WO2012121295A1 - ポリエチレン系構造体 - Google Patents
ポリエチレン系構造体 Download PDFInfo
- Publication number
- WO2012121295A1 WO2012121295A1 PCT/JP2012/055839 JP2012055839W WO2012121295A1 WO 2012121295 A1 WO2012121295 A1 WO 2012121295A1 JP 2012055839 W JP2012055839 W JP 2012055839W WO 2012121295 A1 WO2012121295 A1 WO 2012121295A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyethylene
- acid
- containing polyamide
- metaxylylene group
- density
- Prior art date
Links
- -1 Polyethylene Polymers 0.000 title claims abstract description 230
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 212
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 201
- 239000004952 Polyamide Substances 0.000 claims abstract description 167
- 229920002647 polyamide Polymers 0.000 claims abstract description 167
- 229920001903 high density polyethylene Polymers 0.000 claims description 57
- 239000004700 high-density polyethylene Substances 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 49
- 239000000155 melt Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical group NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 abstract 1
- 230000004888 barrier function Effects 0.000 description 49
- 239000003502 gasoline Substances 0.000 description 36
- 239000000047 product Substances 0.000 description 30
- 229920005989 resin Polymers 0.000 description 30
- 239000011347 resin Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 24
- 239000000463 material Substances 0.000 description 23
- 239000010410 layer Substances 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 21
- 238000005259 measurement Methods 0.000 description 19
- 238000000465 moulding Methods 0.000 description 18
- 230000035699 permeability Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 238000006068 polycondensation reaction Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- 239000008188 pellet Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000004677 Nylon Substances 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 9
- 239000000446 fuel Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 229920001778 nylon Polymers 0.000 description 9
- 125000004437 phosphorous atom Chemical group 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 229920003355 Novatec® Polymers 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 239000002356 single layer Substances 0.000 description 7
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001339 alkali metal compounds Chemical class 0.000 description 4
- 238000007112 amidation reaction Methods 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229920003354 Modic® Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229920006223 adhesive resin Polymers 0.000 description 3
- 239000004840 adhesive resin Substances 0.000 description 3
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 235000013361 beverage Nutrition 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000002828 fuel tank Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 230000013011 mating Effects 0.000 description 3
- 239000006224 matting agent Substances 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011295 pitch Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-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
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 2
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 125000004427 diamine group Chemical group 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001383 lithium hypophosphite Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 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 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 2
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZQHJVIHCDHJVII-OWOJBTEDSA-N (e)-2-chlorobut-2-enedioic acid Chemical compound OC(=O)\C=C(\Cl)C(O)=O ZQHJVIHCDHJVII-OWOJBTEDSA-N 0.000 description 1
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- FGDWASZPMIGAFI-UHFFFAOYSA-N 2-but-1-enylbutanedioic acid Chemical compound CCC=CC(C(O)=O)CC(O)=O FGDWASZPMIGAFI-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 101000652482 Homo sapiens TBC1 domain family member 8 Proteins 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-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
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 102100030302 TBC1 domain family member 8 Human genes 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- QCTBMLYLENLHLA-UHFFFAOYSA-N aminomethylbenzoic acid Chemical compound NCC1=CC=C(C(O)=O)C=C1 QCTBMLYLENLHLA-UHFFFAOYSA-N 0.000 description 1
- 229960003375 aminomethylbenzoic acid Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 229940112016 barium acetate Drugs 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- PHIBEYMUALDAQI-UHFFFAOYSA-N benzylphosphinic acid Chemical compound OP(=O)CC1=CC=CC=C1 PHIBEYMUALDAQI-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- DXKBUOQKKRCAFE-UHFFFAOYSA-N dilithium;dioxido(phenyl)phosphane Chemical compound [Li+].[Li+].[O-]P([O-])C1=CC=CC=C1 DXKBUOQKKRCAFE-UHFFFAOYSA-N 0.000 description 1
- DRXDBDATOLWSNZ-UHFFFAOYSA-L dilithium;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [Li+].[Li+].[O-]P([O-])(=O)C1=CC=CC=C1 DRXDBDATOLWSNZ-UHFFFAOYSA-L 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- GOJNABIZVJCYFL-UHFFFAOYSA-N dimethylphosphinic acid Chemical compound CP(C)(O)=O GOJNABIZVJCYFL-UHFFFAOYSA-N 0.000 description 1
- LZRAWZAXPWKGKD-UHFFFAOYSA-N dipotassium;dioxido(phenyl)phosphane Chemical compound [K+].[K+].[O-]P([O-])C1=CC=CC=C1 LZRAWZAXPWKGKD-UHFFFAOYSA-N 0.000 description 1
- CVFJNXQOIZKPMG-UHFFFAOYSA-L dipotassium;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [K+].[K+].[O-]P([O-])(=O)C1=CC=CC=C1 CVFJNXQOIZKPMG-UHFFFAOYSA-L 0.000 description 1
- WCPNHDCBQKJBDD-UHFFFAOYSA-L dipotassium;ethyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [K+].[K+].CCP([O-])([O-])=O WCPNHDCBQKJBDD-UHFFFAOYSA-L 0.000 description 1
- VRIZGLPHNWWKPU-UHFFFAOYSA-N disodium;dioxido(phenyl)phosphane Chemical compound [Na+].[Na+].[O-]P([O-])C1=CC=CC=C1 VRIZGLPHNWWKPU-UHFFFAOYSA-N 0.000 description 1
- JOQAMSDLZYQHMX-UHFFFAOYSA-L disodium;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [Na+].[Na+].[O-]P([O-])(=O)C1=CC=CC=C1 JOQAMSDLZYQHMX-UHFFFAOYSA-L 0.000 description 1
- ZRRLFMPOAYZELW-UHFFFAOYSA-N disodium;hydrogen phosphite Chemical compound [Na+].[Na+].OP([O-])[O-] ZRRLFMPOAYZELW-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- DJHASRVNBMMHLB-UHFFFAOYSA-N ethoxy(phenyl)phosphinite Chemical compound CCOP([O-])C1=CC=CC=C1 DJHASRVNBMMHLB-UHFFFAOYSA-N 0.000 description 1
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- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 229920001519 homopolymer Polymers 0.000 description 1
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- 230000002401 inhibitory effect Effects 0.000 description 1
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- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
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- 239000011630 iodine Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- GAKBAJRHMOZPAU-UHFFFAOYSA-L lithium sodium diacetate Chemical compound [Na+].CC([O-])=O.[Li]OC(C)=O GAKBAJRHMOZPAU-UHFFFAOYSA-L 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- CGNKSELPNJJTSM-UHFFFAOYSA-N phenylphosphonous acid Chemical compound OP(O)C1=CC=CC=C1 CGNKSELPNJJTSM-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
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- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- FOGKDYADEBOSPL-UHFFFAOYSA-M rubidium(1+);acetate Chemical compound [Rb+].CC([O-])=O FOGKDYADEBOSPL-UHFFFAOYSA-M 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- IYYIUOWKEMQYNV-UHFFFAOYSA-N sodium;ethoxy-oxido-oxophosphanium Chemical compound [Na+].CCO[P+]([O-])=O IYYIUOWKEMQYNV-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 235000015192 vegetable juice Nutrition 0.000 description 1
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Images
Classifications
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L23/04—Homopolymers or copolymers of ethene
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- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
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- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
- Y10T428/1393—Multilayer [continuous layer]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1397—Single layer [continuous layer]
Definitions
- the present invention relates to a polyethylene structure having excellent barrier properties and strength.
- Examples of containers for storing hydrocarbons and various chemicals or pipes for transferring include chemical bottles, fuel tanks for automobiles and small engines, and fuel pipes. Most of the metal and glass that have been used as the material are being replaced by plastic. Compared to metal and glass, plastic has features such as light weight, no need for rust prevention treatment, resistance to cracking, and high degree of freedom in shape.
- HDPE high-density polyethylene
- a method of treating the inner surface of the HDPE container with chlorofluorocarbon treatment or sulfone treatment is known (see, for example, Patent Document 1).
- a method of forming a multilayer structure by laminating a barrier resin such as ethylene-vinyl alcohol copolymer resin (hereinafter sometimes abbreviated as “EVOH”) as an intermediate layer on an HDPE container for example, (See Patent Documents 2 and 3).
- EVOH ethylene-vinyl alcohol copolymer resin
- a method for improving the fuel barrier property of the HDPE container a method is known in which a polyamide resin such as nylon 6,66 or EVOH is blended with HDPE together with an adhesive resin, and a single layer container is manufactured from the composition (for example, see Patent Documents 4 and 5.) Also disclosed is a method of using polymetaxylylene adipamide (hereinafter sometimes abbreviated as “N-MXD6”), which has better barrier properties than nylon 6,66, in the above-mentioned blend single layer container. For example, see Patent Documents 6 and 7.)
- N-MXD6 polymetaxylylene adipamide
- Patent Document 1 for treating the inner surface of an HDPE container with chlorofluorocarbon treatment or sulfone treatment has the merit that the production equipment for HDPE containers that have been produced in the past can be used as it is. It is necessary to ensure the safety of the material, and the recovery method after processing becomes a problem, and further, the quality inspection after fluorination processing is difficult.
- the multilayer containers disclosed in Patent Documents 2 and 3 formed from HDPE and EVOH can provide a barrier property superior to conventional HDPE containers, and the barrier of the container depends on the thickness of the laminated EVOH layer. Since the performance can be controlled, it is easy to produce a container having a desired barrier property. However, this container cannot be handled by HDPE single-layer container manufacturing equipment, and it is necessary to introduce a multi-layer blower equipped with at least three extruders to extrude HDPE, adhesive resin, and EVOH. Yes, economic problems remain.
- HDPE containers are often manufactured by the direct blow method.
- a resin composition melt-mixed in an extruder is extruded from a cylindrical die to form a cylindrical melt (sometimes called a parison), which is sandwiched between molds and gas such as air is placed.
- a molded body is formed by blowing and inflating and closely contacting the inside of the mold.
- a pinch-off portion is always formed by a mold called a pinch-off portion.
- the pinch-off part is a part formed by adhering the inner surfaces of the parison.
- the pinch-off part is insufficiently bonded, resulting in a problem of insufficient strength of the structure.
- the mating surface of the inner layer HDPE is formed in the cross-section of the pinch-off portion, there is a portion where the EVOH layer is cut. If the container is thin, the thickness of the inner layer HDPE mating surface of the cut-off portion will be very thin, and although there are practically few problems, the inner layer HDPE generally has a thickness of a container that requires high strength such as a fuel container. Since it is set to be thick, there is a drawback that the fuel easily permeates through the mating surface.
- the problem to be solved by the present invention is to provide a polyethylene-based structure that can satisfy the strict requirements for barrier performance in recent years and is excellent in strength.
- the present invention provides the following polyethylene-based structures. ⁇ 1> 60 to 90% by mass of polyethylene (A), 5 to 35% by mass of acid-modified polyethylene (B), and 5 to 35% by mass of metaxylylene group-containing polyamide (C).
- the polyethylene (A) is a high density polyethylene (Aa) having a density of 0.94 to 0.97, and the melt flow rate (MFR) of the high density polyethylene (Aa) is 0. .1 to 0.6.
- the density of the acid-modified polyethylene (B) is 0.90 to 0.935, and the MFR of the acid-modified polyethylene (B) is 3 to 10 of the MFR of the high-density polyethylene (Aa). Double the range.
- the polyethylene (A) is a mixture comprising polyethylene (A1) having a density of 0.935 to 0.965 and polyethylene (A2) having a density of 0.91 to 0.93, and the polyethylene (A The mass ratio ((A1) / (A2)) between A1) and polyethylene (A2) is 70/30 to 95/5.
- the density of the high-density polyethylene (Aa) is from 0.94 to 0.97
- MFR melt flow rate of the high-density polyethylene (Aa) is from 0.1 to 0.6.
- the density of the acid-modified polyethylene (B) is 0.90 to 0.935, and the MFR of the acid-modified polyethylene (B) is 3 to 10 times the MFR of the high-density polyethylene (Aa). It is a range.
- the relative viscosity of the metaxylylene group-containing polyamide (C) is 2.5 to 4.5.
- first embodiment of the present invention the polyethylene-based structure described in the above ⁇ 2> is referred to as “first embodiment of the present invention”
- second embodiment of the present invention the polyethylene-based structure described in the above ⁇ 3> is referred to as “second embodiment of the present invention”.
- the polyethylene-based structure of the present invention is excellent in the barrier performance of fuels and chemicals and the barrier performance of various gases such as oxygen, and further exhibits practical strength.
- the microscope picture of the side wall cross section of the tank obtained in Example 101 is shown.
- the microscope picture of the pinch-off part cross section of the tank obtained in Example 101 is shown.
- the microscope picture of the side wall cross section of the tank obtained in Example 204 is shown.
- the microscope picture of the pinch-off part cross section of the tank obtained in Example 204 is shown.
- the polyethylene (A) used in the present invention is a main material constituting the container.
- the polyethylene (A) used in the first embodiment of the present invention is high density polyethylene (Aa).
- the polyethylene (A) used in the second embodiment of the present invention is a mixture composed of at least two kinds of polyethylenes of polyethylene (A1) and polyethylene (A2) having different densities.
- High-density polyethylene (Aa) and polyethylene (A1)> The high-density polyethylene (Aa) used in the first embodiment of the present invention and the polyethylene (A1) used in the second embodiment of the present invention prevent drawdown that causes uneven thickness of the molded product. From the viewpoint of increasing the strength of the structure itself, and from the viewpoint of problems such as cracks and cracks when dropped or when an impact is applied, the melt viscosity, molecular weight, and crystallinity are preferably specified.
- the high-density polyethylene (Aa) used in the first embodiment of the present invention and the polyethylene (A1) used in the second embodiment of the present invention increase the strength and chemical resistance of the container, It is preferable that the property is high.
- a density is mentioned as a parameter
- the density of the high density polyethylene (Aa) used in the first embodiment of the present invention is 0.94 to 0.97, preferably 0.943 to 0.965, more preferably 0.945 to 0.00. 96.
- the density of the polyethylene (A1) used in the second embodiment of the present invention is 0.935 to 0.965, preferably 0.938 to 0.965, more preferably 0.94 to 0.00. 96.
- the density of the high density polyethylene (Aa) is less than 0.94 in the first embodiment of the present invention and when the density of the polyethylene (A1) is less than 0.935 in the second embodiment of the present invention Any of these is not preferable because the crystallinity is insufficient and depending on the type of contents stored in the structure, it may be difficult to preserve.
- the density of the high-density polyethylene (Aa) exceeds 0.97
- the density of the polyethylene (A1) exceeds 0.965. Both are unfavorable because polyethylene (Aa) or (A1) itself tends to become brittle like glass and may not be able to exhibit practical strength as a structure.
- a typical melt viscosity and molecular weight index of polyethylene is melt flow rate (MFR).
- the MFR of the high density polyethylene (Aa) used in the first embodiment of the present invention is 0.1 to 0.6 (g / 10 minutes, as a value measured according to the method described in JIS K7210. 190 ° C., 2.16 kgf), preferably 0.1 to 0.55 (g / 10 min, 190 ° C., 2.16 kgf), more preferably 0.15 to 0.5 (g / 10 min, 190 ° C, 2.16 kgf).
- the MFR of the high-density polyethylene (A1) used in the second embodiment of the present invention is preferably 0.05 to 0.6 (g) as a value measured according to the method described in JIS K7210.
- a metaxylylene group-containing polyamide has a higher density than polyethylene
- a polyethylene compounded with a metaxylylene group-containing polyamide tends to have a large drawdown during molding as compared with a polyethylene-only polyamide. Therefore, in the first embodiment of the present invention, when the MFR of the high-density polyethylene (Aa) exceeds 0.6, the draw-down at the time of molding processing becomes too large, and the thickness accuracy of the molded product may deteriorate. Therefore, it is not preferable.
- the high density polyethylene (Aa) having an MFR of less than 0.1 used in the first embodiment of the present invention has a melt viscosity that is too high and a good dispersion state of the metaxylylene group-containing polyamide (C). Since it becomes difficult to become, it is not preferable.
- the MFR of polyethylene (A1) is 0.05 to 0.6, the drawdown during the molding process becomes too large, and the thickness accuracy of the molded product deteriorates.
- the dispersion state of the metaxylylene group-containing polyamide (C) can be improved while preventing the above.
- the density of polyethylene (A2) is 0.91 to 0.93, preferably 0.913 to 0.928, more preferably 0.915 to 0.925. . If the density of the polyethylene (A2) is less than 0.91, the affinity with the polyethylene (A1) tends to decrease and the strength of the container tends to decrease, such being undesirable. If the density exceeds 0.93, the density will be close to that of polyethylene (A1), so the strength of the container will decrease, the draw down during molding will increase, and the dimensional accuracy of the structure will deteriorate. This is not preferable because of the influence of the influence of the
- the polyethylene (A2) used in the second embodiment of the present invention is added for the purpose of reducing the drawdown caused by the addition of the metaxylylene group-containing polyamide (C) as described above. From such a viewpoint, it is preferable to use polyethylene (A2) that is close to the MFR of polyethylene (A1). On the other hand, polyethylene (A2) also has a role of increasing the affinity (compatibility) between acid-modified polyethylene (B) and polyethylene (A1), which have a relatively low viscosity. From these viewpoints, the MFR of the polyethylene (A2) used in the second embodiment of the present invention is preferably 0.5 to 8 times, more preferably 0.8 to the MFR of the polyethylene (A1).
- the MFR of polyethylene (A2) is 0.5 to 8 times the MFR of polyethylene (A1), thereby reducing the drawdown during molding and preventing the deterioration of the dimensional accuracy of the structure.
- Compatibility of acid-modified polyethylene (B) and polyethylene (A1) can be increased.
- the acid-modified polyethylene (B) is located outside the structure, and in some cases, the metaxylylene group-containing polyamide (C) having an affinity for the acid-modified polyethylene (B) is exposed to the outside of the structure. It is possible to prevent the deterioration of the appearance of the structure and the deterioration of the barrier property.
- the mass ratio of polyethylene (A1) and polyethylene (A2) in polyethylene (A) is 100% by mass of the total of polyethylene (A1) and polyethylene (A2).
- (A1) / (A2) 70/30 to 95/5, preferably 73/27 to 92/8, more preferably 75/25 to 90/10.
- the polyethylene (A1) in the polyethylene (A) is less than 70% by mass, the crystallinity of the structure is deteriorated, the chemical resistance is deteriorated, or the structure is soft and may cause a practical problem. This is not preferable.
- the polyethylene (A1) exceeds 95% by mass, the effect of mixing the polyethylene (A2) is not recognized, the strength of the container is reduced, the drawdown during molding is increased, and the dimensional accuracy of the structure is increased. This is not preferable because of the influence of deterioration.
- Polyethylene (A) used in the present invention includes an antioxidant, a matting agent, a heat resistance stabilizer, a weather resistance stabilizer, an ultraviolet absorber, a nucleating agent, a plasticizer, a flame retardant, and the like within a range not impairing the effects of the present invention.
- Additives such as antistatic agents, anti-coloring agents, and lubricants can be added, and various materials may be mixed without being limited to those shown above.
- the acid-modified polyethylene (B) used in the present invention is obtained by graft-modifying polyethylene with an unsaturated carboxylic acid or an anhydride thereof, and is generally widely used as an adhesive resin. In this invention, it has the role which adhere
- the unsaturated carboxylic acid or anhydride thereof include acrylic acid, methacrylic acid, ⁇ -ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, chloromaleic acid, and butenyl succinic acid. And acid anhydrides thereof. Of these, maleic acid and maleic anhydride are preferably used.
- various conventionally known methods can be used as a method for obtaining acid-modified polyethylene by graft copolymerization of the unsaturated carboxylic acid or its anhydride onto polyethylene.
- a method in which polyethylene is melted with an extruder and a graft monomer is added for copolymerization or a method in which polyethylene is dissolved in a solvent and a graft monomer is added for copolymerization, after the polyethylene is made into an aqueous suspension
- a method in which a graft monomer is added and copolymerized examples thereof include a method in which a graft monomer is added and copolymerized.
- the metaxylylene group-containing polyamide is a relatively hard material, if an impact or the like is applied to the structure, cracks and peeling are likely to occur at the interface, which may impair the strength and barrier properties of the structure. Therefore, as the acid-modified polyethylene (B) used in the present invention, it is possible to reduce the impact strength due to the metaxylylene group-containing polyamide (C) by using a relatively low density having a soft property, This is effective in maintaining the practical strength of the structure. From such a viewpoint, the density of the acid-modified polyethylene (B) used in the first embodiment of the present invention is 0.90 to 0.935, preferably 0.905 to 0.932, more preferably 0.91 to 0.93.
- the density of the acid-modified polyethylene (B) used in the second embodiment of the present invention is preferably 0.90 to 0.935, more preferably 0.905 to 0.932, and still more preferably 0.91. ⁇ 0.93.
- acid-modified polyethylene (B) having a density of 0.90 to 0.935 the compatibility between polyethylene (A) and acid-modified polyethylene (B) is good, and the adhesion of polyamide (C) containing metaxylylene groups Can be increased to increase the strength of the structure, and the strength can be prevented from being lowered when an impact or the like is applied to the structure.
- the MFR of the acid-modified polyethylene (B) used in the first embodiment of the present invention is 3 to 10 times, preferably 3.2 to 9 times that of the high-density polyethylene (Aa). More preferably, it is 3.5 to 8 times.
- the MFR of the acid-modified polyethylene (B) is less than 3 times the MFR of the high-density polyethylene (Aa), as described later, a large amount of the metaxylylene group-containing polyamide (C) is also present inside the parison, and the structure This is not preferable because the adhesive strength of the pinch-off portion may be lowered.
- the metaxylylene group-containing polyamide (C) may float on the surface of the structure, and the appearance and barrier properties It is not preferable because it may cause deterioration of the quality.
- the polyethylene structure of the present invention can be produced by various molding methods, and is particularly suitable for the purpose of increasing the barrier property of the structure produced by the direct blow method.
- a resin composition melt-mixed in an extruder is extruded from a cylindrical die to form a cylindrical melt (sometimes called a parison), which is sandwiched between molds and gas such as air is placed. It is a method in which a molded body is formed by blowing and inflating and closely contacting the inside of the mold.
- a portion (sometimes referred to as a pinch-off portion) eroded by a mold is always formed.
- the pinch-off part is a part formed by adhering the inner surfaces of the parison. Depending on the molding conditions and the type of material constituting the parison, the pinch-off part is insufficiently bonded, resulting in a problem of insufficient strength of the structure.
- the polyethylene-based structure of the present invention contains a metaxylylene group-containing polyamide (C), and the molding processing temperature is excellent in the dispersion state of the metaxylylene group-containing polyamide (C) while preventing oxidative deterioration of polyethylene as described later. Therefore, the metaxylylene group-containing polyamide (C) is softened in the vicinity of the melting point. Therefore, even if the metaxylylene group-containing polyamide (C) in this state is combined, the adhesive strength is very low. Therefore, from the viewpoint of the adhesiveness of the pinch-off part, in the present invention, it is important to reduce the amount of metaxylylene group-containing polyamide (C) present inside the parison as much as possible.
- the MFR of the acid-modified polyethylene (B) is specified to be 3 to 10 times the MFR of the high-density polyethylene (Aa), so that the high-density polyethylene (Aa) is used in the extruder.
- the acid-modified polyethylene (B) having a higher MFR (that is, having a low melt viscosity) and the metaxylylene group-containing polyamide (C) having adhesiveness with the acid-modified polyethylene (B) are relatively closer to the cylinder wall surface than to the screw vicinity. Many come to exist.
- the metaxylylene group-containing polyamide (C) is mainly from the center of the parison when the cross section of the parison is observed. There will be many outside.
- the adhesive strength of the pinch-off part is equivalent to the adhesive strength of the pinch-off part of the structure made of polyethylene alone.
- the polyamide is uniformly layered in the container wall as in the prior art (see, for example, JP-A-2007-177208). Compared to those dispersed in the layer, the metaxylylene group-containing polyamide (C) is dispersed in layers in a portion closer to the outside than the center of the container wall, and takes a structure like a continuous phase. The barrier property can be improved.
- the MFR of the acid-modified polyethylene (B) used in the second embodiment of the present invention is preferably 3 to 10 times the MFR of the polyethylene (A1) which is the main component of the polyethylene (A). It is preferably 3.2 to 9 times, more preferably 3.5 to 8 times.
- the MFR of the acid-modified polyethylene (B) 3 to 10 times the MFR of the polyethylene (A1), it is possible to prevent the bond strength of the pinch-off portion of the structure from being lowered, and the metaxylylene group-containing polyamide (C) It is possible to prevent the appearance and the barrier property from deteriorating by suppressing the surface from rising on the surface of the structure.
- the acid-modified polyethylene (B) used in the present invention preferably has a high melt viscosity from the viewpoint of molding process stability and structural strength retention.
- the MFR of the acid-modified polyethylene (B) measured according to the method described in JIS K7210 is preferably 0.5 to 5 (g / 10 min, 190 ° C., 2.16 kgf), more preferably 0.6. To 4 (g / 10 min, 190 ° C., 2.16 kgf), more preferably 0.7 to 3 (g / 10 min, 190 ° C., 2.16 kgf).
- the acid-modified polyethylene (B) includes an antioxidant, a matting agent, a heat resistance stabilizer, a weather resistance stabilizer, an ultraviolet absorber, a nucleating agent, a plasticizer, a flame retardant, a charge as long as the effects of the present invention are not impaired.
- Additives such as an inhibitor, an anti-coloring agent, and a lubricant can be added, and various materials may be mixed without being limited to those shown above.
- the metaxylylene group-containing polyamide (C) used in the present invention is a material that imparts an effect of improving the barrier performance of the structure.
- the diamine unit constituting the metaxylylene group-containing polyamide preferably contains a metaxylylenediamine unit in an amount of 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more, from the viewpoint of gas barrier properties.
- Diamines that can be used in addition to metaxylylenediamine include paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, tetramethylenediamine, hexamethylenediamine, and nonanemethylenediamine. , 2-methyl-1,5-pentanediamine and the like, but are not limited thereto.
- the dicarboxylic acid unit constituting the metaxylylene group-containing polyamide (C) is preferably ⁇ , ⁇ -aliphatic dicarboxylic acid in an amount of 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol. Including at least%.
- the ⁇ , ⁇ -aliphatic dicarboxylic acid include suberic acid, adipic acid, azelaic acid, sebacic acid, and dodecanoic acid. Adipic acid and sebacic acid are preferably used from the viewpoint of gas barrier properties and crystallinity.
- dicarboxylic acid units other than ⁇ , ⁇ -aliphatic dicarboxylic acids include alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, and xylylene diene.
- aromatic dicarboxylic acids such as carboxylic acid and naphthalenedicarboxylic acid, but are not limited thereto.
- isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferable because a polyamide having excellent barrier properties can be easily obtained without inhibiting the polycondensation reaction during the production of the metaxylylene group-containing polyamide (C).
- the content of isophthalic acid or 2,6-naphthalenedicarboxylic acid is preferably 30 mol% of dicarboxylic acid units from the viewpoint of dispersibility of the metaxylylene group-containing polyamide (C) in the polyethylene structure and the barrier property of the structure. Below, more preferably 20 mol% or less, and still more preferably 15 mol% or less.
- the units constituting the metaxylylene group-containing polyamide (C) are lactams such as ⁇ -caprolactam and laurolactam, aminocaproic acid, amino, and the like as long as the effects of the present invention are not impaired.
- lactams such as ⁇ -caprolactam and laurolactam
- aminocaproic acid amino, and the like as long as the effects of the present invention are not impaired.
- Aliphatic aminocarboxylic acids such as undecanoic acid, aromatic aminocarboxylic acids such as p-aminomethylbenzoic acid, and the like can be used as copolymerized units.
- the metaxylylene group-containing polyamide (C) is produced by a melt polycondensation method (melt polymerization method).
- a melt polycondensation method for example, there is a method in which a nylon salt composed of a diamine and a dicarboxylic acid is heated in the presence of water under pressure and polymerized in a molten state while removing added water and condensed water.
- diamine is directly added to a molten dicarboxylic acid and polycondensed. In this case, in order to keep the reaction system in a uniform liquid state, diamine is continuously added to the dicarboxylic acid, while the reaction system is heated up so that the reaction temperature does not fall below the melting point of the generated oligoamide and polyamide. The polycondensation proceeds.
- a phosphorus atom-containing compound may be added in order to obtain an effect of promoting an amidation reaction and an effect of preventing coloring during polycondensation.
- phosphorus atom-containing compounds include dimethylphosphinic acid, phenylmethylphosphinic acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, ethyl hypophosphite, phenylphosphonous acid, Sodium phenylphosphonite, potassium phenylphosphonite, lithium phenylphosphonite, ethyl phenylphosphonite, phenylphosphonic acid, ethylphosphonic acid, sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphonate, phenylphosphonic acid Examples include diethyl, sodium ethylphosphonate, potassium ethylphosphonate, potassium ethylphosphon
- metal hypophosphite metal salts such as sodium hypophosphite, potassium hypophosphite, lithium hypophosphite and the like are particularly preferable because they are highly effective in promoting amidation reaction and excellent in anti-coloring effect.
- sodium hypophosphite is particularly preferred, the phosphorus atom-containing compounds that can be used in the present invention are not limited to these compounds.
- the addition amount of the phosphorus atom-containing compound added to the polycondensation system of the metaxylylene group-containing polyamide (C) is from the viewpoint of preventing coloring of the metaxylylene group-containing polyamide (C) during polycondensation.
- the concentration is preferably 1 to 500 ppm, more preferably 5 to 450 ppm, and still more preferably 10 to 400 ppm in terms of phosphorus atom concentration.
- the metaxylylene group-containing polyamide (C) it is preferable to add an alkali metal compound or an alkaline earth metal compound in combination with the phosphorus atom-containing compound.
- an alkali metal compound or an alkaline earth metal compound in order to prevent coloring of the metaxylylene group-containing polyamide (C) during polycondensation, a sufficient amount of the phosphorus atom-containing compound needs to be present, but in order to adjust the amidation reaction rate, an alkali metal compound or an alkaline earth is required. It is preferable to coexist a similar metal compound.
- hydroxides of alkali metals / alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and lithium acetate
- sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, barium acetate, and other alkali metal / alkaline earth metal acetates, etc. are not limited to these compounds.
- a value obtained by dividing the number of moles of the compound by the number of moles of the phosphorus atom-containing compound is preferably 0.00. It is 5 to 2.0, more preferably 0.6 to 1.8, and still more preferably 0.7 to 1.5.
- the metaxylylene group-containing polyamide (C) obtained by melt polycondensation is once taken out, pelletized, and dried before use.
- solid phase polymerization may be performed.
- a heating device used in drying or solid-phase polymerization a continuous heating drying device, a tumble dryer, a conical dryer, a rotary drum type heating device called a rotary dryer, etc., and a rotary blade inside a nauta mixer
- a conical heating apparatus provided with can be used suitably, a well-known method and apparatus can be used without being limited to these.
- the heating device of the rotating drum type in the above-mentioned apparatus can seal the inside of the system and facilitate polycondensation in a state where oxygen causing coloring is removed. Are preferably used.
- the relative viscosity of the metaxylylene group-containing polyamide (C) used in the present invention is 2.5 to 4.5, preferably 2.6 to 4.2, more preferably 2.7 to 4.0.
- the amount of the metaxylylene group-containing polyamide (C) inside the parison is reduced with specific physical properties of each material. Therefore, it is easy to form a portion where the concentration of the metaxylylene group-containing polyamide is high. Therefore, if the relative viscosity is less than 2.5, the strength of the structure tends to be lower than that of the conventional technique, which is not preferable. On the other hand, if the relative viscosity exceeds 4.5, the dispersion state of the metaxylylene group-containing polyamide (C) tends to be difficult to control, which is not preferable because the moldability becomes unstable.
- the metaxylylene group-containing polyamide (C) used in the present invention is preferably a component having a number average molecular weight of 1000 or less, preferably 2% by mass or less, as measured by GPC, from the viewpoint of appearance and barrier properties of the structure. Preferably it is 1.5 mass% or less, More preferably, it is 1 mass% or less.
- Metaxylylene group-containing polyamide (C) has antioxidants, matting agents, heat stabilizers, weathering stabilizers, UV absorbers, nucleating agents, plasticizers, flame retardants, antistatics as long as the effects of the present invention are not impaired. Additives such as agents, anti-coloring agents, lubricants, anti-gelling agents, clays such as layered silicates, nanofillers, and the like can be added.
- the dispersed particles of the metaxylylene group-containing polyamide (C) preferably have a major axis of 0.5 mm or more. More preferably, it has a major axis of 1 mm or more, more preferably 2 mm or more. Further, when the cross section of the molded product is observed with a microscope, and the magnification of the side wall of the molded product is magnified to occupy about 80% of one side of the observation field, the total number of dispersed particles of the metaxylylene group-containing polyamide (C) The area ratio of dispersed particles having a major axis of 0.5 mm or more with respect to the area is preferably 20% or more.
- the metaxylylene group-containing polyamide (C) is dispersed in a layered manner, and a part of the continuous phase can be formed, resulting in good barrier properties. .
- the blending ratio of each material constituting the structure of the present invention is 60 to 90% by mass for polyethylene (A), 5 to 35% by mass for acid-modified polyethylene (B), and 5 to 35 for polyamide (C) containing a metaxylylene group.
- the polyethylene (A) is 65 to 90% by mass, the acid-modified polyethylene (B) is 5 to 30% by mass, and the metaxylylene group-containing polyamide (C) is 5 to 30% by mass, more preferably
- the polyethylene (A) is 70 to 90% by mass, the acid-modified polyethylene (B) is 5 to 25% by mass, and the metaxylylene group-containing polyamide (C) is 5 to 25% by mass.
- the polyethylene (A) is 60 to 90% by mass, the acid-modified polyethylene (B) is 5 to 25% by mass, and the metaxylylene group-containing polyamide (C) is 5 to 35% by mass.
- the polyethylene (A) is 65 to 90% by mass, the acid-modified polyethylene (B) is 5 to 20% by mass, the metaxylylene group-containing polyamide (C) is 5 to 30% by mass, and more preferably the polyethylene (A). 70 to 90% by mass, acid-modified polyethylene (B) 5 to 15% by mass, and metaxylylene group-containing polyamide (C) 5 to 25% by mass.
- the total of the three components (A) to (C) does not exceed 100% by mass.
- the structure of the present invention is preferably composed of three components of polyethylene (A), acid-modified polyethylene (B), and metaxylylene group-containing polyamide (C).
- polypropylenes represented by propylene homopolymer, ethylene-propylene block copolymer, ethylene-propylene random copolymer, and the like; homopolymers of ⁇ -olefins having 3 to 20 carbon atoms such as polybutene-1, polymethylpentene, etc .; Copolymers of 3 to 20 ⁇ -olefins; Copolymers of ⁇ -olefins having 3 to 20 carbon atoms and cyclic olefins; Ionomers; Various types such as ethylene-ethyl acrylate copolymers and ethylene-methyl acrylate copolymers Modified polyethylene; polystyrene; various polyesters such as polyethylene terephthalate; various polyamides such as nylon 6 and nylon 66; styrene-
- the polyethylene structure of the present invention can be formed into a molded body such as a tank shape, a bottle shape, or a tube shape.
- the structure is preferably manufactured by the direct blow method.
- polyethylene (A), acid-modified polyethylene (B), and metaxylylene group are used using a molding device equipped with an extruder, an adapter, a cylindrical die, a clamping device, a mold, and a cooling device.
- a mixed material obtained by dry blending the containing polyamide (C), and in some cases, a pulverized product obtained by pulverizing a molded product, is charged into an extruder and melt-kneaded.
- the melt-kneaded material is extruded into a cylindrical shape (sometimes referred to as a parison) through an adapter and a cylindrical die, sandwiched between molds at the timing of being extruded to an appropriate length, and air is blown into the parison to inflate and cool
- the extruder used for producing the structure of the present invention a known extruder can be applied, but it has a suitable kneadability and can be stably extruded even under a high resin pressure.
- An extruder is preferably used.
- the screw of a single screw extruder is usually a feed part for conveying the raw material to the tip of the extruder, a compression part for completely melting the softened resin by absorbing heat, and a metering part for controlling the discharge amount. Consists of two parts. In the present invention, a general screw can be used without limitation.
- a screw generally called full flight without a kneading site called dalmage or mudock of the metaxylylene group-containing polyamide (C). It is preferably used from the viewpoint of preventing excessive dispersion.
- a quick compression type screw having a relatively short compression portion is more preferably used.
- the rapid compression type full flight screw when the number of pitches of the entire screw (one flight is one pitch) is 100, the supply unit is 40-60, the compression unit is 5-20, and the weighing unit is 30-50.
- the pitch distance may be arbitrary.
- a double flight screw which made some flight number two can also be utilized.
- a breaker plate that is usually provided in the extruder head. There is a possibility that the metaxylylene group-containing polyamide (C) dispersed in a layer in the extruder is cut and finely dispersed by the pores formed in the breaker plate.
- the metaxylylene group-containing polyamide (C) needs to be dispersed in layers in order to effectively increase the barrier property.
- the resin pellets are stretched by shear stress in the above-described extruder. When it is in a layered state, it must be discharged from the tip of the extruder.
- a method for realizing this there are mainly a method of lowering the screw rotation speed and a method of optimizing the extruder temperature setting.
- the method of lowering the screw rotation speed seems to be a simple method at first glance, there is a concern that the production efficiency will decrease or the strength of the container will decrease due to the parison being exposed to the atmosphere for a long time. May be limited. In such a case, a method of controlling the resin temperature in the extruder is preferably used.
- the temperature of the extruder so that the resin temperature at the time of melt-kneading the material in the extruder is in the temperature range of the melting point of the metaxylylene group-containing polyamide (C) ⁇ 20 ° C. .
- the temperature range is more preferably a melting point ⁇ 15 ° C., and further preferably the melting point ⁇ 10 ° C.
- the resin temperature is preferably measured by measuring the actual temperature of the resin discharged from the tip of the extruder, but the number measured by the thermocouple provided at the tip of the extruder and the actual temperature of the resin If the difference between them is known to some extent, adjustment may be made with reference to the numerical value.
- the metaxylylene group-containing polyamide (C) Melting and kneading at a resin temperature lower than ⁇ 20 ° C. of the melting point of the metaxylylene group-containing polyamide (C), the metaxylylene group-containing polyamide (C) is not sufficiently softened and unmelted pellets are mixed into the molded product, Since an excessive load may be applied, it is not preferable.
- the temperature exceeds the melting point + 20 ° C. the metaxylylene group-containing polyamide (C) is completely melted and excessively dispersed by shearing stress due to screw rotation, so that the layered dispersion state in the resin composition cannot be maintained. Since it becomes a fine particle shape and the barrier property of the structure is greatly lowered, it is not preferable.
- the structure obtained by the method of the present invention can take various shapes such as bottles, cups, trays, tanks and other containers, tubes, pipes, and the like.
- fuels such as gasoline, kerosene and light oil, lubricating oils such as engine oil and brake oil, various sanitary products such as bleach, detergent and shampoo, chemical substances such as ethanol and oxidol, vegetable juice and milk Since it becomes possible to more effectively suppress permeation of various beverages such as beverages, seasonings, etc., or components contained therein, it can be effectively used as a product that enhances the shelf life of the products. .
- the container in which the pseudo gasoline was sealed was stored in an explosion-proof thermostatic chamber adjusted to 40 ° C., and the total mass was recorded every 24 hours.
- the pseudo gasoline in the container was removed, and the pseudo gasoline was immediately sealed again.
- the container in which the pseudo gasoline was enclosed was stored in an explosion-proof thermostatic chamber adjusted to 40 ° C., the total mass was recorded every 24 hours, and the pseudo gasoline permeability (g / m 2 ⁇ day) was obtained.
- Pinch-off tensile strength A test piece having a width of 10 mm and a length of about 50 mm centered on the pinch-off portion was cut from the bottom of the container produced in the examples and comparative examples. Next, strength was measured at a tensile speed of 50 mm / min using a tensile tester.
- Production Example 1 (Production of metaxylylene group-containing polyamide (C) (PA-1)) 15000 g (102.6 mol) of adipic acid was added to a 50-liter heating jacketed SUS reaction vessel equipped with a partial condenser, total condenser, pressure gauge, nitrogen inlet, liquid inlet, resin outlet valve, and stirrer. Then, 17.3 g (0.16 mol) of sodium hypophosphite and 12.1 g (0.15 mol) of sodium acetate were charged, and the inside of the reaction vessel was purged with nitrogen. Next, while flowing nitrogen at a rate of 10 ml / min, the reaction vessel was heated to 170 ° C.
- PA-1 metaxylylene group-containing polyamide
- the pressure inside the reaction vessel was reduced to 600 mmHg over 10 minutes using an aspirator and a pressure controller while maintaining the internal temperature at 260 ° C.,
- the polycondensation reaction was continued at 600 mmHg. Stirring is stopped when the viscosity of the resin is sufficiently high while observing the torque of the stirrer, the inside of the reaction can is pressurized to 0.2 MPa with nitrogen, and then the resin extraction valve at the bottom of the reaction can be opened to strand the polymer. After being cooled in water and cooled with water, it was pelletized with a pelletizer to obtain about 25 kg of a pellet of metaxylylene group-containing polyamide.
- pellets of metaxylylene group-containing polyamide were charged into a tumble dryer with a jacket provided with a nitrogen gas introduction tube, a vacuum line, a vacuum pump, and a thermocouple for measuring the internal temperature, and the inside of the tumble dryer was rotated while rotating at a constant speed.
- the tumble dryer was heated under the same nitrogen gas stream, and the pellet temperature was raised to 150 ° C. over about 150 minutes.
- the pressure in the system was reduced to 1 torr or less.
- the temperature was further raised, and the pellet temperature was raised to 200 ° C. over about 70 minutes, and then held at 200 ° C. for 70 minutes.
- PA-1 metaxylylene group-containing polyamide
- the obtained polyamide (PA-1) had a relative viscosity of 3.5.
- the amount of components having a number average molecular weight of 1000 or less by GPC measurement was 1.1%.
- Production Example 2 (Production of metaxylylene group-containing polyamide (C) (PA-2)) With respect to the holding time in the tumble dryer, a metaxylylene group-containing polyamide (PA-2) was obtained in the same manner as in Production Example 1 except that it was held at 200 ° C. for 30 minutes. The relative viscosity of the obtained polyamide (PA-2) was 2.7. Moreover, the amount of components having a number average molecular weight of 1000 or less by GPC measurement was 1.5%.
- Production Example 3 (Production of metaxylylene group-containing polyamide (C) (PA-3)) A metaxylylene group-containing polyamide (PA-3) was obtained in the same manner as in Production Example 1 except that the time in the tumble dryer was maintained at 200 ° C. for 120 minutes. The relative viscosity of the obtained polyamide (PA-3) was 4.2. Moreover, the amount of components having a number average molecular weight of 1000 or less by GPC measurement was 0.8%.
- Production Example 4 (Production of metaxylylene group-containing polyamide (C) (PA-4))
- a metaxylylene group-containing polyamide (PA-4) was obtained in the same manner as in Production Example 1 except that the dicarboxylic acid component in the polyamide raw material was changed to 13495 g (92.3 mol) adipic acid and 1705 g (10.3 mol) isophthalic acid. It was.
- the relative viscosity of the obtained polyamide (PA-4) was 3.4.
- the amount of components having a number average molecular weight of 1000 or less as measured by GPC was 1.9%.
- Production Example 5 (Production of metaxylylene group-containing polyamide (C) (PA-5)) With respect to the holding time in the tumble dryer, a metaxylylene group-containing polyamide (PA-5) was obtained in the same manner as in Production Example 4 except that it was held at 200 ° C. for 30 minutes. The relative viscosity of the obtained polyamide (PA-5) was 2.6. Moreover, the amount of components having a number average molecular weight of 1000 or less by GPC measurement was 2.6%.
- Production Example 6 Production of metaxylylene group-containing polyamide (C) (PA-6)
- PA-6 metaxylylene group-containing polyamide
- a metaxylylene group-containing polyamide (PA-6) was obtained in the same manner as in Production Example 1 except that nitrogen gas having a purity of 99% by volume or more was introduced therein and the tumble dryer was cooled while being rotated.
- the relative viscosity of the obtained polyamide (PA-6) was 2.1.
- the amount of components having a number average molecular weight of 1000 or less by GPC measurement was 2.5%.
- Examples 102-111 A screw cap is provided in the same manner as in Example 101 except that the types and blending amounts of high density polyethylene (Aa), acid-modified polyethylene (B), and metaxylylene group-containing polyamide (C) are changed as shown in Table 1.
- the tank was molded. About the obtained tank, the measurement of the pseudo gasoline permeability and the tensile strength of the pinch-off part, and the drop test were carried out. The results are shown in Table 1.
- Examples 112 and 113 The types and blending amounts of high-density polyethylene (Aa), acid-modified polyethylene (B), and metaxylylene group-containing polyamide (C) were changed as shown in Table 1, and the extruder cylinder temperature was 200-220 ° C, adapter temperature was formed in the same manner as in Example 101 except that the temperature was changed to 220 ° C and the die temperature was changed to 215 ° C. About the obtained tank, the measurement of the pseudo gasoline permeability and the tensile strength of the pinch-off part, and the drop test were carried out. The results are shown in Table 1.
- Comparative Example 101 A tank with a screw cap was formed in the same manner as in Example 101 except that only high-density polyethylene (Aa) was used. About the obtained tank, the measurement of the pseudo gasoline permeability and the tensile strength of the pinch-off part, and the drop test were carried out. The results are shown in Table 1.
- Comparative Examples 102 to 107 A screw cap is provided in the same manner as in Example 101 except that the types and blending amounts of high density polyethylene (Aa), acid-modified polyethylene (B), and metaxylylene group-containing polyamide (C) are changed as shown in Table 1.
- the tank was molded. About the obtained tank, the measurement of the pseudo gasoline permeability and the tensile strength of the pinch-off part, and the drop test were carried out. The results are shown in Table 1.
- the polyethylene-based structure of the present invention exhibits excellent pseudo gasoline barrier properties in all examples, and the tensile strength of the pinch-off portion of the obtained structure is sufficient, and the drop strength of the structure itself is excellent. No container cracking occurred during the fall.
- Comparative Example 101 consisting only of high-density polyethylene (Aa) was inferior to the pseudo gasoline barrier property although it was excellent in tensile strength and drop strength.
- Comparative Example 102 in which the MFR ratio between the high-density polyethylene (Aa) and the acid-modified polyethylene (B) is low, due to the dispersed state of the metaxylylene group-containing polyamide (C), the pseudo gasoline barrier property and the tensile strength of the pinch-off part are Inferior, the container cracked when dropped.
- Comparative Example 103 where the density of the acid-modified polyethylene (B) is high, an increase in the number of falling cracks was observed due to the increase in the density of the acid-modified polyethylene (B).
- Comparative Example 104 in which the MFR ratio between the high-density polyethylene (Aa) and the acid-modified polyethylene (B) is high, a place where the metaxylylene group-containing polyamide (C) is raised on the surface of the container is recognized, and the pseudo gasoline barrier property and the pinch-off part The tensile strength was inferior and the container cracked when dropped. Further, in Comparative Examples 105 to 107 using the metaxylylene group-containing polyamide (C) having a low relative viscosity, a place where the metaxylylene group-containing polyamide (C) was raised on the surface of the container was observed, and the pseudo gasoline barrier property and the pinch-off part were observed. The tensile strength was inferior and the container cracked when dropped.
- a tank with a cap was formed. About the obtained tank, the measurement of the pseudo gasoline permeability and the tensile strength of the pinch-off part, and the drop test were carried out. The results are shown in Table 2.
- Examples 213 to 214 The types and blending amounts of polyethylene (A1), polyethylene (A2), acid-modified polyethylene (B), and metaxylylene group-containing polyamide (C) were changed as shown in Table 2, and the extruder cylinder temperature was changed to 200 to 220 ° C. A tank with a screw cap was formed in the same manner as in Example 201 except that the adapter temperature was changed to 220 ° C and the die temperature was changed to 215 ° C. About the obtained tank, the measurement of the pseudo gasoline permeability and the tensile strength of the pinch-off part, and the drop test were carried out. The results are shown in Table 2.
- Comparative Example 201 A tank with a screw cap was formed in the same manner as in Example 201 except that only A1-1 was used. About the obtained tank, the measurement of the pseudo gasoline permeability and the tensile strength of the pinch-off part, and the drop test were carried out. The results are shown in Table 2.
- a tank with a cap was formed. About the obtained tank, the measurement of the pseudo gasoline permeability and the tensile strength of the pinch-off part, and the drop test were carried out. The results are shown in Table 2.
- the polyethylene-based structure of the present invention exhibits excellent pseudo-gasoline barrier properties in all examples, and there is no deformation of the container, and the tensile strength of the pinch-off portion of the obtained structure is sufficient.
- the drop strength itself was excellent, and the container did not crack at the time of dropping.
- Comparative Example 201 made of only high-density polyethylene was inferior to the pseudo gasoline barrier property although it was excellent in tensile strength and drop strength.
- Comparative Example 202 where the blending amount of polyethylene (A2) was small, container cracking occurred when dropped.
- Comparative Example 203 in which the blending amount of polyethylene (A2) was large, the strength of the pinch-off portion was low, and the container expanded during measurement of the pseudo fuel permeability, and deformation was observed.
- Comparative Example 204 in which the blend amount of the acid-modified polyethylene (B) is small, the dispersibility of the metaxylylene group-containing polyamide (C) is poor, so the effect of improving the barrier property is small, the pseudo gasoline permeability is inferior, and the polyethylene (A1) Interlaminar adhesion strength with the metaxylylene group-containing polyamide (C) was low, the strength of the pinch-off portion was low, and drop cracking was observed.
- Comparative Example 205 in which the compounding amount of the metaxylylene group-containing polyamide (C) was small, the effect of improving the barrier property was small, and the pseudo gasoline permeability was inferior.
- Comparative Example 206 in which the compounding amount of the metaxylylene group-containing polyamide (C) was large, the strength of the pinch-off part was remarkably low, and occurrence of container cracking in a drop test was observed.
- Comparative Example 207 using a metaxylylene group-containing polyamide (C) having a low relative viscosity, a place where the metaxylylene group-containing polyamide (C) was raised on the surface of the container was observed, the pseudo gasoline barrier property and the tensile strength of the pinch-off part were inferior, A container crack occurred during the fall.
- Comparative Example 208 using polyethylene having a high density as polyethylene (A2) the rigidity of the container was too high, and the occurrence of container cracking in the drop test was observed.
- micrographs of the cross sections of the side walls of the tanks obtained in Examples 101 and 204 are shown in FIGS. 1 and 3 (magnification 25 times).
- the microscope picture of the pinch-off part cross section of the tank obtained in Examples 101 and 204 is shown to FIG. 2 and 4 (magnification 25 times).
- 1 and 3 the lower side is the outer surface direction of the tank, and the upper side is the inner surface direction of the tank.
- the white part indicates polyethylene
- the black part indicates metaxylylene group-containing polyamide dyed with iodine. 1 to 4, it can be seen that in the tanks obtained in Examples 101 and 204, the metaxylylene group-containing polyamide is dispersed in layers in polyethylene and a continuous phase is formed.
- the metaxylylene group-containing polyamide is present in a large amount on the outside from the center of the cross section, and a large amount of polyethylene is present on the inner side of the cross section.
- the metaxylylene group-containing polyamide is dispersed in a layered manner and forms a continuous phase, the tanks obtained in Examples 101 and 204 exhibit good barrier properties.
- 2 and 4 it can be seen that in the pinch-off portion formed by bonding the inner surfaces of the parison, the inner surfaces of the parison are substantially made of polyethylene, and therefore the inner surfaces of the parison are well bonded. This is high strength without damaging the pinch-off part.
- the metaxylylene group-containing polyamide is dispersed in the pinch-off part, the barrier property of the pinch-off part is also good. Therefore, the tank of the present invention exhibits good barrier properties and excellent strength.
- the polyethylene-based structure of the present invention is excellent in the barrier performance of fuels and chemicals and the barrier performance of various gases such as oxygen, and further exhibits practical strength.
- the polyethylene structure of the present invention is used for working machines such as mowing machines and chainsaws, fuel tanks for motorcycles, outboard motors, automobiles, etc., pipes for gasoline transfer and pipe-shaped parts attached to fuel tanks, pesticides, toiletries, sanitary It can be suitably used for detergent bottles, containers for foods and beverages, and the like.
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Abstract
Description
<1>ポリエチレン(A)60~90質量%、酸変性ポリエチレン(B)5~35質量%、及びメタキシリレン基含有ポリアミド(C)5~35質量%を含有し、前記ポリエチレン(A)中に前記メタキシリレン基含有ポリアミド(C)が層状に分散し、かつ一部連続相を形成しているポリエチレン系構造体であって、前記メタキシリレン基含有ポリアミド(C)の相対粘度が2.5~4.5であり、下記条件1又は2を満足する、ポリエチレン系構造体。
[条件1]
(1-1)前記ポリエチレン(A)が、0.94~0.97の密度を有する高密度ポリエチレン(Aa)であり、かつ、前記高密度ポリエチレン(Aa)のメルトフローレート(MFR)が0.1~0.6である。
(1-2)前記酸変性ポリエチレン(B)の密度が0.90~0.935であり、かつ、前記酸変性ポリエチレン(B)のMFRが前記高密度ポリエチレン(Aa)のMFRの3~10倍の範囲である。
[条件2]
前記ポリエチレン(A)が、0.935~0.965の密度を有するポリエチレン(A1)と、0.91~0.93の密度を有するポリエチレン(A2)とからなる混合物であり、前記のポリエチレン(A1)とポリエチレン(A2)との質量比((A1)/(A2))が70/30~95/5である。
(1)前記高密度ポリエチレン(Aa)の密度が0.94~0.97であり、かつ、前記高密度ポリエチレン(Aa)のメルトフローレート(MFR)が0.1~0.6である。
(2)前記酸変性ポリエチレン(B)の密度が0.90~0.935であり、かつ、前記酸変性ポリエチレン(B)のMFRが前記高密度ポリエチレン(Aa)のMFRの3~10倍の範囲である。
(3)前記メタキシリレン基含有ポリアミド(C)の相対粘度が2.5~4.5である。
本発明で用いられるポリエチレン(A)は、容器を構成する主材料となるものである。本発明の第1の実施態様で用いられるポリエチレン(A)は、高密度ポリエチレン(Aa)である。本発明の第2の実施態様で用いられるポリエチレン(A)は、密度の異なるポリエチレン(A1)及びポリエチレン(A2)の少なくとも2種類のポリエチレンからなる混合物である。
本発明の第1の実施態様で使用される高密度ポリエチレン(Aa)及び本発明の第2の実施態様で使用されるポリエチレン(A1)は、成形品の偏肉原因となるドローダウンを防止する観点、構造体自体の強度を高める観点、さらには落下時や衝撃が加わった際の割れやひび等の問題の観点から、その溶融粘度、分子量、結晶性を特定のものとすることが好ましい。
本発明の第2の実施態様に用いられるポリエチレン(A2)は、メタキシリレン基含有ポリアミド(C)の分散により構造体が硬くかつ脆くなる傾向や比重が高くなることによるドローダウンの軽減を目的に添加されるものである。本発明の第2の実施態様において、ポリエチレン(A2)の密度は、0.91~0.93であり、好ましくは0.913~0.928、より好ましくは0.915~0.925である。ポリエチレン(A2)の密度が0.91未満であると、ポリエチレン(A1)との親和性が低下して容器の強度が低下する傾向にあるので好ましくない。また密度が0.93を超えると、ポリエチレン(A1)と密度が近似してくるため、容器の強度が低下したり、成形加工時のドローダウンが大きくなって構造体の寸法精度が悪化したりするなどの影響があるため好ましくない。
これらの観点から、本発明の第2の実施態様で用いられるポリエチレン(A2)のMFRは、ポリエチレン(A1)のMFRに対して、好ましくは0.5~8倍、より好ましくは0.8~6倍、さらに好ましくは1~5倍である。ポリエチレン(A2)のMFRが、ポリエチレン(A1)のMFRの0.5~8倍とすることで、成形加工時のドローダウンを軽減して構造体の寸法精度が悪化するのを防止しつつ、酸変性ポリエチレン(B)とポリエチレン(A1)との相溶性を高めることができる。これにより、酸変性ポリエチレン(B)が構造体の外側に位置したり、場合によっては酸変性ポリエチレン(B)と親和性のあるメタキシリレン基含有ポリアミド(C)が構造体の外側に露出したりするのを抑制し、構造体の外観悪化やバリア性の低下を防止することができる。
本発明で用いられる酸変性ポリエチレン(B)は、ポリエチレンを不飽和カルボン酸又はその無水物でグラフト変性したもので、一般に接着性樹脂として広く用いられているものである。本発明では、ポリエチレン(A)と該ポリエチレン(A)中に分散したメタキシリレン基含有ポリアミド(C)とを接着させて構造体としての強度を保つことができるようにする役割を有する。
このような観点から、本発明の第1の実施態様に用いられる酸変性ポリエチレン(B)の密度は、0.90~0.935であり、好ましくは0.905~0.932、より好ましくは0.91~0.93である。また、本発明の第2の実施態様に用いられる酸変性ポリエチレン(B)の密度は、好ましくは0.90~0.935、より好ましくは0.905~0.932、さらに好ましくは0.91~0.93である。
密度が0.90~0.935の酸変性ポリエチレン(B)を用いることで、ポリエチレン(A)と酸変性ポリエチレン(B)との相溶性が良好で、メタキシリレン基含有ポリアミド(C)の接着性を高めて構造体の強度を高めることができ、また、構造体に衝撃等が加わった場合の強度低下を防ぐことができる。
本発明のポリエチレン系構造体は種々の成形方法により製造できるものであるが、特にダイレクトブロー法により製造される構造体のバリア性を高める目的に適したものである。ダイレクトブロー法は、押出機内で溶融混合した樹脂組成物を円筒ダイから押し出すことで筒状の溶融体(パリソンと言うことがある)を形成し、これを金型で挟んで空気等のガスを吹き込んで膨らませ、金型内部に密着させて成形体とする方法である。この方法により製造される構造体には必ず金型によって喰いきられた部位(ピンチオフ部と言うことがある)が形成される。ピンチオフ部はパリソンの内面同士が接着して形成される部位であり、成形条件やパリソンを構成する材料の種類によっては、ピンチオフ部の接着が不十分となり、構造体の強度不足という問題を招く。
よって、ピンチオフ部の接着性の観点から、本発明ではメタキシリレン基含有ポリアミド(C)の分散状態については、できるだけパリソンの内側に存在する量を減らすことが重要である。
そのため、本発明の第1の実施態様では、酸変性ポリエチレン(B)のMFRを高密度ポリエチレン(Aa)のMFRの3~10倍と規定することで、押出機内では、高密度ポリエチレン(Aa)よりもMFRが高い(すなわち溶融粘度が低い)酸変性ポリエチレン(B)及び該酸変性ポリエチレン(B)と接着性を有するメタキシリレン基含有ポリアミド(C)が、スクリュー近傍よりもシリンダー壁面近傍に比較的多く存在するようになる。押出機を出た樹脂組成物は、押出機からかかる圧力によってそれ以降混合されることなく円筒ダイから押し出されるため、パリソンの断面を観察するとメタキシリレン基含有ポリアミド(C)は主にパリソンの中心から外側に多く存在するようになる。その結果、パリソンの内側はほぼポリエチレンからなるため、ピンチオフ部の接着強度はポリエチレンのみからなる構造体のピンチオフ部の接着強度と同等になる。また、メタキシリレン基含有ポリアミド(C)はパリソンの中心から外側に多く存在するようになるため、従来技術(例えば特開2007-177208号公報を参照)のように容器壁中に均一にポリアミドが層状に分散したものと比較して、メタキシリレン基含有ポリアミド(C)が容器壁の中心よりも外側に近い部分に層状に分散し、かつ連続相のような構造をとるため、従来以上に構造体のバリア性を改善することができる。
本発明に用いられるメタキシリレン基含有ポリアミド(C)は、構造体のバリア性能を高める効果を付与する材料である。メタキシリレン基含有ポリアミドを構成するジアミン単位は、ガスバリア性の観点から、メタキシリレンジアミン単位を好ましくは70モル%以上、より好ましくは80モル%以上、更に好ましくは90モル%以上含む。
メタキシリレンジアミン以外に使用できるジアミンとしては、パラキシリレンジアミン、1,3-ビス(アミノメチル)シクロヘキサン、1,4-ビス(アミノメチル)シクロヘキサン、テトラメチレンジアミン、ヘキサメチレンジアミン、ノナンメチレンジアミン、2-メチル-1,5-ペンタンジアミン等が例示できるが、これらに限定されるものではない。
α,ω-脂肪族ジカルボン酸としてはスベリン酸、アジピン酸、アゼライン酸、セバシン酸、ドデカン酸等が挙げられるが、ガスバリア性及び結晶性の観点から、アジピン酸やセバシン酸が好ましく用いられる。
α,ω-脂肪族ジカルボン酸以外のジカルボン酸単位としては、1,3-シクロヘキサンジカルボン酸や1,4-シクロヘキサンジカルボン酸等の脂環族ジカルボン酸、テレフタル酸、イソフタル酸、オルソフタル酸、キシリレンジカルボン酸、ナフタレンジカルボン酸などの芳香族ジカルボン酸等が例示できるが、これらに限定されるものではない。
これらの中でも、イソフタル酸や2,6-ナフタレンジカルボン酸は、メタキシリレン基含有ポリアミド(C)の製造時における重縮合反応を阻害することなく、バリア性に優れるポリアミドを容易に得ることができるので好ましい。イソフタル酸や2,6-ナフタレンジカルボン酸の含有量は、ポリエチレン系構造体中のメタキシリレン基含有ポリアミド(C)の分散性及び構造体のバリア性の観点から、ジカルボン酸単位の好ましくは30モル%以下、より好ましくは20モル%以下、さらに好ましくは15モル%以下である。
リン原子含有化合物としては、ジメチルホスフィン酸、フェニルメチルホスフィン酸、次亜リン酸、次亜リン酸ナトリウム、次亜リン酸カリウム、次亜リン酸リチウム、次亜リン酸エチル、フェニル亜ホスホン酸、フェニル亜ホスホン酸ナトリウム、フェニル亜ホスホン酸カリウム、フェニル亜ホスホン酸リチウム、フェニル亜ホスホン酸エチル、フェニルホスホン酸、エチルホスホン酸、フェニルホスホン酸ナトリウム、フェニルホスホン酸カリウム、フェニルホスホン酸リチウム、フェニルホスホン酸ジエチル、エチルホスホン酸ナトリウム、エチルホスホン酸カリウム、亜リン酸、亜リン酸水素ナトリウム、亜リン酸ナトリウム、亜リン酸トリエチル、亜リン酸トリフェニル、ピロ亜リン酸等が挙げられる。これらの中でも特に次亜リン酸ナトリウム、次亜リン酸カリウム、次亜リン酸リチウム等の次亜リン酸金属塩がアミド化反応を促進する効果が高く、かつ着色防止効果にも優れるため好ましく用いられ、特に次亜リン酸ナトリウムが好ましいが、本発明で使用できるリン原子含有化合物はこれらの化合物に限定されない。
例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム、水酸化マグネシウム、水酸化カルシウム、水酸化バリウム等のアルカリ金属/アルカリ土類金属の水酸化物や、酢酸リチウム、酢酸ナトリウム、酢酸カリウム、酢酸ルビジウム、酢酸セシウム、酢酸マグネシウム、酢酸カルシウム、酢酸バリウム等のアルカリ金属/アルカリ土類金属の酢酸塩等が挙げられるが、これらの化合物に限定されることなく用いることができる。
メタキシリレン基含有ポリアミド(C)の重縮合系内にアルカリ金属化合物又はアルカリ土類金属化合物を添加する場合、該化合物のモル数をリン原子含有化合物のモル数で除した値が、好ましくは0.5~2.0、より好ましくは0.6~1.8、さらに好ましくは0.7~1.5である。アルカリ金属化合物又はアルカリ土類金属化合物の添加量を上述の範囲とすることでリン原子含有化合物によるアミド化反応促進効果を得つつゲルの生成を抑制することが可能となる。
本発明ではピンチオフ部の接着強度を高めるために、各材料の物性を特定のものとしてパリソン内側におけるメタキシリレン基含有ポリアミド(C)量を減らすようにしているが、その結果、従来のものと比較してメタキシリレン基含有ポリアミドの濃度が濃い部分ができやすくなりやすい。そのため、相対粘度が2.5未満だと、従来の技術と比較して構造体の強度が低下しやすい傾向があるため好ましくない。また相対粘度が4.5を超えると、メタキシリレン基含有ポリアミド(C)の分散状態を制御しにくくなる傾向があるため、成形加工性が不安定になることから好ましくない。
なお、ここで言う相対粘度は、ポリアミド1gを96%硫酸100mLに溶解し、キャノンフェンスケ型粘度計にて25℃で測定した落下時間(t)と、同様に測定した96%硫酸そのものの落下時間(t0)の比であり、下式で示される。
相対粘度=t/t0
本発明の構造体を構成する各材料の配合比率は、ポリエチレン(A)が60~90質量%、酸変性ポリエチレン(B)が5~35質量%、メタキシリレン基含有ポリアミド(C)が5~35質量%であり、好ましくはポリエチレン(A)が65~90質量%、酸変性ポリエチレン(B)が5~30質量%、メタキシリレン基含有ポリアミド(C)が5~30質量%であり、より好ましくはポリエチレン(A)が70~90質量%、酸変性ポリエチレン(B)が5~25質量%、メタキシリレン基含有ポリアミド(C)が5~25質量%である。本発明の第2の実施態様の場合、ポリエチレン(A)が60~90質量%、酸変性ポリエチレン(B)が5~25質量%、メタキシリレン基含有ポリアミド(C)が5~35質量%であり、好ましくはポリエチレン(A)が65~90質量%、酸変性ポリエチレン(B)が5~20質量%、メタキシリレン基含有ポリアミド(C)が5~30質量%であり、さらに好ましくはポリエチレン(A)が70~90質量%、酸変性ポリエチレン(B)が5~15質量%、メタキシリレン基含有ポリアミド(C)が5~25質量%である。
ただし、(A)~(C)の3成分の合計が100質量%を超えることはない。上述の範囲に各材料の配合比率を設定することによって、構造体のバリア性能を効率的に高めることができ、かつ構造体の強度低下を最小限にすることができる。本発明の構造体は、ポリエチレン(A)、酸変性ポリエチレン(B)、及びメタキシリレン基含有ポリアミド(C)の3成分からなることが好ましい。
その他、本発明の効果を損なわない範囲で上述の材料以外にも様々な材料を配合することができる。例えば、プロピレンホモポリマー、エチレン-プロピレンブロックコポリマー、エチレン-プロピレンランダムコポリマー等に代表されるポリプロピレン類;ポリブテン-1、ポリメチルペンテン等の炭素数3~20のα-オレフィンの単独重合体;炭素数3~20のα-オレフィンの共重合体;炭素数3~20のα-オレフィンと環状オレフィンとの共重合体;アイオノマー;エチレン-エチルアクリレート共重合体やエチレン-メチルアクリレート共重合体等の各種変性ポリエチレン;ポリスチレン;ポリエチレンテレフタレート等の各種ポリエステル;ナイロン6やナイロン66等の各種ポリアミド;スチレン-ブタジエン共重合体やその水添化物;各種熱可塑性エラストマー等を添加することができ、これらに限定されることはない。また、本発明の第1の実施態様において、低密度ポリエチレン、中密度ポリエチレン、直鎖状低密度ポリエチレン等に代表されるポリエチレン類を添加することもできる。
本発明のポリエチレン系構造体は、タンク形状やボトル形状、チューブ形状等の成形体とすることができる。タンク形状やボトル形状の場合、ダイレクトブロー法による構造体の製造が好ましく行われる。例えば、構造体が単層容器の場合、押出機、アダプター、円筒ダイ、型締め装置、金型、冷却装置を備えた成形装置を用い、ポリエチレン(A)、酸変性ポリエチレン(B)、メタキシリレン基含有ポリアミド(C)、場合によっては成形品を粉砕して得た粉砕物をドライブレンドした混合材料を押出機へ投入して溶融混練する。溶融混練されたものはアダプター、円筒ダイを通して筒状(パリソンと言うことがある)に押し出され、適当な長さに押し出されたタイミングで金型で挟み、空気をパリソン内に送り込んで膨らませて冷却された金型内に密着させ、冷却後、金型を開いて成形された容器を取り出す方法が挙げられる。
またスクリューの剪断力で層状に分散したメタキシリレン基含有ポリアミド(C)の状態を保つためにも、押出機ヘッド内に通常設けられるブレーカープレートは設置しないことが好ましい。ブレーカープレートに空けられた細孔により押出機内で層状に分散したメタキシリレン基含有ポリアミド(C)が切断され、微分散化する可能性がある。
本発明の構造体では、バリア性を効果的に高めるため、メタキシリレン基含有ポリアミド(C)が層状に分散している必要があり、そのためには上述の押出機内で樹脂ペレットが剪断応力により引き延ばされて層状の状態にある時に押出機先端から吐出される必要がある。それを実現するための方法としては、主にスクリュー回転数を下げる方法と押出機温度設定を最適化する方法が挙げられる。スクリュー回転数を下げる方法は一見簡便な方法に見えるが、生産効率の低下を招いたり、パリソンが長時間大気に曝されることに起因する容器強度の低下が懸念されるため、その利用範囲は限定されることがある。そのような場合は、押出機内での樹脂温度を制御する方法が好ましく用いられる。具体的には、押出機内で材料を溶融混練する際の樹脂温度がメタキシリレン基含有ポリアミド(C)の融点±20℃の温度範囲になるように、押出機の温度を調節することが好ましく行われる。より好ましくは融点±15℃の温度範囲であり、さらに好ましくは融点±10℃である。樹脂温度は実際に押出機先端から吐出される樹脂の実温度を測定したものを採用することが好ましいが、押出機先端部に設けられた熱電対によって計測される数字と樹脂の実温度との間の差がある程度判明している場合はその数値を参考に調整してもよい。メタキシリレン基含有ポリアミド(C)の融点-20℃を下回る樹脂温度で溶融混練を行うとメタキシリレン基含有ポリアミド(C)が十分軟化せず未溶融のペレットが成形品に混入したり、押出機モーターに過度の負荷がかかることがあるので好ましくない。融点+20℃を超える温度になるとメタキシリレン基含有ポリアミド(C)が完全に融解してスクリュー回転による剪断応力で過度に分散してしまうため、樹脂組成物中での層状の分散状態を保てずに微細な粒子状になり、構造体のバリア性が大きく低下してしまうため好ましくない。
東洋精機製作所製メルトインデクサーを使用し、JIS K7210に準拠して、190℃、2.16kgfの条件にて測定を行った。
押出機、Tダイ、冷却ロール、引き取り機等からなるシート成形装置を用い、厚さが約1mmの単層シートを成形した。次いでシートから縦50mm×横50mmの試験片を切削して真比重計により真比重を求めた。
メタキシリレン基含有ポリアミド(C)1gを精秤し、96%硫酸100mLに20~30℃で撹拌溶解した。完全に溶解した後、速やかにキャノンフェンスケ型粘度計に溶液5mlを取り、25℃の恒温層中で10分間放置後、落下時間(t)を測定した。また同様の条件で96%硫酸そのものの落下時間(t0)を測定した。t及びt0から下式により相対粘度を算出した。
相対粘度=t/t0
メタキシリレン基含有ポリアミド(C)濃度が1.0g/Lとなるようにヘキサフルオロイソプロパノールに溶解させて試料を調製した。次いで、GPC装置(東ソー(株)製、商品名:「HLC-8320GPC/UV-8320」)を用いて、温度40℃、流速0.3mL/minの条件にて数平均分子量の測定を行い、メタキシリレン基含有ポリアミド(C)中における数平均分子量1000以下の低分子量成分の含有率の測定を行った。なお数平均分子量はポリメチルメタクリレート(PMMA)換算にて求めた。
実施例及び比較例で作製した容器に、擬似ガソリン(トルエン/イソオクタン/エタノール=45/45/10vol%)400ml又は1000mlを入れた後、口栓開口部をアルミ箔でシールし、更にキャップをつけて総質量を測定、記録した。実施例101~113及び比較例101~107では擬似ガソリン400mlを使用し、実施例201~214及び比較例201~208では擬似ガソリン1000mlを使用した。
次いで、擬似ガソリンを封入した容器を40℃に調温した防爆型恒温槽に保管して、24時間毎に総質量を記録した。質量減少速度が安定した時点で容器内の擬似ガソリンを抜き、直ちに再度改めて擬似ガソリンを封入した。次いで、擬似ガソリンを封入した容器を40℃に調温した防爆型恒温槽に保管して、24時間毎に総質量を記録し、擬似ガソリン透過率(g/m2・day)を求めた。
擬似ガソリン透過率測定終了後、容器内の擬似ガソリンを抜き、成形直後の製品と外観を比較して変化の有無を目視にて確認した。
実施例及び比較例で作製した容器の底から幅10mm、ピンチオフ部を中心として長さ約50mmの試験片を切削した。次いで、引張試験機を用い、引張速度50mm/minで強度測定を行った。
実施例及び比較例で作製した容器に、水400ml又は1000mlを充填してキャップを閉め、室温下で1週間保管した。次いで、容器の底面を下にして、2mの高さからコンクリート上に30回連続して落下させ、5個の容器のうち、試験中に割れた容器数をカウントした。実施例101~113及び比較例101~107では水400mlを使用し、実施例201~214及び比較例201~208では水1000mlを使用した。
成形したタンクを切断し、断面をカッターで平滑にした後、希ヨードチンキ(月島薬品株式会社製)を断面に塗布してメタキシリレン基含有ポリアミド(C)部分を染色した後、実体顕微鏡により拡大して樹脂組成物中のメタキシリレン基含有ポリアミド(C)の分散状態を観察した。
(メタキシリレン基含有ポリアミド(C)(PA-1)の製造)
分縮器、全縮器、圧力計、窒素導入口、液体注入口、樹脂抜き出しバルブ、撹拌機を備えた内容量50リットルの加熱ジャケット付きSUS製反応缶に、アジピン酸15000g(102.6mol)、次亜リン酸ナトリウム17.3g(0.16mol)、酢酸ナトリウム12.1g(0.15mol)を仕込み、反応缶内部を窒素置換した。次いで、窒素を10ml/minの速度で流通させながら、常圧下で反応缶を170℃まで加熱し、アジピン酸を完全に融解させた後、メタキシリレンジアミン13980g(102.6mol)の滴下を開始した。メタキシリレンジアミンの滴下中は重縮合により生成する水を系内から除去しつつ、反応系内が固化しないように連続的に昇温した。100分かけてメタキシリレンジアミンを全量滴下し、かつ反応缶内温を250℃まで昇温した。次いで常圧のまま10分かけて内温を260℃に上げた後、内温を260℃に保持しつつアスピレーターと圧力調節器を使用して反応缶内を600mmHgまで10分かけて減圧し、600mmHgで重縮合反応を継続した。撹拌機のトルクを観察しながら十分に樹脂の粘度が高くなった時点で撹拌を止め、窒素により反応缶内を0.2MPaに加圧してから反応缶底の樹脂抜き出しバルブを開けてポリマーをストランド状にして抜き出し、水冷後ペレタイザーにてペレット化して、約25kgのメタキシリレン基含有ポリアミドのペレットを得た。
(メタキシリレン基含有ポリアミド(C)(PA-2)の製造)
タンブルドライヤー内で保持する時間について、200℃で30分保持したこと以外は製造例1と同様にしてメタキシリレン基含有ポリアミド(PA-2)を得た。得られたポリアミド(PA-2)の相対粘度は2.7であった。また、GPC測定による数平均分子量1000以下の成分量は1.5%であった。
(メタキシリレン基含有ポリアミド(C)(PA-3)の製造)
タンブルドライヤー内で保持する時間について、200℃で120分保持したこと以外は製造例1と同様にしてメタキシリレン基含有ポリアミド(PA-3)を得た。得られたポリアミド(PA-3)の相対粘度は4.2であった。また、GPC測定による数平均分子量1000以下の成分量は0.8%であった。
(メタキシリレン基含有ポリアミド(C)(PA-4)の製造)
ポリアミド原料のうちジカルボン酸成分を、アジピン酸13495g(92.3mol)、イソフタル酸1705g(10.3mol)に変更したこと以外は製造例1と同様にしてメタキシリレン基含有ポリアミド(PA-4)を得た。得られたポリアミド(PA-4)の相対粘度は3.4であった。また、GPC測定による数平均分子量1000以下の成分量は1.9%であった。
(メタキシリレン基含有ポリアミド(C)(PA-5)の製造)
タンブルドライヤー内で保持する時間について、200℃で30分保持したこと以外は製造例4と同様にしてメタキシリレン基含有ポリアミド(PA-5)を得た。得られたポリアミド(PA-5)の相対粘度は2.6であった。また、GPC測定による数平均分子量1000以下の成分量は2.6%であった。
(メタキシリレン基含有ポリアミド(C)(PA-6)の製造)
溶融重合でポリアミドを得た後、タンブルドライヤー内で保持する時間について、ペレット温度が150℃に達した時点で系内の圧力を1torr以下に減圧した後、150℃で120分保持した後、系内に純度が99容量%以上の窒素ガスを導入して、タンブルドライヤーを回転させたまま冷却したこと以外は製造例1と同様にしてメタキシリレン基含有ポリアミド(PA-6)を得た。得られたポリアミド(PA-6)の相対粘度は2.1であった。また、GPC測定による数平均分子量1000以下の成分量は2.5%であった。
HDPE-1又はA1-1:
日本ポリエチレン(株)製、商品名:ノバテックHD HB420R、MFR=0.2、密度=0.956
HDPE-2又はA1-5:
日本ポリエチレン(株)製、商品名:ノバテックHD HB332R、MFR=0.3、密度=0.952
HDPE-3又はA1-3:
日本ポリエチレン(株)製、商品名:ノバテックHD HB439R、MFR=0.55、密度=0.96
HDPE-4又はA1-6:
日本ポリエチレン(株)製、商品名:ノバテックHD HB424R、MFR=0.25、密度=0.957
HDPE-5又はA1-4:
日本ポリエチレン(株)製、商品名:ノバテックHD HB323R、MFR=0.15、密度=0.953
A1-2:
日本ポリエチレン(株)製、商品名:ノバテックHD HB120R、MFR=0.2、密度=0.938
A2-1:
日本ポリエチレン(株)製、商品名:ノバテックLL UE320、MFR=0.6、密度=0.922
A2-2:
日本ポリエチレン(株)製、商品名:ノバテックLD ZE41K、MFR=0.5、密度=0.922
A2-3:
日本ポリエチレン(株)製、商品名:ハーモレックス NF444N、MFR=2.0、密度=0.912
AD-1:
三菱化学(株)製、商品名:モディック L502、MFR=1.0、密度=0.93
AD-2:
三菱化学(株)製、商品名:モディック H503、MFR=1.5、密度=0.93
AD-3:
三菱化学(株)製、商品名:モディック L504、MFR=4.1、密度=0.91
AD-4:
日本ポリエチレン(株)製、商品名:アドテックス DH0200、MFR=0.5、密度=0.95
AD-5:
三井化学(株)製、商品名:アドマー NF518、MFR=2.4、密度=0.91
AD-6:
日本ポリエチレン(株)製、商品名:アドテックス L6100M、MFR=1.1、密度=0.92
50mm単軸押出機、アダプター、パリソンコントローラー付き円筒ダイ、金型、型締め機、冷却器等を備えた単層ダイレクトブロー容器成形装置を使用し、押出機ホッパー内へ、HDPE-1/AD-1/PA-1=80/10/10(質量%)の割合でドライブレンドした混合ペレットを投入し、押出機シリンダー温度を210~235℃、アダプター温度を235℃、ダイ温度を230℃に設定、スクリュー回転数を30rpmとしてパリソンを押し出し、ダイレクトブロー法によって内容積450ml、平均肉厚3mmのネジ口栓付きタンクの成形を行った。
得られたタンクについて、擬似ガソリン透過率及びピンチオフ部の引張強さの測定、並びに落下試験を実施した。結果を表1に示す。
高密度ポリエチレン(Aa)、酸変性ポリエチレン(B)、メタキシリレン基含有ポリアミド(C)の種類、配合量を表1に示したように変更したこと以外は実施例101と同様にしてネジ口栓付きタンクの成形を行った。
得られたタンクについて、擬似ガソリン透過率及びピンチオフ部の引張強さの測定、並びに落下試験を実施した。結果を表1に示す。
高密度ポリエチレン(Aa)、酸変性ポリエチレン(B)、メタキシリレン基含有ポリアミド(C)の種類、配合量を表1に示したように変更し、さらに押出機シリンダー温度を200~220℃、アダプター温度を220℃、ダイ温度を215℃に変更したこと以外は実施例101と同様にしてネジ口栓付きタンクの成形を行った。
得られたタンクについて、擬似ガソリン透過率及びピンチオフ部の引張強さの測定、並びに落下試験を実施した。結果を表1に示す。
高密度ポリエチレン(Aa)のみを使用したこと以外は実施例101と同様にしてネジ口栓付きタンクの成形を行った。
得られたタンクについて、擬似ガソリン透過率及びピンチオフ部の引張強さの測定、並びに落下試験を実施した。結果を表1に示す。
高密度ポリエチレン(Aa)、酸変性ポリエチレン(B)、メタキシリレン基含有ポリアミド(C)の種類、配合量を表1に示したように変更したこと以外は実施例101と同様にしてネジ口栓付きタンクの成形を行った。
得られたタンクについて、擬似ガソリン透過率及びピンチオフ部の引張強さの測定、並びに落下試験を実施した。結果を表1に示す。
一方、高密度ポリエチレン(Aa)のみからなる比較例101では、引張強度及び落下強度は優れるものの擬似ガソリンバリア性に劣るものであった。高密度ポリエチレン(Aa)と酸変性ポリエチレン(B)とのMFR比が低い比較例102では、メタキシリレン基含有ポリアミド(C)の分散状態に起因して、擬似ガソリンバリア性及びピンチオフ部の引張強度が劣り、落下時の容器割れが発生した。酸変性ポリエチレン(B)の密度が高い比較例103では、酸変性ポリエチレン(B)の密度が高くなったことに起因して、落下割れ数の増加が認められた。高密度ポリエチレン(Aa)と酸変性ポリエチレン(B)とのMFR比が高い比較例104では、メタキシリレン基含有ポリアミド(C)が容器表面に浮き出た箇所が認められ、擬似ガソリンバリア性及びピンチオフ部の引張強度が劣り、落下時の容器割れが発生した。また、相対粘度が低いメタキシリレン基含有ポリアミド(C)を使用した比較例105~107においても、メタキシリレン基含有ポリアミド(C)が容器表面に浮き出た箇所が認められ、擬似ガソリンバリア性及びピンチオフ部の引張強度が劣り、落下時の容器割れが発生した。
55mm単軸押出機、アダプター、パリソンコントローラー付き円筒ダイ、金型、型締め機、冷却器等を備えた単層ダイレクトブロー容器成形装置を使用し、押出機ホッパー内へA1-1/A2-1/AD-1/PA-1=75/5/10/10(質量%)の割合でドライブレンドした混合ペレットを投入し、押出機シリンダー温度を210~235℃、アダプター温度を235℃、ダイ温度を230℃に設定、スクリュー回転数を50rpmとしてパリソンを押し出し、ダイレクトブロー法によって内容積1000ml、平均肉厚3.5mmのネジ口栓付きタンクの成形を行った。
得られたタンクについて、擬似ガソリン透過率及びピンチオフ部の引張強さの測定、並びに落下試験を実施した。結果を表2に示す。
ポリエチレン(A1)、ポリエチレン(A2)、酸変性ポリエチレン(B)、メタキシリレン基含有ポリアミド(C)の種類、配合量を表2に示したように変更したこと以外は実施例201と同様にしてネジ口栓付きタンクの成形を行った。
得られたタンクについて、擬似ガソリン透過率及びピンチオフ部の引張強さの測定、並びに落下試験を実施した。結果を表2に示す。
ポリエチレン(A1)、ポリエチレン(A2)、酸変性ポリエチレン(B)、メタキシリレン基含有ポリアミド(C)の種類、配合量を表2に示したように変更し、さらに押出機シリンダー温度を200~220℃、アダプター温度を220℃、ダイ温度を215℃に変更したこと以外は実施例201と同様にしてネジ口栓付きタンクの成形を行った。
得られたタンクについて、擬似ガソリン透過率及びピンチオフ部の引張強さの測定、並びに落下試験を実施した。結果を表2に示す。
A1-1のみを使用したこと以外は実施例201と同様にしてネジ口栓付きタンクの成形を行った。
得られたタンクについて、擬似ガソリン透過率及びピンチオフ部の引張強さの測定、並びに落下試験を実施した。結果を表2に示す。
ポリエチレン(A1)、ポリエチレン(A2)、酸変性ポリエチレン(B)、メタキシリレン基含有ポリアミド(C)の種類、配合量を表2に示したように変更したこと以外は実施例201と同様にしてネジ口栓付きタンクの成形を行った。
得られたタンクについて、擬似ガソリン透過率及びピンチオフ部の引張強さの測定、並びに落下試験を実施した。結果を表2に示す。
一方、高密度ポリエチレンのみからなる比較例201では、引張強度及び落下強度は優れるものの擬似ガソリンバリア性に劣るものであった。ポリエチレン(A2)の配合量が少ない比較例202では、落下時の容器割れが発生した。ポリエチレン(A2)の配合量が多い比較例203では、ピンチオフ部の強度が低く、また、擬似燃料透過率測定中に容器が膨張し、変形が認められた。酸変性ポリエチレン(B)の配合量が少ない比較例204では、メタキシリレン基含有ポリアミド(C)の分散性が悪いためバリア性の改善効果が小さく、擬似ガソリン透過率に劣り、しかもポリエチレン(A1)とメタキシリレン基含有ポリアミド(C)との層間接着強度が低くピンチオフ部の強度が低くかつ落下割れが認められた。メタキシリレン基含有ポリアミド(C)の配合量が少ない比較例205では、バリア性の改善効果が小さく、擬似ガソリン透過率に劣るものであった。メタキシリレン基含有ポリアミド(C)の配合量が多い比較例206では、ピンチオフ部の強度が顕著に低く、落下試験での容器割れ発生が認められた。相対粘度が低いメタキシリレン基含有ポリアミド(C)を使用した比較例207では、メタキシリレン基含有ポリアミド(C)が容器表面に浮き出た箇所が認められ、擬似ガソリンバリア性及びピンチオフ部の引張強度が劣り、落下時の容器割れが発生した。ポリエチレン(A2)として密度が高いポリエチレンを利用した比較例208では、容器の剛性が高すぎて落下試験での容器割れ発生が認められた。
図1~4から、実施例101及び204で得られたタンクでは、ポリエチレン中にメタキシリレン基含有ポリアミドが層状に分散し、かつ連続相を形成していることがわかる。特に、メタキシリレン基含有ポリアミドは、断面の中心から外側に多く存在しており、断面の内側にはポリエチレンが多く存在していることがわかる。このようにメタキシリレン基含有ポリアミドが層状に分散し、かつ連続相を形成していることから、実施例101及び204で得られたタンクは良好なバリア性を示す。
また、図2及び4から、パリソンの内面同士が接着して形成されるピンチオフ部では、パリソンの内面側がほぼポリエチレンからなっているため、パリソンの内面同士が良好に接着していることがわかる。このことは、ピンチオフ部が破損することなく高強度である。その一方で、ピンチオフ部においてもメタキシリレン基含有ポリアミドが層状に分散しているため、ピンチオフ部のバリア性も良好である。
したがって、本発明のタンクは、良好なバリア性を示しかつ強度に優れる。
Claims (11)
- ポリエチレン(A)60~90質量%、酸変性ポリエチレン(B)5~35質量%、及びメタキシリレン基含有ポリアミド(C)5~35質量%を含有し、前記ポリエチレン(A)中に前記メタキシリレン基含有ポリアミド(C)が層状に分散し、かつ一部連続相を形成しているポリエチレン系構造体であって、前記メタキシリレン基含有ポリアミド(C)の相対粘度が2.5~4.5であり、下記条件1又は2を満足する、ポリエチレン系構造体。
[条件1]
(1-1)前記ポリエチレン(A)が、0.94~0.97の密度を有する高密度ポリエチレン(Aa)であり、かつ、前記高密度ポリエチレン(Aa)のメルトフローレート(MFR)が0.1~0.6である。
(1-2)前記酸変性ポリエチレン(B)の密度が0.90~0.935であり、かつ、前記酸変性ポリエチレン(B)のMFRが前記高密度ポリエチレン(Aa)のMFRの3~10倍の範囲である。
[条件2]
前記ポリエチレン(A)が、0.935~0.965の密度を有するポリエチレン(A1)と、0.91~0.93の密度を有するポリエチレン(A2)とからなる混合物であり、前記のポリエチレン(A1)とポリエチレン(A2)との質量比((A1)/(A2))が70/30~95/5である。 - 前記条件1を満足する、請求項1に記載のポリエチレン系構造体。
- 前記メタキシリレン基含有ポリアミド(C)における数平均分子量1000以下の成分が2質量%以下である、請求項2に記載のポリエチレン系構造体。
- ポリエチレン(A)60~90質量%、酸変性ポリエチレン(B)5~25質量%、及びメタキシリレン基含有ポリアミド(C)5~35質量%を含有し、かつ前記条件2を満足する、請求項1に記載のポリエチレン系構造体。
- 前記酸変性ポリエチレン(B)の密度が0.90~0.935である、請求項4に記載のポリエチレン系構造体。
- 前記ポリエチレン(A1)のメルトフローレート(MFR)が0.05~0.6である、請求項4又は5に記載のポリエチレン系構造体。
- 前記ポリエチレン(A2)のMFRが前記ポリエチレン(A1)のMFRの0.5~8倍である、請求項4~6のいずれかに記載のポリエチレン系構造体。
- 前記酸変性ポリエチレン(B)のMFRが前記ポリエチレン(A1)のMFRの3~10倍である、請求項4~7のいずれかに記載のポリエチレン系構造体。
- 前記メタキシリレン基含有ポリアミド(C)が、メタキシリレンジアミン単位を70モル%以上含有する、請求項1~8のいずれかに記載のポリエチレン系構造体。
- タンク、パイプ又はボトルの形状を有する、請求項1~9のいずれかに記載のポリエチレン系構造体。
- ダイレクトブロー法によって成形された、請求項1~10のいずれかに記載のポリエチレン系構造体。
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WO2018070194A1 (ja) | 2016-10-14 | 2018-04-19 | 三菱瓦斯化学株式会社 | ポリオレフィン系構造体 |
WO2018168720A1 (ja) * | 2017-03-16 | 2018-09-20 | トヨタ紡織株式会社 | 熱可塑性樹脂シート、積層シート及び成形体 |
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JPWO2012121295A1 (ja) | 2014-07-17 |
US9296881B2 (en) | 2016-03-29 |
US20130344270A1 (en) | 2013-12-26 |
CO6751284A2 (es) | 2013-09-16 |
CN103415569B (zh) | 2015-11-25 |
CN103415569A (zh) | 2013-11-27 |
BR112013022448A2 (pt) | 2016-12-06 |
EP2684915B1 (en) | 2016-02-10 |
RU2592540C2 (ru) | 2016-07-20 |
EP2684915A1 (en) | 2014-01-15 |
RU2013144926A (ru) | 2015-04-20 |
EP2684915A4 (en) | 2015-04-08 |
JP5842910B2 (ja) | 2016-01-13 |
KR20140018886A (ko) | 2014-02-13 |
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