胺/十二烷二酰十二烷二胺)共聚物(聚酰胺12/1212)的亚甲基数与酰胺基数之比[CH2]/[NHCO]的亚甲基数与酰胺基数之比[CH2]/[NHCO]均为11.0。
进而,聚(十二酰胺/十一酰胺)共聚物(聚酰胺12/11)的亚甲基数与酰胺基数之比[CH2]/[NHCO]因结构重复单元的摩尔比而发生变化。聚十二酰胺(聚酰胺12)的亚甲基数与酰胺基数之比[CH2]/[NHCO]为11.0,聚十一酰胺(聚酰胺11)的亚甲基数与酰胺基数之比[CH2]/[NHCO]为10.0,因此,如果获知结构重复单元的摩尔比则能够计算,在聚(十二酰胺/十一酰胺)共聚物(聚酰胺12/11)的十二酰胺单元/十一酰胺单元为80:20(摩尔比)的情况下,亚甲基数与酰胺基数之比[CH2]/[NHCO]成为11.0×0.80+10.0×0.20=10.8。如果十一酰胺单元的摩尔比增加,则亚甲基数与酰胺基数之比[CH2]/[NHCO]会减少,但亚甲基数与酰胺基数之比[CH2]/[NHCO]至少不会低于10.0。
像这样,如聚(十二酰胺/十二烷二酰十二烷二胺)共聚物(聚酰胺12/1212)和聚(十二酰胺/十一酰胺)共聚物(聚酰胺12/11)那样,仅使用形成亚甲基数与酰胺基数之比[CH2]/[NHCO]为8.0以上的脂肪族聚酰胺的原料单体(结构重复单元)而得的聚酰胺共聚物(A1XX)无论其结构重复单元的摩尔比如何,亚甲基数与酰胺基数之比[CH2]/[NHCO]均成为8.0以上,包括在本申请的聚酰胺(A1)中。
另一方面,聚酰胺(A1)也可以将形成亚甲基数与酰胺基数之比[CH2]/[NHCO]为8.0以上的脂肪族聚酰胺的原料单体(结构重复单元)作为至少一种组分,并如后所述,使用至少一种形成亚甲基数与酰胺基数之比[CH2]/[NHCO]小于8.0的脂肪族聚酰胺的原料单体(结构重复单元)来共聚,所得的聚酰胺共聚物(A1Y)只要亚甲基数与酰胺基数之比[CH2]/[NHCO]为8.0以上,就包括在本申请的聚酰胺(A1)中。
作为亚甲基数与酰胺基数之比[CH2]/[NHCO]小于8.0的脂肪族聚酰胺,可列举出:聚己酰胺(聚酰胺6):[CH2]/[NHCO]=5.0、聚己二酰乙二胺(聚酰胺26):[CH2]/[NHCO]=3.0、聚丁二酰丁二胺(聚酰胺44):[CH2]/[NHCO]=3.0、聚戊二酰丁二胺(聚酰胺45):[CH2]/[NHCO]=3.5、聚己二酰丁二胺(聚酰胺46):[CH2]/[NHCO]=4.0、聚辛二酰丁二胺(聚酰胺48):[CH2]/[NHCO]=5.0、聚壬二酰丁二胺(聚酰胺49):[CH2]/[NHCO]=5.5、聚癸二酰丁二胺(聚酰胺410):[CH2]/[NHCO]=6.0、聚十二烷二酰丁二胺(聚酰胺412):[CH2]/[NHCO]=7.0、聚丁二酰戊二胺(聚酰胺54):[CH2]/[NHCO]=3.5、聚戊二酰戊二胺(聚酰胺55):[CH2]/[NHCO]=4.0、聚己二酰戊二胺(聚酰胺56):[CH2]/[NHCO]=4.5、聚辛二酰戊二胺(聚酰胺58):[CH2]/[NHCO]=5.5、聚壬二酰戊二胺(聚酰胺59):[CH2]/[NHCO]=6.0、聚癸二酰戊二胺(聚酰胺510):[CH2]/[NHCO]=6.5、聚十二烷二酰戊二胺(聚酰胺512):[CH2]/[NHCO]=7.5、聚丁二酰己二胺(聚酰胺64):[CH2]/[NHCO]=4.0、聚戊二酰己二胺(聚酰胺65):[CH2]/[NHCO]=4.5、聚己二酰己二胺(聚酰胺66):[CH2]/[NHCO]=5.5、聚辛二酰己二胺(聚酰胺68):[CH2]/[NHCO]=6.0、聚壬二酰己二胺(聚酰胺69):[CH2]/[NHCO]=6.5、聚癸二酰己二胺(聚酰胺610):[CH2]/[NHCO]=7.0、聚己二酰壬二胺(聚酰胺96):[CH2]/[NHCO]=6.5、聚辛二酰壬二胺(聚酰胺98):[CH2]/[NHCO]=7.5、聚戊二酰癸二胺(聚酰胺105):[CH2]/[NHCO]=6.5、聚己二酰癸二胺(聚酰胺106):[CH2]/[NHCO]=7.0、聚戊二酰十二烷二胺(聚酰胺125):[CH2]/[NHCO]=7.5等。另外,作为亚甲基数与酰胺基数之比[CH2]/[NHCO]小于8.0的脂肪族聚酰胺,可列举出使用两种以上形成前述的至少1种均聚物的原料单体而得的共聚物。它们可以使用1种或两种以上。
将形成亚甲基数与酰胺基数之比[CH2]/[NHCO]为8.0以上的脂肪族聚酰胺的原料单体(结构重复单元)作为至少一种组分,并使用至少一种形成亚甲基数与酰胺基数之比[CH2]/[NHCO]小于8.0的脂肪族聚酰胺的原料单体(结构重复单元)而得的聚酰胺共聚物(A1Y)的[CH2]/[NHCO]如下那样地求出。例如,聚(十二酰胺/己酰胺)共聚物(聚酰胺12/6)的亚甲基数与酰胺基数之比[CH2]/[NHCO]因结构重复单元的摩尔比而发生变化。聚十二酰胺(聚酰胺12)的亚甲基数与酰胺基数之比[CH2]/[NHCO]为11.0,聚己酰胺(聚酰胺6)的亚甲基数与酰胺基数之比[CH2]/[NHCO]为5.0,因此,如果获知结构重复单元的摩尔比则能够计算,聚(十二酰胺/己酰胺)共聚物(聚酰胺12/6)的十二酰胺单元/己酰胺单元为50.0:50.0~99.5:0.5(摩尔比)的聚酰胺共聚物中,亚甲基数与酰胺基数之比[CH2]/[NHCO]成为8.0以上。其中,为了对聚(十二酰胺/己酰胺)共聚物(聚酰胺12/6)与聚十二酰胺(聚酰胺12)加以区分,在与聚(十二酰胺/己酰胺)共聚物(聚酰胺12/6)的十二酰胺单元/己酰胺单元为99.5:0.5(摩尔比)相比,十二酰胺单元的比例更高的情况下,将其视作聚十二酰胺(聚酰胺12)。以下,均聚物与共聚物同样处理。
即,聚(十二酰胺/己酰胺)共聚物(聚酰胺12/6)的十二酰胺单元/己酰胺单元为50.0:50.0~99.5:0.5(摩尔比)的聚酰胺共聚物中,亚甲基数与酰胺基数之比[CH2]/[NHCO]达到8.0以上,包括在本申请的聚酰胺(A1)中。
像这样,将形成亚甲基数与酰胺基数之比[CH2]/[NHCO]为8.0以上的脂肪族聚酰胺的原料单体(结构重复单元)作为至少一种成分,且使用至少一种形成亚甲基数与酰胺基数之比[CH2]/[NHCO]小于8.0的脂肪族聚酰胺的原料单体(结构重复单元)而得的聚酰胺共聚物(A1Y)中的亚甲基数与酰胺基数之比[CH2]/[NHCO]可根据结构重复单元的摩尔比和各结构重复单元的亚甲基数与酰胺基数之比[CH2]/[NHCO]来计算,只要亚甲基数与酰胺基数之比[CH2]/[NHCO]为8.0以上,就包括在本申请的聚酰胺(A1)中。
这些之中,从充分确保所得层叠体的机械特性、耐热性、耐化学药品性等各物性、以及经济性和获取容易度的观点出发,聚酰胺(A1)更优选为选自由聚十一酰胺(聚酰胺11)、聚十二酰胺(聚酰胺12)、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、使用两种以上形成它们的原料单体而得的至少1种共聚物等,进一步优选为选自由聚十一酰胺(聚酰胺11)、聚十二酰胺(聚酰胺12)、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、使用两种以上形成它们的原料单体而得的至少1种共聚物。
另外,从单体、低聚物的耐溶出性的观点出发,特别优选为选自由聚十二烷二酰己二胺(聚酰胺612)、聚癸二酰癸二胺(聚酰胺1010)和/或聚十二烷二酰癸二胺(聚酰胺1012)组成的组中的至少1种均聚物、和/或、使用两种以上形成它们的原料单体而得的至少1种共聚物。
[聚酰胺(A2)]
聚酰胺(A2)为包含如下共聚物的脂肪族聚酰胺(以下,有时称为聚酰胺(A2)),所述共聚物包含:由ε-己内酰胺或ε-氨基己酸衍生的单元a、以及由氨基十二烷酸或ω-月桂内酰胺衍生的单元b。
聚酰胺(A2)只要包含如下共聚物且为脂肪族聚酰胺即可,以满足其的方式适当选择,所述共聚物包含:由ε-己内酰胺或ε-氨基己酸衍生的单元a、以及由氨基十二烷酸或ω-月桂内酰胺衍生的单元b。另外,聚酰胺(A2)优选包含50质量%以上的由ε-己内酰胺或ε-氨基己酸衍生的单元a。
作为包含如下共聚物且该共聚物包含由ε-己内酰胺或ε-氨基己酸衍生的单元a以及由氨基十二烷酸或ω-月桂内酰胺衍生的单元b的脂肪族聚酰胺(A2),优选为聚(己酰胺/十二酰胺)共聚物(聚酰胺6/12)、聚(己酰胺/己二酰己二胺/十二酰胺)共聚物(聚酰胺6/66/12)、聚(己酰胺/癸二酰己二胺/十二酰胺)共聚物(聚酰胺6/610/12)、聚(己酰胺/十二烷二酰己二胺/十二酰胺)共聚物(聚酰胺6/612/12)、以及它们的混合物,更优选为聚(己酰胺/十二酰胺)共聚物(聚酰胺6/12)和/或聚(己酰胺/己二酰己二胺/十二酰胺)共聚物(聚酰胺6/66/12)。
从充分确保获取容易度、经济性、所得层叠体的机械特性、耐化学药品性、柔软性等各物性,且充分获得与前述脂肪族聚酰胺组合物(A)的层间粘接性及其耐久性的观点出发,聚酰胺(A2)优选从包含如下共聚物且该共聚物包含由ε-己内酰胺或ε-氨基己酸衍生的单元a以及由氨基十二烷酸或ω-月桂内酰胺衍生的单元b的脂肪族聚酰胺中以由ε-己内酰胺或ε-氨基己酸衍生的单元a满足50质量%以上的方式适当选择。
作为聚酰胺(A1)和聚酰胺(A2)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。
从确保所得层叠体的机械性质、以及将熔融时的粘度设为适当范围而确保层叠体的期望的成形性的观点出发,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)和聚酰胺(A2)的相对粘度优选为1.5以上且5.0以下、更优选为1.8以上且4.5以下。
将每1g聚酰胺(A1)的末端氨基浓度记作[A1](μeq/g),并将末端羧基浓度记作[B1](μeq/g)时,从充分确保所得层叠体的层间粘接性及其耐久性的观点出发,优选为[A1]>[B1]+5、更优选为[A1]>[B1]+10、进一步优选为[A1]>[B1]+15。进而,从聚酰胺的熔融稳定性和抑制凝胶状物发生的观点出发,优选为[A1]>20、更优选为30<[A1]<120。
另外,将每1g聚酰胺(A2)的末端氨基浓度记作[A2](μeq/g),并将末端羧基浓度记作[B2](μeq/g)时,从充分确保所得层叠体的层间粘接性及其耐久性的观点出发,更优选为[A2]>[B2]+5、进一步优选为[A2]>[B1]+10、特别优选为[A2]>[B2]+15。进而,从聚酰胺的熔融稳定性和抑制凝胶状物发生的观点出发,更优选为[A2]>20、进一步优选为30<[A2]<120。
在包含聚酰胺(A1)和聚酰胺(A2)的脂肪族聚酰胺组合物(A)中,将每1g脂肪族聚酰胺组合物(A)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,从充分获得所得层叠体的层间粘接性及其耐久性的观点出发,更优选为[A]>[B]+5、进一步优选为[A]>[B]+10、特别优选为[A]>[B]+15。进而,从聚酰胺的熔融稳定性和抑制凝胶状物发生的观点出发,更优选为[A]>30、进一步优选为30<[A]<120。
此处,每1g脂肪族聚酰胺组合物(A)的末端氨基浓度[A](μeq/g)、末端羧基浓度[B](μeq/g)设为如下值:将聚酰胺(A1)和聚酰胺(A2)各自的末端氨基浓度(μeq/g)、末端羧基浓度(μeq/g)乘以各自的混合质量比,并将两者加合而得的值。
另外,末端氨基浓度(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(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)和聚酰胺(A2)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,考虑到所得层叠体的层间粘接性时,优选在聚合时的阶段进行添加。
作为前述胺类,可列举出单胺、二胺、三胺、四胺和多胺。另外,除了胺类之外,只要不偏离前述末端基团浓度条件的范围,就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,后述例示的胺类、羧酸类可以使用1种或两种以上。
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种或两种以上。
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种或两种以上。
作为所添加的三胺和四胺的具体例,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、1,4,5,8-四氨基萘等。它们可以使用1种或两种以上。
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。它们可以使用1种或两种以上。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。
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种或两种以上进行聚合而得到的均聚物和/或共聚物。它们可以使用1种或两种以上。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,可以包含乙二胺、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、双氨基丙基乙二胺等。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和/或仲氨基(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3,000以下、更优选为8以上且1,500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20,000以下、更优选为200以上且10,000以下、进一步优选为500以上且8,000以下。
所添加的胺类的用量可考虑想要制造的聚酰胺(A1)和聚酰胺(A2)的末端氨基浓度、末端羧基浓度和相对粘度,并通过公知的方法来适当决定。通常,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),从获得充分的反应性且容易制造具有期望粘度的聚酰胺的观点出发,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1meq/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(摩尔比)发生反应而形成酰胺基的氨基量设为1当量)。
对于聚酰胺(A1)和聚酰胺(A2)而言,在前述例示的胺类之中,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,从抑制凝胶发生的观点出发,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,进一步优选在聚合时添加聚亚烷基亚胺。
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、间苯二甲酸、对苯二甲酸、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。
[弹性体聚合物(A3)]
脂肪族聚酰胺组合物(A)含有弹性体聚合物(A3)(以下,有时称为弹性体聚合物(A3)),所述弹性体聚合物(A3)任选含有由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元。
作为弹性体聚合物(A3),可列举出含有由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元的(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)系共聚物和芳香族乙烯基化合物/共轭二烯化合物系嵌段共聚物;以及不含由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元的(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)系共聚物和芳香族乙烯基化合物/共轭二烯化合物系嵌段共聚物,它们可以使用1种或两种以上。
从机械物性、流动性的观点出发,弹性体聚合物(A3)优选在前述弹性体聚合物(A3)100质量%中包含60质量%以上的如下弹性体聚合物、更优选包含75质量%以上且95质量%以下的如下弹性体聚合物,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。
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1,4-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。
另外,前述芳香族乙烯基化合物/共轭二烯化合物系嵌段共聚物为包含芳香族乙烯基化合物系聚合物嵌段和共轭二烯化合物系聚合物嵌段的嵌段共聚物,可以使用具有至少1个芳香族乙烯基化合物系聚合物嵌段和至少1个共轭二烯化合物系聚合物嵌段的嵌段共聚物。前述嵌段共聚物中,共轭二烯化合物系聚合物嵌段中的不饱和键可以进行了加氢。
芳香族乙烯基化合物系聚合物嵌段是主要由源自芳香族乙烯基化合物的单元形成的聚合物嵌段。作为此时的芳香族乙烯基化合物,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,它们可以使用1种或两种以上。另外,芳香族乙烯基化合物系聚合物嵌段根据情况可以具有少量的由其它不饱和单体形成的单元。
共轭二烯化合物系聚合物嵌段是由1,3-丁二烯、氯丁二烯、异戊二烯、2,3-二甲基-1,3-丁二烯、1,3-戊二烯、4-甲基-1,3-戊二烯、1,3-己二烯等共轭二烯系化合物中的1种或两种以上形成的聚合物嵌段,在经加氢的芳香族乙烯基化合物/共轭二烯化合物系嵌段共聚物中,该共轭二烯化合物系聚合物嵌段中的不饱和键部分的一部分或全部通过加氢而形成饱和键。
芳香族乙烯基化合物/共轭二烯化合物系嵌段共聚物及其加氢物的分子结构可以为直链状、支链状、放射状或它们的任意组合中的任一者。这些之中,作为芳香族乙烯基化合物/共轭二烯化合物系嵌段共聚物和/或其加氢物,优选使用1个芳香族乙烯基化合物聚合物嵌段与1个共轭二烯化合物系聚合物嵌段键合成直链状而得的二嵌段共聚物、按照芳香族乙烯基化合物系聚合物嵌段-共轭二烯化合物系聚合物嵌段-芳香族乙烯基化合物系聚合物嵌段的顺序将3个聚合物嵌段键合成直链状而得的三嵌段共聚物、以及它们的加氢物中的1种或两种以上,可列举出未加氢或加氢苯乙烯/丁二烯嵌段共聚物、未加氢或加氢苯乙烯/异戊二烯嵌段共聚物、未加氢或加氢苯乙烯/丁二烯/苯乙烯嵌段共聚物、未加氢或加氢苯乙烯/异戊二烯/苯乙烯嵌段共聚物、未加氢或加氢苯乙烯/(乙烯/丁二烯)/苯乙烯嵌段共聚物、未加氢或加氢苯乙烯/(异戊二烯/丁二烯)/苯乙烯嵌段共聚物等。它们可以使用1种或两种以上。
作为任选形成弹性体聚合物(A3)的结构单元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。它们可以使用1种或两种以上。作为任选形成弹性体聚合物(A3)的结构单元的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种或两种以上。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。
从改良低温耐冲击性的效果、充分获得与后述脂肪族聚酰胺组合物(B)的层间粘接性及其耐久性、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(A3)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(A3)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剂,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。
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30质量%以上且85质量%以下,优选为35质量%以上且80质量%以下,更优选为40质量%以上且70质量%以下。若聚酰胺(A1)的含量小于前述值,则所得层叠体的机械特性有时差,另一方面,若超过前述值,则所得层叠体的低温耐冲击性、层间粘接性及其耐久性有时差。
脂肪族聚酰胺组合物(A)中的聚酰胺(A2)的含量相对于脂肪族聚酰胺组合物(A)100质量%为10质量%以上且35质量%以下,优选为13质量%以上且30质量%以下,更优选为15质量%以上且27质量%以下。若聚酰胺(A2)的含量小于前述值,则所得层叠体的层间粘接性及其耐久性有时差,另一方面,若超过前述值,则所得层叠体的化学溶液隔绝性和耐化学药品性有时差。
脂肪族聚酰胺组合物(A)中的弹性体聚合物(A3)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27质量%以下,更优选为10质量%以上且25质量%以下。若弹性体聚合物(A3)的含量小于前述值,则所得层叠体的低温耐冲击性、层间粘接性及其耐久性有时差,另一方面,若超过前述值,则所得层叠体的机械特性和所得脂肪族聚酰胺组合物(A)的流动性有时差。
将聚酰胺(A1)、聚酰胺(A2)和弹性体聚合物(A3)进行混合的方法没有特别限定,可根据需要来配混各种添加剂,并采用以往公知的各种方法。可通过例如下述方法来制造:使用转鼓和/或搅拌器,以聚酰胺(A1)、聚酰胺(A2)和弹性体聚合物(A3)的粒料彼此达到前述混合比例的方式,将两者均匀地干混的方法;将两者与根据需要而添加的其它成分一同以成形时使用的浓度预先干混,并进行熔融混炼的方法等。熔融混炼可使用单螺杆挤出机、双螺杆挤出机、捏合机、班伯里密炼机等混炼机来进行。
脂肪族聚酰胺组合物(A)可以是与其它热塑性树脂的混合物。脂肪族聚酰胺组合物(A)中的其它热塑性树脂的含量相对于脂肪族聚酰胺组合物(A)100质量%优选为20质量%以下、更优选为15质量%以下。
作为要混合的其它热塑性树脂,可列举出高密度聚乙烯(HDPE)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)、直链状低密度聚乙烯(LLDPE)、超高分子量聚乙烯(UHMWPE)、聚丙烯(PP)、聚丁烯(PB)、聚甲基戊烯(TPX)、乙烯/乙酸乙烯酯共聚物皂化物(EVOH)等聚烯烃系树脂;聚苯乙烯(PS)、间同立构聚苯乙烯(SPS)、甲基丙烯酸甲酯/苯乙烯共聚物(MS)、甲基丙烯酸甲酯/苯乙烯/丁二烯共聚物(MBS)等聚苯乙烯系树脂;含有羧基及其盐、酸酐基、环氧基等官能团的前述聚烯烃系树脂和聚苯乙烯系树脂;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;聚酮(PK)、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;聚乙烯醇(PVA)、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乙烯基系树脂;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;聚酰胺弹性体、聚氨酯弹性体、聚酯弹性体、聚偏二氟乙烯(PVDF)、聚氟乙烯(PVF)、聚四氟乙烯(PTFE)、聚氯氟乙烯(PCTFE)、四氟乙烯/乙烯共聚物(ETFE)、乙烯/三氟氯乙烯共聚物(ECTFE)、四氟乙烯/六氟丙烯共聚物(FEP)、四氟乙烯/六氟丙烯/偏二氟乙烯共聚物(THV)、四氟乙烯/六氟丙烯/偏二氟乙烯/全氟(烷基乙烯基醚)共聚物、四氟乙烯/全氟(烷基乙烯基醚)共聚物(PFA)、四氟乙烯/六氟丙烯/全氟(烷基乙烯基醚)共聚物、三氟氯乙烯/全氟(烷基乙烯基醚)/四氟乙烯共聚物(CPT)等含氟系聚合物、含有对于氨基具有反应性的官能团的前述含氟系聚合物。它们可以使用1种或两种以上。
进而,根据需要,可以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、光稳定剂、润滑剂、无机填充剂、抗静电剂、阻燃剂、结晶化促进剂、着色剂等。
2.(b)层
层叠体的(b)层包含脂肪族聚酰胺组合物(B)。从耐热性、机械物性的观点出发,在(b)层中,脂肪族聚酰胺组合物(B)优选包含60质量%以上且100质量%以下,更优选包含70质量%以上且100质量%以下。
前述脂肪族聚酰胺组合物(B)包含聚酰胺(B1)和弹性体聚合物(B2),聚酰胺(B1)是亚甲基数与酰胺基数之比小于8.0的脂肪族聚酰胺,在前述聚酰胺组合物(B)中的含量为55质量%以上且95质量%以下,弹性体聚合物(B2)为含有由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元的弹性体聚合物,在前述聚酰胺组合物(B)中的含量为5质量%以上且30质量%以下(以下,有时称为脂肪族聚酰胺组合物(B))。
聚酰胺(B1)为选自由聚己酰胺(聚酰胺6)、聚己二酰己二胺(聚酰胺66)、聚壬二酰己二胺(聚酰胺69)和聚癸二酰己二胺(聚酰胺610)组成的组中的至少1种均聚物、和/或、使用两种以上形成它们的原料单体而得的至少1种共聚物。
聚酰胺(B1)的制造方法和制造装置与聚酰胺(A1)和(A2)相同。
从确保所得层叠体的机械性质、以及将熔融时的粘度设为适当范围而确保层叠体的期望的成形性的观点出发,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(B1)的相对粘度优选为1.5以上且5.0以下、更优选为1.8以上且4.5以下。
脂肪族聚酰胺组合物(B)中的聚酰胺(B1)的含量相对于脂肪族聚酰胺组合物(B)100质量%为55质量%以上且95质量%以下,优选为60质量%以上且93质量%以下、更优选为70质量%以上且90质量%以下。若脂肪族聚酰胺(B1)的含量小于前述值,则所得层叠体的机械物性有时差,另一方面,若超过前述值,则所得层叠管的低温耐冲击性和耐化学药品性有时差。
前述脂肪族聚酰胺组合物(B)包含弹性体聚合物(B2),所述弹性体聚合物(B2)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。
作为弹性体聚合物(B2),可列举出含有由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元的(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)系共聚物和芳香族乙烯基化合物/共轭二烯化合物系嵌段共聚物。它们可以使用1种或两种以上。
作为它们的例示,可列举出与作为弹性体聚合物(A3)而例示的物质相同的物质。作为弹性体聚合物(B2),可以使用与弹性体聚合物(A3)相同的物质,也可以使用不同的物质。它们可以使用1种或两种以上。
脂肪族聚酰胺组合物(B)中的弹性体聚合物(B2)的含量相对于脂肪族聚酰胺组合物(B)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。若弹性体聚合物(B2)的含量小于前述值,则所得层叠体的低温耐冲击性、层间粘接性及其耐久性有时差,另一方面,若超过前述值,则所得层叠体的机械特性和所得脂肪族聚酰胺组合物(B)的流动性有时差。
将聚酰胺(B1)与弹性体聚合物(B2)进行混合的方法可列举出在前述脂肪族聚酰胺组合物(A)的说明中记载的公知方法。
脂肪族聚酰胺组合物(B)可以含有其它热塑性树脂。作为其它热塑性树脂,可列举出与前述脂肪族聚酰胺组合物(A)的情况相同的树脂。它们可以使用1种或两种以上。脂肪族聚酰胺组合物(B)中的其它的热塑性树脂的含量相对于脂肪族聚酰胺组合物(B)100质量%优选为20质量%以下、更优选为15质量%以下。
进而,脂肪族聚酰胺组合物(B)可根据需要而添加抗氧化剂、热稳定剂、紫外线吸收剂、光稳定剂、润滑剂、无机填充剂、抗静电剂、阻燃剂、结晶化促进剂、着色剂、润滑剂、增塑剂等。
[层叠体]层叠体的方式包含(a)层和(b)层这至少两层,且至少1组的(a)层与(b)层邻接配置。
作为层叠体,可列举出层叠中空体、层叠薄膜、层叠板。
作为层叠中空体,可列举出管、软管。
通过包含(b)层,从而使层叠体在负载环境应力后的低温耐冲击性变得良好。进而,通过使(a)层与(b)层邻接配置,能够得到层间粘接性及其耐久性优异的层叠体。
作为优选的层叠中空体的实施方式,具有与(a)层相比配置在内侧的至少1个(b)层。此时,只要至少1组的(a)层与(b)层邻接,则可以是与(a)层相比配置在内侧的(b)层以与(a)层邻接的方式配置,也可以在(a)层与(b)层之间配置有其它层。例如,在最外层(a)层与最内层(a)层之间包含1个中间层(b)层的3层结构的情况下,作为邻接的(a)层和(b)层,有最外层(a)层与中间层(b)层的组合、以及最内层(a)层与中间层(b)层的组合,在两个组合中,至少一个组合中的(b)层与(a)层相比配置在内侧,因此,满足前述必要条件。
作为更优选的层叠中空体的实施方式,从层叠体的外侧起朝向内侧依次配置(a)层、(b)层。通过使(a)层配置于外层,能够得到耐化学药品性优异的层叠体。通过使(b)层配置于内侧,能够抑制因与含醇汽油接触而导致的单体、低聚物等低分子量成分的溶出。
作为进一步优选的层叠中空体的实施方式,从层叠体的外侧起朝向内侧依次配置(a)层、(b)层、(a)层,且彼此邻接。通过使(a)层配置于外层和内层,能够得到耐化学药品性和柔软性优异的层叠体。
在该层构成中,从层叠体的成形稳定性、耐化学药品性的观点出发,外层的(a)层相对于层叠体整体的层厚度优选为15%以上、更优选为20%以上。
另外,在前述层叠中空体中,若在层叠中空体的最内层进一步配置有含有导电性填料且包含脂肪族聚酰胺组合物(A)或脂肪族聚酰胺组合物(B)的导电层,则耐劣化燃料性优异,并且,在用作燃料配管的管的情况下,能够防止因在配管内循环的燃料的内部摩擦或者燃料与管壁的摩擦而产生的火花点燃燃料。此时,通过使包含不具有导电性的脂肪族聚酰胺组合物(A)或脂肪族聚酰胺组合物(B)的层与前述导电层相比配置在外侧,能够兼顾低温耐冲击性和导电性,另外,经济上也有利。
导电性是指:例如,汽油之类的起火性流体连续地接触树脂之类的绝缘体时,静电会蓄积而有可能起火,但具有不会蓄积该静电这一程度的电特性。由此,能够防止燃料等流体在输送时产生的静电所导致的爆炸。
导电性填料包括为了对树脂赋予导电性能而添加的所有填充剂,可列举出粒状、薄片状、纤维状填料等。
作为粒状填料,可列举出炭黑、石墨等。作为薄片状填料,可列举出铝薄片、镍薄片、镍涂覆云母等。另外,作为纤维状填料,可列举出碳纤维、碳覆盖陶瓷纤维、碳晶须、碳纳米管、铝纤维、铜纤维、黄铜纤维、不锈钢纤维等金属纤维等。它们可以使用1种或两种以上。这些之中,优选为碳纳米管、炭黑。
碳纳米管被称为中空碳原纤,该原纤是具有内部中空区域和由规则排列的碳原子本质上连续的多个层构成的外侧区域,且各层与中空区域实质上同心地配置在该原纤的圆柱轴周围的本质上为圆柱状的原纤。进而,前述外侧区域的规则排列的碳原子为石墨状,前述中空区域的直径优选为2nm以上且20nm以下。从赋予在树脂中的充分分散性和所得树脂成形体的良好导电性的观点出发,碳纳米管的外径优选为3.5nm以上且70nm以下、更优选为4nm以上且60nm以下。碳纳米管的长径比(长度/外径之比)优选为5以上、更优选为100以上、进一步优选为500以上。通过满足该长径比,从而容易形成导电性网络,通过少量添加即可表现出优异的导电性。
炭黑包括全部通常用于赋予导电性的炭黑,作为优选的炭黑,可列举出将乙炔气体不完全燃烧而得的乙炔黑、将原油作为原料并通过炉式不完全燃烧而制造的科琴黑等炉黑、油黑、萘黑、热炭黑、灯黑、槽法炭黑、辊黑、盘黑等,但不限定于它们。它们可以使用1种或两种以上。这些之中,更优选为乙炔黑、炉黑。
另外,炭黑可制造其粒径、表面积、DBP吸油量、灰分等特性不同的各种碳粉末。该炭黑的特性没有限定,优选具有良好的链状结构且聚集密度大。从耐冲击性的观点出发,不优选大量配混炭黑,从以更少的量来获得优异电导率的观点出发,平均粒径优选为500nm以下、更优选为5nm以上且100nm以下、进一步优选为10nm以上且70nm以下,表面积(BET法)优选为10m2/g以上、更优选为30m2/g以上、进一步优选为50m2/g以上,进而,DBP(邻苯二甲酸二丁酯)吸油量优选为50ml/100g以上、更优选为100ml/100g以上、进一步优选为150ml/100g以上。灰分优选为0.5质量%以下、更优选为0.3质量%以下。此处提及的DBP吸油量是按照ASTM D-2414中规定的方法而测得的值。另外,炭黑的挥发成分含量优选小于1质量%。
这些导电性填料可以用钛酸酯系、铝系、硅烷系等的表面处理剂实施了表面处理。进而,为了提高熔融混炼作业性,也可以使用经造粒的填料。
导电性填料的含量因所使用的导电性填料的种类而异,因此无法一概而论,从与导电性、流动性、机械强度等的平衡的观点出发,相对于脂肪族聚酰胺组合物(A)和脂肪族聚酰胺组合物(B)100质量份,通常优选为3质量份以上且30质量份以下。
另外,关于所述导电性填料,从获得充分的抗静电性能的观点出发,熔融挤出物的表面固有电阻值优选为108Ω/square以下、更优选为106Ω/square以下。其中,前述导电性填料的添加容易导致强度、流动性的恶化。因此,如果能够获得目标的导电水准,则期望前述导电性填料的含量尽可能少。
在层叠体中,各层的厚度没有特别限定,可根据构成各层的聚合物的种类、层叠体中的整体层数、用途等来调节,各个层的厚度考虑到层叠体的化学溶液隔绝性、低温耐冲击性、柔软性等特性来决定。一般而言,(a)层和(b)层的厚度相对于层叠体整体的厚度分别优选为3%以上且90%以下。考虑到低温耐冲击性与化学溶液隔绝性的平衡,(b)层的厚度相对于层叠体整体的厚度更优选为20%以上且80%以下、进一步优选为30%以上且70%以下。
另外,关于层叠体中的整体层数,只要是具有(a)层和(b)层的至少两层,就没有特别限定。进而,层叠体除了具有(a)层和(b)层这两层之外,为了赋予更多的功能或获得经济上有利的层叠体,也可以具有1层或两层以上的包含其它热塑性树脂的层。层叠体的层数为两层以上,但根据制管装置的机理来判断,优选为8层以下、更优选为3层以上且7层以下。
作为层叠体中的包含其它热塑性树脂的层中的热塑性树脂,可列举出:除聚酰胺(A1)、聚酰胺(A2)和聚酰胺(B1)之外的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-2,5-呋喃二甲胺)(聚酰胺2,5-F4)、聚(戊二酰-2,5-呋喃二甲胺)(聚酰胺2,5-F5)、聚(己二酰-2,5-呋喃二甲胺)(聚酰胺2,5-F6)、聚(辛二酰-2,5-呋喃二甲胺)(聚酰胺2,5-F8)、
聚(壬二酰-2,5-呋喃二甲胺)(聚酰胺2,5-F9)、聚(癸二酰-2,5-呋喃二甲胺)(聚酰胺2,5-F10)、聚(十二烷二酰-2,5-呋喃二甲胺)(聚酰胺2,5-F12)、聚(对苯二甲酰-2,5-呋喃二甲胺)(聚酰胺2,5-FT)、聚(间苯二甲酰-2,5-呋喃二甲胺)(聚酰胺2,5-FI)、聚(六氢对苯二甲酰-2,5-呋喃二甲胺)(聚酰胺2,5-FT(H))、聚(萘二甲酰-2,5-呋喃二甲胺)(聚酰胺2,5-FN)、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(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(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(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(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(丁二酰-2,5-四氢呋喃二甲胺)(聚酰胺2,5-F(H)4)、聚(戊二酰-2,5-四氢呋喃二甲胺)(聚酰胺2,5-F(H)5)、聚(己二酰-2,5-四氢呋喃二甲胺)(聚酰胺2,5-F(H)6)、聚(辛二酰-2,5-四氢呋喃二甲胺)(聚酰胺2,5-F(H)8)、聚(壬二酰-2,5-四氢呋喃二甲胺)(聚酰胺2,5-F(H)9)、聚(癸二酰-2,5-四氢呋喃二甲胺)(聚酰胺2,5-F(H)10)、聚(十二烷二酰-2,5-四氢呋喃二甲胺)(聚酰胺2,5-F(H)12)、聚(对苯二甲酰-2,5-四氢呋喃二甲胺)(聚酰胺2,5-F(H)T)、聚(间苯二甲酰-2,5-四氢呋喃二甲胺)(聚酰胺2,5-F(H)I)、聚(六氢对苯二甲酰-2,5-四氢呋喃二甲胺)(聚酰胺2,5-F(H)T(H))、聚(萘二甲酰-2,5-四氢呋喃二甲胺)(聚酰胺2,5-F(H)N)、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)、聚萘二甲酰丁二胺(聚酰胺4N)、聚六氢对苯二甲酰丁二胺(聚酰胺4T(H))、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)、聚萘二甲酰戊二胺(聚酰胺5N)、聚六氢对苯二甲酰戊二胺(聚酰胺5T(H))、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)、聚萘二甲酰己二胺(聚酰胺6N)、聚六氢对苯二甲酰己二胺(聚酰胺6T(H))、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(萘二甲酰-2-甲基戊二胺(聚酰胺M5N)、
聚(六氢对苯二甲酰-2-甲基戊二胺)(聚酰胺M5T(H))、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)、聚萘二甲酰壬二胺(聚酰胺9N)、聚六氢对苯二甲酰壬二胺(聚酰胺9T(H))、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(萘二甲酰-2-甲基辛二胺)(聚酰胺M8N)、聚(六氢对苯二甲酰-2-甲基辛二胺)(聚酰胺M8T(H))、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)、聚萘二甲酰三甲基己二胺(聚酰胺TMHN)、聚六氢对苯二甲酰三甲基己二胺(聚酰胺TMHT(H))、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)、聚萘二甲酰癸二胺(聚酰胺10N)、聚六氢对苯二甲酰癸二胺(聚酰胺10T(H))、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)、
聚萘二甲酰十一烷二胺(聚酰胺11N)、聚六氢对苯二甲酰十一烷二胺(聚酰胺11T(H))、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)、聚萘二甲酰十二烷二胺(聚酰胺12N)、聚六氢对苯二甲酰十二烷二胺(聚酰胺12T(H))、聚(2,5-呋喃二甲酰丁二胺)(聚酰胺4F)、聚(2,5-呋喃二甲酰戊二胺)(聚酰胺5F)、聚(2,5-呋喃二甲酰己二胺)(聚酰胺6F)、聚(2,5-呋喃二甲酰-2-甲基戊二胺)(聚酰胺M5F)、聚(2,5-呋喃二甲酰壬二胺)(聚酰胺9F)、聚(2,5-呋喃二甲酰-2-甲基辛二胺)(聚酰胺M8F)、聚(2,5-呋喃二甲酰三甲基己二胺)(聚酰胺TMHF)、聚(2,5-呋喃二甲酰癸二胺)(聚酰胺10F)、聚(2,5-呋喃二甲酰十一烷二胺)(聚酰胺11F)、聚(2,5-呋喃二甲酰十二烷二胺)(聚酰胺12F)、聚(2,5-四氢呋喃二甲酰丁二胺)(聚酰胺4F(H))、
聚(2,5-四氢呋喃二甲酰戊二胺)(聚酰胺5F(H))、聚(2,5-四氢呋喃二甲酰己二胺)(聚酰胺6F(H))、聚(2,5-四氢呋喃二甲酰-2-甲基戊二胺)(聚酰胺M5F(H))、聚(2,5-四氢呋喃二甲酰壬二胺)(聚酰胺9F(H))、聚(2,5-四氢呋喃二甲酰-2-甲基辛二胺)(聚酰胺M8F(H))、聚(2,5-四氢呋喃二甲酰三甲基己二胺)(聚酰胺TMHF(H))、聚(2,5-四氢呋喃二甲酰癸二胺)(聚酰胺10F(H))、聚(2,5-四氢呋喃二甲酰十一烷二胺)(聚酰胺11F(H))、聚(2,5-四氢呋喃二甲酰十二烷二胺)(聚酰胺12F(H))和使用两种以上的这些聚酰胺的原料单体和/或形成选自由前述聚酰胺(A1)、聚酰胺(A2)和聚酰胺(B1)组成的组中的至少1种均聚物的原料单体而得的共聚物等聚酰胺系树脂。它们可以使用1种或两种以上。
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、含有对氨基具有反应性的官能团的前述含氟系聚合物。它们可以使用1种或两种以上。
进而,可列举出高密度聚乙烯(HDPE)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)、直链状低密度聚乙烯(LLDPE)、超高分子量聚乙烯(UHMWPE)、聚丙烯(PP)、聚丁烯(PB)、聚甲基戊烯(TPX)、乙烯/丙烯共聚物(EPR)、乙烯/丁烯共聚物(EBR)、乙烯/乙酸乙烯酯共聚物(EVA)、乙烯/丙烯酸共聚物(EAA)、乙烯/甲基丙烯酸共聚物(EMAA)、乙烯/丙烯酸甲酯共聚物(EMA)、乙烯/甲基丙烯酸甲酯共聚物(EMMA)、乙烯/丙烯酸乙酯共聚物(EEA)、乙烯/乙酸乙烯酯共聚物皂化物(EVOH)等聚烯烃系树脂;聚苯乙烯(PS)、间同立构聚苯乙烯(SPS)、甲基丙烯酸甲酯/苯乙烯共聚物(MS)、甲基丙烯酸甲酯/苯乙烯/丁二烯共聚物(MBS)、苯乙烯/丁二烯共聚物(SBR)、苯乙烯/异戊二烯共聚物(SIR)、苯乙烯/异戊二烯/丁二烯共聚物(SIBR)、苯乙烯/丁二烯/苯乙烯共聚物(SBS)、苯乙烯/异戊二烯/苯乙烯共聚物(SIS)、苯乙烯/乙烯/丁烯/苯乙烯共聚物(SEBS)、苯乙烯/乙烯/丙烯/苯乙烯共聚物(SEPS)等聚苯乙烯系树脂;含有丙烯酸、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-2,3-二羧酸等的羧基及其金属盐(Na、Zn、K、Ca、Mg)、马来酸酐、衣康酸酐、柠康酸酐、内双环-[2.2.1]-5-庚烯-2,3-二羧酸酐等的酸酐基、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、乙基丙烯酸缩水甘油酯、衣康酸缩水甘油酯、柠康酸缩水甘油酯等的环氧基等官能团的前述聚烯烃系树脂和聚苯乙烯系树脂;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;聚酮(PK)、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;聚酰胺弹性体、聚氨酯弹性体、聚酯弹性体等。它们可以使用1种或两种以上。
此外,在层叠体中,从熔融稳定性和成形稳定性的观点出发,优选使用前述例示的热塑性树脂之中的熔点为290℃以下的聚酯系树脂、聚酰胺系树脂、聚硫醚系树脂、聚烯烃系树脂和含氟系聚合物。
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、金属化合物、以及由它们中的两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。它们可以使用1种或两种以上。
作为层叠体制造方法,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前述方法而制造的层叠体,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)。层叠体优选通过下述共挤出成形法来制造:将各种材料在熔融状态下共挤出,使两者热熔接(熔融粘接),从而通过一个阶段来制造层叠结构的管。即,层叠体的制造方法优选包括共挤出成形。
另外,所得层叠体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,也可以在形成前述层叠体后,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。
层叠体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。不仅可以遍及层叠体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层叠体后,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体的外周的全部或一部分而言,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)、氯磺化聚乙烯橡胶(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、酰胺系等的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凹部的块状构件,所述凹部用于容纳作为层叠体的一个方式的层叠管。为筒状构件时,可以在预先制作的筒状构件中随后插入层叠管,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,并将层叠管插入或镶嵌于其中,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,考虑到化学溶液(例如含醇汽油等燃料)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。
本实施方式的层叠体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,层叠体适合作为化学溶液和/或气体输送管。作为化学溶液,可列举出例如苯、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;苯酚溶剂;二甲基醚、二丙基醚、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;丙酮、甲乙酮、二乙基酮、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、乙基叔丁基醚共混含氧汽油、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。
作为气体,可列举出氢、氦、氩、氙、氪、氖、氟、氯、溴、碘、一氧化碳、二氧化碳、硫化氢、碳酰硫、硫氧化物(SOx)、氮氧化物(NOx)、氧、臭氧、氮、空气、氨、甲烷、乙烷、丙烷、异丁烷、正丁烷等烃;乙炔、乙烯、丙烯、1-丁烯、2-丁烯、异丁烯、苯乙烯和丁二烯等不饱和烃;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碳-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碳-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(三氯氟甲烷)、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(二氟氯甲烷)、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)和它们的混合物等卤代烯烃类等。
层叠体适合作为运输前述化学溶液和/或气体的管,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;燃料电池用氢运输管、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阀控制辊管、风窗洗涤液用管、发动机冷却液(LLC)管、储罐管、尿素溶液运输管、冷却水、制冷剂等用冷却器管、空调制冷剂用管、加热器管、散热器管、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、墨、涂料散布管、其它化学溶液管。特别适合作为燃料管。即,本发明包括前述层叠体的作为燃料管的用途。
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。
另外,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。
聚酰胺的特性通过以下的方法进行测定。
[相对粘度]
按照JIS K-6920,在96%的硫酸中,在聚酰胺浓度为1%、温度为25℃的条件下进行测定。
[聚酰胺(A1)、聚酰胺(A2)的末端氨基浓度]
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。
[聚酰胺(A1)、聚酰胺(A2)的末端羧基浓度]
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。
[弹性体聚合物(A3)的羧基和酸酐基的合计浓度]
向三口茄型烧瓶中投入规定量的弹性体聚合物试样,溶解于甲苯170mL,进一步添加乙醇30mL,使用由此制备的试样溶液,以酚酞作为指示剂,用0.1N的KOH乙醇溶液进行滴定,求出羧基和酸酐基的合计浓度。
层叠管的各物性通过以下的方法进行测定。
[层间粘接性(初始剥离强度)]
将切成200mm的管进一步对半切成螺旋状,制作测试片。使用万能材料试验机(ORIENTEC公司制、TENSILON UTMIII-200),以50mm/min的拉伸速度实施90°剥离试验。由S-S曲线的极大点读取剥离强度,评价层间粘接性。
[层间粘接性的耐久性(热处理后的剥离强度)]
将切成200mm的管投入至160℃的烘箱中,处理30分钟。按照前述方法来评价所取出的管的层间粘接性。热处理后的剥离强度为2.0N/mm以上时,判断为层间粘接性的耐久性优异。
[实施例和比较例中使用的材料]
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,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2.10、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)的亚甲基数与酰胺基数之比[CH2]/[NHCO]为11.0,满足8.0以上。
聚酰胺(A2)
聚酰胺6/12(A2-1)的制造
向内容积为70升且附带搅拌机的耐压反应容器中投入己内酰胺9.90kg(87.5摩尔)、12-氨基十二烷酸2.69kg(12.5摩尔)、5-氨基-1,3,3-三甲基环己烷甲胺20.0g(0.12摩尔)和蒸馏水2.0L,加热至100℃,在该温度下搅拌以使得反应体系内成为均匀状态。接着,进一步使温度升温至260℃为止,在2.5MPa的压力下搅拌1小时。其后,释放压力,边使水分从反应容器中挥散边在常压下以260℃进行2小时的聚合反应,进而,在260℃、53kPa的减压下进行4小时的聚合反应。在反应结束后,将从反应容器的下部喷嘴以股线状取出的反应物导入至水槽中,进行冷却并切割,从而得到粒料。将该粒料浸渍在热水中,提取并去除未反应单体后,进行减压干燥,得到相对粘度为2.63、末端氨基浓度为54μeq/g、末端羧基浓度为40μeq/g的聚酰胺6/12(己酰胺单元/十二酰胺单元=87.5/12.5摩尔%)(以下,将该聚酰胺6/12称为(A2-1))。聚酰胺6/12(A2-1)的亚甲基数与酰胺基数之比[CH2]/[NHCO]为5.75,小于8.0。
聚酰胺(B1)
聚酰胺6(B1-1)的制造
在聚酰胺6/12(A2-1)的制造中,将己内酰胺9.90kg(87.5摩尔)、12-氨基十二烷酸2.69kg(12.5摩尔)变更为己内酰胺11.32kg(100.0摩尔),将5-氨基-1,3,3-三甲基环己烷甲胺20.0g(0.12摩尔)变更为80.0g(0.47摩尔),除此之外,利用与聚酰胺6/12(A2-1)的制造相同的方法,得到相对粘度为2.50、末端氨基浓度为112μeq/g、末端羧基浓度为33μeq/g的聚酰胺6(以下,将该聚酰胺6称为(B1-1))。聚酰胺6(B1-1)的亚甲基数与酰胺基数之比[CH2]/[NHCO]为5.0,小于8.0。
含有和/或不含由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元的弹性体聚合物(A3)
马来酸酐改性乙烯/1-丁烯共聚物(A3-1)(三井化学公司制、Tafmer MH5010、酸酐基浓度:50μeq/g)
马来酸酐改性乙烯/1-丁烯共聚物(A3-2)(三井化学公司制、Tafmer MH5020、酸酐基浓度:100μeq/g)
脂肪族聚酰胺组合物(A)
聚酰胺12组合物(A-1)的制造
向聚酰胺12(A1-1)中预先混合聚酰胺6/12(A2-1)、马来酸酐改性乙烯/1-丁烯共聚物(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](BASF JAPAN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),并供给至双螺杆熔融混炼机(日本制钢所制、型号:TEX44)中,以180℃~270℃的料筒温度进行熔融混炼,将熔融树脂挤出成线料状后,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)/聚酰胺6/12(A2-1)/马来酸酐改性弹性体聚合物(A3-1)=55.0/25.0/20.0(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质量份的聚酰胺12组合物的粒料(以下,将该聚酰胺12组合物称为(A-1))。另外,聚酰胺12组合物(A-1)的末端氨基浓度[A](μeq/g)、末端羧基浓度[B](μeq/g)(将由每1g脂肪族聚酰胺组合物(A)中的聚酰胺(A1)和聚酰胺(A2)各自的末端氨基浓度(μeq/g)、末端羧基浓度(μeq/g)和各自的混合质量比算出的值作为每1g脂肪族聚酰胺组合物(A)中的末端氨基浓度[A](μeq/g)、末端羧基浓度[B](μeq/g)。以下相同)满足[A]>[B]+5。
聚酰胺12组合物(A-2)的制造
在聚酰胺12组合物(A-1)的制造中,变更聚酰胺12(A1-1)和聚酰胺6/12(A2-1)的添加量,除此之外,利用与聚酰胺12组合物(A-1)的制造相同的方法,得到相对于聚酰胺12(A1-1)/聚酰胺6/12(A2-1)/马来酸酐改性弹性体聚合物(A3-1)=65.0/15.0/20.0(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质量份的聚酰胺12组合物的粒料(以下,将该聚酰胺12组合物称为(A-2))。另外,聚酰胺12组合物(A-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。
聚酰胺12组合物(A-3)的制造
在聚酰胺12组合物(A-1)的制造中,变更聚酰胺12(A1-1)和聚酰胺6/12(A2-1)的添加量,除此之外,利用与聚酰胺12组合物(A-1)的制造相同的方法,得到相对于聚酰胺12(A1-1)/聚酰胺6/12(A2-1)/马来酸酐改性弹性体聚合物(A3-1)=60.0/20.0/20.0(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质量份的聚酰胺12组合物的粒料(以下,将该聚酰胺12组合物称为(A-3))。另外,聚酰胺12组合物(A-3)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12组合物(A-4)的制造
在聚酰胺12组合物(A-1)的制造中,将马来酸酐改性乙烯/1-丁烯共聚物(A3-1)变更为(A3-2),除此之外,利用与聚酰胺12组合物(A-1)的制造相同的方法,得到相对于聚酰胺12(A1-1)/聚酰胺6/12(A2-1)/弹性体聚合物(A3-2)=55.0/25.0/20.0(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质量份的聚酰胺12组合物的粒料(以下,将该聚酰胺12组合物称为(A-5))。另外,聚酰胺12组合物(A-4)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12组合物(A-5)的制造
在聚酰胺12组合物(A-1)的制造中,不使用聚酰胺6/12(A2-1),从双螺杆熔融混炼机的料筒中部,利用定量泵注入作为增塑剂的苯磺酸丁基酰胺,除此之外,利用与聚酰胺12组合物(A-1)的制造相同的方法,得到相对于聚酰胺12(A1-1)/马来酸酐改性弹性体聚合物(A3-1)/增塑剂=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质量份的聚酰胺12组合物的粒料(以下,将该聚酰胺12组合物称为(A-5))。另外,聚酰胺12组合物(A-5)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12组合物(A-6)的制造
在聚酰胺12组合物(A-1)的制造中,不使用聚酰胺6/12(A2-1),除此之外,利用与聚酰胺12组合物(A-1)的制造相同的方法,得到相对于聚酰胺12(A1-1)/马来酸酐改性弹性体聚合物(A3-1)=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质量份的聚酰胺12组合物的粒料(以下,将该聚酰胺12组合物称为(A-6))。另外,聚酰胺12组合物(A-6)的末端氨基浓度[A](μeq/g)、末端羧基浓度[B](μeq/g)满足[A]>[B]+5。
聚酰胺组合物(B)
聚酰胺6组合物(B-1)的制造
在聚酰胺12组合物(A-1)的制造中,将聚酰胺12(A1-1)变更为聚酰胺6(B1-1),且不使用聚酰胺6/12(A2-1),除此之外,利用与聚酰胺12组合物(A-1)的制造相同的方法,得到相对于聚酰胺6(B1-1)/马来酸酐改性弹性体聚合物(A3-1)=85.0/15.0(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质量份的聚酰胺6组合物的粒料(以下,将该聚酰胺6组合物称为(B-1))。
聚酰胺6组合物(B-2)的制造
在聚酰胺6组合物(B-1)的制造中,利用定量泵注入作为增塑剂的苯磺酸丁基酰胺,除此之外,利用与聚酰胺6组合物(B-1)的制造相同的方法,得到聚酰胺6(B1-1)/马来酸酐改性弹性体聚合物(A3-1)/增塑剂=75.0/10.0/15.0(质量%)的聚酰胺6组合物的粒料(以下,将该聚酰胺6组合物称为(B-2))。
导电性聚酰胺6组合物(B-3)的制造
在聚酰胺6组合物(B-1)的制造中,作为导电性填料而使用炭黑(Cabot公司制、VULCAN XC-72),将料筒温度从270℃变更为300℃,除此之外,利用与聚酰胺6组合物(B-1)的制造相同的方法,得到聚酰胺6(B1-1)/马来酸酐改性弹性体聚合物(A3-1)/导电性填料=60.0/20.0/20.0(质量%)的导电性聚酰胺6组合物的粒料(以下,将该导电性聚酰胺6组合物称为(B-3))。
实施例1
使用前述示出的聚酰胺12组合物(A-1)、聚酰胺6组合物(B-1),利用PAL32(Maillefer公司制)双层管成形机,使(A-1)以260℃的挤出温度、使(B-1)以260℃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取出,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)=0.70/0.30mm且内径为6.0mm、外径为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,将最外层所使用的聚酰胺12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3
在实施例1中,将最外层所使用的聚酰胺12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4
在实施例1中,将最外层所使用的聚酰胺12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5
在实施例3中,将最内层所使用的聚酰胺6组合物(B-1)变更为聚酰胺6组合物(B-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6
在实施例3中,将最内层所使用的聚酰胺6组合物(B-1)变更为聚酰胺6组合物(B-3),将(B-3)的挤出温度从260℃变更为280℃,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。另外,按照SAE J-2260来测定该层叠管的导电性的结果,为106Ω/square以下,可确认静电去除性能优异。
实施例7
使用前述示出的聚酰胺12组合物(A-1)和聚酰胺6组合物(B-1),利用PAL32(Maillefer公司制)三层管成形机,使(A-1)以260℃的挤出温度、使(B-1)以260℃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取出,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(A-1)形成的(a’)层(最内层)时,得到层构成为(a)/(b)/(a’)=0.30/0.50/0.20mm且内径为6.0mm、外径为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8
在实施例7中,将最外层和最内层所使用的聚酰胺12组合物(A-1)变更为聚酰胺12组合物(A-2),除此之外,利用与实施例7相同的方法,得到表2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。
在实施例9
在实施例7中,将最外层和最内层所使用的聚酰胺12组合物(A-1)变更为聚酰胺12组合物(A-3),除此之外,利用与实施例7相同的方法,得到表2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。
在实施例10
在实施例7中,将最外层和最内层所使用的聚酰胺12组合物(A-1)变更为聚酰胺12组合物(A-4),除此之外,利用与实施例7相同的方法,得到表2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。
在实施例11
在实施例9中,将聚酰胺6组合物(B-1)变更为(B-2),除此之外,利用与实施例9相同的方法,得到表2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,将最外层所使用的聚酰胺12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。
比较例2
在实施例1中,将最外层所使用的聚酰胺12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。
比较例3
在实施例7中,将最外层和最内层所使用的聚酰胺12组合物(A-1)变更为(A-5),除此之外,利用与实施例7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4
在实施例7中,将最外层和最内层所使用的聚酰胺12组合物(A-1)变更为(A-6),除此之外,利用与实施例7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。
[表1]
[表2]
由表1和表2可以明确:具有未使用本发明所规定的聚酰胺(A2)的(a)层的比较例1、2、3和4的层叠管的层间粘接性及其耐久性差。另一方面,可明确:满足本发明规定条件的实施例1~11的层叠管的层间粘接性及其耐久性等各特性良好。
Claims (15)
1.一种层叠管,其为包含a层和b层的两层以上的层叠管,
至少1组所述a层与所述b层邻接配置,
所述a层包含脂肪族聚酰胺组合物A,
所述b层包含脂肪族聚酰胺组合物B,
所述脂肪族聚酰胺组合物A包含聚酰胺A1、聚酰胺A2和弹性体聚合物A3,
所述聚酰胺A1是亚甲基数与酰胺基数之比为8.0以上的脂肪族聚酰胺,且该脂肪族聚酰胺不含如下共聚物,所述共聚物包含:由ε-己内酰胺或ε-氨基己酸衍生的单元a、以及由氨基十二烷酸或ω-月桂内酰胺衍生的单元b,所述脂肪族聚酰胺组合物A中包含30质量%以上且85质量%以下的所述聚酰胺A1,
所述聚酰胺A2为包含如下共聚物的脂肪族聚酰胺,所述共聚物包含:由ε-己内酰胺或ε-氨基己酸衍生的单元a、以及由氨基十二烷酸或ω-月桂内酰胺衍生的单元b,所述脂肪族聚酰胺组合物A中包含10质量%以上且35质量%以下的所述聚酰胺A2,
所述弹性体聚合物A3为任选含有由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元的弹性体聚合物,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A3,
所述脂肪族聚酰胺组合物B包含聚酰胺B1和弹性体聚合物B2,
所述聚酰胺B1是亚甲基数与酰胺基数之比小于8.0的脂肪族聚酰胺,所述脂肪族聚酰胺组合物B中包含55质量%以上且95质量%以下的所述聚酰胺B1,
所述弹性体聚合物B2为含有由具有羧基和/或酸酐基的不饱和化合物衍生的结构单元的弹性体聚合物,所述脂肪族聚酰胺组合物B中包含5质量%以上且30质量%以下所述弹性体聚合物B2。
2.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、使用两种以上形成它们的原料单体而得的至少1种共聚物。
3.根据权利要求1所述的层叠管,其中,所述聚酰胺A2为聚酰胺6/12和/或聚酰胺6/66/12。
4.根据权利要求1~3中任一项所述的层叠管,其中,所述聚酰胺A2包含50质量%以上的由ε-己内酰胺或ε-氨基己酸衍生的单元a。
5.根据权利要求1~3中任一项所述的层叠管,其中,所述弹性体聚合物A3包含在所述弹性体聚合物A3 100质量%中为60质量%以上的如下弹性体聚合物,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。
6.根据权利要求1~3中任一项所述的层叠管,其中,所述聚酰胺B1为选自由聚己酰胺(聚酰胺6)、聚己二酰己二胺(聚酰胺66)、聚壬二酰己二胺(聚酰胺69)和聚癸二酰己二胺(聚酰胺610)组成的组中的至少1种均聚物、和/或、使用两种以上形成它们的原料单体而得的至少1种共聚物。
7.根据权利要求1~3中任一项所述的层叠管,其中,将每1g脂肪族聚酰胺组合物A中的聚酰胺A1和聚酰胺A2各自的末端氨基浓度(μeq/g)乘以其混合质量比而得的值进行求和而得到的末端氨基浓度记作[A](μeq/g),并将每1g脂肪族聚酰胺组合物A中的聚酰胺A1和聚酰胺A2各自的末端羧基浓度(μeq/g)乘以其混合质量比而得的值进行求和而得到的末端羧基浓度记作[B](μeq/g)时,[A]>[B]+5。
8.根据权利要求1~3中任一项所述的层叠管,其中,所述a层包含40质量%以上且100质量%以下的所述脂肪族聚酰胺组合物A,所述b层包含60质量%以上且100质量%以下的所述脂肪族聚酰胺组合物B。
9.根据权利要求1~3中任一项所述的层叠管,其通过共挤出成形来制造。
10.根据权利要求1~3中任一项所述的层叠管,其用作化学溶液和/或气体输送管。
11.根据权利要求1~3中任一项所述的层叠管,其具有与所述a层相比配置在内侧的至少1个所述b层。
12.根据权利要求1~3中任一项所述的层叠管,其中,从外侧起依次层叠所述a层、所述b层、所述a层,且彼此邻接。
13.根据权利要求1~3中任一项所述的层叠管,其中,按照JIS K-6920在96%硫酸、聚合物浓度为1%、25℃的条件下测得的所述聚酰胺A1和所述聚酰胺A2的相对粘度为1.8以上且4.5以下。
14.根据权利要求1~3中任一项所述的层叠管,其中,所述弹性体聚合物A3中的羧基和/或酸酐基浓度为25μeq/g以上且200μeq/g以下。
15.根据权利要求1~3中任一项所述的层叠管,其中,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B1的相对粘度为1.8以上且4.5以下。
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