TW201425422A - Polyethylene structure - Google Patents
Polyethylene structure Download PDFInfo
- Publication number
- TW201425422A TW201425422A TW101151018A TW101151018A TW201425422A TW 201425422 A TW201425422 A TW 201425422A TW 101151018 A TW101151018 A TW 101151018A TW 101151018 A TW101151018 A TW 101151018A TW 201425422 A TW201425422 A TW 201425422A
- Authority
- TW
- Taiwan
- Prior art keywords
- polyethylene
- acid
- container
- mass
- xylylene group
- Prior art date
Links
- -1 Polyethylene structure Polymers 0.000 title claims abstract description 201
- 239000004698 Polyethylene Substances 0.000 claims abstract description 131
- 229920000573 polyethylene Polymers 0.000 claims abstract description 131
- 239000002253 acid Substances 0.000 claims abstract description 36
- 239000011342 resin composition Substances 0.000 claims abstract description 24
- 229920000768 polyamine Polymers 0.000 claims description 59
- 239000000155 melt Substances 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 abstract description 3
- 229920002647 polyamide Polymers 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 description 48
- 238000000034 method Methods 0.000 description 37
- 229920005989 resin Polymers 0.000 description 23
- 239000011347 resin Substances 0.000 description 23
- 229920001903 high density polyethylene Polymers 0.000 description 21
- 239000004700 high-density polyethylene Substances 0.000 description 21
- 239000003502 gasoline Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- 238000006068 polycondensation reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 125000004437 phosphorous atom Chemical group 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000000446 fuel Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000004677 Nylon Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229920001778 nylon Polymers 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000000071 blow moulding Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- 229920002292 Nylon 6 Polymers 0.000 description 5
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920002302 Nylon 6,6 Polymers 0.000 description 4
- 150000001339 alkali metal compounds Chemical class 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- 239000004840 adhesive resin Substances 0.000 description 3
- 229920006223 adhesive resin Polymers 0.000 description 3
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 3
- 238000007112 amidation reaction Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003484 crystal nucleating agent Substances 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
- 239000012760 heat stabilizer Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000006224 matting agent Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000011295 pitch Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 239000008096 xylene Substances 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
- 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 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920003355 Novatec® Polymers 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical group NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004140 cleaning 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
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 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
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910001383 lithium hypophosphite Inorganic materials 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
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 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
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 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
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 101000652482 Homo sapiens TBC1 domain family member 8 Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910018879 Pt—Pd Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 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
- PRFAJWUBOMPPSE-UHFFFAOYSA-M [K+].[O-][PH2]=O.c1ccccc1 Chemical compound [K+].[O-][PH2]=O.c1ccccc1 PRFAJWUBOMPPSE-UHFFFAOYSA-M 0.000 description 1
- HLVGRHTXNNDPPI-UHFFFAOYSA-M [Li+].[O-]P(=O)c1ccccc1 Chemical compound [Li+].[O-]P(=O)c1ccccc1 HLVGRHTXNNDPPI-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001336 alkenes 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
- 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
- 230000002528 anti-freeze Effects 0.000 description 1
- 239000007900 aqueous suspension Substances 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
- 239000007844 bleaching agent Substances 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 239000004595 color masterbatch Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005336 cracking Methods 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
- HCAJEUSONLESMK-UHFFFAOYSA-N cyclohexylsulfamic acid Chemical compound OS(=O)(=O)NC1CCCCC1 HCAJEUSONLESMK-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- VZEGPPPCKHRYGO-UHFFFAOYSA-N diethoxyphosphorylbenzene Chemical compound CCOP(=O)(OCC)C1=CC=CC=C1 VZEGPPPCKHRYGO-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
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- WCPNHDCBQKJBDD-UHFFFAOYSA-L dipotassium;ethyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [K+].[K+].CCP([O-])([O-])=O WCPNHDCBQKJBDD-UHFFFAOYSA-L 0.000 description 1
- JOQAMSDLZYQHMX-UHFFFAOYSA-L disodium;dioxido-oxo-phenyl-$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
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- YJSXLGKPMXKZJR-UHFFFAOYSA-N ethoxy-oxo-phenylphosphanium Chemical compound CCO[P+](=O)C1=CC=CC=C1 YJSXLGKPMXKZJR-UHFFFAOYSA-N 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 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
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229920000831 ionic polymer 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
- 238000004898 kneading 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
- 239000007788 liquid Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene 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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000020124 milk-based beverage Nutrition 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006146 oximation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 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
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- VENHOSDSAVICHW-UHFFFAOYSA-M potassium phenylphosphinate Chemical compound [K+].[O-]P(=O)C1=CC=CC=C1 VENHOSDSAVICHW-UHFFFAOYSA-M 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003330 sebacic acids Chemical class 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 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
- HHJJPFYGIRKQOM-UHFFFAOYSA-N sodium;oxido-oxo-phenylphosphanium Chemical compound [Na+].[O-][P+](=O)C1=CC=CC=C1 HHJJPFYGIRKQOM-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004149 tartrazine Substances 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
- UJJLJRQIPMGXEZ-UHFFFAOYSA-N tetrahydro-2-furoic acid Chemical compound OC(=O)C1CCCO1 UJJLJRQIPMGXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-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
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 235000015192 vegetable juice Nutrition 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本發明係關於一種阻隔性及強度優異之聚乙烯系結構體。 The present invention relates to a polyethylene-based structure excellent in barrier properties and strength.
作為用於保存烴類或各種藥品之容器、或用於輸送之管，例如可列舉藥品瓶、汽車或小型引擎之燃料槽、燃料管等。以往作為其素材所利用之金屬或玻璃，其大多逐漸被塑膠取代。相較於金屬或玻璃，塑膠具有輕盈、不需防鏽處理、不易破損、形狀之自由度高等特點。 Examples of the container for storing hydrocarbons or various medicines or the tubes for transportation include a medicine bottle, a fuel tank for an automobile or a small engine, a fuel tube, and the like. Most of the metals or glass used in the past as materials have been gradually replaced by plastics. Compared with metal or glass, plastic has the characteristics of lightness, no need for anti-rust treatment, not easy to break, and high degree of freedom of shape.
上述用途大多係利用高密度聚乙烯(以下有簡稱為「HDPE」之情形)者，雖然在機械強度、成形加工性及經濟層面優異，卻有保存於容器內部之物品容易穿透HDPE壁而飛散於空氣中之缺點。近年來，由於從環境污染之觀點來看，對於樹脂製汽油槽或其周邊構件之汽油穿透量的規定正逐年變得嚴格，因此由HDPE構成之容器變得難以對應，而正強烈期望用於提升汽油阻隔性之技術。 Most of the above-mentioned uses are made of high-density polyethylene (hereinafter referred to as "HDPE"). Although they are excellent in mechanical strength, formability, and economics, articles stored in the inside of the container easily penetrate the HDPE wall and scatter. The shortcomings in the air. In recent years, from the viewpoint of environmental pollution, the regulations on the amount of gasoline penetration of the resin-made gasoline tank or its peripheral members are becoming stricter year by year. Therefore, containers made of HDPE are difficult to cope with, and it is strongly desired to use them. Technology for improving the barrier properties of gasoline.
作為提升HDPE容器之燃料阻隔性的方法之一，已知有於HDPE容器之內面施以氟氯碳化物(flon)處理或碸處理之方法(例如參照專利文獻1)。又，已知有於HDPE容器積層如乙烯-乙烯醇共聚合樹脂(以下有簡稱為「EVOH」之情形)之阻隔性樹脂作為中間層而成為多層結構之方法(例如參照專利文獻2及3)。再者，作為提升HDPE容器之燃料阻隔性的方法，已知有將耐綸6,66等聚醯胺樹脂或EVOH，與黏著性樹脂一同和HDPE混合， 且自其組成物製造單層容器之方法(例如參照專利文獻4及5)。又，亦有揭示在上述混合單層容器中，使用阻隔性比耐綸6,66更優異之聚間亞二甲苯己二醯胺(以下有簡稱為「N-MXD6」之情形)之方法(例如參照專利文獻6及7)。 As one of methods for improving the fuel barrier properties of the HDPE container, a method of applying a flocculation treatment or a ruthenium treatment to the inner surface of the HDPE container is known (for example, refer to Patent Document 1). In addition, a method in which a barrier resin such as an ethylene-vinyl alcohol copolymer resin (hereinafter referred to as "EVOH") is used as an intermediate layer to form a multilayer structure is known (for example, refer to Patent Documents 2 and 3). . Further, as a method for improving the fuel barrier property of the HDPE container, it is known to mix a polyamide resin such as nylon 6,66 or EVOH with an adhesive resin together with HDPE. Further, a method of producing a single-layered container from the composition thereof (for example, refer to Patent Documents 4 and 5). Further, in the above-mentioned mixed single-layered container, a method of using polymethylene xylene hexamethylenediamine (hereinafter abbreviated as "N-MXD6") which is more excellent in barrier properties than nylon 6,66 is also disclosed. For example, refer to Patent Documents 6 and 7).
【專利文獻1】日本特開昭60-006735號公報 [Patent Document 1] Japanese Laid-Open Patent Publication No. 60-006735
【專利文獻2】日本特開平06-328634號公報 [Patent Document 2] Japanese Patent Laid-Open No. Hei 06-328634
【專利文獻3】日本特開平07-052333號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 07-052333
【專利文獻4】日本特開昭55-121017號公報 [Patent Document 4] Japanese Patent Laid-Open No. 55-121017
【專利文獻5】日本特開昭58-209562號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. SHO 58-209562
【專利文獻6】日本特開2005-206806號公報 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2005-206806
【專利文獻7】日本特開2007-177208號公報 [Patent Document 7] Japanese Patent Laid-Open Publication No. 2007-177208
然而，專利文獻1所揭示之對於HDPE容器之內面施以氟氯碳化物處理或碸處理之方法，雖然具有可以直接地利用以往所生產之HDPE容器的製造設備之優點，卻也有不僅必須確保對於氟處理時操作有害氣體之安全性，處理後之回收方法成為問題，而且尚有氟化處理後之品質檢查困難等缺點。 However, the method of applying the chlorofluorocarbon treatment or the ruthenium treatment to the inner surface of the HDPE container disclosed in Patent Document 1 has the advantages of being able to directly utilize the manufacturing equipment of the conventionally produced HDPE container, but it is not only necessary to ensure For the safety of handling harmful gases during fluorine treatment, the recovery method after the treatment becomes a problem, and there are disadvantages such as difficulty in quality inspection after fluorination treatment.
專利文獻2及3所揭示之由HDPE與EVOH所形成的多層容器，可以賦予比以往的HDPE容器更優異之阻隔性，且由於可以藉由積層的EVOH層之厚度來控制該容器的阻隔性能，因此易於製造具有所欲阻隔性之容器。然而，該容器無法對應HDPE單層容器之製造設備，為了分別擠製HDPE、黏著性樹脂、EVOH而必須導入至少設置3台以上的擠製機之多層吹塑裝置，遺留經濟層面的問題。又，藉由直接吹塑法所製造之容器，必定會殘留稱為夾斷部之以鑄模夾斷型坯的部位，在上述多層容器中，由於 在其夾斷部的剖面會形成內層HDPE的結合面，因此產生EVOH層被切斷的部位。若為厚度薄的容器，則夾斷部之內層HDPE結合面的厚度會變得非常薄，事實上很少問題，然而在如燃料容器般要求高強度之容器中，由於一般而言內層HDPE的厚度會設定為較厚，因此有燃料將會經由該結合面輕易穿透之缺點。 The multilayer container formed of HDPE and EVOH disclosed in Patent Documents 2 and 3 can provide superior barrier properties to the conventional HDPE container, and since the barrier property of the container can be controlled by the thickness of the laminated EVOH layer, It is therefore easy to manufacture a container having the desired barrier properties. However, this container cannot cope with the manufacturing equipment of the HDPE single-layer container. In order to separately extrude HDPE, adhesive resin, and EVOH, it is necessary to introduce a multi-layer blow molding apparatus in which at least three or more extruders are installed, leaving a problem of economical level. Moreover, in the container manufactured by the direct blow molding method, a portion called a pinch-off portion in which a parison is cut by a mold is always left, and in the above-mentioned multilayer container, The cross section of the pinch-off portion forms a bonding surface of the inner layer HDPE, and thus a portion where the EVOH layer is cut is generated. In the case of a container having a small thickness, the thickness of the inner layer HDPE bonding surface of the pinch-off portion becomes very thin, and in fact, there is little problem, but in a container requiring high strength like a fuel container, since the inner layer is generally The thickness of the HDPE will be set to be thicker, so there is a disadvantage that the fuel will easily penetrate through the bonding surface.
另一方面，專利文獻4及5之方法則是於HDPE中使耐綸6,66分散為層狀，藉由複合材料來形成單層容器。若依據本方法，不僅可以大致沿用以往用於製造HDPE容器的設備，而且可以藉由聚醯胺樹脂的層狀分散，賦予近似多層結構的阻隔性。又，由於構成在製造容器時產生之零碎材料和碎屑的樹脂材料，與構成容器的樹脂材料相同，因此與氟化處理容器不同，可以再利用作為回收材料、作為構成容器之材料。 On the other hand, in the methods of Patent Documents 4 and 5, in the HDPE, the nylon 6, 66 is dispersed in a layer form, and a single layer container is formed by a composite material. According to this method, not only the apparatus conventionally used for manufacturing HDPE containers but also the layered dispersion of the polyamide resin can impart a barrier property to the multilayer structure. Further, since the resin material constituting the scrap material and the scrap generated at the time of manufacturing the container is the same as the resin material constituting the container, unlike the fluorination treatment container, a material which is a recycled material and a constituent container can be reused.
然而，由於作為阻隔性樹脂所利用之耐綸6,66，其本身之阻隔性能並非十分優異，因此在對於阻隔性之要求逐漸嚴格的近年而言，性能不足之情形逐漸增加。又，為了使耐綸6,66的分散狀態接近理想以能表現良好的阻隔性能，必須嚴格控制成形加工條件，而亦多有無法適用於近年來容器形狀逐漸多樣化之情形。 However, since nylon 6 and 66 used as a barrier resin are not excellent in barrier properties per se, in the recent years in which the requirements for barrier properties are gradually strict, the situation of insufficient performance is gradually increasing. Further, in order to make the dispersion state of the nylon 6 and 66 close to the ideal to exhibit good barrier properties, it is necessary to strictly control the molding processing conditions, and many of them cannot be applied to the case where the shape of the container is gradually diversified in recent years.
又，若依據專利文獻6及7所揭示之替換耐綸6,66為使N-MXD6層狀分散之方法，則由於阻隔性樹脂其本身之性能大為優異，因此可以得到阻隔性能比使用耐綸6,66之容器更優異者。 Further, if the replacement of Nylon 6,66 as disclosed in Patent Documents 6 and 7 is a method of dispersing N-MXD6 layeredly, since the barrier resin itself is excellent in performance, it is possible to obtain barrier properties than use resistance. The container of nylon 6,66 is more excellent.
然而，對於阻隔性能之要求逐年嚴格，因而開始發生無法提供既滿足對於阻隔性能之嚴格要求，同時又具有優異強度之容器的情形。 However, the demand for barrier properties has been strict year by year, and thus it has not been possible to provide a container which is capable of satisfying the strict requirements for barrier properties while having excellent strength.
本發明之課題係提供一種聚乙烯系結構體，其可以滿足近年來對於阻隔性能之嚴格要求，且強度優異。 An object of the present invention is to provide a polyethylene-based structure which satisfies the stringent requirements for barrier properties in recent years and is excellent in strength.
本發明提供以下之聚乙烯系結構體。 The present invention provides the following polyethylene-based structure.
亦即一種聚乙烯系結構體，其係由含有聚乙烯(A)60~90質量%、酸改 性聚乙烯(B)5~35質量%、及含間亞二甲苯基之聚醯胺(C)5~35質量%之樹脂組成物構成之聚乙烯系結構體，其特徵為該含間亞二甲苯基之聚醯胺(C)於該結構體中分散為層狀，且酸改性聚乙烯(B)之酸價為5~30mg/g。 That is, a polyethylene-based structure, which is composed of polyethylene (A) containing 60 to 90% by mass, acid modified a polyethylene-based structure composed of a resin composition having 5 to 35% by mass of a polyethylene (B) and 5 to 35% by mass of a polydecylamine (C) containing m-xylylene group, which is characterized by The polymethylamine (C) of xylyl is dispersed in a layered form in the structure, and the acid value of the acid-modified polyethylene (B) is 5 to 30 mg/g.
本發明之聚乙烯系結構體係燃料或藥品之阻隔性能及氧氣等各種氣體之阻隔性能優異，更發揮實用層面之強度者。 The polyethylene-based structural system fuel of the present invention has excellent barrier properties and barrier properties of various gases such as oxygen, and is more effective in practical use.
1‧‧‧含間亞二甲苯基之聚醯胺 1‧‧‧metamethylene containing metaxylylene
2‧‧‧樹脂組成物 2‧‧‧Resin composition
圖1顯示實施例1所得之槽的側壁剖面之SEM照片。 Figure 1 shows an SEM photograph of a side wall section of the groove obtained in Example 1.
圖2顯示比較例2所得之槽的側壁剖面之SEM照片。 2 shows an SEM photograph of a side wall section of the groove obtained in Comparative Example 2.
以下針對本發明之一種實施形態來說明。 Hereinafter, an embodiment of the present invention will be described.
本發明之聚乙烯系結構體係由含有聚乙烯(A)、酸改性聚乙烯(B)、及含間亞二甲苯基之聚醯胺(C)之樹脂組成物所形成者。以下針對樹脂組成物所含有之此等各成分作詳細說明。 The polyethylene-based structural system of the present invention is formed of a resin composition containing polyethylene (A), acid-modified polyethylene (B), and meta-xylylene group-containing polyamine (C). Hereinafter, each component contained in the resin composition will be described in detail.
本發明所用之聚乙烯(A)係構成結構體之主材料。本發明所使用之聚乙烯(A)，從防止成為成形品厚度不均之原因的垂伸(draw down)之觀點、提升結構體本身的強度之觀點、及從掉落時或施加衝撃時之破損或裂痕等問題之觀點來看，較佳為將其熔融黏度、分子量、結晶性設為特定值者。 The polyethylene (A) used in the present invention constitutes a main material of the structure. The polyethylene (A) used in the present invention has a viewpoint of preventing drawdown which is a cause of uneven thickness of a molded article, a viewpoint of enhancing the strength of the structural body itself, and when dropping or applying a punch. From the viewpoint of problems such as breakage or cracks, it is preferred to set the melt viscosity, molecular weight, and crystallinity to specific values.
以成為聚乙烯的結晶性之指標者而言，可列舉密度。本發明所用之聚乙烯(A)之密度較佳為0.94~0.97g/cm3，更佳為0.943~0.965g/cm3，特佳為0.945~0.96g/cm3。若聚乙烯(A)之密度為0.94g/cm3以上，則結晶性變得充 分，變得無論結構體所收納之內容物的種類為何，均可保存。又，若密度為0.97g/cm3以下，則聚乙烯(A)不會如玻璃般脆化，可以發揮以結構體而言為實用的強度。 The density is an indicator of the crystallinity of polyethylene. The density of the polyethylene (A) used in the present invention is preferably from 0.94 to 0.97 g/cm 3 , more preferably from 0.943 to 0.965 g/cm 3 , particularly preferably from 0.945 to 0.96 g/cm 3 . When the density of the polyethylene (A) is 0.94 g/cm 3 or more, the crystallinity is sufficient, and it can be stored regardless of the type of the contents contained in the structure. Moreover, when the density is 0.97 g/cm 3 or less, the polyethylene (A) is not brittle like glass, and the strength which is practical for the structure can be exhibited.
以成為聚乙烯的熔融黏度及分子量之指標者而言，熔融流動速率(melt flow rate，MFR)為具代表性者。本發明所用之聚乙烯(A)之MFR，作為依據JIS K7210記載之方法所測定之值，較佳為0.1~1(g/10分、190℃、2.16kgt)，更佳為0.1~0.6(g/10分、190℃、2.16kgf)，進一步更佳為0.1~0.55(g/10分、190℃、2.16kgf)，最佳為0.15~0.40(g/10分、190℃、2.16kgf)。 The melt flow rate (MFR) is representative of the melt viscosity and molecular weight of polyethylene. The MFR of the polyethylene (A) used in the present invention is preferably 0.1 to 1 (g/10 minutes, 190 ° C, 2.16 kgt), more preferably 0.1 to 0.6 as a value measured according to the method described in JIS K7210 ( g/10 points, 190 ° C, 2.16 kgf), further preferably 0.1 to 0.55 (g/10 minutes, 190 ° C, 2.16 kgf), preferably 0.15 to 0.40 (g/10 minutes, 190 ° C, 2.16 kgf) .
一般而言，由於含間亞二甲苯基之聚醯胺的密度較聚乙烯大，摻合有含間亞二甲苯基之聚醯胺的聚乙烯，相較於僅由聚乙烯構成者，有成形加工時之垂伸變大的傾向。因此，本發明藉由使聚乙烯(A)之MFR為1以下，可以抑制成形加工時之垂伸的發生，進而使所得之結構體的厚度精度更為優異。又，若聚乙烯(A)之MFR為0.1以上，不但熔融黏度成為適合成形時之黏度，而且含間亞二甲苯基之聚醯胺(C)於構成所得之結構體的樹脂組成物中之分散狀態亦變得良好，結果可以得到阻隔性能優異之成形體。 In general, since m-xylylene-containing polyamide has a higher density than polyethylene, polyethylene blended with m-xylylene-containing polyamine is compared to polyethylene-only ones. The tendency of the drawdown during forming is increased. Therefore, in the present invention, by setting the MFR of the polyethylene (A) to 1 or less, it is possible to suppress the occurrence of the drawdown during the forming process, and further improve the thickness accuracy of the obtained structure. In addition, when the MFR of the polyethylene (A) is 0.1 or more, not only the melt viscosity is suitable for the viscosity at the time of molding, but also the metaxylylene group-containing polyamine (C) is in the resin composition constituting the obtained structure. The dispersed state also became good, and as a result, a molded body excellent in barrier properties was obtained.
再者，在無損於本發明之效果的範圍內，可於聚乙烯(A)添加抗氧化劑、消光劑、耐熱安定劑、耐候安定劑、紫外線吸收劑、晶核劑、塑化劑、阻燃劑、抗靜電劑、抗著色劑、潤滑劑等添加劑等，亦可混合不限於以上所示者之各種材料。又，聚乙烯(A)較佳為由高密度聚乙烯單體構成，而在無損於本發明之效果的範圍內，亦可包含低密度聚乙烯、中密度聚乙烯、直鏈狀低密度聚乙烯等其它的聚乙烯類、於聚乙烯類添加顏料之著色母料等。 Further, in the range which does not impair the effects of the present invention, an antioxidant, a matting agent, a heat stabilizer, a weathering stabilizer, an ultraviolet absorber, a crystal nucleating agent, a plasticizer, and a flame retardant may be added to the polyethylene (A). Additives such as an agent, an antistatic agent, an anti-coloring agent, and a lubricant may be mixed, and are not limited to the various materials shown above. Further, the polyethylene (A) is preferably composed of a high-density polyethylene monomer, and may also contain low-density polyethylene, medium-density polyethylene, and linear low-density polyethylene insofar as the effects of the present invention are not impaired. Other polyethylenes such as ethylene, color masterbatches for adding pigments to polyethylene, and the like.
本發明所用之酸改性聚乙烯(B)係以不飽和羧酸或其酐接枝改性聚乙烯者，一般而言係作為黏著性樹脂而廣泛使用。 The acid-modified polyethylene (B) used in the present invention is a graft-modified polyethylene with an unsaturated carboxylic acid or an anhydride thereof, and is generally used as an adhesive resin.
作為不飽和羧酸或其酐之具體例，可列舉丙烯酸、甲基丙烯酸、α-乙基丙烯酸、順丁烯二酸、反丁烯二酸、亞甲基丁二酸、甲基順丁烯二酸、四氫酞酸、氯順丁烯二酸、丁烯基丁二酸、及此等之酸酐。其中又以使用順 丁烯二酸及順丁烯二酸酐為較佳。作為於聚乙烯接枝共聚合上述不飽和羧酸或其酐來得到酸改性聚乙烯之方法，可以使用以往周知的各種方法。例如可列舉以擠製機等來熔融聚乙烯，並添加接枝單體而使其共聚合之方法；或者使聚乙烯溶解於溶劑中，並添加接枝單體而使其共聚合之方法；將聚乙烯製成水懸浮液後，添加接枝單體而使其共聚合之方法等。 Specific examples of the unsaturated carboxylic acid or its anhydride include acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, methylene succinic acid, and methylbutylene. Diacids, tetrahydrofurfuric acid, chloro-maleic acid, butenyl succinic acid, and anhydrides thereof. Which uses Butenedioic acid and maleic anhydride are preferred. As a method of graft-polymerizing the above-mentioned unsaturated carboxylic acid or its anhydride to polyethylene to obtain an acid-modified polyethylene, various conventionally known methods can be used. For example, a method of melting polyethylene by an extruder or the like and adding a graft monomer to copolymerize it, or a method of dissolving polyethylene in a solvent and adding a graft monomer to copolymerize it may be mentioned; After the polyethylene is made into an aqueous suspension, a graft monomer is added to copolymerize the same.
又，由於含間亞二甲苯基之聚醯胺(C)係比較硬的材料，因此若於結構體施加衝撃等，則易於界面發生龜裂或剝離，有損害結構體的強度或阻隔性之虞。因此，作為本發明所用之酸改性聚乙烯(B)，藉由利用具有密度較低、較柔軟之性質者，於緩和含間亞二甲苯基之聚醯胺(C)所造成之衝撃強度降低，並保持結構體之實用的強度之方面係為有效。 Further, since the m-xylylene group-containing polyamine (C) is a relatively hard material, if a punch or the like is applied to the structure, cracking or peeling at the interface is liable to occur, and the strength or barrier property of the structure is impaired. Hey. Therefore, as the acid-modified polyethylene (B) used in the present invention, the punching strength caused by the m-xylylene group-containing polydecylamine (C) is alleviated by utilizing a property having a lower density and a softer property. The aspect of lowering and maintaining the practical strength of the structure is effective.
從這種觀點來看，本發明所用之酸改性聚乙烯(B)之密度較佳為0.90~0.96g/cm3，更佳為0.905~0.945g/cm3，特佳為0.91~0.93g/cm3。只要酸改性聚乙烯(B)之密度為0.90g/cm3以上，則本發明之適宜的聚乙烯(A)與酸改性聚乙烯(B)之互溶性變得良好，進而提升含間亞二甲苯基之聚醯胺(C)的黏著性，而使結構體之強度或阻隔性變得優異。又，若酸改性聚乙烯(B)之密度為0.96g/cm3以下，則由於酸改性聚乙烯(B)具有適度的柔軟性，因此即使在施加衝擊於結構體之情形，亦可抑制招致強度或阻隔性降低之情形。 From this viewpoint, the acid-modified polyethylene (B) used in the present invention, the preferred density of 0.90 ~ 0.96g / cm 3, more preferably 0.905 ~ 0.945g / cm 3, particularly preferably 0.91 ~ 0.93g /cm 3 . When the density of the acid-modified polyethylene (B) is 0.90 g/cm 3 or more, the compatibility between the suitable polyethylene (A) of the present invention and the acid-modified polyethylene (B) becomes good, and the content of the mixture is improved. The adhesion of the xylylene polyamine (C) makes the strength or barrier property of the structure excellent. Further, when the density of the acid-modified polyethylene (B) is 0.96 g/cm 3 or less, since the acid-modified polyethylene (B) has moderate flexibility, even when an impact is applied to the structure, Suppresses situations in which strength or barrier properties are reduced.
本發明中，酸改性聚乙烯(B)具有黏著聚乙烯(A)與含間亞二甲苯基之聚醯胺(C)的作用。而且，茲認為在構成本發明之結構體的樹脂組成物中，含間亞二甲苯基之聚醯胺(C)係處於與酸改性聚乙烯(B)經酸改性之取代基作化學鍵結之狀態，其結果為含間亞二甲苯基之聚醯胺(C)存在於酸改性聚乙烯(B)的附近，且酸改性率之差異對黏著力作出極大貢獻。因此，本發明藉由將酸改性聚乙烯(B)之酸改性率調整為特定的範圍，可以大幅提升聚乙烯(A)與含間亞二甲苯基之聚醯胺(C)之黏著強度，其結果為大幅提升所得之結構體的阻隔性。 In the present invention, the acid-modified polyethylene (B) has a function of adhering polyethylene (A) to m-xylylene-containing polyamine (C). Further, it is considered that in the resin composition constituting the structure of the present invention, the metaxylylene group-containing polydecylamine (C) is in a chemical bond with the acid-modified substituent of the acid-modified polyethylene (B). As a result, the result is that m-xylylene group-containing polyamine (C) is present in the vicinity of the acid-modified polyethylene (B), and the difference in acid modification rate greatly contributes to the adhesion. Therefore, the present invention can greatly enhance the adhesion of the polyethylene (A) to the metaxylylene group-containing polyamine (C) by adjusting the acid modification ratio of the acid-modified polyethylene (B) to a specific range. The strength, as a result, greatly increases the barrier properties of the resulting structure.
以成為酸改性聚乙烯(B)的酸改性率之指標者而言，可列舉酸價，本發明中之酸價係依據JIS K0070記載之方法來測定。在本發明中，酸改性聚乙 烯(B)之酸價為5~30mg/g。 The acid value is an indicator of the acid modification rate of the acid-modified polyethylene (B), and the acid value in the present invention is measured in accordance with the method described in JIS K0070. In the present invention, acid modified polyethylene The acid value of the alkene (B) is 5 to 30 mg/g.
在本發明中，若酸改性聚乙烯(B)之酸價小於5mg/g，則樹脂組成物中的聚乙烯(A)與含間亞二甲苯基之聚醯胺(C)的黏著性變得不充分，而在兩者的黏著界面產生空隙，其結果為所得之結構體的阻隔性能降低，更有結構體之強度惡化之虞。又，若酸改性聚乙烯(B)之酸價大於30mg/g，則有成形加工時之垂伸變大，招致結構體之厚度精度和阻隔性的惡化之情形。 In the present invention, if the acid value of the acid-modified polyethylene (B) is less than 5 mg/g, the adhesion of the polyethylene (A) in the resin composition to the polymethyleneamine (C) containing m-xylylene group It becomes insufficient, and a void is generated at the adhesion interface between the two, and as a result, the barrier property of the obtained structure is lowered, and the strength of the structure is deteriorated. In addition, when the acid value of the acid-modified polyethylene (B) is more than 30 mg/g, the drawdown during the forming process is increased, which causes a deterioration in the thickness precision and the barrier property of the structure.
酸改性聚乙烯(B)之酸價更佳為10~30mg/g，特佳為15~25mg/g。藉由使酸價在這種範圍，可以不發生垂伸，而藉由少量的酸改性聚乙烯(B)提升阻隔性能或結構體之強度，尤其提升低溫下的結構體之強度。 The acid value of the acid-modified polyethylene (B) is preferably from 10 to 30 mg/g, particularly preferably from 15 to 25 mg/g. By setting the acid value in this range, it is possible to increase the barrier property or the strength of the structure by a small amount of the acid-modified polyethylene (B) without causing the drawdown, and particularly to increase the strength of the structure at a low temperature.
又，作為亦考慮含間亞二甲苯基之聚醯胺(C)之量的酸改性率之指標，則是將構成結構體之樹脂組成物中的酸改性聚乙烯(B)之酸價，換算為樹脂組成物中的含間亞二甲苯基之聚醯胺(C)的每單位質量之酸價所得之以下述式(1)所表示之值A。本發明中，若連值A亦進一步考慮，則由於可以因應黏著對象之含間亞二甲苯基之聚醯胺(C)的摻合量來摻合酸性基，易於調整黏著性能至適當程度而更佳。 In addition, as an index of the acid modification ratio in which the amount of the polymethyleneamine (C) containing m-xylylene group is also considered, the acid of the acid-modified polyethylene (B) in the resin composition constituting the structure is used. The valence is a value A represented by the following formula (1) obtained by converting the acid value per unit mass of the m-xylylene group-containing polydecylamine (C) in the resin composition. In the present invention, if the value A is further considered, since the acid group can be blended in accordance with the blending amount of the m-xylylene group-containing polyamine (C) to be adhered to the object, it is easy to adjust the adhesive property to an appropriate degree. Better.
A=A(b)×P(b)/P(c) (1) A=A(b)×P(b)/P(c) (1)
(上述式中，A(b)係酸改性聚乙烯(B)之酸價，P(b)係構成聚乙烯系結構體之樹脂組成物中的酸改性聚乙烯(B)之質量比例，P(c)係構成聚乙烯系結構體之樹脂組成物中的含間亞二甲苯基之聚醯胺(C)之質量比例。) (In the above formula, A(b) is the acid value of the acid-modified polyethylene (B), and P(b) is the mass ratio of the acid-modified polyethylene (B) in the resin composition constituting the polyethylene-based structure. P(c) is a mass ratio of m-xylylene group-containing polyamine (C) constituting the resin composition of the polyethylene-based structure.
亦即，值A係藉由將酸改性聚乙烯(B)之酸價〔A(b)〕乘以酸改性聚乙烯(B)在樹脂組成物中的質量比例〔P(b)〕，並將所得之值除以含間亞二甲苯基之聚醯胺(C)在樹脂組成物中的質量比例〔P(c)〕而算出。 That is, the value A is obtained by multiplying the acid value [A(b)] of the acid-modified polyethylene (B) by the mass ratio of the acid-modified polyethylene (B) in the resin composition [P(b)] The value obtained was calculated by dividing the mass ratio [P(c)] of the metaxylylene group-containing polyamine (C) in the resin composition.
在本發明中，值A之較佳數值為5~40mg/g，更佳為10~40mg/g，進一步更佳為20~40mg/g，特佳為25~40mg/g。藉由使上述值A為5mg/g以上，提升樹脂組成物中之聚乙烯(A)與含間亞二甲苯基之聚醯胺(C)的黏著性，並隨之提升結構體強度及阻隔性能。又，藉由使值A為40mg/g以下，變得更不易發生成形加工時之垂伸。此外，藉由為15~40mg/g，變得更易於減少黏著不足或垂伸。 In the present invention, the value of the value A is preferably 5 to 40 mg/g, more preferably 10 to 40 mg/g, still more preferably 20 to 40 mg/g, and particularly preferably 25 to 40 mg/g. By setting the above value A to 5 mg/g or more, the adhesion of the polyethylene (A) to the m-xylylene group-containing polyamine (C) in the resin composition is increased, and the strength and barrier of the structure are increased accordingly. performance. Moreover, when the value A is 40 mg/g or less, the drawdown during the forming process is less likely to occur. In addition, by 15 to 40 mg/g, it becomes easier to reduce the adhesion or the drawdown.
本發明所用之酸改性聚乙烯(B)之MFR，從成形加工安定性、保持結構體的強度之觀點來看，較佳為使用熔融黏度較高者。具體而言，作為依據JIS K7210記載之方法所測定之值，較佳為0.1~5(g/10分、190℃、2.16kgf)，更佳為0.3~4(g/10分、190℃、2.16kgf)，進一步更佳為0.5~3(g/10分、190℃、2.16kgf)，特佳為1.0~2(g/10分、190℃、2.16kgf)。 The MFR of the acid-modified polyethylene (B) used in the present invention is preferably one having a higher melt viscosity from the viewpoint of forming process stability and maintaining the strength of the structure. Specifically, the value measured by the method described in JIS K7210 is preferably 0.1 to 5 (g/10 minutes, 190 ° C, 2.16 kgf), more preferably 0.3 to 4 (g/10 minutes, 190 ° C, 2.16 kgf), further preferably 0.5 to 3 (g/10 minutes, 190 ° C, 2.16 kgf), particularly preferably 1.0 to 2 (g/10 minutes, 190 ° C, 2.16 kgf).
再者，在無損於本發明之效果的範圍內，可於酸改性聚乙烯(B)添加抗氧化劑、消光劑、耐熱安定劑、耐候安定劑、紫外線吸收劑、晶核劑、塑化劑、阻燃劑、抗靜電劑、抗著色劑、潤滑劑等添加劑等，亦可混合不限於以上所示者之各種材料。 Further, in the range which does not impair the effects of the present invention, an antioxidant, a matting agent, a heat stabilizer, a weathering stabilizer, a UV absorber, a crystal nucleating agent, a plasticizer may be added to the acid-modified polyethylene (B). Additives such as a flame retardant, an antistatic agent, an anti-coloring agent, a lubricant, etc., may be mixed, and are not limited to the various materials shown above.
本發明所用之含間亞二甲苯基之聚醯胺(C)係賦予提升結構體之阻隔性能的效果之材料。構成含間亞二甲苯基之聚醯胺的二胺單元，從氣體阻隔性之觀點來看，較佳為包含間亞二甲苯二胺單元70莫耳%以上，更佳為80莫耳%以上，進一步更佳為90莫耳%以上。 The m-xylylene group-containing polydecylamine (C) used in the present invention is a material which imparts an effect of improving the barrier properties of the structure. The diamine unit constituting the m-xylylene group-containing polyamine is preferably 70 mol% or more, more preferably 80 mol% or more, including m-xylylenediamine unit from the viewpoint of gas barrier properties. Further preferably more than 90% by mole.
作為間亞二甲苯二胺以外可使用之二胺，可例示對亞二甲苯二胺、1,3-雙(胺甲基)環己烷、1,4-雙(胺甲基)環己烷、四甲基二胺、六甲基二胺、九甲基二胺、2-甲基-1,5-戊二胺等，但不限於此等。 Examples of the diamine which can be used other than meta-xylylenediamine include p-xylylenediamine, 1,3-bis(aminomethyl)cyclohexane, and 1,4-bis(aminomethyl)cyclohexane. And tetramethyldiamine, hexamethyldiamine, nonamethyldiamine, 2-methyl-1,5-pentanediamine, etc., but are not limited thereto.
構成含間亞二甲苯基之聚醯胺(C)的二羧酸單元，從結晶性之觀點來看，較佳為包含α,ω-脂肪族二羧酸50莫耳%以上，更佳為60莫耳%以上，進一步更佳為70莫耳%以上。 The dicarboxylic acid unit constituting the m-xylylene group-containing polydecylamine (C) preferably contains 50 mol% or more of the α,ω-aliphatic dicarboxylic acid from the viewpoint of crystallinity, more preferably More than 60% by mole, and even more preferably 70% by mole or more.
作為α,ω-脂肪族二羧酸，可列舉辛二酸、己二酸、壬二酸、癸二酸、十二酸等，而從氣體阻隔性及結晶性之觀點來看，以使用己二酸和癸二酸為較佳。 Examples of the α,ω-aliphatic dicarboxylic acid include suberic acid, adipic acid, sebacic acid, sebacic acid, and dodecanoic acid, and from the viewpoint of gas barrier properties and crystallinity, Diacids and sebacic acids are preferred.
作為α,ω-脂肪族二羧酸以外之二羧酸單元，可例示1,3-環己烷二羧酸和1,4-環己烷二羧酸等脂環族二羧酸、對酞酸、間酞酸、鄰酞酸、亞二甲苯二羧酸、萘二羧酸等芳香族二羧酸等，但不限於此等。 Examples of the dicarboxylic acid unit other than the α,ω-aliphatic dicarboxylic acid include an alicyclic dicarboxylic acid such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and palladium. An aromatic dicarboxylic acid such as an acid, meta-antimonic acid, o-nonanoic acid, xylene dicarboxylic acid or naphthalene dicarboxylic acid, but is not limited thereto.
此等之中，又以間酞酸或2,6-萘二羧酸因為不會阻礙含間亞二甲苯基之 聚醯胺(C)製造時之聚縮合反應，且可以輕易地得到阻隔性優異之聚醯胺而較佳。間酞酸或2,6-萘二羧酸之含量，從聚乙烯系結構體中之含間亞二甲苯基之聚醯胺(C)的分散性及結構體的阻隔性之觀點來看，二羧酸單元較佳為30莫耳%以下，更佳為20莫耳%以下，進一步更佳為15莫耳%以下。 Among these, m-decanoic acid or 2,6-naphthalene dicarboxylic acid does not hinder the m-xylylene group. Polycondensation reaction in the production of polyamine (C) is preferable, and polyamine which is excellent in barrier property can be easily obtained. The content of the m-decanoic acid or the 2,6-naphthalenedicarboxylic acid is from the viewpoint of the dispersibility of the m-xylylene group-containing polyamine (C) in the polyethylene-based structure and the barrier property of the structure. The dicarboxylic acid unit is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 15 mol% or less.
又，除了上述二胺單元及二羧酸單元以外，作為構成含間亞二甲苯基之聚醯胺(C)的單元，在無損於本發明之效果的範圍內，亦可使用ε-己內醯胺或十二內醯胺等內醯胺類，己胺酸、胺十一酸等脂肪族胺基羧酸類，如對胺基甲基苯甲酸之芳香族胺基羧酸等作為共聚合單元。 Further, in addition to the above-mentioned diamine unit and dicarboxylic acid unit, as a unit constituting the metaxylylene group-containing polydecylamine (C), ε-内内 may be used within a range not impairing the effects of the present invention. An internal amine such as decylamine or dodecylamine, an aliphatic aminocarboxylic acid such as hexamic acid or amine undecanoic acid, such as an aromatic aminocarboxylic acid such as p-aminomethylbenzoic acid; .
含間亞二甲苯基之聚醯胺(C)可藉由熔融聚縮合法(熔融聚合法)來製造。例如有於水存在下，在加壓下加溫由二胺與二羧酸構成之耐綸鹽，在去除添加之水及縮合水的同時，於熔融狀態下使其聚合之方法。又，亦可藉由於熔融狀態的二羧酸直接添加二胺而聚縮合之方法來製造。在此情形，為了使反應系統保持均勻的液體狀態，會於二羧酸連續地添加二胺，且在這期間，以反應溫度不低於生成的寡醯胺及聚醯胺之熔點的方式加溫反應系統，而進行聚縮合。 The metaxylylene group-containing polyamine (C) can be produced by a melt polycondensation method (melt polymerization method). For example, in the presence of water, a nylon salt composed of a diamine and a dicarboxylic acid is heated under pressure, and the added water and the condensed water are removed while being polymerized in a molten state. Further, it can also be produced by a method of polycondensation by directly adding a diamine to a dicarboxylic acid in a molten state. In this case, in order to maintain the reaction system in a uniform liquid state, the diamine is continuously added to the dicarboxylic acid, and during this period, the reaction temperature is not lower than the melting point of the produced oligoamine and polyamine. The reaction system is warmed and polycondensation is carried out.
為了得到在含間亞二甲苯基之聚醯胺(C)之聚縮合系統內促進醯胺化反應之效果、或防止聚縮合時的著色之效果，亦可添加含磷原子之化合物。 In order to obtain the effect of promoting the oximation reaction in the polycondensation system of the m-xylylene group-containing polydecylamine (C) or to prevent the coloration during the polycondensation, a compound containing a phosphorus atom may be added.
作為含磷原子之化合物，可列舉二甲基次膦酸、苯甲基次膦酸、次亞磷酸、次亞磷酸鈉、次亞磷酸鉀、次亞磷酸鋰、次亞磷酸乙酯、苯基亞膦酸、苯基亞膦酸鈉、苯基亞膦酸鉀、苯基亞膦酸鋰、苯基亞膦酸乙酯、苯基膦酸、乙基膦酸、苯基膦酸鈉、苯基膦酸鉀、苯基膦酸鋰、苯基膦酸二乙酯、乙基膦酸鈉、乙基膦酸鉀、亞磷酸、亞磷酸氫鈉、亞磷酸鈉、亞磷酸三乙酯、亞磷酸三苯酯、焦亞磷酸等。此等之中，尤其以次亞磷酸鈉、次亞磷酸鉀、次亞磷酸鋰等次亞磷酸金屬鹽因為促進醯胺化反應之效果高，且抗著色效果亦優異而較佳使用，特佳為次亞磷酸鈉，但在本發明可使用的含磷原子之化合物並不限於此等化合物。 Examples of the phosphorus atom-containing compound include dimethylphosphinic acid, benzylphosphinic acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, ethyl hypophosphite, and phenyl. Phosphite, sodium phenylphosphinate, potassium phenylphosphinate, lithium phenylphosphinate, ethyl phenylphosphinate, phenylphosphonic acid, ethylphosphonic acid, sodium phenylphosphonate, benzene Potassium phosphinate, lithium phenylphosphonate, diethyl phenylphosphonate, sodium ethylphosphonate, potassium ethylphosphonate, phosphorous acid, sodium hydrogen phosphite, sodium phosphite, triethyl phosphite, sub Triphenyl phosphate, pyrophosphoric acid, and the like. Among these, a metal hypophosphite such as sodium hypophosphite, potassium hypophosphite or lithium hypophosphite is preferred because it has a high effect of promoting the amidation reaction and is excellent in anti-coloring effect. The compound containing a phosphorus atom, but a phosphorus atom-containing compound which can be used in the present invention is not limited to these compounds.
在含間亞二甲苯基之聚醯胺(C)的聚縮合系統內添加的含磷原子之化合物的添加量，從防止聚縮合中的含間亞二甲苯基之聚醯胺(C)的著色之觀點來看，以含間亞二甲苯基之聚醯胺(C)中之磷原子濃度換算較佳為1~500ppm、更佳為5~450ppm、進一步更佳為10~400ppm。 The amount of the phosphorus atom-containing compound added in the polycondensation system of the m-xylylene group-containing polyamine (C) is from the prevention of the m-xylylene group-containing polyamine (C) in the polycondensation. From the viewpoint of coloring, the concentration of the phosphorus atom in the polymethyleneamine (C) containing m-xylylene group is preferably from 1 to 500 ppm, more preferably from 5 to 450 ppm, still more preferably from 10 to 400 ppm.
在含間亞二甲苯基之聚醯胺(C)的聚縮合系統內，較佳為與含磷原子之化合物併用而添加鹼金屬化合物或鹼土金屬化合物。為了防止聚縮合中的含間亞二甲苯基之聚醯胺(C)的著色而必須存在足夠量的含磷原子之化合物，而為了調整醯胺化反應速度，亦以共存鹼金屬化合物或鹼土金屬化合物為較佳。 In the polycondensation system of the m-xylylene group-containing polyamine (C), it is preferred to use an alkali metal compound or an alkaline earth metal compound in combination with a compound containing a phosphorus atom. In order to prevent the coloration of the m-xylylene group-containing polyamine (C) in the polycondensation, a sufficient amount of the compound containing a phosphorus atom must be present, and in order to adjust the rate of the amidation reaction, a coexisting alkali metal compound or alkaline earth is also used. Metal compounds are preferred.
例如可列舉氫氧化鋰、氫氧化鈉、氫氧化鉀、氫氧化銣、氫氧化銫、氫氧化鎂、氫氧化鈣、氫氧化鋇等鹼金屬/鹼土金屬之氫氧化物，或乙酸鋰、乙酸鈉、乙酸鉀、乙酸銣、乙酸銫、乙酸鎂、乙酸鈣、乙酸鋇等鹼金屬/鹼土金屬之乙酸鹽等，而可不限於此等化合物地使用。 For example, an alkali metal/alkaline earth hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, barium hydroxide, magnesium hydroxide, calcium hydroxide or barium hydroxide, or lithium acetate or acetic acid may be mentioned. An alkali metal/alkaline earth metal acetate such as sodium, potassium acetate, barium acetate, barium acetate, magnesium acetate, calcium acetate or barium acetate, and the like, and is not limited to such a compound.
在含間亞二甲苯基之聚醯胺(C)的聚縮合系統內添加鹼金屬化合物或鹼土金屬化合物之情形，將該化合物的莫耳數除以含磷原子之化合物的莫耳數得到之值較佳為0.5~2.0，更佳為0.6~1.8，進一步更佳為0.7~1.5。藉由使鹼金屬化合物或鹼土金屬化合物之添加量在上述範圍，變得可以在得到含磷原子之化合物所致醯胺化反應促進效果的同時，抑制凝膠之生成。 In the case where an alkali metal compound or an alkaline earth metal compound is added to a polycondensation system of m-xylylene group-containing polyamine (C), the molar number of the compound is divided by the molar number of the compound containing a phosphorus atom. The value is preferably from 0.5 to 2.0, more preferably from 0.6 to 1.8, still more preferably from 0.7 to 1.5. When the amount of the alkali metal compound or the alkaline earth metal compound added is in the above range, it is possible to suppress the formation of the gel while obtaining the effect of promoting the amidation reaction by the compound containing a phosphorus atom.
熔融聚縮合所得之含間亞二甲苯基之聚醯胺(C)先取出並丸粒化後，可乾燥而使用。又，亦可為了進一步提升聚合度而進行固相聚合。作為乾燥乃至固相聚合所用之加熱裝置，可適當使用連續式之加熱乾燥裝置、或稱為轉筒式乾燥機、錐形乾燥機、旋轉式乾燥機等之轉桶式的加熱裝置、以及稱為瑙塔混合機之於內部具備旋翼之圓錐型的加熱裝置，但不限於此等，可使用周知的方法、裝置。尤其在進行聚醯胺之固相聚合之情形，上述裝置之中，以轉桶式的加熱裝置因為可以密閉化系統內部、且在去除著色原因之氧氣的狀態下易於進行聚縮合而較理想。 The m-xylylene group-containing polydecylamine (C) obtained by melt-condensation is first taken out and pelletized, and then dried and used. Further, solid phase polymerization may be carried out in order to further increase the degree of polymerization. As a heating device for drying or solid phase polymerization, a continuous heating and drying device, or a rotary drum type heating device called a tumble dryer, a conical dryer, a rotary dryer, or the like can be suitably used. The Nauta mixer is a cone-shaped heating device having a rotor inside, but is not limited thereto, and a well-known method and apparatus can be used. In particular, in the case of performing solid phase polymerization of polyamine, among the above-described apparatuses, a rotary drum type heating device is preferable because it is possible to seal the inside of the system and to easily perform polycondensation in a state where oxygen is removed for coloring.
作為含間亞二甲苯基之聚醯胺的聚合度之指標有數種選擇，而相對黏 度為一般使用者。本發明所用之含間亞二甲苯基之聚醯胺(C)之相對黏度較佳為2.5~4.5，更佳為3.0~4.3，最佳為3.5~4.2。含間亞二甲苯基之聚醯胺(C)係隨著相對黏度變高而變得不易與聚乙烯(A)互溶化，且變得易於形成層狀分散狀態。然而，若欲提升含間亞二甲苯基之聚醯胺(C)之相對黏度，則聚合時間變長、製造成本增加。藉由使含間亞二甲苯基之聚醯胺(C)之相對黏度設定為上述範圍，可以形成良好的層狀分散狀態，且可以壓低製造成本。 As an indicator of the degree of polymerization of m-xylylene-containing polydecylamine, there are several choices, and the relative viscosity Degree is for general users. The relative viscosity of the m-xylylene group-containing polyamine (C) used in the present invention is preferably from 2.5 to 4.5, more preferably from 3.0 to 4.3, most preferably from 3.5 to 4.2. The metaxylylene group-containing polyamine (C) is less likely to be mutually soluble with polyethylene (A) as the relative viscosity becomes higher, and it becomes easy to form a layered dispersion state. However, if the relative viscosity of the m-xylylene group-containing polyamine (C) is to be increased, the polymerization time becomes long and the production cost increases. By setting the relative viscosity of the m-xylylene group-containing polyamine (C) to the above range, a favorable layered dispersion state can be formed, and the production cost can be reduced.
此外，在此所說的相對黏度，係將聚醯胺1g溶解於96%硫酸100mL中，且以坎農芬斯克(Cannon-Fenske)型黏度計於25℃測定之掉落時間(t)，與同樣地測定之96%硫酸本身的掉落時間(t0)之比，以下式表示。 In addition, the relative viscosity referred to herein is 1 g of polyamido dissolved in 100 mL of 96% sulfuric acid, and the drop time (t) measured at 25 ° C by a Cannon-Fenske type viscometer. The ratio of the drop time (t0) of 96% sulfuric acid itself measured in the same manner is represented by the following formula.
相對黏度=t/t0．．．(2) Relative viscosity = t / t0. . . (2)
又，本發明所使用之含間亞二甲苯基之聚醯胺(C)，從結構體的外觀及阻隔性之觀點來看，GPC所測定之數量平均分子量1000以下的成分較佳為2質量%以下，更佳為1.5質量%以下，進一步更佳為1質量%以下。為了得到這種含間亞二甲苯基之聚醯胺(C)，較佳為將以熔融聚縮合所製造者，藉由熱水洗淨、真空乾燥或固相聚合來進行寡聚物之去除。 Further, the metaxylylene group-containing polydecylamine (C) used in the present invention preferably has a mass average molecular weight of 1,000 or less and a mass of 2 or less as measured by GPC from the viewpoint of the appearance and barrier properties of the structure. % or less is more preferably 1.5% by mass or less, still more preferably 1% by mass or less. In order to obtain such m-xylylene group-containing polyamine (C), it is preferred to carry out the removal of the oligomer by hot water washing, vacuum drying or solid phase polymerization, which is produced by melt polycondensation. .
在無損於本發明之效果的範圍內，可於含間亞二甲苯基之聚醯胺(C)添加抗氧化劑、消光劑、耐熱安定劑、耐候安定劑、紫外線吸收劑、晶核劑、塑化劑、阻燃劑、抗靜電劑、抗著色劑、潤滑劑、抗凝膠化劑等添加劑、層狀矽酸鹽等黏土或奈米填料等。又，以含間亞二甲苯基之聚醯胺(C)之改質(modification)為目的，亦可因應需要而添加耐綸6或耐綸66、將芳香族二羧酸作為單體而利用之非晶耐綸等各種聚醯胺或其改性樹脂、聚烯烴或其改性樹脂、於骨架中具有苯乙烯之彈性體等。又，亦可混合不限於以上所示者之各種材料。 In the range which does not impair the effects of the present invention, an antioxidant, a matting agent, a heat stabilizer, a weathering stabilizer, a UV absorber, a crystal nucleating agent, a plastic may be added to the metaxylylene group-containing polydecylamine (C). Additives such as chemicals, flame retardants, antistatic agents, anti-colorants, lubricants, anti-gelling agents, clays such as layered niobates, or nano fillers. Further, for the purpose of modification of the m-xylylene group-containing polyamine (C), nylon 6 or nylon 66 may be added as needed, and the aromatic dicarboxylic acid may be used as a monomer. Various polyamines such as amorphous nylon or modified resins thereof, polyolefins or modified resins thereof, elastomers having styrene in the skeleton, and the like. Further, it is also possible to mix various materials not limited to those shown above.
構成本發明之結構體的各材料之摻合比率係聚乙烯(A)為60~90質量%、酸改性聚乙烯(B)為5~35質量%、含間亞二甲苯基之聚醯胺(C)為5~ 35質量%。較佳為聚乙烯(A)為65~90質量%、酸改性聚乙烯(B)為5~30質量%、含間亞二甲苯基之聚醯胺(C)為5~30質量%，更佳為聚乙烯(A)為70~90質量%、酸改性聚乙烯(B)為5~25質量%、含間亞二甲苯基之聚醯胺(C)為5~25質量%。惟(A)~(C)之3成分的合計不會大於100質量%。藉由使各材料之摻合比率設定為上述範圍，可以有效率地提升結構體之阻隔性能，且可使結構體之強度降低保持於最低限度。本發明之結構體較佳為由聚乙烯(A)、酸改性聚乙烯(B)、及含間亞二甲苯基之聚醯胺(C)之3成分構成。 The blending ratio of each of the materials constituting the structure of the present invention is 60 to 90% by mass of polyethylene (A), 5 to 35% by mass of acid-modified polyethylene (B), and polymethylene containing metaxylylene group. Amine (C) is 5~ 35 mass%. Preferably, the polyethylene (A) is 65 to 90% by mass, the acid-modified polyethylene (B) is 5 to 30% by mass, and the m-xylylene group-containing polyamine (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 m-xylylene group-containing polyamine (C) is 5 to 25% by mass. However, the total of the three components (A) to (C) is not more than 100% by mass. By setting the blending ratio of each material to the above range, the barrier property of the structure can be efficiently improved, and the strength reduction of the structure can be kept to a minimum. The structure of the present invention is preferably composed of three components of polyethylene (A), acid-modified polyethylene (B), and meta-xylylene group-containing polyamine (C).
又，在使用更高酸價(10~30mg/g或15~25mg/g)之酸改性聚乙烯(B)之情形，構成本發明之結構體的各材料之摻合比率特佳為聚乙烯(A)為70~90質量%、酸改性聚乙烯(B)為5~20質量%、含間亞二甲苯基之聚醯胺(C)為5~20質量%。高酸價之酸改性聚乙烯(B)比較容易發生垂伸，但藉由減少摻合量變得不易發生垂伸。又，由於高酸價之酸改性聚乙烯(B)能以少量得到高度的黏著性能改善效果，所以即使少量亦可明顯提升阻隔性能，能以低成本獲得高性能之結構體。 Further, in the case of using an acid-modified polyethylene (B) having a higher acid value (10 to 30 mg/g or 15 to 25 mg/g), the blending ratio of each of the materials constituting the structure of the present invention is particularly preferable. The ethylene (A) is 70 to 90% by mass, the acid-modified polyethylene (B) is 5 to 20% by mass, and the m-xylylene group-containing polyamine (C) is 5 to 20% by mass. The acid-modified polyethylene (B) having a high acid value is more likely to cause a drawdown, but it is less likely to cause a drawdown by reducing the blending amount. Further, since the acid-modified polyethylene (B) having a high acid value can obtain a high adhesion improving effect in a small amount, even a small amount can significantly improve the barrier property, and a high-performance structure can be obtained at low cost.
此外，在無損於本發明之效果的範圍內，除了上述材料以外，亦可於樹脂組成物添加以丙烯均聚物、乙烯-丙烯嵌段共聚物、乙烯-丙烯無規共聚物等為代表之聚丙烯類；聚丁烯-1、聚甲基戊烯等碳原子數3~20的α-烯烴之單獨聚合物；碳原子數3~20的α-烯烴之共聚物；碳原子數3~20的α-烯烴與環狀烯烴之共聚物；離子聚合物；乙烯-丙烯酸乙酯共聚物或乙烯-丙烯酸甲酯共聚物等各種改性聚乙烯；聚苯乙烯；聚對酞酸乙二酯等各種聚酯；耐綸6或耐綸66等各種聚醯胺；苯乙烯-丁二烯共聚物或其氫化物；各種熱塑性彈性體等，可混合不限於以上所示者之各種材料。 Further, in addition to the above materials, a propylene homopolymer, an ethylene-propylene block copolymer, an ethylene-propylene random copolymer or the like may be added to the resin composition insofar as the effects of the present invention are not impaired. Polypropylene; single polymer of α-olefin having 3 to 20 carbon atoms such as polybutene-1 and polymethylpentene; copolymer of α-olefin having 3 to 20 carbon atoms; carbon number 3~ a copolymer of an α-olefin and a cyclic olefin of 20; an ionic polymer; various modified polyethylenes such as an ethylene-ethyl acrylate copolymer or an ethylene-methyl acrylate copolymer; polystyrene; polyethylene terephthalate Various polyesters such as nylon 6 or nylon 66; styrene-butadiene copolymer or a hydride thereof; various thermoplastic elastomers and the like can be mixed and are not limited to the various materials shown above.
本發明之聚乙烯系結構體係中空成形體，更具體而言係瓶狀、槽狀、桶狀、杯狀、盤狀、管狀等，較佳為槽、管、桶或瓶之形狀，係藉由吹塑法等周知的成形方法所成形者。又，該結構體為瓶狀、槽狀、桶狀等之容 器之情形，該結構體較佳為藉由直接吹塑法來製造。 The hollow molded body of the polyethylene structural system of the present invention is more specifically a bottle shape, a trough shape, a barrel shape, a cup shape, a disk shape, a tubular shape or the like, and is preferably in the shape of a groove, a tube, a barrel or a bottle. It is formed by a known molding method such as a blow molding method. Moreover, the structure is in the form of a bottle, a groove, a barrel, or the like. In the case of a device, the structure is preferably manufactured by direct blow molding.
關於直接吹塑法，例如結構體為單層容器之情形，可列舉使用具備擠製機、連接器、圓筒模具、合模裝置、鑄模、冷卻裝置之成形裝置，將聚乙烯(A)、酸改性聚乙烯(B)、含間亞二甲苯基之聚醯胺(C)、視情形而言粉碎成形品所得之粉碎物乾摻後之混合材料投入擠製機而熔融混練。經熔融混練者通過連接器、圓筒模具而擠製成為筒狀(有稱為型坯之情形)，於擠製成為適當長度之時機以鑄模夾起，朝型坯內送入空氣而使其膨脹、緊貼於經冷卻之鑄模內，冷卻後，打開鑄模而取出經成形之容器之方法。 In the direct blow molding method, for example, in the case where the structure is a single-layered container, a polyethylene (A), a polyethylene (A), and a molding apparatus including an extruder, a connector, a cylindrical mold, a mold clamping device, a mold, and a cooling device are used. The acid-modified polyethylene (B), the m-xylylene group-containing polyamine (C), and, if appropriate, the pulverized product obtained by pulverizing the molded product, are mixed and put into an extruder to be melt-kneaded. The melt-kneader is extruded into a cylindrical shape (in the case of a parison) through a connector or a cylindrical mold, and is clamped by a mold at a timing of being extruded into an appropriate length, and air is introduced into the parison to cause it to be introduced into the parison. The method of expanding and adhering to the cooled mold, cooling, and then opening the mold to take out the formed container.
含間亞二甲苯基之聚醯胺(C)於結構體中分散為層狀，且該分散之含間亞二甲苯基之聚醯胺(C)，亦可部分連續而形成連續相。分散為層狀之含間亞二甲苯基之聚醯胺(C)較佳為成為於結構體之厚度方向與其它的樹脂成分交互存在般之分散狀態。又，於結構體中，含間亞二甲苯基之聚醯胺(C)較佳為配置成外側多於結構體之厚度中心。此外，結構體通常係由包含上述成分(A)~(C)之樹脂組成物所形成之單層結構所構成者。 The m-xylylene group-containing polyamine (C) is dispersed in a layer in the structure, and the dispersed m-xylylene group-containing polyamine (C) may be partially continuous to form a continuous phase. The polymethyleneamine (C) containing the m-xylylene group dispersed in a layer form is preferably in a dispersed state in which the thickness direction of the structure interacts with other resin components. Further, in the structure, the metaxylylene group-containing polyamine (C) is preferably disposed such that the outer side is more than the thickness center of the structure. Further, the structure is usually composed of a single layer structure comprising a resin composition of the above components (A) to (C).
又，本發明中之聚乙烯系結構體，其厚度較佳為0.5mm以上，更佳為大於1.5mm，最佳為大於2.5mm。又，厚度較佳為10mm以下，更佳為5mm以下者。 Further, the polyethylene-based structure of the present invention preferably has a thickness of 0.5 mm or more, more preferably more than 1.5 mm, and most preferably more than 2.5 mm. Further, the thickness is preferably 10 mm or less, more preferably 5 mm or less.
本發明中即使因為使用高酸價之酸改性聚乙烯(B)而發生厚度不均，藉由使厚度成為如上述般較厚者，不易發生厚度不均所致之阻隔性能降低、強度降低、外觀不良等。此外，厚度係於容器一半的高度水平切斷，測定前後左右4處之厚度而算出平均值者。 In the present invention, even if thickness is uneven due to the use of the acid-modified polyethylene (B) having a high acid value, and the thickness is made thick as described above, the barrier property due to thickness unevenness is less likely to occur, and the strength is lowered. , poor appearance, etc. Further, the thickness was cut at a height level of half of the container, and the thickness was measured at four places before, after, and after, and the average value was calculated.
製造本發明之結構體時所使用之擠製機可適用周知者，而從具有適度的混練性，且即使於高樹脂壓力下亦可安定擠製之觀點來看，以使用單軸擠製機為較佳。單軸擠製機之螺旋軸通常係由用於運送原料至擠製機前端的供給部、用於完全熔融經吸熱軟化之樹脂的壓縮部、用於控制吐出量的計量部之3種部位所構成。本發明中只要是一般的螺旋軸即可無限制地使用，而從防止含間亞二甲苯基之聚醯胺(C)過度分散之觀點來看，以使用沒 有稱為DULMAGE或MADDOCK之混練部位，一般稱為全螺紋之螺旋軸為較佳。此外，為了易於控制含間亞二甲苯基之聚醯胺(C)之分散狀態，螺旋軸以使用壓縮部較短之急壓縮型者為更佳。作為急壓縮型之全螺紋螺旋軸，以螺旋軸全體之螺距數(螺桿旋轉1次為1個螺距)為100之情形，較佳為選擇供給部為40~60、壓縮部為5~20、計量部為30~50者，更佳為供給部為45~55、壓縮部為10~15、計量部為35~45者。此外，螺距間距離為任意即可。又，亦可利用部分的螺桿數為2根之稱為雙螺桿螺旋軸者。 The extruder used in the manufacture of the structure of the present invention can be applied to a well-known person, and from the viewpoint of having moderate kneadability and stable extrusion even under high resin pressure, a uniaxial extruder is used. It is better. The screw shaft of the uniaxial extruder usually consists of a supply portion for conveying the raw material to the front end of the extruder, a compression portion for completely melting the resin which is softened by heat absorption, and a measuring portion for controlling the discharge amount. Composition. In the present invention, as long as it is a general screw axis, it can be used without limitation, and from the viewpoint of preventing excessive dispersion of m-xylylene group-containing polyamine (C), There is a kneading part called DULMAGE or MADDOCK, which is generally referred to as a full-threaded screw shaft. Further, in order to easily control the dispersion state of the m-xylylene group-containing polyamine (C), it is more preferable that the screw axis is a short compression type using a compression portion. In the case of the full-thread screw shaft of the sudden compression type, the number of pitches of the entire screw shaft (one pitch of the screw rotation) is 100, preferably 40 to 60 for the supply portion and 5 to 20 for the compression portion. The measuring unit is 30 to 50, and more preferably, the supply unit is 45 to 55, the compression unit is 10 to 15, and the measurement unit is 35 to 45. In addition, the distance between the pitches may be any. Further, a part of the number of screws having two screws may be used as a twin-screw screw shaft.
又，為了保持以螺旋軸之剪力分散為層狀之含間亞二甲苯基之聚醯胺(C)的狀態，亦以不設置通常設置於擠製機頭內之碎料板(breaker plate)為較佳。有因碎料板所挖出之微孔而使於擠製機內分散為層狀之含間亞二甲苯基之聚醯胺(C)被切斷且微分散化之可能性。 Further, in order to maintain the state of the m-xylylene group-containing polyamine (C) dispersed in the layered shape by the shearing force of the screw axis, the breaker plate which is usually provided in the extrusion head is not provided. ) is better. There is a possibility that the m-xylylene group-containing polyamine (C) dispersed in a layered state in the extruder is cut and finely dispersed due to the micropores excavated by the particle board.
作為於擠製機內少量成分之樹脂分散於多量成分之樹脂中之一般行為，首先於擠製機內，樹脂全體藉由接受來自加熱器之熱而軟化。其次重複所謂由於螺旋軸旋轉所致之剪應力而熔融，少量成分之樹脂因剪應力而延伸，若進一步承受剪應力則切斷為層狀(=分散)、均勻地分散於全體(=分配)之行為，而細微均勻地混練於多量成分中。 As a general behavior in which a resin of a small amount of components in an extruder is dispersed in a resin of a plurality of components, first, in the extruder, the entire resin is softened by receiving heat from a heater. Next, the so-called shear stress due to the rotation of the screw shaft is repeated and melted, and the resin of a small amount of the component is extended by the shear stress, and if it is further subjected to the shear stress, it is cut into a layer shape (=dispersion) and uniformly dispersed throughout (=distribution). The behavior is finely and evenly mixed in a large amount of ingredients.
本發明之結構體為了有效地提升阻隔性能，必須使含間亞二甲苯基之聚醯胺(C)分散為層狀，為此必須在樹脂丸粒於上述擠製機內因剪應力而延伸為層狀之狀態時自擠製機前端吐出。作為用於實現其之方法，主要可列舉降低螺旋軸轉速之方法、與將擠製機溫度設定調整為最佳化之方法。降低螺旋軸轉速之方法乍看之下係容易的方法，然而由於有招致生產效率降低、招致因型坯長時間曝露於空氣所致之容器強度降低之虞，其利用範圍有所限制。這種情形以使用控制擠製機內之樹脂溫度之方法為較佳。具體而言，較佳為於擠製機內以使材料熔融混練時之樹脂溫度成為含間亞二甲苯基之聚醯胺(C)之熔點±20℃之溫度範圍的方式，調節擠製機之溫度來進行。更佳為熔點±15℃之溫度範圍，進一步更佳為熔點±10℃。樹脂溫度較佳為採用測定實際自擠製機前端吐出之樹脂的實際溫度者，而在對於藉由設置於擠製機前端部之熱電偶所測量之數字、與樹脂的實際溫度之間的差異已有初步了解之情形，亦可參考該數值來調整。藉由以含間亞二甲苯基 之聚醯胺(C)之熔點-20℃以上之樹脂溫度來進行熔融混練，含間亞二甲苯基之聚醯胺(C)充分軟化，可防止未熔融之丸粒混入成形品，或造成擠製機馬達過度負荷。又，藉由設為熔點+20℃以下之樹脂溫度，可防止含間亞二甲苯基之聚醯胺(C)不完全熔解而因螺旋軸旋轉所致之剪應力而過度分散，且即使於結構體中亦可保持樹脂組成物中的層狀之分散狀態，使結構體之阻隔性為良好。 In order to effectively improve the barrier property, the structure of the present invention must disperse the m-xylylene group-containing polyamine (C) into a layer. Therefore, it is necessary to extend the resin pellet in the above-mentioned extruder due to shear stress. In the layered state, it is spouted from the front end of the extruder. As a method for realizing the method, a method of reducing the number of revolutions of the screw shaft and a method of optimizing the temperature setting of the extruder are mainly mentioned. The method of lowering the rotation speed of the screw shaft is an easy method at first glance. However, the utilization range is limited due to the decrease in the production efficiency and the decrease in the strength of the container due to the long exposure of the parison to the air. In this case, it is preferred to use a method of controlling the temperature of the resin in the extruder. Specifically, it is preferred to adjust the extrusion machine in a manner that the temperature of the resin when the material is melt-kneaded into a temperature range of ±20 ° C of the melting point of the m-xylylene group-containing polyamine (C) in the extruder The temperature is carried out. More preferably, it is a temperature range of ±15 ° C, and still more preferably a melting point of ± 10 ° C. The resin temperature is preferably determined by measuring the actual temperature of the resin ejected from the front end of the actual self-extrusion machine, and the difference between the number measured by the thermocouple disposed at the front end portion of the extruder and the actual temperature of the resin. If you have a preliminary understanding, you can also adjust it by referring to this value. M-xylylene The polydecylamine (C) has a melting point of -20 ° C or higher and is melt-kneaded, and the m-xylylene group-containing polyamine (C) is sufficiently softened to prevent the unmelted pellets from being mixed into the molded article or caused The extruder motor is overloaded. Further, by setting the resin temperature of the melting point + 20 ° C or lower, it is possible to prevent the metaxylylene group-containing polydecylamine (C) from being excessively melted and excessively dispersed due to the shear stress caused by the rotation of the helical axis, and even if The layered dispersion state in the resin composition can also be maintained in the structure, and the barrier property of the structure is good.
依據本發明之方法所得之結構體可採用瓶狀、杯狀、盤狀、槽狀、桶狀等之容器、毛細管、管等各種形狀。又，相較於以往商品，由於變得可以更有效地抑制汽油或燈油、輕油等燃料、機油、煞車油等潤滑油、漂白劑、清潔劑、洗髮精等各種清潔用品、乙醇、雙氧水等各種化學藥品、蔬菜汁或乳類飲料等各種飲料、調味料等各種物品、或者包含於其中之成分之穿透，因此可以有效地利用作為提升物品保存性者。 The structure obtained by the method of the present invention may be in various shapes such as a bottle, a cup, a disk, a groove, a barrel, or the like, a capillary tube, a tube, or the like. In addition, compared with the conventional products, it is possible to more effectively suppress various cleaning products such as gasoline, kerosene, light oil, fuels such as fuel oil, engine oil, and brake oil, bleach, detergent, shampoo, etc., ethanol, and hydrogen peroxide. Various kinds of articles such as various chemicals, vegetable juices, and milk beverages, such as various beverages and seasonings, or penetration of components contained therein, can be effectively utilized as a preservative for improving articles.
以下藉由實施例來進一步詳細說明本發明。此外，於實施例等中之各種評價係依據下述方法來進行。 The invention will now be described in further detail by way of examples. Further, various evaluations in the examples and the like were carried out in accordance with the following methods.
使用東洋精機製作所製MELT INDEXER，依據JIS K7210，以190℃、2.16kgf之條件進行測定。 The MELT INDEXER manufactured by Toyo Seiki Seisakusho Co., Ltd. was measured at 190 ° C and 2.16 kgf in accordance with JIS K7210.
使用由擠製機、T模、冷卻輥、牽引機等構成之薄片成形裝置，成形厚度為約1mm之單層薄片。其次自薄片切割長50mm×寬50mm之試驗片，藉由真比重計來求出真比重。 A single-layer sheet having a thickness of about 1 mm is formed using a sheet forming apparatus composed of an extruder, a T-die, a cooling roll, a tractor, or the like. Next, a test piece having a length of 50 mm and a width of 50 mm was cut from the sheet, and the true specific gravity was obtained by a true hydrometer.
依據JIS K0070，藉由中和滴定來進行測定。精確稱量酸改性聚乙烯1g，於二甲苯100mL中以約120℃攪拌溶解。完全溶解後，添加酚酞溶液， 使用預先求得正確濃度之0.1mol/L氫氧化鉀乙醇溶液來進行中和滴定。藉由式(3)從滴定量(T)、0.1mol/L氫氧化鉀乙醇溶液之因數(f)、氫氧化鉀之式量56.11之1/10(5.611)、酸改性聚乙烯之質量(S)算出酸價。 The measurement was carried out by neutralization titration in accordance with JIS K0070. 1 g of the acid-modified polyethylene was accurately weighed and dissolved by stirring at about 120 ° C in 100 mL of xylene. After completely dissolved, add phenolphthalein solution, Neutralization titration was carried out using a 0.1 mol/L potassium hydroxide ethanol solution of the correct concentration previously determined. By the formula (3) from the titration (T), 0.1 mol / L potassium hydroxide ethanol solution factor (f), potassium hydroxide formula amount of 56.11 1/10 (5.611), the quality of acid-modified polyethylene (S) Calculate the acid value.
酸價=T×f×5.611/S．．．(3) Acid value = T × f × 5.611 / S. . . (3)
精確稱量含間亞二甲苯基之聚醯胺1g，於96%硫酸100mL以20~30℃攪拌溶解。完全溶解後，迅速地量取溶液5ml於坎農芬斯克型黏度計，於25℃之恆溫槽中放置10分鐘後，測定掉落時間(t)。又以同樣的條件測定96%硫酸本身之掉落時間(t0)。藉由式(2)從t及t0算出相對黏度。 1 g of metaxylamine containing m-xylylene was accurately weighed and dissolved in 100 mL of 96% sulfuric acid at 20 to 30 ° C. After completely dissolving, 5 ml of the solution was quickly weighed into a Cannon Fenske type viscometer, and after standing in a thermostat at 25 ° C for 10 minutes, the drop time (t) was measured. The dropping time (t0) of 96% sulfuric acid itself was measured under the same conditions. The relative viscosity is calculated from t and t0 by the formula (2).
相對黏度=t/t0．．．(2) Relative viscosity = t / t0. . . (2)
於實施例及比較例所製作之容器加入模擬汽油(甲苯/異辛烷/乙醇=45/45/10vol%)400ml後，以鋁箔密封口蓋開口部，再蓋上蓋子，測定總質量並記錄。其次，將封入模擬汽油之容器保管於溫度調整為40℃之防爆型恆溫槽，每24小時記錄總質量。當質量減少速度安定時倒出容器內之模擬汽油，立刻再度重新封入模擬汽油，同樣地繼續測定。重量減少量之部分相當於穿透之模擬汽油量。將模擬汽油穿透量除以容器之表面積0.0429m2來求出模擬汽油穿透率(g/m2．day)。 After adding 400 ml of simulated gasoline (toluene/isooctane/ethanol = 45/45/10 vol%) to the container prepared in the examples and the comparative examples, the opening of the flap was sealed with an aluminum foil, and the lid was closed, and the total mass was measured and recorded. Next, the container sealed with simulated gasoline was stored in an explosion-proof type thermostatic bath whose temperature was adjusted to 40 ° C, and the total mass was recorded every 24 hours. When the quality of the speed is reduced, the simulated gasoline in the container is poured out, and the simulated gasoline is immediately re-sealed, and the measurement is continued in the same manner. The amount of weight reduction is equivalent to the amount of simulated gasoline that is penetrated. The model gasoline permeation rate divided by the surface area of 0.0429m 2 vessel obtains a model gasoline transmittance (g / m 2 .day).
於實施例及比較例所製作之容器填充水400ml後關閉蓋子，於23℃之恆溫室調整溫度4小時後，使容器之底面朝下，自2m之高度連續30次掉落至水泥地上，計數5個容器之中，於試驗中破損之容器數。 After the container made in the examples and the comparative examples was filled with water 400 ml, the lid was closed, and the temperature was adjusted in a constant temperature chamber at 23 ° C for 4 hours, and then the bottom surface of the container was turned downward, and dropped from the height of 2 m 30 times to the concrete floor, and counted. Among the five containers, the number of containers that were damaged during the test.
於實施例及比較例所製作之容器填充不凍液400m1後關閉蓋子，於-20℃之恆溫室調整溫度4小時後，使容器之底面朝下，自2m之高度連續30次掉落至水泥地上，計數5個容器之中，於試驗中破損之容器數。 After the container made in the examples and the comparative examples was filled with the antifreeze 400 m1, the lid was closed, and the temperature was adjusted in a constant temperature chamber at -20 ° C for 4 hours, and then the bottom surface of the container was turned down, and dropped to the concrete floor 30 times in succession from a height of 2 m. Count the number of containers that were damaged during the test among the five containers.
切斷成形之槽，並利用微切片機(REICHERT-JUNG LIMITED製，商品名：ULTRACUT E)使剖面平滑後，於剖面塗布稀碘酊(月島藥品股份有限公司製)來染色含間亞二甲苯基之聚醯胺部分。利用蒸鍍裝置(日立製作所(股)製，商品名：E102)於其蒸鍍Pt-Pd後，藉由SEM(日立製作所(股)製、商品名：S-4800)觀察樹脂組成物中之聚乙烯(A)與含間亞二甲苯基之聚醯胺(C)的界面之狀態。 The formed groove was cut, and the cross section was smoothed by a microtome (manufactured by REICHERT-JUNG LIMITED, trade name: ULTRACUT E), and the mixture was coated with dilute iodine (manufactured by Yuedo Pharmaceutical Co., Ltd.) to dye the m-xylylene group. The polyamine moiety. After the Pt-Pd was vapor-deposited by a vapor deposition apparatus (manufactured by Hitachi, Ltd., trade name: E102), the resin composition was observed by SEM (manufactured by Hitachi, Ltd., trade name: S-4800). The state of the interface between the polyethylene (A) and the m-xylylene group-containing polyamine (C).
HDPE-1：日本聚乙烯(股)製，商品名：Novatec HD HB420R，MFR=0.2，密度=0.956g/cm3 HDPE-1: Japanese polyethylene (stock), trade name: Novatec HD HB420R, MFR = 0.2, density = 0.956 g / cm 3
HDPE-2：日本聚乙烯(股)製，商品名：Novatec HD HB439R，MFR=0.55，密度=0.96g/cm3 HDPE-2: made of Japanese polyethylene (stock), trade name: Novatec HD HB439R, MFR=0.55, density=0.96g/cm 3
AD-1：三井化學(股)製，商品名：Admer AT2490，MFR=0.3，密度=0.923g/cm3，酸價19.0mg/g AD-1: Mitsui Chemicals Co., Ltd., trade name: Admer AT2490, MFR=0.3, density=0.923g/cm 3 , acid value 19.0mg/g
AD-2：日本聚乙烯(股)製，商品名：ADTX L6100M，MFR=1.1，密度=0.92g/cm3，酸價9.8mg/g AD-2: Japanese polyethylene (stock), trade name: ADTX L6100M, MFR = 1.1, density = 0.92g / cm 3 , acid price 9.8mg / g
AD-3：三井化學(股)製，商品名：Admer NB550，MFR=0.9，密度=0.92g/cm3，酸價3.2mg/g AD-3: Mitsui Chemicals Co., Ltd., trade name: Admer NB550, MFR=0.9, density=0.92g/cm 3 , acid value 3.2mg/g
PA-1：三菱瓦斯化學(股)製，商品名：MX Nylon S6121，相對黏度3.5，熔點238℃ PA-1: Mitsubishi Gas Chemical Co., Ltd., trade name: MX Nylon S6121, relative viscosity 3.5, melting point 238 ° C
PA-2：三菱瓦斯化學(股)製，商品名：MX Nylon S7007，相對黏度2.6，熔點229℃ PA-2: Mitsubishi Gas Chemical Co., Ltd., trade name: MX Nylon S7007, relative viscosity 2.6, melting point 229 ° C
使用具備50mm單軸擠製機、連接器、附有型坯控制器之圓筒模具、鑄模、合模機、冷卻器等之單層直接吹塑容器成形裝置，朝擠製機進料斗內投入以HDPE-1/AD-1/PA-1=80/10/10(質量%)之比例乾摻之混合丸粒，設定擠製機料筒溫度為210~235℃、連接器溫度為235℃、模具溫度為230℃，使螺旋軸轉速為30rpm而擠製型坯，藉由直接吹塑法進行內容積450ml、平均厚度3mm之附有螺口蓋之槽的成形。 Use a single-layer direct blown container forming device with a 50mm uniaxial extruder, a connector, a cylindrical mold with a parison controller, a mold, a mold clamping machine, a cooler, etc., and put it into the hopper of the extruder Mix the pellets in a ratio of HDPE-1/AD-1/PA-1=80/10/10 (% by mass), set the barrel temperature of the extruder to 210~235°C, and the connector temperature to 235°C. The mold temperature was 230 ° C, and the parison was extruded at a screw shaft rotation speed of 30 rpm, and a groove having a screw cap with an inner volume of 450 ml and an average thickness of 3 mm was formed by a direct blow molding method.
針對所得之槽，實施模擬汽油之穿透率測定及掉落試驗。將結果示於表1。又，將槽側壁剖面之SEM影像示於圖1(觀察倍率5000倍)。圖中，斜向橫斷中央者為含間亞二甲苯基之聚醯胺(C)，將其夾住者為聚乙烯(A)。 For the obtained tank, the penetration rate measurement and the drop test of the simulated gasoline were carried out. The results are shown in Table 1. Further, the SEM image of the sidewall cross section of the groove is shown in Fig. 1 (the observation magnification is 5000 times). In the figure, the center of the oblique cross is the metaxylylene group-containing polyamine (C), and the holder is polyethylene (A).
除了使聚乙烯(A)、酸改性聚乙烯(B)、含間亞二甲苯基之聚醯胺(C)之種類、摻合量如表1所示般變更以外，與實施例1同樣地進行附有螺口蓋之槽的成形。 The same as in Example 1 except that the type of polyethylene (A), the acid-modified polyethylene (B), and the m-xylylene group-containing polyamine (C) and the blending amount were changed as shown in Table 1. The formation of the groove with the screw cap is performed.
針對所得之槽，實施模擬汽油之穿透率測定及掉落試驗。將結果示於表1。 For the obtained tank, the penetration rate measurement and the drop test of the simulated gasoline were carried out. The results are shown in Table 1.
除了僅使用聚乙烯(A)以外，與實施例1同樣地進行附有螺栓之槽的成形。 The molding of the groove with the bolt was carried out in the same manner as in Example 1 except that only the polyethylene (A) was used.
針對所得之槽，實施模擬汽油之穿透率測定及掉落試驗。將結果示於表1。 For the obtained tank, the penetration rate measurement and the drop test of the simulated gasoline were carried out. The results are shown in Table 1.
除了使聚乙烯(A)、酸改性聚乙烯(B)之種類、摻合量如表1所示般變更以外，與實施例1同樣地進行附有螺栓之槽的成形。 The molding of the groove with the bolt was carried out in the same manner as in Example 1 except that the type of the polyethylene (A) and the acid-modified polyethylene (B) and the blending amount were changed as shown in Table 1.
針對所得之槽，實施模擬汽油之穿透率測定及掉落試驗。將結果示於表1。又，將比較例2所得之槽側壁剖面之SEM影像示於圖2(觀察倍率5000倍)。圖中，斜向橫斷中央者為含間亞二甲苯基之聚醯胺(C)，將其夾住者為聚乙烯(A)。 For the obtained tank, the penetration rate measurement and the drop test of the simulated gasoline were carried out. The results are shown in Table 1. Further, the SEM image of the cross section of the groove side wall obtained in Comparative Example 2 is shown in Fig. 2 (the observation magnification is 5000 times). In the figure, the center of the oblique cross is the metaxylylene group-containing polyamine (C), and the holder is polyethylene (A).
本發明之聚乙烯系結構體於所有實施例中顯示優異之模擬汽油阻隔性。又，所得之結構體之掉落強度優異，且完全未發生室溫掉落時之容器破損。代表各實施例，以SEM觀察實施例1所得之結構體的容器側壁之剖面(圖1)。其結果證實於樹脂組成物中，聚乙烯(A)與含間亞二甲苯基之聚醯胺(C)之界面為緊貼，界面之黏著性為良好。 The polyethylene-based structure of the present invention exhibited excellent simulated gasoline barrier properties in all of the examples. Further, the obtained structure had excellent drop strength, and the container was not damaged at the time of room temperature drop. Representative of each example, the cross section of the container side wall of the structure obtained in Example 1 was observed by SEM (Fig. 1). As a result, it was confirmed that the interface between the polyethylene (A) and the m-xylylene group-containing polyamine (C) was in close contact with the resin composition, and the adhesion at the interface was good.
另一方面，僅由高密度聚乙烯構成之比較例1雖然掉落強度優異，卻為模擬汽油阻隔性低劣者。 On the other hand, Comparative Example 1 composed only of high-density polyethylene was excellent in drop strength, but was inferior in simulating gasoline barrier properties.
其次，關於低酸價之比較例2，針對所得之結構體之容器側壁之剖面，與實施例1同樣以SEM觀察(圖2)，結果由於聚乙烯(A)與含間亞二甲苯基之聚醯胺(C)之黏著性不佳，發生了界面剝離，因此造成模擬汽油阻隔性降低，並且頻繁發生低溫掉落時之容器破損。又，關於比較例3，雖然由於酸改性聚乙烯(B)之添加量大於比較例2，因此模擬汽油阻隔性及掉落強度相較於比較例2已有改善，但若與各實施例比較則為低劣。 Next, with respect to Comparative Example 2 having a low acid value, the cross section of the container side wall of the obtained structure was observed by SEM in the same manner as in Example 1 (Fig. 2), and as a result, polyethylene (A) and m-xylylene group were contained. The adhesiveness of the polyamine (C) is poor, and interfacial peeling occurs, so that the barrier property of the simulated gasoline is lowered, and the container is frequently broken when the temperature is dropped. Further, in Comparative Example 3, since the addition amount of the acid-modified polyethylene (B) was larger than that of Comparative Example 2, the simulated gasoline barrier property and the drop strength were improved as compared with Comparative Example 2, but The comparison is inferior.
本發明之聚乙烯系結構體係燃料或藥品之阻隔性能及氧氣等各種氣體之阻隔性能優異，更發揮實用層面之強度者。本發明之聚乙烯系結構體可適宜地利用於割草機或鏈鋸等作業機械、機車或船外馬達、汽車等之燃料槽、汽油輸送用管或安裝於燃料槽之管狀零件、農藥或化妝用品、清潔用清潔劑、各種化學藥品之容器、食品或飲料等之容器等。 The polyethylene-based structural system fuel of the present invention has excellent barrier properties and barrier properties of various gases such as oxygen, and is more effective in practical use. The polyethylene-based structure of the present invention can be suitably used for a working machine such as a lawn mower or a chain saw, a locomotive or an outboard motor, a fuel tank of an automobile or the like, a gasoline conveying pipe, a tubular part attached to a fuel tank, a pesticide or Cosmetics, cleaning detergents, containers for various chemicals, containers for foods or beverages, etc.
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