WO2016104095A1 - 多層中空成形体 - Google Patents
多層中空成形体 Download PDFInfo
- Publication number
- WO2016104095A1 WO2016104095A1 PCT/JP2015/084004 JP2015084004W WO2016104095A1 WO 2016104095 A1 WO2016104095 A1 WO 2016104095A1 JP 2015084004 W JP2015084004 W JP 2015084004W WO 2016104095 A1 WO2016104095 A1 WO 2016104095A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyamide
- aliphatic
- acid
- hollow molded
- structural unit
- Prior art date
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- 230000004888 barrier function Effects 0.000 claims abstract description 73
- 239000004953 Aliphatic polyamide Substances 0.000 claims abstract description 60
- 229920003231 aliphatic polyamide Polymers 0.000 claims abstract description 60
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 49
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims abstract description 36
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims abstract description 31
- 239000000446 fuel Substances 0.000 claims abstract description 31
- 239000011342 resin composition Substances 0.000 claims abstract description 22
- 239000004952 Polyamide Substances 0.000 claims description 84
- 229920002647 polyamide Polymers 0.000 claims description 84
- 125000004432 carbon atom Chemical group C* 0.000 claims description 70
- -1 aliphatic diamine Chemical class 0.000 claims description 55
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 43
- 125000001931 aliphatic group Chemical group 0.000 claims description 29
- 150000004985 diamines Chemical class 0.000 claims description 28
- 150000003951 lactams Chemical class 0.000 claims description 14
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 13
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims description 12
- 229920000571 Nylon 11 Polymers 0.000 claims description 10
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims description 10
- 229920000299 Nylon 12 Polymers 0.000 claims description 7
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 4
- 229920006121 Polyxylylene adipamide Polymers 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 22
- 239000007788 liquid Substances 0.000 abstract description 10
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 116
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 24
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 16
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 125000004427 diamine group Chemical group 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000006068 polycondensation reaction Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003502 gasoline Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 239000001361 adipic acid Substances 0.000 description 8
- 235000011037 adipic acid Nutrition 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 8
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 8
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 8
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 8
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 8
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000032258 transport Effects 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 6
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 5
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 4
- BDBZTOMUANOKRT-UHFFFAOYSA-N 4-[2-(4-aminocyclohexyl)propan-2-yl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1C(C)(C)C1CCC(N)CC1 BDBZTOMUANOKRT-UHFFFAOYSA-N 0.000 description 4
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 4
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 4
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920006122 polyamide resin Polymers 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-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
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 3
- IIHKGAZZIDXOAT-UHFFFAOYSA-N NCC12CCCCC2(CCCC1)CN Chemical compound NCC12CCCCC2(CCCC1)CN IIHKGAZZIDXOAT-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Chemical class 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 3
- 229920001778 nylon Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 3
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 3
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 2
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 2
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical compound FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N N-undecane Natural products CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- XAUQWYHSQICPAZ-UHFFFAOYSA-N 10-amino-decanoic acid Chemical compound NCCCCCCCCCC(O)=O XAUQWYHSQICPAZ-UHFFFAOYSA-N 0.000 description 1
- VPRCINUSGGYBRP-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,1-diamine Chemical compound CCC(C)(C)CC(C)C(N)N VPRCINUSGGYBRP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- QKHWUKPTSMULMZ-UHFFFAOYSA-N 2-(aminomethyl)-3,3,5-trimethylcyclopentan-1-amine Chemical compound CC1CC(C)(C)C(CN)C1N QKHWUKPTSMULMZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PAOXFRSJRCGJLV-UHFFFAOYSA-N 2-[4-(2-aminoethyl)piperazin-1-yl]ethanamine Chemical compound NCCN1CCN(CCN)CC1 PAOXFRSJRCGJLV-UHFFFAOYSA-N 0.000 description 1
- GAGWMWLBYJPFDD-UHFFFAOYSA-N 2-methyloctane-1,8-diamine Chemical compound NCC(C)CCCCCCN GAGWMWLBYJPFDD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- FJSUFIIJYXMJQO-UHFFFAOYSA-N 3-methylpentane-1,5-diamine Chemical compound NCCC(C)CCN FJSUFIIJYXMJQO-UHFFFAOYSA-N 0.000 description 1
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- ZHVYIZVNKGAJBE-UHFFFAOYSA-N 4-[2-(4-amino-3-methylcyclohexyl)propan-2-yl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1C(C)(C)C1CC(C)C(N)CC1 ZHVYIZVNKGAJBE-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- XDOLZJYETYVRKV-UHFFFAOYSA-N 7-Aminoheptanoic acid Chemical compound NCCCCCCC(O)=O XDOLZJYETYVRKV-UHFFFAOYSA-N 0.000 description 1
- VWPQCOZMXULHDM-UHFFFAOYSA-N 9-aminononanoic acid Chemical compound NCCCCCCCCC(O)=O VWPQCOZMXULHDM-UHFFFAOYSA-N 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920012310 Polyamide 9T (PA9T) Polymers 0.000 description 1
- WPWNSTTVSOUHRP-UHFFFAOYSA-N [1-(aminomethyl)naphthalen-2-yl]methanamine Chemical compound C1=CC=CC2=C(CN)C(CN)=CC=C21 WPWNSTTVSOUHRP-UHFFFAOYSA-N 0.000 description 1
- ABPUBUORTRHHDZ-UHFFFAOYSA-N [4-(aminomethyl)-3-bicyclo[2.2.1]heptanyl]methanamine Chemical compound C1CC2(CN)C(CN)CC1C2 ABPUBUORTRHHDZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- F16L11/125—Hoses, i.e. flexible pipes made of rubber or flexible plastics with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting non-inflammable or heat-resistant hoses
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Definitions
- the present invention relates to a multilayer hollow molded body, and more particularly to a multilayer hollow molded body that can be suitably used as a fuel transport piping material for transporting high-temperature liquid fuel.
- a multilayer tube in which a layer made of an ethylene-vinyl alcohol copolymer (EVOH) is laminated on a layer made of aliphatic polyamide such as polyamide 11 and polyamide 12 have been proposed (Japanese Patent Laid-Open No. 2003-239819 (Patent Document 1), Japanese Patent Laid-Open No. 2006-341615 (Patent Document 2)).
- EVOH is a material that is extremely excellent in barrier properties, it has a drawback of low burst resistance and low heat resistance, and a fuel transport piping material that transports high-temperature liquid fuel that requires high pressure resistance and heat resistance. When used as, the burst resistance and heat resistance may be insufficient.
- multilayer hollow molding that has a sufficiently high barrier property, burst resistance and heat resistance, is excellent in impact resistance, and can be suitably used as a fuel transportation piping material for transporting high-temperature liquid fuel.
- the body is desired.
- the multilayer hollow molded article of the present invention is excellent in impact resistance, and can be suitably used as a fuel transport piping material for transporting high-temperature liquid fuel.
- a multilayer hollow molded article having at least one aliphatic polyamide layer (A) and at least one barrier layer (B),
- the aliphatic polyamide layer (A) is composed of a resin composition containing the aliphatic polyamide (a) as a main component,
- EVOH ethylene-vinyl alcohol copolymer
- b semi-aromatic polyamide
- the semiaromatic polyamide (b) is derived from a diamine structural unit containing 70 mol% or more of a diamine structural unit derived from xylylenediamine and an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 8 carbon atoms.
- a multilayer hollow molded article according to any one of the above.
- the aliphatic polyamide (a) is at least one selected from the group consisting of polyamide 11, polyamide 12, polyamide 10, 10, polyamide 10, 12, polyamide 6, 11, and polyamide 6, 12.
- the multilayer hollow molded article according to any one of [4] to [4].
- the mass ratio of the ethylene-vinyl alcohol copolymer (EVOH) and the semiaromatic polyamide (b) in the resin composition constituting the barrier layer (B) (EVOH: semiaromatic polyamide (b))
- the multilayer hollow molded article according to any one of [1] to [6] which is a fuel tube, a fuel pipe, a fuel hose or a connector.
- a multilayer hollow laminate excellent in barrier properties, burst resistance, heat resistance and impact resistance can be obtained.
- the multilayer hollow molded article of the present invention is suitably used as a fuel transport piping material for transporting high-temperature liquid fuel such as gasoline, alcohol-containing gasoline, methanol, ethanol, light oil, kerosene, and heavy oil.
- the multilayer hollow molded article of the present invention has at least one aliphatic polyamide layer (A) and at least one barrier layer (B), and the aliphatic polyamide layer (A) mainly comprises the aliphatic polyamide (a). It consists of a resin composition as a component, and the barrier layer (B) is characterized by comprising a resin composition containing an ethylene-vinyl alcohol copolymer (EVOH) and a semi-aromatic polyamide (b).
- the aliphatic polyamide layer (A) is obtained by using a resin composition containing an ethylene-vinyl alcohol copolymer (EVOH) and a semi-aromatic polyamide (b) as a material for the barrier layer (B).
- the aliphatic polyamide layer (A) and the barrier layer (B) constituting the multilayer hollow molded article of the present invention a method for producing the multilayer hollow molded article, and the like will be described.
- Aliphatic polyamide layer (A) The aliphatic polyamide layer (A) used in the present invention is a layer made of a resin composition containing the aliphatic polyamide (a) as a main component.
- “having aliphatic polyamide (a) as a main component” means that the aliphatic polyamide (a) in the resin composition is 70% or more, preferably 75% or more, more preferably 80% by mass. % Is included.
- chemical resistance and flexibility can be improved.
- the aliphatic polyamide (a) that can be used in the present invention contains an amide bond ⁇ —N—H—C ( ⁇ O 2) — ⁇ , and is essentially composed of a structural unit that does not contain an aromatic ring in the molecular skeleton.
- the chain is not particularly limited as long as it is a chain polyamide.
- the term “main component” means that 60% by mole or more, preferably 80 to 100% by mole, more preferably 90 to 100% by mole of the structural unit of the aliphatic polyamide (a) that does not contain an aromatic ring. It means to occupy mol%.
- the aliphatic polyamide (a) has a structural unit derived from lactam having 10 to 12 carbon atoms and the number of carbon atoms.
- the polyamide (a1) contains at least one of a structural unit derived from a lactam having 10 to 12 carbon atoms and a structural unit derived from an aminocarboxylic acid having 10 to 12 carbon atoms.
- the number of carbon atoms in the structural unit derived from lactam and the structural unit derived from aminocarboxylic acid is preferably 11 to 12 from the viewpoints of flexibility and availability.
- the structural unit derived from a lactam having 10 to 12 carbon atoms and the structural unit derived from an aminocarboxylic acid having 10 to 12 carbon atoms are usually composed of an ⁇ -aminocarboxylic acid unit represented by the following general formula.
- p represents an integer of 9 to 11, and preferably 10 to 11.
- Specific examples of the compound constituting the structural unit derived from lactam having 10 to 12 carbon atoms include decane lactam, undecane lactam, and dodecane lactam.
- Examples of the compound constituting the structural unit derived from an aminocarboxylic acid having 10 to 12 carbon atoms include 10-aminodecanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.
- the polyamide (a1) is not limited to those composed only of structural units derived from lactams having 10 to 12 carbon atoms and aminocarboxylic acids having 10 to 12 carbon atoms, and may be those having these structural units as the main components.
- “main component” is intended to allow other structural units to be included within a range that does not hinder the effects of the present invention, and is not particularly limited.
- At least one of a lactam structural unit having 10 to 12 carbon atoms and a structural unit derived from an aminocarboxylic acid having 10 to 12 carbon atoms is, for example, 60 mol% or more, preferably 80 to 100, as a monomer. It occupies a range of mol%, more preferably 90 to 100 mol%.
- the other structural unit in the polyamide (a1) is, for example, a lactam other than a lactam having 10 to 12 carbon atoms, an aminocarboxylic acid other than an aminocarboxylic acid having 10 to 12 carbon atoms, or a nylon salt composed of a diamine and a dicarboxylic acid. These structural units are listed.
- lactams other than those having 10 to 12 carbon atoms include lactams having 3 or more members, and specific examples include ⁇ -caprolactam, ⁇ -enantolactam, ⁇ -pyrrolidone, ⁇ -piperidone, and the like.
- aminocarboxylic acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid and the like.
- the diamine constituting the nylon salt is ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine.
- dicarboxylic acid constituting the nylon salt examples include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1 Aliphatic dicarboxylic acids such as 1,12-dodecanedicarboxylic acid; alicyclic dicarboxylic acids such as 1,3- or 1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4′-dicarboxylic acid, norbornane dicarboxylic acid; Mention may be made of aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, 1,4-, 2,6- or 2,7-naphthalenedicarboxylic acid.
- Polyamide (a1) includes, as a main component, at least one of a structural unit derived from undecane lactam and a structural unit derived from 11-aminoundecanoic acid, or a structural unit derived from dodecane lactam and 12-aminododecanoic acid
- a polyamide 12 having at least one of the structural units as a main component, or a mixture of these polyamide 11 and polyamide 12 is preferred.
- Polyamide (a1) can be obtained by polymerizing the above constituent monomers, and can be obtained by ring-opening polymerization of lactam or polycondensation of aminocarboxylic acid.
- the polymerization method is not particularly limited, and known methods such as melt polymerization, solution polymerization, and solid phase polymerization can be employed. These polymerization methods can be used alone or in appropriate combination.
- Production equipment includes known polyamides such as batch reaction kettles, single tank or multi-tank continuous reaction apparatuses, tubular continuous reaction apparatuses, kneading reaction extruders such as uniaxial kneading extruders and biaxial kneading extruders, etc. Manufacturing equipment can be used.
- a small amount of monoamine, monocarboxylic acid or the like may be added as a molecular weight regulator.
- a phosphorus atom-containing compound, an alkali metal compound, an alkaline earth metal compound, etc. may be added.
- the melting point Tm of the polyamide (a1) is preferably 160 to 240 ° C., more preferably 165 to 230 ° C., and further preferably 170 to 220 ° C. from the viewpoints of heat resistance and melt moldability.
- the melting point is determined by DSC measurement (differential scanning calorimetry) using a differential scanning calorimeter (manufactured by Shimadzu Corporation, trade name: DSC-60) at a heating rate of 10 ° C./min in a nitrogen stream. ) Is measured.
- the polyamide (a2) includes a structural unit derived from an aliphatic diamine having 6 to 12 carbon atoms and a structural unit derived from an aliphatic dicarboxylic acid having 10 to 12 carbon atoms.
- the compound that can constitute the diamine unit of the polyamide (a2) is an aliphatic diamine having 6 to 12 carbon atoms.
- the aliphatic group of the aliphatic diamine having 6 to 12 carbon atoms is a linear or branched divalent aliphatic hydrocarbon group, and may be a saturated aliphatic group or an unsaturated aliphatic group. Usually, it is a linear saturated aliphatic group.
- the aliphatic group preferably has 8 to 12 carbon atoms, more preferably 9 to 12 carbon atoms, and still more preferably 10 to 12 carbon atoms.
- Examples of the compound that can constitute the diamine unit of the polyamide (a2) include aliphatic diamines such as hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, and dodecamethylene diamine. However, it is not limited to these. These can be used alone or in combination of two or more.
- the diamine unit in the polyamide (a2) is preferably a constituent unit derived from an aliphatic diamine having 6 to 12 carbon atoms from the viewpoint of flexibility and the like, preferably 70 mol% or more, more preferably 80 to 100 mol%, still more preferably. 90 to 100 mol% is contained.
- the diamine unit in the polyamide (a2) may be composed only of a structural unit derived from an aliphatic diamine having 6 to 12 carbon atoms, but contains a structural unit derived from a diamine other than an aliphatic diamine having 6 to 12 carbon atoms. Also good.
- examples of diamines other than aliphatic diamines having 6 to 12 carbon atoms include aliphatic diamines such as ethylenediamine, propylenediamine, tetramethylenediamine, and pentamethylenediamine; 1,3- or 1,4-bis ( Aminomethyl) cyclohexane, 1,3- or 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminomethyl) decalin, bis (aminomethyl) ) Alicyclic diamines such as tricyclodecane; diamines having an aromatic ring such as bis (4-aminophenyl) ether, paraphenylenediamine, bis (aminomethyl) naphthalene, and the like, but are not limited thereto. Is not to be done.
- the compound that can constitute the dicarboxylic acid unit in the polyamide (a2) is an aliphatic dicarboxylic acid having 10 to 12 carbon atoms, such as sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, and the like. It is done. These can be used alone or in combination of two or more.
- the dicarboxylic acid unit in the polyamide (a2) preferably has a structural unit derived from an aliphatic dicarboxylic acid having 10 to 12 carbon atoms, more preferably 70 mol% or more, more preferably 80 to It is contained in an amount of 100 mol%, more preferably 90 to 100 mol%.
- the dicarboxylic acid unit in the polyamide (a2) may consist only of a structural unit derived from an aliphatic dicarboxylic acid having 10 to 12 carbon atoms, but a structural unit derived from a dicarboxylic acid other than an aliphatic dicarboxylic acid having 10 to 12 carbon atoms. It may contain.
- examples of the dicarboxylic acid other than the aliphatic dicarboxylic acid having 10 to 12 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, 1,11-undecanedicarboxylic acid, 1 , 12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid and other aliphatic carboxylic acids having 9 or less carbon atoms or more; terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid Although aromatic dicarboxylic acid etc., such as an acid, can be illustrated, it is not limited to these.
- Polyamide (a2) is preferably a polyamide mainly composed of a structural unit derived from an aliphatic diamine having 10 or more carbon atoms as a diamine structural unit from the viewpoint of improving flexibility, and polyamides 10, 10, polyamides 10, 12, Polyamide 6,11 and polyamide 6,12 are mentioned. More preferably, a polyamide 10,10 having a structural unit derived from an aliphatic diamine having 10 carbon atoms and a structural unit derived from an aliphatic dicarboxylic acid having 10 carbon atoms, and a structural unit derived from an aliphatic diamine having 10 carbon atoms, respectively. And polyamides 10 and 12 each having a structural unit derived from an aliphatic dicarboxylic acid having 12 carbons as a main component, or a mixture thereof.
- the polyamide (a2) is obtained by polycondensation of a diamine component and a dicarboxylic acid component.
- a polyamide resin can be produced by a method in which a salt composed of a diamine component and a dicarboxylic acid component is heated in a pressurized state in the presence of water and polymerized in a molten state while removing added water and condensed water.
- the polyamide resin can also be produced by a method in which a diamine component is directly added to a molten dicarboxylic acid component and polycondensed under normal pressure.
- the diamine component is continuously added to the dicarboxylic acid component, and the reaction system is increased so that the reaction temperature does not fall below the melting point of the generated oligoamide and polyamide.
- the polycondensation proceeds while warming.
- a small amount of monoamine, monocarboxylic acid or the like may be added as a molecular weight regulator.
- a phosphorus atom-containing compound in order to obtain an effect of promoting an amidation reaction and an effect of preventing coloring at the time of polycondensation, a phosphorus atom-containing compound, an alkali metal compound, an alkaline earth metal compound, etc.
- Known additives may be added.
- the melting point Tm of the polyamide (a2) is preferably 160 to 240 ° C., more preferably 165 to 230 ° C., and further preferably 170 to 220 ° C. from the viewpoints of heat resistance and melt moldability.
- polyamide 11, polyamide 12, polyamide 10, 10, polyamide 10, 12, polyamide 6, 11, and polyamide 6, 12 are used as the aliphatic polyamide (a) used for the aliphatic polyamide layer (A). Any one or more selected from the group consisting of: polyamide 11, polyamide 12, or a mixture thereof is more preferable.
- the resin composition constituting the aliphatic polyamide layer (A) may be blended with various commonly used additives in addition to the aliphatic polyamide (a) as long as the object and effects of the present invention are not impaired.
- additives include inorganic fillers, flame retardants, conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, anti-coloring agents, and heat stability.
- examples include, but are not limited to, agents, mold release agents, antistatic agents, plasticizers, impact resistance improvers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, and coupling agents.
- the compounding amount of these additives is preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less in terms of mass ratio with respect to the resin composition constituting the aliphatic polyamide layer (A).
- the thickness of the aliphatic polyamide layer (A) is not particularly limited, but is usually preferably in the range of 10 to 2000 ⁇ m, more preferably 100 to 1500 ⁇ m, still more preferably 200 to 1000 ⁇ m.
- the barrier layer (B) used in the present invention is composed of a resin composition containing an ethylene-vinyl alcohol copolymer (EVOH) and a semi-aromatic polyamide (b).
- EVOH ethylene-vinyl alcohol copolymer
- b semi-aromatic polyamide
- the barrier layer (B) has good barrier properties, burst resistance and heat resistance. A barrier layer can be obtained.
- the barrier layer is also excellent in impact resistance.
- Ethylene-vinyl alcohol copolymer (EVOH)
- the ethylene-vinyl alcohol copolymer (EVOH) used in the present invention is a random copolymer of ethylene and vinyl alcohol.
- the ethylene-vinyl alcohol copolymer (EVOH) used in the present invention is obtained by, for example, saponifying vinyl acetate after copolymerizing ethylene, vinyl acetate, and if necessary, a small amount of other copolymerization components. It can be obtained by changing vinyl acetate units to vinyl alcohol units.
- copolymer components include, for example, ⁇ -olefins such as propylene, isobutene, ⁇ -octene, ⁇ -dodecene, ⁇ -octadecene, unsaturated carboxylic acids or salts thereof, partial alkyl esters, fully alkyl esters, nitriles, amides , Anhydrides, unsaturated sulfonic acids or salts thereof.
- the ethylene-vinyl alcohol copolymer (EVOH) used in the present invention preferably has an ethylene content of 15 to 60 mol% and a vinyl acetate component having a saponification degree of 90 mol% or more.
- the ethylene content is more preferably 20 to 55 mol%, still more preferably 29 to 44 mol%.
- the saponification degree of the vinyl acetate component is more preferably 95 mol% or more. When the ethylene content and the saponification degree of the vinyl acetate component are within the above ranges, the barrier property, oil resistance and chemical resistance are excellent.
- the melting point Tm of the ethylene-vinyl alcohol copolymer (EVOH) is preferably 150 to 200 ° C., more preferably 190 to 160 ° C. from the viewpoint of heat resistance and melt moldability.
- the semi-aromatic polyamide (b) used in the present invention refers to a resin in which either the diamine structural unit or the dicarboxylic acid structural unit contains more than 50 mol% of a structural unit derived from an aromatic compound.
- Examples include a structural unit in which more than 50 mol% is derived from a non-aromatic diamine, and a polyamide containing a structural unit in which more than 50 mol% of a dicarboxylic acid structural unit is derived from phthalic acid.
- the semi-aromatic polyamide (b) has 70 mol% or more of diamine structural units derived from xylylenediamine, and 70 mol% of dicarboxylic acid structural units, since the barrier property of the multilayer hollow molded article is improved.
- the polyamide (b1) and the polyamide (b2) will be described in more detail.
- Polyamide (b1) In the polyamide (b1), 70 mol% or more of the diamine structural unit is derived from xylylenediamine, and 70 mol% or more of the dicarboxylic acid structural unit is derived from an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 8 carbon atoms. Containing structural units.
- the diamine unit in the polyamide (b1) contains 70 mol% or more of a structural unit derived from xylylenediamine, preferably 80 to 80% from the viewpoint of appropriately expressing the barrier properties and thermal properties such as glass transition temperature and melting point. It is contained in an amount of 100 mol%, more preferably 90 to 100 mol%.
- the diamine unit in the polyamide (b1) may be composed only of a structural unit derived from xylylenediamine, but may contain a structural unit derived from diamine other than xylylenediamine.
- Compounds that constitute diamine units other than xylylenediamine include tetramethylenediamine, pentamethylenediamine, 2-methyl-1,5-pentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, Aliphatic diamines such as methylene diamine, dodecamethylene diamine, 2,2,4- or 2,4,4-trimethylhexamethylene diamine; 1,3- or 1,4-bis (aminomethyl) cyclohexane, 1,3- Or an alicyclic group such as 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminomethyl) decalin, bis (aminomethyl) tricyclodecane Diamine; Bis (4-aminophen Le) ether, p-phenylenediamine,
- Examples of the compound capable of constituting an aliphatic dicarboxylic acid unit having 4 to 8 carbon atoms in the polyamide (b1) include ⁇ , ⁇ -linear aliphatic dicarboxylic acids having 4 to 8 carbon atoms.
- Examples of the ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 8 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, and suberic acid, but the barrier property of the multilayer hollow molded article is good. Adipic acid is preferred because it is easily available.
- the dicarboxylic acid unit in the polyamide (b1) is an aliphatic dicarboxylic acid having 4 to 8 carbon atoms from the viewpoint of appropriately expressing the barrier properties of the multilayer hollow molded article and the thermal properties such as glass transition temperature and melting point. It contains 70 mol% or more of derived structural units, preferably 80 to 100 mol%, more preferably 90 to 100 mol%.
- the dicarboxylic unit in the polyamide (b1) may consist only of a structural unit derived from an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 8 carbon atoms, but an ⁇ , ⁇ -linear fatty acid having 4 to 8 carbon atoms.
- a structural unit derived from a dicarboxylic acid other than the group dicarboxylic acid may be contained.
- examples of the dicarboxylic acid other than the ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 8 carbon atoms include aliphatic dicarboxylic acids having 3 or less carbon atoms such as oxalic acid and malonic acid; azelaic acid and sebacin C9 or more aliphatic dicarboxylic acids such as acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid However, it is not limited to these. These can be used alone or in combination of two or more.
- polyxylylene adipamide in which all diamine units are composed of xylylenediamine-derived structural units and all dicarboxylic acid units are composed of adipic acid-derived structural units is preferable.
- the structural unit derived from xylylenediamine the structural unit derived from metaxylylenediamine:
- the structural unit derived from paraxylylenediamine is preferably 100: 0 to 50:50, more preferably 100: 0. 60:40, more preferably 100: 0 to 65:35.
- the melting point Tm of the polyamide (b1) is preferably 200 to 280 ° C., more preferably 220 to 260 ° C. from the viewpoint of heat resistance and melt moldability.
- Polyamide (b2) In the polyamide (b2), 70 mol% or more of the diamine structural unit is derived from an aliphatic diamine having 9 to 12 carbon atoms, and 70 mol% or more of the dicarboxylic acid structural unit includes a structural unit derived from terephthalic acid.
- the compound that can constitute the diamine unit of the polyamide (b2) is an aliphatic diamine having 9 to 12 carbon atoms.
- the aliphatic group of the aliphatic diamine having 9 to 12 carbon atoms is a linear or branched divalent aliphatic hydrocarbon group, and may be a saturated aliphatic group or an unsaturated aliphatic group. Usually, it is a linear saturated aliphatic group.
- Examples of the aliphatic diamine having 9 to 12 carbon atoms include nonamethylene diamine, 2,2,4- or 2,4,4-trimethylhexamethylene diamine, decamethylene diamine, undecamethylene diamine, and dodecamethylene diamine. Can be mentioned.
- the diamine unit in the polyamide (b2) contains 70 mol% or more, preferably 80 to 100 mol%, more preferably a structural unit derived from an aliphatic diamine having 9 to 12 carbon atoms from the viewpoint of maintaining good barrier properties. Contains from 90 to 100 mol%.
- the diamine unit in the polyamide (b2) may be composed only of a structural unit derived from an aliphatic diamine having 9 to 12 carbon atoms, but contains a structural unit derived from a diamine other than an aliphatic diamine having 9 to 12 carbon atoms. Also good.
- diamines other than aliphatic diamines having 9 to 12 carbon atoms include tetramethylene diamine, pentamethylene diamine, 2-methyl-1,5-pentane diamine, hexamethylene diamine, heptamethylene diamine, octamethylene.
- Aliphatic diamines having 8 or less carbon atoms such as diamine; 1,3- or 1,4-bis (aminomethyl) cyclohexane, 1,3- or 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2 , 2-bis (4-aminocyclohexyl) propane, bis (aminomethyl) decalin, bis (aminomethyl) tricyclodecane, and other alicyclic diamines; bis (4-aminophenyl) ether, paraphenylenediamine, bis (amino Diamines having aromatic rings such as methyl) naphthalene Although such can be exemplified, but the invention is not limited thereto.
- the compound that can constitute the dicarboxylic acid unit in the polyamide (b2) is terephthalic acid, and from the viewpoint of improving the barrier properties, it contains 70 mol% or more of a terephthalic acid-derived structural unit, preferably 80 To 100 mol%, more preferably 90 to 100 mol%.
- the dicarboxylic acid unit in the polyamide (b2) may be composed only of structural units derived from terephthalic acid, but may also contain structural units derived from dicarboxylic acids other than terephthalic acid.
- dicarboxylic acids other than terephthalic acid include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, and 1,10-decanedicarboxylic acid.
- Acids aliphatic carboxylic acids such as 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid; isophthalic acid, 2,6-naphthalenedicarboxylic acid An aromatic dicarboxylic acid other than terephthalic acid such as an acid can be exemplified, but it is not limited thereto.
- the polyamide (b2) is preferably polyamide 9T (PA9T) mainly composed of a structural unit derived from nonamethylenediamine and a structural unit derived from terephthalic acid.
- PA9T polyamide 9T
- the melting point Tm of the polyamide (b2) is preferably 250 to 315 ° C., more preferably 260 to 300 ° C., and further preferably 260 to 280 ° C. from the viewpoint of heat resistance and melt moldability.
- Polyamide (b1) and polyamide (b2) are obtained by polycondensation of a diamine component and a dicarboxylic acid component.
- the manufacturing method is the same as that of polyamide (a2).
- the mass ratio of the ethylene-vinyl alcohol copolymer (EVOH) and the semiaromatic polyamide (b) in the resin composition constituting the barrier layer (B) is 80:20 to 20:80, preferably 70:30 to 20:80, more preferably 60:40 to 30:70.
- the resin composition constituting the barrier layer (B) is blended with various commonly used additives in addition to EVOH and semi-aromatic polyamide (b) within the range that does not impair the object and effects of the present invention. Also good.
- the same thing as what was illustrated in the aliphatic polyamide layer (A) can be mentioned.
- the barrier layer (B) has good impact resistance. However, when the impact resistance of the barrier layer (B) is further improved, it is preferable to add an impact resistance improving material. .
- the olefin polymer and elastomer which were acid-modified by carboxylic acid and / or its derivative from the point which is excellent in heat resistance and compatibility with a polyamide component.
- the compounding amount of these additives is preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less, as a mass ratio with respect to the resin composition constituting the barrier layer (B).
- the thickness of the barrier layer (B) is not particularly limited, but is usually preferably in the range of 10 to 1000 ⁇ m, more preferably 20 to 750 ⁇ m, still more preferably 50 to 500 ⁇ m.
- the layer structure of the multilayer hollow molded article of the present invention is not particularly limited as long as it has at least one aliphatic polyamide layer (A) and one barrier layer (B).
- aliphatic polyamide layer Preferable examples include a five-layer structure of (A) / barrier layer (B) / aliphatic polyamide layer (A) / barrier layer (B) / aliphatic polyamide layer (A).
- the barrier layer (B) is disposed on the inner side.
- each layer may have the same composition or different compositions.
- the aliphatic polyamide layer (A) can have different compositions by changing the type or blending ratio of the aliphatic polyamide (a).
- a barrier layer (B) can be made into a different composition by changing the compounding ratio of the kind of semi-aromatic polyamide (b), and EVOH and a semi-aromatic polyamide (b).
- the multilayer hollow molded article of the present invention has other layers as required in addition to the aliphatic polyamide layer (A) and the barrier layer (B) as long as the objects and effects of the present invention are not impaired. Also good.
- an adhesive layer may be provided for the purpose of increasing the interlayer adhesive strength between the aliphatic polyamide layer (A) and the barrier layer (B).
- the adhesive layer preferably contains a thermoplastic resin having adhesiveness.
- the thermoplastic resin having adhesiveness for example, an acid modification in which a polyolefin resin such as polyethylene or polypropylene is modified with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc.
- Polyolefin resin polyester-based thermoplastic elastomer mainly composed of a polyester-based block copolymer.
- the aliphatic polyamide layer (A) and the barrier layer (B) since the adhesion between the aliphatic polyamide layer (A) and the barrier layer (B) is enhanced, the aliphatic polyamide (a), the ethylene-vinyl alcohol copolymer (EVOH), and the semi-aromatic polyamide (b)
- a layer made of a resin composition containing at least one of the above may be provided as an adhesive layer.
- the thickness of the adhesive layer is not particularly limited, but is preferably in the range of 10 to 200 ⁇ m, more preferably 15 to 150 ⁇ m, and still more preferably 20 to 20 ⁇ m from the viewpoint of ensuring the moldability while exhibiting practical adhesive strength. 100 ⁇ m.
- a protective layer is provided on the inside or outside of these layers. Also good.
- protective layer materials include polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE), and ethylene / chlorotrifluoroethylene copolymer.
- Fluorine such as polymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV) -Based resins, polyethylenes such as high-density polyethylene, propylene homopolymers, propylene-ethylene random copolymers, polypropylenes such as propylene-ethylene block copolymers, polyesters such as PET, and combinations thereof To and the like.
- ECTFE polymer
- TFE / HFP tetrafluoroethylene / hexafluoropropylene copolymer
- TFE / HFP tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer
- polyethylenes such as high-
- the thickness of the protective layer is not particularly limited, but is preferably in the range of 10 to 300 ⁇ m, more preferably 15 to 200 ⁇ m, still more preferably 20 to 100 ⁇ m.
- other barrier layers include a layer made of an ethylene-vinyl alcohol copolymer (EVOH), a layer made of a semi-aromatic polyamide (b), and the like.
- the thickness of the other barrier layer is not particularly limited, but is preferably in the range of 10 to 500 ⁇ m, more preferably 20 to 400 ⁇ m, and still more preferably 50 to 300 ⁇ m.
- the manufacturing method of the multilayer hollow molded body of the present invention is not particularly limited, and can be manufactured by a method conventionally used for manufacturing a multilayer hollow molded body.
- the material constituting each layer is melted and mixed in advance by a melt-kneading apparatus such as an extruder, and then provided to the hollow molded body molding apparatus.
- Method of forming by melt extrusion with an extruder Method of forming and supplying each material constituting each layer in a hollow molded body molding apparatus by melt extrusion with each extruder provided in the apparatus; or configuring each layer
- Examples include a method in which materials obtained by dry blending are supplied to a hollow molded body forming apparatus and melt-extruded by an extruder provided in the apparatus.
- each material constituting each layer is melt-extruded by using an extruder corresponding to the number of layers or the number of materials, and is supplied into the die, and after each forming an annular flow, the material is formed inside or outside the die.
- the shape of the multilayer hollow molded body of the present invention is not particularly limited, and various shapes such as a tube, a pipe, a hose and a connector can be mentioned.
- the multilayer hollow molded body of the present invention has a complicated shape or is subjected to heat bending after molding to form a molded body, the multilayer hollow molded body is formed to remove residual distortion of the molded product. After that, the target molded product can be obtained by heat treatment at a temperature lower than the lowest melting point of the resin constituting the multilayer hollow molded body.
- the multilayer hollow molded body of the present invention may have a corrugated region at least partially.
- the waveform area means an area formed in a waveform shape, a bellows shape, an accordion shape, a corrugated shape, or the like.
- a hollow molded body having a corrugated region can be easily formed by molding a straight tubular hollow molded body and then molding to form a predetermined corrugated shape.
- the multilayer hollow molded body of the present invention can be formed into a shape such as an L shape or a U shape by adding necessary parts such as a connector or by bending.
- the outer diameter and thickness of the multilayer hollow molded article of the present invention are not particularly limited and may be appropriately determined depending on the application.
- the outer diameter is usually preferably in the range of 3 to 100 mm, more preferably 5 to 50 mm, More preferably, it is 7 to 20 mm.
- the wall thickness is usually preferably in the range of 0.1 to 10 mm, more preferably 0.3 to 5 mm, and still more preferably 0.5 to 3 mm.
- the multilayer hollow molded body of the present invention can be used as pipes, hoses, tubes or connectors for various purposes.
- the multilayer hollow molded article of the present invention is excellent in barrier properties, burst resistance, heat resistance and impact resistance, so gasoline, alcohol-containing gasoline, methanol, ethanol, light oil, It can be suitably used as a fuel transport piping material for transporting high-temperature liquid fuel such as kerosene or heavy oil, for example, a fuel pipe, a fuel hose, a fuel tube, or a connector that can connect these.
- Relative viscosity 0.2 g of polyamide (b) is precisely weighed and dissolved in 20 ml of 96% by mass sulfuric acid at 20 to 30 ° C. with stirring and completely dissolved to prepare a solution.
- the sample was taken in a Cannon Fenceke viscometer and stored in a constant temperature bath at 25 ° C. for 10 minutes, and then the dropping speed (t) was measured. Similarly, the dropping rate (t 0 ) of 96% by mass sulfuric acid was also measured. From the measured values of t and t 0, the following equation was calculated relative viscosity of the polyamide (b).
- Relative viscosity of polyamide (b) t / t 0
- Synthesis example 1 Synthesis of polyamide resin (b1-1) In a reaction vessel having a volume of about 3 L equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet, 730.8 g of adipic acid, 0.6322 g of sodium hypophosphite monohydrate and After 0.4404 g of sodium acetate was charged and the inside of the container was sufficiently purged with nitrogen, it was melted at 170 ° C. while supplying nitrogen gas at 20 ml / min.
- the semi-aromatic polyamide resin (b1-1) obtained had a relative viscosity ( ⁇ r) of 2.1 and a melting point (Tm) of 237.4 ° C.
- Synthesis example 2 Synthesis of polyamide resin (b1-2) In a reaction vessel having a volume of about 3 L equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet, 730.8 g of adipic acid, 0.6322 g of sodium hypophosphite monohydrate and After 0.4404 g of sodium acetate was charged and the inside of the container was sufficiently purged with nitrogen, it was melted at 170 ° C. while supplying nitrogen gas at 20 ml / min.
- Example 1 80 parts by weight of the semi-aromatic polyamide resin (b1-1) obtained in Synthesis Example 1 for forming the barrier layer (B), and EVOH (product name: EVAL (trademark) F101B) 20 manufactured by Kuraray Co., Ltd.
- a resin composition obtained by dry blending parts by weight and nylon 11 for forming the aliphatic polyamide layer (A) are respectively charged into a single screw extruder, and two single screw extruders and two types of two layers
- a multi-layer tube forming machine having a flow path for forming a multi-layer structure was obtained to obtain a multi-layer tube (outer layer: aliphatic polyamide layer (A), inner layer: barrier layer (B)) having an outer diameter of 8 mm and a wall thickness of 1 mm.
- the thickness of the aliphatic polyamide layer (A) was 800 ⁇ m
- the thickness of the barrier layer (B) was 200 ⁇ m.
- Examples 2, 3 and 4 A multilayer tube having an outer diameter of 8 mm and a wall thickness of 1 mm was obtained in the same manner as in Example 1 except that the blending amounts of the semi-aromatic polyamide (b1-1) and EVOH were changed to the blending amounts shown in Table 1, respectively.
- the thickness of the aliphatic polyamide layer (A) was 800 ⁇ m
- the thickness of the barrier layer (B) was 200 ⁇ m.
- Examples 5 and 6 The semi-aromatic polyamide (b1-2) obtained in Synthesis Example 2 was used instead of the semi-aromatic polyamide (b1-1), and the blending amounts of the semi-aromatic polyamide (b1-2) and EVOH are shown in Table 1, respectively.
- a multilayer tube having an outer diameter of 8 mm and a wall thickness of 1 mm was obtained in the same manner as in Example 1 except that the blending amounts described were used.
- the aliphatic polyamide layer (A) had a thickness of 800 ⁇ m
- the barrier layer (B) had a thickness of 200 ⁇ m.
- Comparative Example 1 EVOH (manufactured by Kuraray Co., Ltd., product name EVAL (trademark) F101B) for forming the barrier layer (B) and nylon 11 for forming the aliphatic polyamide layer (A) are each a single screw extruder.
- the multi-layer tube having an outer diameter of 8 mm and a wall thickness of 1 mm was obtained with a multi-layer tube forming machine comprising two single-screw extruders and a flow path that forms a multi-layer structure of two types and two layers.
- the thickness of the aliphatic polyamide layer (A) was 800 ⁇ m
- the thickness of the barrier layer (B) was 200 ⁇ m.
- Comparative Example 2 A multilayer tube having an outer diameter of 8 mm and a wall thickness of 1 mm was prepared in the same manner as in Comparative Example 1 except that the semi-aromatic polyamide (b1-1) obtained in Synthesis Example 1 was used instead of EVOH in Comparative Example 1. Obtained. In any case, the aliphatic polyamide layer (A) had a thickness of 800 ⁇ m, and the barrier layer (B) had a thickness of 200 ⁇ m.
- the multilayer hollow molded article of the present invention is excellent in barrier properties, burst resistance, heat resistance and impact resistance.
- the burst resistance and heat resistance are poor (Comparative Example 1)
- the semi-aromatic polyamide (b) is used as the barrier layer
- the burst resistance and heat resistance are good.
- the impact resistance was low (Comparative Example 2).
- the multilayer hollow molded article of the present invention is excellent in barrier properties, burst resistance, heat resistance and impact resistance, and is therefore suitably used as a fuel transport piping material or a fuel storage container.
- it is suitably used as a material for fuel tubes, fuel pipes, fuel hoses or connectors.
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Abstract
Description
しかし、EVOHはバリア性に非常に優れる材料である一方で、耐バースト性及び耐熱性が低いという欠点があり、高い耐圧性及び耐熱性が要求される高温の液体燃料を輸送する燃料輸送配管材として用いる場合、耐バースト性及び耐熱性が不足することがあった。
[1]少なくとも一層の脂肪族ポリアミド層(A)と少なくとも一層のバリア層(B)とを有する多層中空成形体であって、
脂肪族ポリアミド層(A)が、脂肪族ポリアミド(a)を主成分とする樹脂組成物からなり、
バリア層(B)が、エチレン‐ビニルアルコール共重合体(EVOH)と半芳香族ポリアミド(b)とを含む樹脂組成物からなる、多層中空成形体。
[2]半芳香族ポリアミド(b)が、キシリレンジアミンに由来するジアミン構成単位を70モル%以上含むジアミン構成単位と、炭素数4~8のα,ω-直鎖脂肪族ジカルボン酸に由来するジカルボン酸単位を70モル%以上を含むジカルボン酸単位とを含むポリアミドである、[1]に記載の多層中空成形体。
[3]半芳香族ポリアミド(b)が、ポリキシリレンアジパミドである、[1]又は[2]に記載の多層中空成形体。
[4]脂肪族ポリアミド(a)が、炭素数10~12のラクタム由来の構成単位及び炭素数10~12のアミノカルボン酸由来の構成単位の少なくとも一方を含むポリアミド(a1)、及び、炭素数6~12の脂肪族ジアミン由来の構成単位及び炭素数10~12の脂肪族ジカルボン酸由来の構成単位を含むポリアミド(a2)からなる群から選ばれる少なくとも一種である、[1]~[3]の何れか一項に記載の多層中空成形体。
[5]脂肪族ポリアミド(a)が、ポリアミド11、ポリアミド12、ポリアミド10,10、ポリアミド10,12、ポリアミド6,11及びポリアミド6,12からなる群から選ばれる少なくとも一種である、[1]~[4]の何れか一項に記載の多層中空成形体。
[6]バリア層(B)を構成する樹脂組成物におけるエチレン‐ビニルアルコール共重合体(EVOH)と半芳香族ポリアミド(b)との質量比率(EVOH:半芳香族ポリアミド(b))が、80:20~20:80の範囲である、[1]~[5]の何れか一項に記載の多層中空成形体。
[7]燃料用チューブ、燃料用パイプ、燃料用ホース又はコネクタである、[1]~[6]の何れか一項に記載の多層中空成形体。
本発明においては、バリア層(B)の材料として、エチレン‐ビニルアルコール共重合体(EVOH)と半芳香族ポリアミド(b)とを含む樹脂組成物を用いることにより、脂肪族ポリアミド層(A)との組み合わせにおいて、バリア性に加えて、燃料輸送配管材として使用するに十分な耐バースト性及び耐熱性を付与することができる。また、良好な耐衝撃性を得ることができる。以下、本発明の多層中空成形体を構成する脂肪族ポリアミド層(A)及びバリア層(B)ならびに多層中空成形体の製造方法等について説明する。
本発明に用いられる脂肪族ポリアミド層(A)は、脂肪族ポリアミド(a)を主成分とする樹脂組成物からなる層である。ここで、「脂肪族ポリアミド(a)を主成分とする」とは、樹脂組成物中に脂肪族ポリアミド(a)が、質量比率で、70%以上、好ましくは75%以上、より好ましくは80%以上含まれていることをいう。脂肪族ポリアミド層中に脂肪族ポリアミド(a)が上記の範囲で含まれることにより、耐薬品性及び柔軟性を良好なものとすることができる。
本発明に用いることができる脂肪族ポリアミド(a)は、アミド結合{-N H-C(=O )-}を含み、分子骨格中に芳香環を含まない構成単位を主成分とする、本質的に鎖状のポリアミドであれば特に制限されない。ここで「主成分とする」とは、脂肪族ポリアミド(a)の構成単位のうち、芳香環を含まない構成単位が60モル%以上、好ましくは80~100モル%、より好ましくは90~100モル%占めることをいう。これらの中でも、本発明の多層中空成形体の耐薬品性を更に良好なものとすることができることから、脂肪族ポリアミド(a)としては、炭素数10~12のラクタム由来の構成単位及び炭素数10~12のアミノカルボン酸由来の構成単位の少なくとも一方を含むポリアミド(a1)、及び、炭素数6~12の脂肪族ジアミン由来の構成単位及び炭素数10~12の脂肪族ジカルボン酸由来の構成単位を含むポリアミド(a2)からなる群から選ばれる一種又は二種以上であることが好ましい。
ポリアミド(a1)は、炭素数10~12のラクタム由来の構成単位及び炭素数10~12のアミノカルボン酸由来の構成単位の少なくとも一方を含む。
ラクタム由来の構成単位及びアミノカルボン酸由来の構成単位の炭素数は、柔軟性及び入手容易性等の観点から11~12が好ましい。
炭素数10~12のラクタム由来の構成単位及び炭素数10~12のアミノカルボン酸由来の構成単位は、通常、下記一般式で示されるω-アミノカルボン酸単位からなる。
ここで、上記式において、pは9~11の整数を表し、好ましくは10~11である。
炭素数10~12のラクタム由来の構成単位を構成する化合物としては、具体的には、デカンラクタム、ウンデカンラクタム、ドデカンラクタムが挙げられる。また、炭素数10~12のアミノカルボン酸由来の構成単位を構成する化合物としては、10-アミノデカン酸、11-アミノウンデカン酸、12-アミノドデカン酸が挙げられる。
ポリアミド(a1)における他の構成単位としては、例えば、炭素数10~12のラクタム以外のラクタム、炭素数10~12のアミノカルボン酸以外のアミノカルボン酸、又はジアミンとジカルボン酸からなるナイロン塩由来の構成単位が挙げられる。
その重合方法は、特に限定されず、溶融重合、溶液重合、固相重合など公知の方法を採用できる。これらの重合方法は単独で、あるいは適宜、組合せて用いることができる。製造装置としては、バッチ式反応釜、一槽式ないし多槽式の連続反応装置、管状連続反応装置、一軸型混練押出機、二軸型混練押出機などの混練反応押出機等、公知のポリアミド製造装置を用いることができる。
ポリアミド(a1)の重縮合時には、分子量調整剤として少量のモノアミン、モノカルボン酸等を加えてもよい。
さらに、ポリアミド(a1)の重縮合時には、アミド化反応を促進する効果や、重縮合時の着色を防止する効果を得るために、リン原子含有化合物、アルカリ金属化合物及びアルカリ土類金属化合物等の公知の添加剤を添加してもよい。
なお、本明細書において、融点は、示差走査熱量計〔島津製作所社製、商品名:DSC-60〕を用い、昇温速度10℃/分で、窒素気流下にDSC測定(示差走査熱量測定)を行うことにより測定される。
ポリアミド(a2)は、炭素数6~12の脂肪族ジアミン由来の構成単位及び炭素数10~12の脂肪族ジカルボン酸由来の構成単位を含む。
ポリアミド(a2)のジアミン単位を構成し得る化合物は炭素数6~12の脂肪族ジアミンである。炭素数6~12の脂肪族ジアミンの脂肪族基は、直鎖状又は分岐状の2価の脂肪族炭化水素基であり、飽和脂肪族基であっても、不飽和脂肪族基であってもよいが、通常は、直鎖状の飽和脂肪族基である。脂肪族基の炭素数は、好ましくは8~12であり、より好ましくは9~12であり、更に好ましくは10~12である。
ポリアミド(a2)のジアミン単位を構成しうる化合物は、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、ウンデカメチレンジアミン、ドデカメチレンジアミン等の脂肪族ジアミンが挙げられるが、これらに限定されない。これらは、単独で、または2種以上を組み合わせて用いることができる。
ポリアミド(a2)におけるジアミン単位は、炭素数6~12の脂肪族ジアミン由来の構成単位のみからなってもよいが、炭素数6~12の脂肪族ジアミン以外のジアミン由来の構成単位を含有してもよい。
ポリアミド(a2)中のジカルボン酸単位は、柔軟性をより良好なものとすることから、炭素数10~12の脂肪族ジカルボン酸由来の構成単位を好ましくは70モル%以上、より好ましくは80~100モル%、更に好ましくは90~100モル%含有する。
ポリアミド(a2)におけるジカルボン酸単位は、炭素数10~12の脂肪族ジカルボン酸由来の構成単位のみからなってもよいが、炭素数10~12の脂肪族ジカルボン酸以外のジカルボン酸由来の構成単位を含有してもよい。
ポリアミド(a2)の重縮合時には、分子量調整剤として少量のモノアミン、モノカルボン酸等を加えてもよい。
さらに、ポリアミド(a2)の重縮合時には、アミド化反応を促進する効果や、重縮合時の着色を防止する効果を得るために、リン原子含有化合物、アルカリ金属化合物及びアルカリ土類金属化合物等の公知の添加剤を添加してもよい。
本発明に用いられるバリア層(B)は、エチレン‐ビニルアルコール共重合体(EVOH)と半芳香族ポリアミド(b)とを含む樹脂組成物からなる。バリア層(B)がエチレン‐ビニルアルコール共重合体(EVOH)と半芳香族ポリアミド(b)とを含む樹脂組成物から形成されることにより、良好なバリア性、耐バースト性及び耐熱性を有するバリア層を得ることができる。また、該バリア層は、耐衝撃性にも優れている。
本発明に用いられるエチレン‐ビニルアルコール共重合体(EVOH)は、エチレンとビニルアルコールとのランダム共重合体である。本発明に用いられるエチレン‐ビニルアルコール共重合体(EVOH)は、例えば、エチレンと酢酸ビニルと必要に応じて少量の他の共重合成分とを共重合させた後に、酢酸ビニルをけん化することにより、酢酸ビニル単位をビニルアルコール単位に変えることによって得ることができる。
他の共重合成分としては、例えば、プロピレン、イソブテン、α-オクテン、α-ドデセン、α-オクタデセンなどのα-オレフィン、不飽和カルボン酸またはその塩、部分アルキルエステル、完全アルキルエステル、ニトリル、アミド、無水物、不飽和スルホン酸またはその塩などが挙げられる。
本発明に用いられるエチレン‐ビニルアルコール共重合体(EVOH)としては、エチレン含量が15~60モル%であり、且つ、酢酸ビニル成分のケン化度が90モル%以上のものが好ましい。エチレン含量は、より好ましくは20~55モル%、更に好ましくは29~44モル%である。また、酢酸ビニル成分のケン化度は、より好ましくは95モル%以上である。エチレン含量及び酢酸ビニル成分のケン化度が上記の範囲であると、バリア性、耐油性及び耐薬品性に優れる。
エチレン‐ビニルアルコール共重合体(EVOH)の融点Tmは、耐熱性及び溶融成形性の観点から、好ましくは150~200℃、より好ましくは190~160℃である。
本発明に用いられる半芳香族ポリアミド(b)は、ジアミン構成単位又はジカルボン酸構成単位の何れか一方が、芳香族化合物に由来する構成単位を50モル%を超えて含む樹脂をいう。例えば、ジアミン構成単位の50モル%超がキシリレンジアミンに由来する構成単位であり、ジカルボン酸構成単位の50モル%超が非芳香族ジカルボン酸に由来する構成単位を含むポリアミド;ジアミン構成単位の50モル%超が非芳香族ジアミンに由来する構成単位であり、ジカルボン酸構成単位の50モル%超がフタル酸に由来する構成単位を含むポリアミド等が挙げられる。
多層中空成形体のバリア性をより良好なものとすることから、半芳香族ポリアミド(b)は、ジアミン構成単位の70モル%以上がキシリレンジアミンに由来し、ジカルボン酸構成単位の70モル%以上が炭素数4~8のα,ω-直鎖脂肪族ジカルボン酸に由来する構成単位を含むポリアミド(b1)、又は、ジアミン構成単位の70モル%以上が炭素数9~12の脂肪族ジアミンに由来し、ジカルボン酸構成単位の70モル%以上がテレフタル酸に由来する構成単位を含むポリアミド(b2)であることが好ましい。以下、ポリアミド(b1)及びポリアミド(b2)について、より詳細に説明する。
ポリアミド(b1)は、ジアミン構成単位の70モル%以上がキシリレンジアミンに由来し、ジカルボン酸構成単位の70モル%以上が炭素数4~8のα,ω-直鎖脂肪族ジカルボン酸に由来する構成単位を含む。
ポリアミド(b1)におけるジアミン単位は、キシリレンジアミン由来の構成単位のみからなってもよいが、キシリレンジアミン以外のジアミン由来の構成単位を含有してもよい。
ポリアミド(b1)におけるジカルボン単位は、炭素数4~8のα,ω-直鎖脂肪族ジカルボン酸由来の構成単位のみからなってもよいが、炭素数4~8のα,ω-直鎖脂肪族ジカルボン酸以外のジカルボン酸由来の構成単位を含有してもよい。
ポリアミド(b2)は、ジアミン構成単位の70モル%以上が炭素数9~12の脂肪族ジアミンに由来し、ジカルボン酸構成単位の70モル%以上がテレフタル酸に由来する構成単位を含む。
ポリアミド(b2)のジアミン単位を構成し得る化合物は炭素数9~12の脂肪族ジアミンである。炭素数9~12の脂肪族ジアミンの脂肪族基は、直鎖状又は分岐状の2価の脂肪族炭化水素基であり、飽和脂肪族基であっても、不飽和脂肪族基であってもよいが、通常は、直鎖状の飽和脂肪族基である。
炭素数9~12の脂肪族ジアミンとしては、例えば、ノナメチレンジアミン、2,2,4-又は2,4,4-トリメチルヘキサメチレンジアミン、デカメチレンジアミン、ウンデカメチレンジアミン、ドデカメチレンジアミン等が挙げられる。
ポリアミド(b2)において、テレフタル酸以外のジカルボン酸としては、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、1,9-ノナンジカルボン酸、1,10-デカンジカルボン酸、1,11-ウンデカンジカルボン酸、1,12-ドデカンジカルボン酸、1,13-トリデカンジカルボン酸、1,14-テトラデカンジカルボン酸等の脂肪族カルボン酸;イソフタル酸、2,6-ナフタレンジカルボン酸等のテレフタル酸以外の芳香族ジカルボン酸等を例示できるが、これらに限定されない。
本発明において、バリア層(B)は良好な耐衝撃性を有しているが、バリア層(B)の耐衝撃性を更に良好なものとする場合、耐衝撃改良材を配合することが好ましい。耐衝撃改良材としては、特に制限されないが、耐熱性及びポリアミド成分との相溶性に優れる点で、カルボン酸および/またはその誘導体で酸変性されたオレフィン系重合体及びエラストマーを用いることが好ましい。
これらの添加剤の配合量は、バリア層(B)を構成する樹脂組成物に対する質量比率で、30%以下が好ましく、より好ましくは25%以下であり、更に好ましくは20%以下である。
例えば、脂肪族ポリアミド層(A)/バリア層(B)の二層構造、脂肪族ポリアミド層(A)/バリア層(B)/脂肪族ポリアミド層(A)の三層構造、脂肪族ポリアミド層(A)/バリア層(B)/脂肪族ポリアミド層(A)/バリア層(B)/脂肪族ポリアミド層(A)の五層構造などが好ましく挙げられる。バリア性をより効果的に発揮するためにはバリア層(B)がより内側に配置されていることが好ましい。
本発明の多層中空成形体が、脂肪族ポリアミド層(A)及びバリア層(B)をそれぞれ二層以上有している場合、各層は、同一の組成を有していてもよいし、異なる組成を有していてもよい。例えば、脂肪族ポリアミド層(A)は、脂肪族ポリアミド(a)の種類又は配合比を変えることにより異なる組成とすることができる。また、バリア層(B)は、半芳香族ポリアミド(b)の種類及びEVOHと半芳香族ポリアミド(b)との配合比を変えることにより異なる組成とすることができる。
例えば、脂肪族ポリアミド層(A)とバリア層(B)との間の層間接着強度を高める目的で、接着層を設けてもよい。接着層は、接着性を有する熱可塑性樹脂を含むことが好ましい。接着性を有する熱可塑性樹脂としては、例えば、ポリエチレン又はポリプロピレン等のポリオレフィン系樹脂をアクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、フマル酸、イタコン酸等の不飽和カルボン酸で変性した酸変性ポリオレフィン樹脂;ポリエステル系ブロック共重合体を主成分としたポリエステル系熱可塑性エラストマー等が挙げられる。また、脂肪族ポリアミド層(A)とバリア層(B)との密着性を高めることから、脂肪族ポリアミド(a)と、エチレン‐ビニルアルコール共重合体(EVOH)及び半芳香族ポリアミド(b)の1種以上とを含む樹脂組成物からなる層を接着層として設けてもよい。接着層の厚みは、特に制限されないが、実用的な接着強度を発揮しつつ成形加工性を確保するという観点から、10~200μmの範囲が好ましく、より好ましくは15~150μm、更に好ましくは20~100μmである。
また、脂肪族ポリアミド層(A)又はバリア層(B)の破損又はピンホールを防ぐため、あるいは、内容物と直接接触することを防ぐために、これらの層の内側又は外側に保護層を設けてもよい。保護層の材料としては、例えば、ポリフッ化ビニリデン(PVDF)、ポリフッ化ビニル(PVF)、ポリクロルフルオロエチレン(PCTFE)、テトラフルオロエチレン/エチレン共重合体(ETFE)、エチレン/クロロトリフルオロエチレン共重合体(ECTFE)、テトラフルオロエチレン/ヘキサフルオロプロピレン共重合体(TFE/HFP,FEP)、テトラフルオロエチレン/ヘキサフルオロプロピレン/ビニリデンフルオライド共重合体(TFE/HFP/VDF,THV)等のフッ素系樹脂、高密度ポリエチレン等のポリエチレン類、プロピレンホモポリマー、プロピレン-エチレンランダム共重合体、プロピレン-エチレンブロック共重合体等のポリプロピレン類、PET等のポリエステル類およびこれらの組み合わせなどが挙げられる。保護層の厚みは、特に制限されないが、10~300μmの範囲が好ましく、より好ましくは15~200μm、更に好ましくは20~100μmである。
また、バリア層(B)以外の他のバリア層を更に設けてもよい。他のバリア層としては、エチレン‐ビニルアルコール共重合体(EVOH)からなる層、半芳香族ポリアミド(b)からなる層などが挙げられる。他のバリア層の厚みは、特に制限されないが、10~500μmの範囲が好ましく、より好ましくは20~400μm、更に好ましくは50~300μmである。
例えば、各層を構成する材料をそれぞれ、層の数もしくは材料の数に対応する押出機を用いて溶融押出して、ダイ内に供給し、各々環状の流れをなした後、ダイ内もしくはダイ外に同時押出により積層する方法(共押出法)、あるいは、一旦、単層の中空成形体を製造しておき、外側に順次、必要に応じて接着剤を使用し、樹脂を一体化しながら積層する方法(コーティング法)により製造することができる。
本発明の多層中空成形体が複雑な形状を有している場合あるいは成形後に加熱曲げ加工を施して成形体とする場合は、成形品の残留歪みを除去するために、多層中空成形体を形成した後、多層中空成形体を構成する樹脂の融点のうち最も低い融点未満の温度で熱処理して目的の成形品を得ることができる。
本発明の多層中空成形体は、少なくとも一部に波形領域を有していてもよい。ここで波形領域とは、波形形状、蛇腹形状、アコーディオン形状、又はコルゲート形状等に形成した領域をいう。波形領域を有する中空成形体は、直管状の中空成形体を成形した後、モールド成形し、所定の波形形状を形成することにより容易に形成することができる。また、本発明の多層中空成形体は、例えば、コネクタなどの必要な部品を付加したり、曲げ加工によりL字もしくはU字などの形状に成形することもできる。
実施例及び比較例で得られた各々のチューブについて、SAE J 2260に準拠し、23℃もしくは80℃の雰囲気下、チューブ内に23℃もしくは80℃の水を充填し、7MPa/minの昇圧速度で加圧を行い、チューブにバーストが生じた際の圧力を測定した。23℃条件で30MPa以上、80℃条件で10MPa以上のものを合格とした。なお、多層中空成形体の耐熱性は、80℃条件での耐バースト性により評価することができる。
実施例及び比較例で得られた各々のチューブについて、200mmにカットしたチューブの片端を密栓し、内部にFuelC(イソオクタン/トルエン=50/50体積比)とエタノールとを90/10体積比に混合したアルコール/ガソリンを入れ、残りの端部も密栓した。その後、全体の質量を測定し、次いで試験チューブを40℃のオーブンに入れ、24時間、静置した。その後、試験チューブをオーブンから取り出し、質量変化を測定し、次式に基づいて、1m2あたりのアルコールガソリン透過性を評価した。1g/m2_day以下の透過率を合格とした。
式:アルコールガソリン透過率(g/m2_day)=24時間の重量変化(g)/(チューブ内径(m)*円周率π*チューブ長さ(m))
チューブをステンレス鋼製の作業台上に静置し、30cmの高さから直径10cm、重さ900gの鉄球をチューブ上に垂直に落下させた。試験はそれぞれの実施例及び比較例で得られた各々のチューブについて、10箇所の部位について行った。試験後のチューブの衝撃が与えられた部位に対してチューブの周方向に90°の位置でチューブをカットして切り開き、目視にて内層側及び外層側の衝撃部位を観察し、10箇所の衝撃部位について、いずれの箇所のいずれの層にもクラックが生じなかったものを合格(A)とし、いずれかの箇所のいずれかの層にクラックが生じたものを不合格(B)とした。
ポリアミド(b)0.2gを精秤し、96質量%硫酸20mlに20~30℃で撹拌溶解し、完全に溶解し溶液を調製した後、調製した当該溶液5mlを、速やかにキャノンフェンスケ型粘度計に取り、25℃の恒温漕中で10分間保存後、落下速度(t)を測定した。また、同様にして、96質量%硫酸の落下速度(t0)も測定した。
測定したt及びt0の値から、下記式により、ポリアミド(b)の相対粘度を算出した。
ポリアミド(b)の相対粘度=t/t0
融点は、示差走査熱量計〔島津製作所社製、商品名:DSC-60〕を用い、昇温速度10℃/分で、窒素気流下にDSC(示差走査熱量測定)により測定した。
多層中空成形体の各層の厚み及び中空成形体の厚みは、チューブを成形時の流れ方向と垂直に切削し、その断面をデジタル顕微鏡にて100倍に拡大して観察して、その厚みを測定した。
ポリアミド樹脂(b1-1)の合成
撹拌機、窒素ガス導入口、縮合水排出口を備えた容積約3Lの反応容器にアジピン酸730.8g、次亜リン酸ナトリウム一水和物0.6322g及び酢酸ナトリウム0.4404gを仕込み、容器内を十分窒素置換した後、窒素ガスを20ml/分で供給しながら170℃で溶融させた。250℃まで徐々に昇温しながら、そこへメタキシリレンジアミン(MXDA)(三菱ガス化学(株)製)681.0gを滴下し約2時間重合を行い、半芳香族ポリアミド樹脂(b1-1)を得た。得られた半芳香族ポリアミド樹脂(b1-1)の相対粘度(ηr)は2.1、融点(Tm)は237.4℃であった。
ポリアミド樹脂(b1-2)の合成
撹拌機、窒素ガス導入口、縮合水排出口を備えた容積約3Lの反応容器にアジピン酸730.8g、次亜リン酸ナトリウム一水和物0.6322g及び酢酸ナトリウム0.4404gを仕込み、容器内を十分窒素置換した後、窒素ガスを20ml/分で供給しながら170℃で溶融させた。275℃まで徐々に昇温しながら、そこへメタキシリレンジアミン(MXDA)(三菱ガス化学(株)製)476.70gとパラキシリレンジアミン(PXDA)(三菱ガス化学(株)製)204.30g(モル比(MXDA/PXDA=70/30))の混合液を滴下し約2時間重合を行い、半芳香族ポリアミド樹脂(b1-2)を得た。得られた半芳香族ポリアミド樹脂(b1-2)の相対粘度(ηr)は2.1、融点(Tm)は257.0℃であった。
バリア層(B)を形成するための、合成例1で得られた半芳香族ポリアミド樹脂(b1-1)80重量部、及びEVOH((株)クラレ製、製品名 エバール(商標)F101B)20重量部をドライブレンドした樹脂組成物と、脂肪族ポリアミド層(A)を形成するためのナイロン11とを、それぞれ単軸押出機に投入し、2台の単軸押出機と、2種2層の多層構造を形成する流路からなる多層チューブ成形機にて、外径8mm、肉厚1mmの多層チューブ(外層:脂肪族ポリアミド層(A)、内層:バリア層(B))を得た。脂肪族ポリアミド層(A)の厚みは800μmであり、バリア層(B)の厚みは200μmであった。
半芳香族ポリアミド(b1-1)とEVOHの配合量をそれぞれ表1に記載の配合量としたこと以外は、実施例1と同様にして外径8mm、肉厚1mmの多層チューブを得た。いずれも、脂肪族ポリアミド層(A)の厚みは800μmであり、バリア層(B)の厚みは200μmであった。
半芳香族ポリアミド(b1-1)の代わりに合成例2で得られた半芳香族ポリアミド(b1-2)を用い、半芳香族ポリアミド(b1-2)とEVOHの配合量をそれぞれ表1に記載の配合量としたこと以外は、実施例1と同様にして外径8mm、肉厚1mmの多層チューブを得た。いずれも脂肪族ポリアミド層(A)の厚みは800μmであり、バリア層(B)の厚みは200μmであった。
バリア層(B)を形成するためのEVOH((株)クラレ製、製品名 エバール(商標)F101B)と、脂肪族ポリアミド層(A)を形成するためのナイロン11とを、それぞれ単軸押出機に投入し、2台の単軸押出機と、2種2層の多層構造を形成する流路からなる多層チューブ成形機にて、外径8mm、肉厚1mmの多層チューブを得た。脂肪族ポリアミド層(A)の厚みは800μmであり、バリア層(B)の厚みは200μmであった。
比較例1におけるEVOHの代わりに合成例1で得られた半芳香族ポリアミド(b1-1)を用いたこと以外は、比較例1と同様にして、外径8mm、肉厚1mmの多層チューブを得た。いずれも脂肪族ポリアミド層(A)の厚みは800μmであり、バリア層(B)の厚みは200μmであった。
Claims (7)
- 少なくとも一層の脂肪族ポリアミド層(A)と少なくとも一層のバリア層(B)とを有する多層中空成形体であって、
脂肪族ポリアミド層(A)が、脂肪族ポリアミド(a)を主成分とする樹脂組成物からなり、
バリア層(B)が、エチレン‐ビニルアルコール共重合体(EVOH)と半芳香族ポリアミド(b)とを含む樹脂組成物からなる、多層中空成形体。 - 半芳香族ポリアミド(b)が、キシリレンジアミンに由来するジアミン構成単位を70モル%以上含むジアミン構成単位と、炭素数4~8のα,ω-直鎖脂肪族ジカルボン酸に由来するジカルボン酸単位を70モル%以上含むジカルボン酸単位とを含むポリアミドである、請求項1に記載の多層中空成形体。
- 半芳香族ポリアミド(b)が、ポリキシリレンアジパミドである、請求項1又は2に記載の多層中空成形体。
- 脂肪族ポリアミド(a)が、炭素数10~12のラクタム由来の構成単位及び炭素数10~12のアミノカルボン酸由来の構成単位の少なくとも一方を含むポリアミド(a1)、及び、炭素数6~12の脂肪族ジアミン由来の構成単位及び炭素数10~12の脂肪族ジカルボン酸由来の構成単位を含むポリアミド(a2)からなる群から選ばれる少なくとも一種である、請求項1~3の何れか一項に記載の多層中空成形体。
- 脂肪族ポリアミド(a)が、ポリアミド11、ポリアミド12、ポリアミド10,10、ポリアミド10,12、ポリアミド6,11及びポリアミド6,12からなる群から選ばれる少なくとも一種である、請求項1~4の何れか一項に記載の多層中空成形体。
- バリア層(B)を構成する樹脂組成物におけるエチレン‐ビニルアルコール共重合体(EVOH)と半芳香族ポリアミド(b)との質量比率(EVOH:半芳香族ポリアミド(b))が、80:20~20:80の範囲である、請求項1~5の何れか一項に記載の多層中空成形体。
- 燃料用チューブ、燃料用パイプ、燃料用ホース又はコネクタである、請求項1~6の何れか一項に記載の多層中空成形体。
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WO2018088347A1 (ja) * | 2016-11-09 | 2018-05-17 | 日本合成化学工業株式会社 | 樹脂組成物及びそれを用いた多層構造体 |
WO2018123563A1 (ja) * | 2016-12-26 | 2018-07-05 | ユニチカ株式会社 | ポリアミド樹脂組成物、その製造方法およびそれからなる成形体 |
JP2018521872A (ja) * | 2016-01-15 | 2018-08-09 | アルケマ フランス | バイオ燃料中への耐溶出性が向上した多層管状構造体および当該多層管状構造体の使用 |
WO2021137612A1 (ko) * | 2019-12-30 | 2021-07-08 | 한화솔루션 주식회사 | 연료 튜브용 조성물, 상기 조성물을 포함하는 복합재료 및 이를 이용한 연료 튜브 |
KR20210086515A (ko) * | 2019-12-30 | 2021-07-08 | 한화솔루션 주식회사 | 연료 튜브용 조성물, 상기 조성물을 포함하는 복합재료 및 이를 이용한 연료 튜브 |
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WO2017094564A1 (ja) * | 2015-11-30 | 2017-06-08 | 三菱瓦斯化学株式会社 | 多層構造体 |
FR3046827B1 (fr) | 2016-01-15 | 2018-05-25 | Arkema France | Structure tubulaire multicouche possedant une meilleure resistance a l'extraction dans la bio-essence et son utilisation |
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KR20210086515A (ko) * | 2019-12-30 | 2021-07-08 | 한화솔루션 주식회사 | 연료 튜브용 조성물, 상기 조성물을 포함하는 복합재료 및 이를 이용한 연료 튜브 |
KR102458558B1 (ko) * | 2019-12-30 | 2022-10-25 | 한화솔루션 주식회사 | 연료 튜브용 조성물, 상기 조성물을 포함하는 복합재료 및 이를 이용한 연료 튜브 |
Also Published As
Publication number | Publication date |
---|---|
EP3238937B1 (en) | 2019-08-14 |
JPWO2016104095A1 (ja) | 2017-10-05 |
EP3238937A4 (en) | 2018-05-23 |
US20170348941A1 (en) | 2017-12-07 |
EP3238937A1 (en) | 2017-11-01 |
JP6801456B2 (ja) | 2020-12-16 |
TW201634250A (zh) | 2016-10-01 |
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