JP4922606B2 - Multi-layer hollow container - Google Patents
Multi-layer hollow container Download PDFInfo
- Publication number
- JP4922606B2 JP4922606B2 JP2005350412A JP2005350412A JP4922606B2 JP 4922606 B2 JP4922606 B2 JP 4922606B2 JP 2005350412 A JP2005350412 A JP 2005350412A JP 2005350412 A JP2005350412 A JP 2005350412A JP 4922606 B2 JP4922606 B2 JP 4922606B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- weight
- ethylene
- less
- hollow container
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000010410 layer Substances 0.000 claims description 186
- 229920000573 polyethylene Polymers 0.000 claims description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 42
- 229910052751 metal Inorganic materials 0.000 claims description 42
- 239000002184 metal Substances 0.000 claims description 42
- 230000004888 barrier function Effects 0.000 claims description 37
- 238000010828 elution Methods 0.000 claims description 37
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 35
- 239000005977 Ethylene Substances 0.000 claims description 35
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 229920000642 polymer Polymers 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 21
- 238000005452 bending Methods 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000012790 adhesive layer Substances 0.000 claims description 19
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 11
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 10
- 229920001903 high density polyethylene Polymers 0.000 claims description 8
- 239000004700 high-density polyethylene Substances 0.000 claims description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims 2
- 230000003405 preventing effect Effects 0.000 claims 1
- 239000004711 α-olefin Substances 0.000 description 28
- 238000000465 moulding Methods 0.000 description 25
- 239000000047 product Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- -1 polyethylene Polymers 0.000 description 13
- 239000002685 polymerization catalyst Substances 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 11
- 239000000155 melt Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 10
- 230000002265 prevention Effects 0.000 description 10
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 9
- 239000004611 light stabiliser Substances 0.000 description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000005856 abnormality Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 101001095088 Homo sapiens Melanoma antigen preferentially expressed in tumors Proteins 0.000 description 7
- 102100037020 Melanoma antigen preferentially expressed in tumors Human genes 0.000 description 7
- 239000004840 adhesive resin Substances 0.000 description 7
- 229920006223 adhesive resin Polymers 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 229910021642 ultra pure water Inorganic materials 0.000 description 7
- 239000012498 ultrapure water Substances 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 230000003749 cleanliness Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 4
- 230000001143 conditioned effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 4
- 239000011990 phillips catalyst Substances 0.000 description 4
- 150000003623 transition metal compounds Chemical class 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000004380 ashing Methods 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 2
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 230000002528 anti-freeze Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GKHRLTCUMXVTAV-UHFFFAOYSA-N dimoracin Chemical compound C1=C(O)C=C2OC(C3=CC(O)=C(C(=C3)O)C3C4C(C5=C(O)C=C(C=C5O3)C=3OC5=CC(O)=CC=C5C=3)C=C(CC4(C)C)C)=CC2=C1 GKHRLTCUMXVTAV-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
Description
本発明は、エチレン系重合体を用いた多層中空容器に関し、詳しくは、成形加工性、耐久性に優れ、且つ耐衝撃性及び剛性のバランスに優れ、バリア性、透過防止性及び低溶出性に優れた多種多層積層体からなる中空容器に関する。 The present invention relates to a multilayer hollow container using an ethylene polymer. Specifically, it has excellent moldability, durability, and excellent balance of impact resistance and rigidity, and has barrier properties, permeation prevention properties and low elution properties. The present invention relates to a hollow container made of an excellent multi-layer laminate.
近年、大型容器分野では軽量化、省エネルギー化といった目的で製品容器のプラスチック化が活発に押し進められている。プラスチック材料としては、価格、強度、耐候性、耐薬品性及び環境問題といった観点からポリオレフィン樹脂が一般に用いられている。
ポリオレフィン樹脂の中でも、特にポリエチレンは、中空成形用樹脂として好適な樹脂であり、一般に比較的分子量分布が広く、溶融張力が大きく、均一延伸性が良好な材料として使用されている。
In recent years, in the large container field, plasticization of product containers has been actively promoted for the purpose of weight reduction and energy saving. As a plastic material, a polyolefin resin is generally used from the viewpoints of price, strength, weather resistance, chemical resistance and environmental problems.
Among polyolefin resins, polyethylene is particularly suitable as a resin for hollow molding, and is generally used as a material having a relatively wide molecular weight distribution, a large melt tension, and a good uniform stretchability.
大型容器の用途に最適な材料として、例えば、成形加工性や耐環境応力亀裂性（以下ＥＳＣＲともいう）に優れた極限粘度が３．１〜５．０、密度が０．９４０〜０．９６０ｇ／ｃｍ３の新規なエチレン・α−オレフィン共重合体であるエチレン共重合体（例えば、特許文献１参照。）などが提案されている。しかしながら、これらの高密度ポリエチレン等を単独で用いた場合、内溶液によっては、バリア性が十分でなく、ガス成分や液成分が透過するといったケースがあり、環境面や安全面で不十分なことがある。
また、特定のエチレン系共重合体を用いた、ＥＳＣＲ、耐衝撃性及び剛性のバランスに優れ、且つバリア性に優れた、最外層、バリア層、接着層及びバリ回収層とからなる中空成形品（例えば、特許文献２参照。）が開示されているが、内溶液への金属等の溶出等があり、更なる改良が求められている。
Also, a hollow molded article comprising an outermost layer, a barrier layer, an adhesive layer, and a burr recovery layer, which uses a specific ethylene copolymer and has an excellent balance of ESCR, impact resistance and rigidity, and excellent barrier properties. (For example, refer to Patent Document 2), however, there is elution of metals and the like into the inner solution, and further improvements are required.
本発明の目的は、上記問題点に鑑み、成形加工性、耐久性、耐衝撃性、剛性に優れ、且つバリア性、透過防止性及び容器内容液への金属溶出量が少ない低溶出性のポリオレフィン系樹脂を用いた多層中空容器を提供することにある。 In view of the above problems, an object of the present invention is a low-elution polyolefin having excellent molding processability, durability, impact resistance, rigidity, barrier properties, permeation-prevention properties, and a small amount of metal elution into a container liquid. It is to provide a multilayer hollow container using a resin.
本発明者は、上記目的を達成するために鋭意検討を重ねた結果、最内層に金属溶出性の低いエチレン系重合体材料を使用することにより、成形加工性、耐久性、耐衝撃性、剛性に優れ、且つバリア性、透過防止性及び容器内容液への金属溶出量が少ない低溶出性に優れたポリオレフィン系多層中空容器が得られることを見出し、本発明を完成した。 As a result of intensive studies in order to achieve the above object, the present inventor uses an ethylene polymer material having a low metal elution property as the innermost layer, thereby enabling molding processability, durability, impact resistance, and rigidity. It was found that a polyolefin-based multilayer hollow container excellent in the barrier property, permeation-preventing property, and low elution property with a small amount of metal elution into the container liquid was obtained, and the present invention was completed.
すなわち、本発明の第１の発明によれば、外側から最外層、バリ回収層、接着層、バリア層及び最内層の順に積層された多層中空容器であって、最外層が下記特性（１）〜（３）の条件を満足するエチレン系重合体からなり、最内層が下記特性（１）〜（３）の条件を満足し、鉄及びアルミニウム含有量が各々１０重量ｐｐｍ以下、鉄及びアルミニウム以外の金属の合計含有量が３００重量ｐｐｍ以下であり、且つステアリン酸カルシウム以外の添加剤を含まないエチレン系重合体からなり、層厚みの構成比が最外層１０〜３０％、バリ回収層３０〜６０％、接着層１〜１５％、バリア層１〜１５％、最内層２０〜５０％（ただし、全ての層厚み構成比の合計が１００％）であることで、透過防止性及び容器内容液への金属溶出量が少ないことを特徴とする多層中空容器が提供される。
特性（１）温度１９０℃、荷重２１．６ｋｇのメルトフローレートが０．０１〜１００ｇ／１０分
特性（２）密度が０．９４１ｇ／ｃｍ３以上０．９８０ｇ／ｃｍ３以下
特性（３）オルゼン曲げ剛性が６００ＭＰａ以上１３００ＭＰａ以下
That is, according to the first aspect of the present invention, the outermost layer, the burr collecting layer, the adhesive layer, the barrier layer, and the innermost layer are laminated in this order from the outer side, and the outermost layer has the following characteristics (1) It consists of an ethylene polymer that satisfies the conditions of (3), the innermost layer satisfies the conditions of the following characteristics (1) to (3), the iron and aluminum contents are each 10 wt ppm or less, other than iron and aluminum The total metal content is 300 ppm by weight or less and is composed of an ethylene-based polymer that does not contain any additive other than calcium stearate. The composition ratio of the layer thickness is 10-30% for the outermost layer, and the burr recovery layer is 30-60. %, Adhesive layer 1 to 15%, barrier layer 1 to 15%, innermost layer 20 to 50% (however, the total of all layer thickness composition ratios is 100%). Less metal elution Multilayer hollow container is provided, wherein.
Characteristics (1) Temperature 190 ° C., a melt flow rate of 0.01 to 100 g / 10 min characteristic of the load 21.6 kg (2) density of 0.941 g / cm 3 or more 0.980 g / cm 3 or less characteristic (3) Olsen Flexural rigidity is 600MPa or more and 1300MPa or less
また、本発明の第２の発明によれば、第１の発明において、バリア層が、エチレンビニルアルコール樹脂からなることを特徴とする多層中空容器が提供される。 According to a second aspect of the present invention, there is provided a multilayer hollow container according to the first aspect, wherein the barrier layer is made of an ethylene vinyl alcohol resin.
また、本発明の第３の発明によれば、第１又は２の発明において、接着層が、高密度ポリエチレンを不飽和カルボン酸又はその誘導体０．０１〜５重量％でグラフト変性したものであることを特徴とする多層中空容器が提供される。 According to the third invention of the present invention, in the first or second invention, the adhesive layer is obtained by graft-modifying high-density polyethylene with an unsaturated carboxylic acid or its derivative 0.01 to 5% by weight. A multilayer hollow container is provided.
また、本発明の第４の発明によれば、第１〜３のいずれかの発明において、最内層が、４０℃、１０００時間接触後の水への鉄溶出量が水に対して０．５重量ｐｐｂ以下であるエチレン系重合体で構成されることを特徴とする多層中空容器が提供される。 According to a fourth invention of the present invention, in any one of the first to third inventions, the innermost layer has an iron elution amount of 0.5% with respect to water after contact at 40 ° C. for 1000 hours. A multilayer hollow container comprising an ethylene-based polymer having a weight of ppb or less is provided.
また、本発明の第５の発明によれば、第１〜４のいずれかの発明において、最内層が、４０℃、１０００時間接触後の水へのアルミニウム溶出量が水に対して０．５重量ｐｐｂ以下であるエチレン系重合体で構成されることを特徴とする多層中空容器が提供される。 According to the fifth invention of the present invention, in any one of the first to fourth inventions, the innermost layer has an aluminum elution amount of 0.5% with respect to water after contact at 40 ° C. for 1000 hours. A multilayer hollow container comprising an ethylene-based polymer having a weight of ppb or less is provided.
本発明の多層中空容器は、最内層に金属溶出性の低いエチレン系重合体材料を使用し、成形加工性、耐久性、耐衝撃性、剛性に優れ、且つバリア性、透過防止性及び容器内容液への金属溶出量が少ないエチレン系重合体多層中空容器である。 The multilayer hollow container of the present invention uses an ethylene polymer material having a low metal elution property for the innermost layer, is excellent in molding processability, durability, impact resistance and rigidity, and has barrier properties, permeation prevention properties and container contents. This is an ethylene polymer multilayer hollow container with a small amount of metal elution into the liquid.
本発明の多層中空容器は、最外層、バリ回収層、接着層、バリア層及び最内層を含む多層中空容器である。以下各層の構成及び容器の特徴、用途等について詳細に説明する。 The multilayer hollow container of the present invention is a multilayer hollow container including an outermost layer, a burr recovery layer, an adhesive layer, a barrier layer, and an innermost layer. Hereinafter, the configuration of each layer, the characteristics of the container, the use, and the like will be described in detail.
１．多層中空容器を構成する層
（１）最外層
本発明の多層中空容器の最外層を形成するエチレン系重合体（Ａ）は、エチレン単独重合体、又は、エチレンと炭素数３〜２０のα−オレフィンとの共重合体で、α−オレフィン含有量が１０重量％以下であるエチレン・α−オレフィン共重合体である。ここで、エチレン・α−オレフィン共重合体におけるα−オレフィンは、炭素数が３〜２０、好ましくは３〜１５、より好ましくは３〜１０のα−オレフィンであり、具体的には、プロピレン、ブテン−１、３−メチルブテン−１、３−メチルペンテン−１、４−メチルペンテン−１、ヘキセン−１、オクテン−１、ペンテン−１、デセン−１、テトラデセン−１、ヘキサデセン−１、オクタデセン−１、エイコセン−１等が挙げられ、特に、ブテン−１、ヘキセン−１、が好ましい。これらα−オレフィンは１種のみでもよく、また２種以上が併用されていてもよい。更に、ビニルシクロヘキサンあるいはスチレン及びその誘導体などのビニル化合物も使用することができる。
また、エチレン・α−オレフィン共重合体中におけるα−オレフィンの含有量は、１０重量％以下、好ましくは０．１〜１０重量％であり、より好ましくは０．１〜５重量％である。α−オレフィンの含有量がこれより多くなると、エチレン・α−オレフィン共重合体の剛性が低下するなどして好ましくない。
1. Layer constituting multilayer hollow container (1) Outermost layer The ethylene-based polymer (A) forming the outermost layer of the multilayer hollow container of the present invention is an ethylene homopolymer or ethylene and an α- having 3 to 20 carbon atoms. An ethylene / α-olefin copolymer having an α-olefin content of 10% by weight or less. Here, the α-olefin in the ethylene / α-olefin copolymer is an α-olefin having 3 to 20, preferably 3 to 15, more preferably 3 to 10 carbon atoms, specifically, propylene, Butene-1, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, hexene-1, octene-1, pentene-1, decene-1, tetradecene-1, hexadecene-1, octadecene- 1, eicosene-1 and the like, and butene-1 and hexene-1 are particularly preferable. These α-olefins may be used alone or in combination of two or more. Furthermore, vinyl compounds such as vinylcyclohexane or styrene and derivatives thereof can also be used.
The content of α-olefin in the ethylene / α-olefin copolymer is 10% by weight or less, preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight. If the α-olefin content is higher than this, it is not preferable because the rigidity of the ethylene / α-olefin copolymer is lowered.
本発明の最外層を形成するエチレン系重合体（Ａ）は、下記の特性（１）〜（３）を満足する必要がある。
特性（１）メルトフローレート
本発明の最外層を形成するエチレン系重合体の温度１９０℃、荷重２．１６ｋｇのメルトフローレートは、０．０１〜１００ｇ／１０分、好ましくは０．０１〜８０ｇ／１０分、より好ましくは０．０１〜５０ｇ／１０分である。温度１９０℃、荷重２．１６ｋｇのメルトフローレートが０．０１ｇ／１０分未満であると、押し出し成形時に押し出し量が不足し、成形不安定な状態となり実用的では無い。また、１００ｇ／１０分を超えると押し出し成形時に中空体を形成するための溶融パリソン形成が溶融粘度不足のため不安定となり実用的では無い。温度１９０℃、荷重２．１６ｋｇのメルトフローレートは、エチレン系重合体の重合触媒の種類や重合時における重合温度や水素濃度の制御などの方法で調整することができる。
ここで、メルトフローレートはＪＩＳ−Ｋ７２１０に準拠して測定される値である。
The ethylene polymer (A) forming the outermost layer of the present invention needs to satisfy the following characteristics (1) to (3).
Characteristics (1) Melt Flow Rate The ethylene polymer forming the outermost layer of the present invention has a melt flow rate of 0.01 to 100 g / 10 min, preferably 0.01 to 80 g at a temperature of 190 ° C. and a load of 2.16 kg. / 10 minutes, more preferably 0.01 to 50 g / 10 minutes. When the melt flow rate at a temperature of 190 ° C. and a load of 2.16 kg is less than 0.01 g / 10 minutes, the amount of extrusion is insufficient at the time of extrusion molding, and the molding becomes unstable, which is not practical. On the other hand, if it exceeds 100 g / 10 min, formation of a melt parison for forming a hollow body during extrusion molding becomes unstable due to insufficient melt viscosity, which is not practical. The melt flow rate at a temperature of 190 ° C. and a load of 2.16 kg can be adjusted by a method such as control of the type of polymerization catalyst of the ethylene polymer, the polymerization temperature during the polymerization, and the hydrogen concentration.
Here, the melt flow rate is a value measured according to JIS-K7210.
特性（２）密度
本発明の最外層を形成するエチレン系重合体の密度は、０．９４１ｇ／ｃｍ３以上０．９８０ｇ／ｃｍ３以下、好ましくは０．９４１ｇ／ｃｍ３以上０．９７０ｇ／ｃｍ３以下である。密度が０．９４１ｇ／ｃｍ３未満であると、中空成形品の剛性不足が顕在化し、０．９８０ｇ／ｃｍ３を超えると衝撃性能が不足する。密度は、エチレン系重合体の重合触媒の種類やα−オレフィンの種類や含有量の制御などの方法で調整することができる。
ここで、密度は、ＪＩＳ−Ｋ７１１２に準拠し、ペレットを温度１６０℃の熱圧縮成形機により溶融後２５℃／分の速度で降温し厚み２ｍｍのシートを成形し、このシートを温度２３℃の室内で４８時間状態調節した後、密度勾配管に入れ密度を測定される値である。
Characteristics (2) Density The density of the ethylene-based polymer forming the outermost layer of the present invention, 0.941 g / cm 3 or more 0.980 g / cm 3 or less, preferably 0.941 g / cm 3 or more 0.970 g / cm 3 or less. When the density is less than 0.941 g / cm 3 , the lack of rigidity of the hollow molded article becomes obvious, and when it exceeds 0.980 g / cm 3 , the impact performance becomes insufficient. The density can be adjusted by a method such as control of the type of polymerization catalyst of the ethylene polymer, the type of α-olefin, and the content.
Here, the density is in accordance with JIS-K7112, and the pellet is melted by a hot compression molding machine at a temperature of 160 ° C. and then cooled at a rate of 25 ° C./minute to form a sheet having a thickness of 2 mm. It is a value in which the density is measured after being conditioned in a room for 48 hours and then placed in a density gradient tube.
特性（３）オルゼン曲げ剛性
本発明の最外層を形成するエチレン系重合体のオルゼン曲げ剛性は、６００ＭＰａ以上１３００ＭＰａ以下、好ましくは７００ＭＰａ以上１３００ＭＰａ以下、より好ましくは８００ＭＰａ以上１３００ＭＰａ以下である。オルゼン曲げ剛性が６００ＭＰａ未満であると、中空成形製品の剛性不足が顕在化し、１３００ＭＰａを超えると衝撃性能が不足する。オルゼン曲げ剛性は、エチレン系重合体の重合触媒の種類やα−オレフィンの種類や含有量の制御などの方法で調整することができる。
ここで、オルゼン曲げ剛性は、ＪＩＳ−Ｋ７１０６に準拠し、スパン間３０ｍｍ、つかみ部３０ｍｍ、全曲げモーメントが６ｋｇｆ・ｃｍの条件で６０℃／分で片持ち曲げ応力を測定することにより得られる値である。
Characteristic (3) Olsen bending stiffness The Olsen bending stiffness of the ethylene polymer forming the outermost layer of the present invention is 600 MPa to 1300 MPa, preferably 700 MPa to 1300 MPa, more preferably 800 MPa to 1300 MPa. When the Olsen bending rigidity is less than 600 MPa, the rigidity of the hollow molded product becomes insufficient, and when it exceeds 1300 MPa, the impact performance is insufficient. The Olsen bending stiffness can be adjusted by a method such as control of the type of polymerization catalyst of ethylene polymer, the type and content of α-olefin.
Here, Olsen bending stiffness is a value obtained by measuring cantilever bending stress at 60 ° C./min under the conditions of 30 mm between spans, 30 mm gripping part, and total bending moment of 6 kgf · cm in accordance with JIS-K7106. It is.
本発明の最外層に用いるエチレン系重合体（Ａ）は、チーグラー触媒、フィリップス触媒、メタロセン触媒等の公知の各種触媒を用いてエチレンを主として重合することにより得られる。例えば、一般的には、チタン、ジルコニウム等の遷移金属化合物、マグネシウム化合物からなるチーグラー触媒、酸化クロム系触媒を代表とするフィリップス触媒及びジルコニウム、ハフニウム、チタン等の遷移金属化合物に少なくとも１つのシクロペンタジエニル基又は置換シクロペンタジエニル基を有するメタロセン系触媒を重合触媒として重合することにより得られる。
重合に際しては、エチレンを単独で重合するか、又はエチレンと炭素数３〜１８のα−オレフィンから選ばれる１種又はそれ以上のコモノマーを所定の密度になるよう共重合することにより得られる。
The ethylene-based polymer (A) used for the outermost layer of the present invention can be obtained by mainly polymerizing ethylene using various known catalysts such as a Ziegler catalyst, a Phillips catalyst, and a metallocene catalyst. For example, in general, transition metal compounds such as titanium and zirconium, Ziegler catalysts composed of magnesium compounds, Phillips catalysts typified by chromium oxide-based catalysts, and transition metal compounds such as zirconium, hafnium, and titanium have at least one cyclopenta It can be obtained by polymerizing a metallocene catalyst having a dienyl group or a substituted cyclopentadienyl group as a polymerization catalyst.
In the polymerization, it is obtained by polymerizing ethylene alone or by copolymerizing ethylene and one or more comonomers selected from α-olefins having 3 to 18 carbon atoms so as to have a predetermined density.
（２）最内層
本発明の多層中空容器の最内層を形成するエチレン系重合体（Ｂ）は、エチレン単独重合体、又は、エチレンと炭素数３〜２０のα−オレフィンとの共重合体で、α−オレフィン含有量が１０重量％以下であるエチレン・α−オレフィン共重合体である。ここで、エチレン・α−オレフィン共重合体におけるα−オレフィンは、炭素数が３〜２０、好ましくは３〜１５、より好ましくは３〜１０のα−オレフィンであり、具体的には、プロピレン、ブテン−１、３−メチルブテン−１、３−メチルペンテン−１、４−メチルペンテン−１、ヘキセン−１、オクテン−１、ペンテン−１、デセン−１、テトラデセン−１、ヘキサデセン−１、オクタデセン−１、エイコセン−１等が挙げられ、特に、ブテン−１、ヘキセン−１、が好ましい。これらα−オレフィンは１種のみでもよく、また２種以上が併用されていてもよい。更に、ビニルシクロヘキサンあるいはスチレン及びその誘導体などのビニル化合物も使用することができる。
エチレン・α−オレフィン共重合体中におけるα−オレフィンの含有量は、１０重量％以下、好ましくは０．１〜１０重量％であり、より好ましくは０．１〜５重量％である。α−オレフィンの含有量がこれより多くなると、エチレン・α−オレフィン共重合体の剛性が低下するなどして好ましくない。
(2) Innermost layer The ethylene polymer (B) forming the innermost layer of the multilayer hollow container of the present invention is an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. , An ethylene / α-olefin copolymer having an α-olefin content of 10% by weight or less. Here, the α-olefin in the ethylene / α-olefin copolymer is an α-olefin having 3 to 20, preferably 3 to 15, more preferably 3 to 10 carbon atoms, specifically, propylene, Butene-1, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, hexene-1, octene-1, pentene-1, decene-1, tetradecene-1, hexadecene-1, octadecene- 1, eicosene-1 and the like, and butene-1 and hexene-1 are particularly preferable. These α-olefins may be used alone or in combination of two or more. Furthermore, vinyl compounds such as vinylcyclohexane or styrene and derivatives thereof can also be used.
The content of α-olefin in the ethylene / α-olefin copolymer is 10% by weight or less, preferably 0.1 to 10% by weight, and more preferably 0.1 to 5% by weight. If the α-olefin content is higher than this, it is not preferable because the rigidity of the ethylene / α-olefin copolymer is lowered.
本発明の最内層を形成するエチレン系重合体（Ｂ）は、下記の特性（１）〜（４）を満足する必要がある。
特性（１）メルトフローレート
本発明の最内層を形成するエチレン系重合体の温度１９０℃、荷重２．１６ｋｇのメルトフローレートは、０．０１〜１００ｇ／１０分、好ましくは０．０１〜８０ｇ／１０分、より好ましくは０．０１〜５０ｇ／１０分である。温度１９０℃、荷重２．１６ｋｇのメルトフローレートが０．０１ｇ／１０分未満であると、押し出し成形時に押し出し量が不足し、成形不安定な状態となり実用的では無い。また、１００ｇ／１０分を超えると押し出し成形時に中空体を形成するための溶融パリソン形成が溶融粘度不足のため不安定となり実用的では無い。温度１９０℃、荷重２．１６ｋｇのメルトフローレートは、エチレン系重合体の重合触媒の種類や重合時における重合温度や水素濃度の制御などの方法で調整することができる。
ここで、メルトフローレートはＪＩＳ−Ｋ７２１０に準拠して測定される値である。
Ethylene polymer to form the innermost layer (B) of the present invention, it is necessary to satisfy the following characteristics (1) to (4).
Characteristics (1) Melt Flow Rate The ethylene polymer forming the innermost layer of the present invention has a melt flow rate of 0.01 to 100 g / 10 min, preferably 0.01 to 80 g at a temperature of 190 ° C. and a load of 2.16 kg. / 10 minutes, more preferably 0.01 to 50 g / 10 minutes. When the melt flow rate at a temperature of 190 ° C. and a load of 2.16 kg is less than 0.01 g / 10 minutes, the amount of extrusion is insufficient at the time of extrusion molding, and the molding becomes unstable, which is not practical. On the other hand, if it exceeds 100 g / 10 min, formation of a melt parison for forming a hollow body during extrusion molding becomes unstable due to insufficient melt viscosity, which is not practical. The melt flow rate at a temperature of 190 ° C. and a load of 2.16 kg can be adjusted by a method such as control of the type of polymerization catalyst of the ethylene polymer, the polymerization temperature during the polymerization, and the hydrogen concentration.
Here, the melt flow rate is a value measured according to JIS-K7210.
特性（２）密度
本発明の最内層を形成するエチレン系重合体の密度は、０．９４１ｇ／ｃｍ３以上０．９８０ｇ／ｃｍ３以下、好ましくは０．９４１ｇ／ｃｍ３以上０．９７０ｇ／ｃｍ３以下である。密度が０．９４１ｇ／ｃｍ３未満であると、中空成形品の剛性不足が顕在化し、０．９８０ｇ／ｃｍ３を超えると衝撃性能が不足する。密度は、エチレン系重合体の重合触媒の種類やα−オレフィンの種類や含有量の制御などの方法で調整することができる。
ここで、密度は、ＪＩＳ−Ｋ７１１２に準拠し、ペレットを温度１６０℃の熱圧縮成形機により溶融後２５℃／分の速度で降温し厚み２ｍｍのシートを成形し、このシートを温度２３℃の室内で４８時間状態調節した後、密度勾配管に入れ密度を測定される値である。
Characteristics (2) Density Density of the ethylene-based polymer which forms the innermost layer of the present invention, 0.941 g / cm 3 or more 0.980 g / cm 3 or less, preferably 0.941 g / cm 3 or more 0.970 g / cm 3 or less. When the density is less than 0.941 g / cm 3 , the lack of rigidity of the hollow molded article becomes obvious, and when it exceeds 0.980 g / cm 3 , the impact performance becomes insufficient. The density can be adjusted by a method such as control of the type of polymerization catalyst of the ethylene polymer, the type of α-olefin, and the content.
Here, the density is in accordance with JIS-K7112, and the pellet is melted by a hot compression molding machine at a temperature of 160 ° C. and then cooled at a rate of 25 ° C./minute to form a sheet having a thickness of 2 mm. It is a value in which the density is measured after being conditioned in a room for 48 hours and then placed in a density gradient tube.
特性（３）オルゼン曲げ剛性
本発明の最内層を形成するエチレン系重合体のオルゼン曲げ剛性は、６００ＭＰａ以上１３００ＭＰａ以下、好ましくは７００ＭＰａ以上１３００ＭＰａ以下、より好ましくは８００ＭＰａ以上１３００ＭＰａ以下である。オルゼン曲げ剛性が６００ＭＰａ未満であると、中空成形製品の剛性不足が顕在化し、１３００ＭＰａを超えると衝撃性能が不足する。オルゼン曲げ剛性は、エチレン系重合体の重合触媒の種類やα−オレフィンの種類や含有量の制御などの方法で調整することができる。
ここで、オルゼン曲げ剛性は、ＪＩＳ−Ｋ７１０６に準拠し、スパン間３０ｍｍ、つかみ部３０ｍｍ、全曲げモーメントが６ｋｇｆ・ｃｍの条件で６０℃／分で片持ち曲げ応力を測定することにより得られる値である。
Characteristic (3) Olsen bending stiffness The Olsen bending stiffness of the ethylene polymer forming the innermost layer of the present invention is 600 MPa to 1300 MPa, preferably 700 MPa to 1300 MPa, more preferably 800 MPa to 1300 MPa. When the Olsen bending rigidity is less than 600 MPa, the rigidity of the hollow molded product becomes insufficient, and when it exceeds 1300 MPa, the impact performance is insufficient. The Olsen bending stiffness can be adjusted by a method such as control of the type of polymerization catalyst of ethylene polymer, the type and content of α-olefin.
Here, Olsen bending stiffness is a value obtained by measuring cantilever bending stress at 60 ° C./min under the conditions of 30 mm between spans, 30 mm gripping part, and total bending moment of 6 kgf · cm in accordance with JIS-K7106. It is.
特性（４）鉄及びアルミニウム含有量
本発明の最内層を形成するエチレン系重合体は、鉄及びアルミニウム含有量が１０重量ｐｐｍ以下、好ましくは５重量ｐｐｍ以下のものである。鉄及びアルミニウム含有量が１０重量ｐｐｍを超えると容器内容物への金属溶出が大きくなり、容器として好ましくない。
また、鉄及びアルミニウム以外の金属、例えば、ナトリウム、マグネシウム、ケイ素、カルシウム、バナジウム、ニッケル、銅、亜鉛、バリウムについても金属としての合計量が３００重量ｐｐｍ以下であることが好ましい。
Characteristic (4) Iron and Aluminum Content The ethylene polymer forming the innermost layer of the present invention has an iron and aluminum content of 10 ppm by weight or less, preferably 5 ppm by weight or less. If the iron and aluminum contents exceed 10 ppm by weight, metal elution into the container contents increases, which is not preferable as a container.
Further, the total amount of metals other than iron and aluminum, such as sodium, magnesium, silicon, calcium, vanadium, nickel, copper, zinc, and barium, is preferably 300 ppm by weight or less.
本発明の多層容器をクリーン容器として用いる場合は、最内層を形成するエチレン系重合体のアルミニウム含有量は、１重量ｐｐｍ以下が好ましく、より好ましくは０．５重量ｐｐｍ以下である。また、鉄含有量は、１重量ｐｐｍ以下が好ましく、より好ましくは０．５重量ｐｐｍ以下である。さらに、チタン含有量が１重量ｐｐｍ以下、マグネシウム含有量が１重量ｐｐｍ以下、クロム含有量が２０重量ｐｐｍ以下、ケイ素含有量が２５０重量ｐｐｍ以下のものがクリーン容器適性が向上しより好ましい。
ここで、鉄及びアルミニウム含有量は、ＩＣＰ−ＭＳ法により測定される。測定はサンプルに硫酸添加、乾式灰化後ＩＣＰ−ＭＳにより行う。
When the multilayer container of the present invention is used as a clean container, the aluminum content of the ethylene polymer forming the innermost layer is preferably 1 ppm by weight or less, more preferably 0.5 ppm by weight or less. Further, the iron content is preferably 1 ppm by weight or less, more preferably 0.5 ppm by weight or less. Furthermore, those having a titanium content of 1 ppm by weight or less, a magnesium content of 1 ppm by weight or less, a chromium content of 20 ppm by weight or less, and a silicon content of 250 ppm by weight or less are more preferable because clean container suitability is improved.
Here, the iron and aluminum contents are measured by the ICP-MS method. Measurement is performed by ICP-MS after adding sulfuric acid to the sample and dry ashing.
本発明の多層中空容器の最内層に用いるエチレン系重合体は、上記のように鉄及びアルミニウム含有量が少ないので、水への鉄分、アルミニウム分の溶出量が非常に少なくすることができる。特に、４０℃、１０００時間接触後の水への鉄溶出量が水に対して０．５重量ｐｐｂ以下であることが好ましく、また、４０℃、１０００時間接触後の水へのアルミニウム溶出量が水に対して０．５重量ｐｐｂ以下であることが好ましい。
ここで、水への鉄、アルミニウムの溶出量は、金属が溶出した水を濃縮、酸添加、乾式灰化後ＩＣＰ−ＭＳにより測定する。具体的には、０．５μｍ以下の粒子が１ｍｌあたり１個以下の超純水を容器いっぱいに入れ、よく振った後、水を捨て、この操作を５回繰返した後、超純水を容器いっぱい入れて４０℃、１０００時間放置後、超純水中の金属を測定する。金属測定は、上記超純水の一部を採取し、加熱蒸散させ、硫酸及び硝酸にて加熱分解後、純水で希釈し、ＩＣＰ−ＭＳ法により測定する。以上の操作はクリーンな環境で行なう。
Since the ethylene polymer used for the innermost layer of the multilayer hollow container of the present invention has a low iron and aluminum content as described above, the elution amount of iron and aluminum in water can be extremely reduced. In particular, it is preferable that the iron elution amount in water after contact at 40 ° C. for 1000 hours is 0.5 weight ppb or less with respect to water, and the aluminum elution amount in water after contact at 40 ° C. for 1000 hours is It is preferably 0.5 ppb or less with respect to water.
Here, the elution amount of iron and aluminum in water is measured by ICP-MS after concentration, acid addition, and dry ashing of the metal-eluted water. Specifically, 1 μl or less of ultrapure water with a particle size of 0.5 μm or less is put into a container, shaken well, thrown away the water, and after repeating this operation five times, After fully filling and leaving at 40 ° C. for 1000 hours, the metal in ultrapure water is measured. For metal measurement, a part of the ultrapure water is collected, heated and evaporated, diluted with sulfuric acid and nitric acid, diluted with pure water, and measured by the ICP-MS method. Perform these operations in a clean environment.
本発明の最内層に用いるエチレン系重合体（Ｂ）は、チーグラー触媒、フィリップス触媒、メタロセン触媒等の公知の各種触媒を用いてエチレンを主として重合することにより得られる。例えば、一般的には、チタン、ジルコニウム等の遷移金属化合物、マグネシウム化合物からなるチーグラー触媒、酸化クロム系触媒を代表とするフィリップス触媒及びジルコニウム、ハフニウム、チタン等の遷移金属化合物に少なくとも１つのシクロペンタジエニル基又は置換シクロペンタジエニル基を有するメタロセン系触媒を重合触媒として重合することにより得られる。
重合に際しては、エチレンを単独で重合するか、又はエチレンと炭素数３〜１８のα−オレフィンから選ばれる１種又はそれ以上のコモノマーを所定の密度になるよう共重合することにより得られる。
エチレン系重合体（Ｂ）中の触媒残渣等の混入量は、０．２重量％以下、好ましくは０．１重量％以下、さらに好ましくは０．０５重量％以下に止めるべきである。この混入量が０．２重量％を超えると、金属溶出量が多くなる。
金属含有量の少ないエチレン系重合体（Ｂ）は、エチレン系重合体（Ａ）の製造触媒量より少ない量の触媒を使用するか、エチレン重合触媒残渣失活剤以外の添加剤は使用しない若しくはごく少量使用することにより製造することができる。
The ethylene-based polymer (B) used in the innermost layer of the present invention can be obtained by mainly polymerizing ethylene using various known catalysts such as Ziegler catalysts, Phillips catalysts, metallocene catalysts. For example, in general, transition metal compounds such as titanium and zirconium, Ziegler catalysts composed of magnesium compounds, Phillips catalysts typified by chromium oxide-based catalysts, and transition metal compounds such as zirconium, hafnium, and titanium have at least one cyclopenta It can be obtained by polymerizing a metallocene catalyst having a dienyl group or a substituted cyclopentadienyl group as a polymerization catalyst.
In the polymerization, it is obtained by polymerizing ethylene alone or by copolymerizing ethylene and one or more comonomers selected from α-olefins having 3 to 18 carbon atoms so as to have a predetermined density.
The mixing amount of catalyst residues and the like in the ethylene polymer (B) should be stopped at 0.2 wt% or less, preferably 0.1 wt% or less, more preferably 0.05 wt% or less. If this amount exceeds 0.2% by weight, the metal elution amount increases.
For the ethylene polymer (B) having a low metal content, an amount of catalyst smaller than the production catalyst amount of the ethylene polymer (A) is used, or additives other than the ethylene polymerization catalyst residue deactivator are not used, or It can be manufactured by using a very small amount.
本発明のエチレン系重合体は、エチレン重合触媒残渣失活剤以外の添加剤を含まないことが望ましく、エチレン重合触媒残渣失活剤としては金属石鹸等が挙げられ、特にステアリン酸カルシウム以外の添加剤を含まないものが好ましい。 The ethylene-based polymer of the present invention preferably contains no additives other than the ethylene polymerization catalyst residue quencher, and examples of the ethylene polymerization catalyst residue quencher include metal soaps, particularly additives other than calcium stearate. Those not containing are preferred.
本発明のエチレン系重合体は、エチレン重合触媒残渣失活剤以外の添加剤を含まないことが望ましいが、一種又は二種以上のヒンダードフェノール系酸化防止剤を使用することができる。ヒンダードフェノール系酸化防止剤とは、ラジカル捕捉機能を有し立体的に束縛された構造を有するフェノール化合物であり、フェノールの水酸基に対してオルト位置にｔ−ブチル基のようなバルキーなアルキル基が少なくとも１個置換したアルキルフェノール構造を分子内に有する化合物が好ましい。使用されるヒンダードフェノール系酸化防止剤は、その金属含有量が１０重量ｐｐｍ以下であることが好ましい。金属含有量が１０重量ｐｐｍを超えると、容器内容物に対して金属の溶出が顕著となり、クリーン容器として不都合である。使用されるヒンダードフェノール系酸化防止剤に含有されうる金属としては、周期表第８、９、１０又は１３族の金属が例示され、これらの金属含有量が１０重量ｐｐｍ以下であることが好ましい。金属含有量が１０重量ｐｐｍ以下のヒンダードフェノール系酸化防止剤を用いることにより、容器内容物への金属溶出量が減少する。エチレン系重合体に対するヒンダードフェノール系酸化防止剤の添加量は、重量比で０．０１〜０．２５重量％、好ましくは、０．０２〜０．２５重量％である。エチレン系重合体に対するヒンダードフェノール系酸化防止剤の添加量が０．０１重量％未満では、成形時に発熱及び酸化劣化を起こしやすい。また、その添加量が０．２５重量％を超えると金属溶出量が多くなる。
ヒンダードフェノール系酸化防止剤の中で特に好ましいのは、テトラキス−［メチレン（３，５−ジ−ｔ−ブチル−４−ヒドロキシヒドロ−シンナメート）］メタン（ＩＲＧＡＮＯＸ１０１０）、ｎ−オクタデシル−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート（ＩＲＧＡＮＯＸ１０７６）が挙げられる。
The ethylene polymer of the present invention desirably contains no additives other than the ethylene polymerization catalyst residue quencher, but one or more hindered phenolic antioxidants can be used. The hindered phenol antioxidant is a phenol compound having a radical scavenging function and a sterically constrained structure, and is a bulky alkyl group such as a t-butyl group at the ortho position with respect to the hydroxyl group of phenol. Is preferably a compound having an alkylphenol structure in which at least one is substituted in the molecule. The hindered phenol antioxidant used preferably has a metal content of 10 ppm by weight or less. If the metal content exceeds 10 ppm by weight, metal elution becomes significant with respect to the contents of the container, which is inconvenient as a clean container. Examples of the metal that can be contained in the hindered phenol-based antioxidant used include metals of Group 8, 9, 10 or 13 of the periodic table, and the metal content is preferably 10 ppm by weight or less. . By using a hindered phenol-based antioxidant having a metal content of 10 ppm by weight or less, the metal elution amount to the container contents is reduced. The amount of hindered phenolic antioxidant added to the ethylene polymer is 0.01 to 0.25% by weight, preferably 0.02 to 0.25% by weight. If the amount of hindered phenol antioxidant added to the ethylene polymer is less than 0.01% by weight, heat generation and oxidative deterioration are likely to occur during molding. Moreover, when the addition amount exceeds 0.25% by weight, the metal elution amount increases.
Of the hindered phenolic antioxidants, tetrakis- [methylene (3,5-di-tert-butyl-4-hydroxyhydro-cinnamate)] methane (IRGANOX1010), n-octadecyl-3- ( 3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate (IRGANOX1076).
本発明のエチレン系重合体は、エチレン重合触媒残渣失活剤以外の添加剤を含まないことが望ましいが、一種又は二種以上のヒンダードアミン系光安定剤を使用することができる。ヒンダードアミン系光安定剤（以下、ＨＡＬＳと称することがある）とは、立体的に束縛された構造を有するアミン化合物であり、特開平７−２８６０５２号公報などに示される化合物であり、特に分子量が２５０以上で４位に置換基を有する２，２，６，６−テトラアルキルピペリジン誘導体が挙げられ、中でもピペリジンの２位および６位の炭素上のすべての水素がメチル基で置換された構造を有する化合物が好ましい。使用されるヒンダードアミン系光安定剤は、その金属含有量が１０重量ｐｐｍ以下であることが好ましい。金属含有量が１０重量ｐｐｍを超えると、容器内容物に対して金属の溶出が顕著となり、クリーン容器として不都合である。使用されるヒンダードアミン系光安定剤に含有されうる金属としては、周期表第８、９、１０または１３族の金属が例示され、これらの金属含有量が１０重量ｐｐｍ以下であることが好ましい。金属含有量が１０重量ｐｐｍ以下のヒンダードアミン系酸化防止剤を用いることにより、容器内容物への金属溶出量が減少する。使用されるヒンダードアミン系光安定剤は、その平均分子量が２５０以上、好ましくは１８００以上、更に好ましくは２０００以上のものを使用することが適当である。ヒンダードアミン系光安定剤の平均分子量が２５０未満のものでは、金属溶出量が多くなる。エチレン系重合体に対するヒンダードアミン系光安定剤の添加量は、それら重量比で、０．１５〜０．２５重量％、好ましくは０．１７〜０．２３重量％、さらに好ましくは０．１８〜０．２２重量％である。エチレン系重合体に対するヒンダードアミン系光安定剤の添加量が０．１５重量％未満では、耐候性が悪く容器としての性能が低下する傾向がある。また、その添加量が０．２５重量％を超える時には、金属溶出量が多くなる。
ヒンダードアミン系光安定剤の中で特に好ましいのは、ポリ［｛６−（１，１，３，３−テトラメチルブチル）アミノ−１，３，５−トリアジン−２，４−ジイル）｝｛（２，２，６，６−テトラメチル−４−ピペリジル）イミノ｝ヘキサメチレン｛（２，２，６，６−テトラメチル−４−ピペリジル）イミノ｝］重縮合物（ＣＨＩＭＡＳＳＯＲＢ９４４ＬＤ）が挙げられる。
The ethylene polymer of the present invention desirably contains no additives other than the ethylene polymerization catalyst residue quencher, but one or more hindered amine light stabilizers can be used. The hindered amine light stabilizer (hereinafter sometimes referred to as HALS) is an amine compound having a sterically constrained structure, and is a compound shown in JP-A-7-286052, and particularly has a molecular weight. Examples include a 2,2,6,6-tetraalkylpiperidine derivative having a substituent at the 4-position of 250 or more, and in particular, a structure in which all hydrogens on the 2-position and 6-position carbons of the piperidine are substituted with methyl groups. The compound which has is preferable. The hindered amine light stabilizer used preferably has a metal content of 10 ppm by weight or less. If the metal content exceeds 10 ppm by weight, metal elution becomes significant with respect to the contents of the container, which is inconvenient as a clean container. Examples of the metal that can be contained in the hindered amine light stabilizer to be used include metals of Group 8, 9, 10 or 13 of the periodic table, and the metal content is preferably 10 ppm by weight or less. By using a hindered amine antioxidant having a metal content of 10 ppm by weight or less, the amount of metal elution into the container contents is reduced. The hindered amine light stabilizer used has an average molecular weight of 250 or more, preferably 1800 or more, more preferably 2000 or more. When the hindered amine light stabilizer has an average molecular weight of less than 250, the metal elution amount increases. The amount of hindered amine light stabilizer added to the ethylene polymer is 0.15 to 0.25% by weight, preferably 0.17 to 0.23% by weight, and more preferably 0.18 to 0% by weight. .22% by weight. When the amount of the hindered amine light stabilizer added to the ethylene polymer is less than 0.15% by weight, the weather resistance is poor and the performance as a container tends to be lowered. Moreover, when the addition amount exceeds 0.25% by weight, the metal elution amount increases.
Among the hindered amine light stabilizers, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl)} {( 2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] polycondensate (CHIMASSORB944LD).
（３）バリア層
本発明の多層中空容器のバリア層を形成する樹脂（Ｃ）は、エチレンビニルアルコール樹脂、ポリアミド樹脂、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂等から選ばれるものであるが、特に、エチレンビニルアルコール樹脂からなることが好ましい。エチレンビニルアルコール樹脂は、ケン化度が９３％以上、望ましくは９６％以上でエチレン含量が２５〜５０モル％（樹脂の特徴、組成比、分子量などを記載）であることがより好ましい。
(3) Barrier layer The resin (C) that forms the barrier layer of the multilayer hollow container of the present invention is selected from ethylene vinyl alcohol resin, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, etc. It is preferably made of an ethylene vinyl alcohol resin. More preferably, the ethylene vinyl alcohol resin has a saponification degree of 93% or more, desirably 96% or more and an ethylene content of 25 to 50 mol% (describes resin characteristics, composition ratio, molecular weight, etc.).
（４）接着層
本発明の多層中空容器の接着層を形成する樹脂（Ｄ）は、不飽和カルボン酸又はその誘導体によりグラフト変性した高密度ポリエチレン、低密度ポリエチレン樹脂、直鎖状低密度ポリエチレン等から選ばれるものであるが、特に不飽和カルボン酸又はその誘導体によりグラフト変性した高密度ポリエチレンからなることが好ましい。
不飽和カルボン酸又はその誘導体の含有量は０．０１〜５重量％、好ましくは０．０１〜３重量％、さらに好ましくは、０．０１〜１重量％である。グラフト変性量が、０．０１重量％未満であると十分な接着性能が発現せず、５重量％を超えると接着性に寄与しない不飽和カルボン酸が接着性に悪影響を与える。
(4) Adhesive layer The resin (D) forming the adhesive layer of the multilayer hollow container of the present invention is a high-density polyethylene, low-density polyethylene resin, linear low-density polyethylene or the like graft-modified with an unsaturated carboxylic acid or a derivative thereof. In particular, it is preferably made of high-density polyethylene graft-modified with an unsaturated carboxylic acid or a derivative thereof.
Content of unsaturated carboxylic acid or its derivative (s) is 0.01-5 weight%, Preferably it is 0.01-3 weight%, More preferably, it is 0.01-1 weight%. When the graft modification amount is less than 0.01% by weight, sufficient adhesion performance is not exhibited, and when it exceeds 5% by weight, unsaturated carboxylic acid that does not contribute to adhesion adversely affects adhesion.
（５）バリ回収層
本発明の多層中空容器のバリ回収層の樹脂は、前記最外層を形成するエチレン系重合体（Ａ）、最内層を形成するエチレン系重合体（Ｂ）、バリア層を構成する樹脂（Ｃ）及び接着層を構成する樹脂（Ｄ）を含む組成物である。各成分の配合量は（Ａ）成分１０〜３０重量％、（Ｂ）成分３０〜５０重量％、（Ｃ）成分１〜１５重量％、（Ｄ）成分１〜１５重量％であるのが望ましい。
（Ａ）〜（Ｄ）の各成分は新品を使用することもできるし、（Ａ）〜（Ｄ）成分からなる各層を含む多層積層体のスクラップ、バリ等の不要部分を回収、再利用して、このようなリサイクル品を各成分の成分原料とすることもできる。リサイクル品を使用する場合、（Ａ）〜（Ｄ）のすべての成分を全量リサイクル品から供給することもできるし、新品と混合して使用することもできる。
多層積層体を作製する際に発生した成形バリや未使用パリソンをリサイクル材として使用する場合、各種成分の相溶性が低下することがあるので、相溶化剤や本発明の接着層を構成する樹脂を更に混合してもよい。
(5) Burr collection layer The resin of the burr collection layer of the multilayer hollow container of the present invention comprises an ethylene polymer (A) that forms the outermost layer, an ethylene polymer (B) that forms the innermost layer, and a barrier layer. It is a composition containing resin (C) which comprises and resin (D) which comprises an adhesive layer. The blending amount of each component is preferably (A) component 10 to 30% by weight, (B) component 30 to 50% by weight, (C) component 1 to 15% by weight, and (D) component 1 to 15% by weight. .
(A)-(D) each component can use a new article, and collect and reuse unnecessary parts such as scraps, burrs, etc. of the multilayer laminate including each layer composed of the components (A)-(D). Such recycled products can also be used as component raw materials for each component. When using a recycled product, all the components (A) to (D) can be supplied from the recycled product, or can be mixed with a new product.
When using molded burrs or unused parisons that are generated when producing multilayer laminates as recycled materials, the compatibility of various components may decrease, so the compatibilizer and the resin that constitutes the adhesive layer of the present invention May be further mixed.
（６）各層の厚み比
本発明の多層中空容器の各層の厚み構成は、厚み比で、最外層が１０〜３０％、最内層２０〜５０％、バリア層１〜１５％、接着層１〜１５％、及びバリ回収層３０〜６０％（ただし全ての層厚み構成比の合計が１００％）である。さらに詳細説明する。
(6) Thickness ratio of each layer The thickness constitution of each layer of the multilayer hollow container of the present invention is 10 to 30% of the outermost layer, 20 to 50% of the innermost layer, 1 to 15% of the barrier layer, and 1 to 1 of the adhesive layer. 15% and burr recovery layer 30 to 60% (however, the sum of all layer thickness components is 100%). Further details will be described.
最外層の層構成比は、１０〜３０％、好ましくは１０〜２５％、より好ましくは１０〜２０％である。最外層の層構成比が１０％未満であると、衝撃性能が不足し、３０％を超えると、中空成形製品の成形安定性が損なわれる。
最内層の層構成比は、２０〜５０％、好ましくは３５〜５０％、より好ましくは４０〜５０％である。最内層の層構成比が２０％未満であると、中空成形製品の剛性不足が顕在化し、５０％を超えると、中空成形製品の成形安定性が損なわれる。
バリア層の層構成比は、１〜１５％、好ましくは１〜１０％、より好ましくは１〜５％である。バリア層の層構成比が１％未満であると、バリア性能が不満足であり、１５％を超えると、衝撃性能が不足する。
接着層の層構成比は、１〜１５％、好ましくは１〜１０％、より好ましくは１〜５％である。接着層の層構成比が１％未満であると、接着性能に不安が生じ、１５％を超えると、中空成形製品の剛性不足が顕在化する。
バリ回収層の層構成比は、３０〜６０％、好ましくは３５〜５０％、より好ましくは３５〜４５％である。バリ回収層の層構成比が３０％未満であると、中空成形製品の成形安定性が損なわれ、６０％を超えると、衝撃性能が不足する。
The layer composition ratio of the outermost layer is 10 to 30%, preferably 10 to 25%, more preferably 10 to 20%. When the layer composition ratio of the outermost layer is less than 10%, the impact performance is insufficient, and when it exceeds 30%, the molding stability of the hollow molded product is impaired.
The layer composition ratio of the innermost layer is 20 to 50%, preferably 35 to 50%, more preferably 40 to 50%. When the layer composition ratio of the innermost layer is less than 20%, the rigidity of the hollow molded product becomes insufficient, and when it exceeds 50%, the molding stability of the hollow molded product is impaired.
The layer composition ratio of the barrier layer is 1 to 15%, preferably 1 to 10%, more preferably 1 to 5%. When the layer composition ratio of the barrier layer is less than 1%, the barrier performance is unsatisfactory, and when it exceeds 15%, the impact performance is insufficient.
The layer composition ratio of the adhesive layer is 1 to 15%, preferably 1 to 10%, more preferably 1 to 5%. When the layer composition ratio of the adhesive layer is less than 1%, anxiety is caused in the adhesive performance, and when it exceeds 15%, the lack of rigidity of the hollow molded product becomes obvious.
The layer composition ratio of the burr recovery layer is 30 to 60%, preferably 35 to 50%, more preferably 35 to 45%. If the layer composition ratio of the burr recovery layer is less than 30%, the molding stability of the hollow molded product is impaired, and if it exceeds 60%, the impact performance is insufficient.
２．多層中空容器
本発明の多層中空容器は、外側から最外層、バリ回収層、接着層、バリア層、接着層、最内層の順に積層されていることが好ましい。バリア層を接着層で挟むことにより、高度なバリア性が発揮される。最外層と接着層の間にバリ回収層を有することにより、コストダウンという効果が発揮される。
2. Multilayer hollow container The multilayer hollow container of the present invention is preferably laminated in the order of the outermost layer, the burr recovery layer, the adhesive layer, the barrier layer, the adhesive layer, and the innermost layer from the outside. By sandwiching the barrier layer between the adhesive layers, a high level of barrier properties is exhibited. By having the burr recovery layer between the outermost layer and the adhesive layer, the effect of cost reduction is exhibited.
また、本発明の多層中空容器は、４０℃、１０００時間接触後の水への鉄溶出量が水に対して０．５重量ｐｐｂ以下にすることができる。鉄溶出量が０．５重量ｐｐｂを超えるものは、クリーン性を低下させる傾向にある。また、４０℃、１０００時間接触後の水へのアルミニウム溶出量が水に対して０．５重量ｐｐｂ以下にすることができる。アルミニウム溶出量が０．５重量ｐｐｂを超えるものは、クリーン性を低下させる傾向にある。 Moreover, the multilayer hollow container of this invention can make the iron elution amount to the water after 1000-hour contact at 40 degreeC 0.5 weight ppb or less with respect to water. When the iron elution amount exceeds 0.5 weight ppb, the cleanliness tends to be lowered. Moreover, the aluminum elution amount to the water after 1000 degreeC contact at 40 degreeC can be 0.5 weight ppb or less with respect to water. When the aluminum elution amount exceeds 0.5 weight ppb, the cleanliness tends to be lowered.
さらに、本発明の多層中空容器には、所望により酸化防止剤、中和剤、耐候剤等の各種添加剤を添加できる。しかし、これらの添加剤はそれぞれ０．２重量％以下、好ましくは０．１重量％以下、さらに好ましくは０．０５重量％以下に止めるべきである。これら添加剤が０．２重量％を超えると、金属溶出量が多くなる。 Furthermore, various additives such as an antioxidant, a neutralizing agent and a weathering agent can be added to the multilayer hollow container of the present invention as desired. However, each of these additives should be kept at 0.2 wt% or less, preferably 0.1 wt% or less, more preferably 0.05 wt% or less. When these additives exceed 0.2% by weight, the amount of metal elution increases.
本発明の多層中空容器は、ブロー成形法によりブロー成形品、特に大型ブロー成形品とすることができ、得られたブロー成形品は表面性、剛性、耐衝撃性等の機械強度及びクリーン性及び耐候性に優れ、コンテナ容器、クリーン容器として好適に用いることができる。また、本発明の容器は、ドラムのほか、パレットコンテナ、燃料タンクにも適している。 The multilayer hollow container of the present invention can be made into a blow molded product, particularly a large blow molded product by a blow molding method, and the obtained blow molded product has mechanical strength such as surface properties, rigidity, impact resistance, and cleanliness, It is excellent in weather resistance and can be suitably used as a container container or a clean container. Moreover, the container of this invention is suitable also for a pallet container and a fuel tank besides a drum.
以下、本発明を実施例によってさらに詳細に説明するが、本発明は実施例に限定されるものではない。なお、実施例で用いた測定法、樹脂は以下の通りである。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to an Example. The measurement methods and resins used in the examples are as follows.
１．各種測定方法
（１）温度１９０℃、荷重２１．６ｋｇのメルトフローレート：ＪＩＳ−Ｋ７２１０に準拠し、温度１９０℃、荷重２１．６ｋｇの条件で測定した。
（２）密度：ＪＩＳ−Ｋ７１１２に準拠し、ペレットを温度１６０℃の熱圧縮成形機により溶融後２５℃／分の速度で降温し厚み２ｍｍのシートを成形し、このシートを温度２３℃の室内で４８時間状態調節した後、密度勾配管に入れ密度を測定した。
（３）オルゼン曲げ剛性：ＪＩＳ−Ｋ７１０６に準拠し、東洋精機（株）製のスティフネスメーターにて、スパン間３０ｍｍ、つかみ部３０ｍｍ、全曲げモーメントが６ｋｇｆ・ｃｍの条件で６０℃／分で片持ち曲げ応力を測定した。
なお、試験片は、ペレットを温度１６０℃の熱圧縮成形機により溶融後２５℃／分の速度で降温し厚み２ｍｍのシート成形した。このシートを温度２３℃の室内で４８時間状態調節した後、長さ８５ｍｍ、幅１５ｍｍになるようにダンベル刃型で打ち抜いて試験片とした。
（４）混合溶媒透過性：容器に２，２，４−トリメチルペンタン４５容量部、トルエン４５容量部及びエチルアルコール１０容量部の混合溶媒を入れ、試験温度４０℃で、１週間状態調整実施した。その後、２，２，４−トリメチルペンタン４５容量部、トルエン４５容量部及びエチルアルコール１０容量部の混合溶媒を入れ替え、重量の経時的変化を測定した。
（５）落下衝撃性：内容積が２０Ｌ以上の容器については、容器に不凍液を満注し、その容器をマイナス１８℃に冷却し、所定の高さからコンクリート面に落下させ、割れ発生の高さを測定評価した。内容積が２０Ｌ未満の容器については、容器に不凍液を満注し、その容器をマイナス１８℃に冷却し、２ｍの高さからコンクリート面に１０回落下させ、異常の有無をチェックした。異常がないものを○、割れ等の異常が発生したものを×とした。
（６）座屈強度：円筒状（柱状）の容器を垂直に立て、圧縮試験機にて５０ｍｍ／分の速度で容器の上部から下部に向けて垂直方向に圧縮し、最大圧縮強度を測定した。
（７）酸素バリア性：小型多層中空成形機にて１００ｍｌボトルを作製した。酸素透過率測定装置（ＭＯＣＯＮ社製ＯＸ−ＴＲＡＮ １０／５０）を使用し、ＪＩＳ−Ｋ７１２６に準じて測定した。
（８）窒素バリア性：小型多層中空成形機にて１００ｍｌボトルを作製した。混合ガス透過度テスター（ＬＹＳＳＹ社製ＧＰＭ−５００）を使用し測定した。
（９）金属溶出量：０．５μｍ以下の粒子が１ｍｌあたり１個以下の超純水を容器いっぱいに入れ、よく振った後、水を捨てた。この操作を５回繰返した後、超純水を容器いっぱい入れて４０℃、１０００時間放置後、超純水中の金属を測定した。金属測定は、上記超純水の一部を採取し、加熱蒸散させ、硫酸及び硝酸にて加熱分解後、純水で希釈し、ＩＣＰ−ＭＳ法により測定した。以上の操作はクリーンな環境で行なった。
（１０）ボトルＥＳＣＲ法：４５０ｍｌ容量の口部付円筒状の中空容器（重量３００ｇ、外径８０ｍｍ、高さ１００ｍｍの円筒本体に、外形３０ｍｍ、高さ１５ｍｍの口部が丸み付きで結合した構造の瓶型容器、厚さ１ｍｍ）１０本の各々にポリオキシエチレンジスチレン化フェニルエーテル（ＧＦＡ社製 イゲパール）１０重量％水溶液２００ｍｌを充填、密栓し、６５℃のオーブンに入れ、容器内部に０．３５ｋｇｆ／ｃｍ２の圧力をかけた状態で、容器５本にクラックが発生するまでの時間を測定した。
（１１）大型容器耐久性：容器にポリオキシエチレンジスチレン化フェニルエーテル（ＧＦＡ社製 イゲパール）１０重量％水溶液１００Ｌ入れ密封し、４０℃で１年放置し、異常の有無をチェックした。異常がないものを○、クラック又は変色等の異常が発生したものを×とした。
（１２）成形加工性：成形中の押し出し機トラブルの発生有無をチェックした。異常がないものを○、圧力上昇等の異常が発生したものを×とした。
（１３）金属含有量：サンプルに硫酸添加、乾式灰化後ＩＣＰ−ＭＳ法により測定した。
1. Various measurement methods (1) Melt flow rate at a temperature of 190 ° C. and a load of 21.6 kg: Measured according to JIS-K7210 under the conditions of a temperature of 190 ° C. and a load of 21.6 kg.
(2) Density: In accordance with JIS-K7112, the pellets were melted by a hot compression molding machine at a temperature of 160 ° C. and then cooled at a rate of 25 ° C./minute to form a sheet having a thickness of 2 mm. Was conditioned for 48 hours and placed in a density gradient tube to measure the density.
(3) Olsen bending rigidity: according to JIS-K7106, using a stiffness meter manufactured by Toyo Seiki Co., Ltd., with a span of 30 mm, a gripping part of 30 mm, and a total bending moment of 6 kgf · cm at 60 ° C./min. The holding bending stress was measured.
The test piece was formed into a sheet having a thickness of 2 mm by cooling the pellet at a rate of 25 ° C./min after melting the pellet with a hot compression molding machine having a temperature of 160 ° C. The sheet was conditioned for 48 hours in a room at a temperature of 23 ° C., and then punched out with a dumbbell blade so as to have a length of 85 mm and a width of 15 mm to obtain a test piece.
(4) Mixed solvent permeability: A mixed solvent of 45 parts by volume of 2,2,4-trimethylpentane, 45 parts by volume of toluene and 10 parts by volume of ethyl alcohol was placed in a container, and the condition was adjusted for 1 week at a test temperature of 40 ° C. . Thereafter, the mixed solvent of 45 parts by volume of 2,2,4-trimethylpentane, 45 parts by volume of toluene and 10 parts by volume of ethyl alcohol was replaced, and the change with time in weight was measured.
(5) Drop impact: For containers with an internal volume of 20L or more, fill the container with antifreeze, cool the container to minus 18 ° C, drop it from the specified height onto the concrete surface, and increase cracking. The thickness was measured and evaluated. For containers with an internal volume of less than 20 L, the container was filled with antifreeze, the container was cooled to minus 18 ° C., dropped 10 times from a height of 2 m onto the concrete surface, and checked for abnormalities. A sample having no abnormality was marked with ◯, and a sample with an abnormality such as cracking was marked with ×.
(6) Buckling strength: A cylindrical (columnar) container was set up vertically and compressed in the vertical direction from the upper part to the lower part of the container at a speed of 50 mm / min with a compression tester, and the maximum compressive strength was measured. .
(7) Oxygen barrier property: A 100 ml bottle was produced with a small multilayer hollow molding machine. Using an oxygen transmission rate measuring device (OX-TRAN 10/50 manufactured by MOCON), measurement was performed according to JIS-K7126.
(8) Nitrogen barrier property: A 100 ml bottle was produced with a small multilayer hollow molding machine. Measurement was performed using a mixed gas permeability tester (GPM-500 manufactured by LYSSY).
(9) Metal elution amount: Ultrapure water with 1 or less particles of 0.5 μm or less per ml was put in a container, shaken well, and then discarded. After this operation was repeated 5 times, the ultrapure water was filled in a container and left at 40 ° C. for 1000 hours, and then the metal in the ultrapure water was measured. For the metal measurement, a part of the ultrapure water was collected, evaporated by heating, thermally decomposed with sulfuric acid and nitric acid, diluted with pure water, and measured by ICP-MS method. The above operation was performed in a clean environment.
(10) Bottle ESCR method: 450 ml capacity cylindrical hollow container with a mouth (weight 300 g, outer diameter 80 mm, height 100 mm cylindrical body with a rounded 30 mm outer diameter and 15 mm height mouth Each of 10 bottle-shaped containers (thickness 1 mm) was filled with 200 ml of 10% by weight aqueous solution of polyoxyethylene distyrenated phenyl ether (manufactured by GFA Igepearl), sealed, put in an oven at 65 ° C., and 0 inside the container. In a state where a pressure of .35 kgf / cm 2 was applied, the time until cracks occurred in five containers was measured.
(11) Durability of large container: The container was sealed with 100 L of 10% polyoxyethylene distyrenated phenyl ether (Igepearl manufactured by GFA) and sealed, and left at 40 ° C. for 1 year to check for abnormalities. A sample having no abnormality was evaluated as ◯, and a sample having an abnormality such as crack or discoloration was evaluated as ×.
(12) Molding workability: The presence / absence of an extruder trouble during molding was checked. The case where there was no abnormality was rated as ○, and the case where an abnormality such as a pressure increase occurred was rated as x.
(13) Metal content: Measured by ICP-MS method after adding sulfuric acid to sample and dry ashing.
２．使用樹脂
（１）エチレン系重合体（ＰＥ−１）
温度１９０℃、荷重２１．６ｋｇのメルトフローレートが３．０ｇ／１０分、密度が０．９５４ｇ／ｃｍ３、オルゼン曲げ剛性が１２００ＭＰａ、鉄含有量が１５重量ｐｐｍ、アルミニウム含有量が１５重量ｐｐｍである高密度ポリエチレンを使用した。
（２）エチレン系重合体（ＰＥ−２）
温度１９０℃、荷重２１．６ｋｇのメルトフローレートが３．０ｇ／１０分、密度が０．９５４ｇ／ｃｍ３、オルゼン曲げ剛性が１２００ＭＰａ、鉄含有量が０．１重量ｐｐｍ、アルミニウム含有量が０．２重量ｐｐｍである高密度ポリエチレンを使用した。
（３）エチレン系重合体（ＰＥ−３）
温度１９０℃、荷重２１．６ｋｇのメルトフローレートが５．０ｇ／１０分、密度が０．９５７ｇ／ｃｍ３、オルゼン曲げ剛性が１３５０ＭＰａ、鉄含有量が０．１重量ｐｐｍ、アルミニウム含有量が０．２重量ｐｐｍである高密度ポリエチレンを使用した。
（４）接着性樹脂（ＭＡＰＥ）
無水マレイン酸が０．１重量％グラフトされた日本ポリエチレン社製無水マレイン酸変性ポリエチレンを使用した。
（５）バリア性樹脂（ＥＶＯＨ）
クラレ社製エチレンビニルアルコール樹脂エバールを使用した。
2. Resin used (1) Ethylene polymer (PE-1)
Temperature 190 ° C, load 21.6 kg, melt flow rate 3.0 g / 10 min, density 0.954 g / cm 3 , Olsen bending stiffness 1200 MPa, iron content 15 ppm by weight, aluminum content 15 ppm by weight High density polyethylene was used.
(2) Ethylene polymer (PE-2)
Melt flow rate at a temperature of 190 ° C., a load of 21.6 kg is 3.0 g / 10 min, density is 0.954 g / cm 3 , Olsen bending rigidity is 1200 MPa, iron content is 0.1 wt ppm, aluminum content is 0 High density polyethylene with 2 ppm by weight was used.
(3) Ethylene polymer (PE-3)
Melt flow rate at a temperature of 190 ° C., a load of 21.6 kg is 5.0 g / 10 min, a density is 0.957 g / cm 3 , an Olzen bending rigidity is 1350 MPa, an iron content is 0.1 wt ppm, and an aluminum content is 0 High density polyethylene with 2 ppm by weight was used.
(4) Adhesive resin (MAPE)
Maleic anhydride-modified polyethylene manufactured by Nippon Polyethylene Co., Ltd. grafted with 0.1% by weight of maleic anhydride was used.
(5) Barrier resin (EVOH)
Kuraray's ethylene vinyl alcohol resin Eval was used.
（実施例１）
以下の内容で２００Ｌドラムを成形し、性能を評価した。結果を表１に示す。
（１）使用成形機
５種６層の大型多層ブロー成形機（日本製鋼所社製ＮＢ１５０）を用い、押し出し機スクリューと層構成は以下の条件で成形した。
最外層（外側から１層目）系９０ｍｍφ、Ｌ／Ｄ２２
第２層（外側から２層目）系１２０ｍｍφ、Ｌ／Ｄ２８
第３層（外側から３層目）系５０ｍｍφ、Ｌ／Ｄ２２
第４層（外側から４層目）系５０ｍｍφ、Ｌ／Ｄ２８
第５層（外側から５層目）系５０ｍｍφ、Ｌ／Ｄ２２
最内層（外側から６層目）系１２０ｍｍφ、Ｌ／Ｄ２４１
（２）成形条件
成形温度２１０℃、ブロー金型冷却温度２０℃、冷却時間１８０秒の条件にてドラム重量１０ｋｇ、容量２００Ｌの５種６層多層ドラムを成形した。ドラムの形状は、胴体外径５８０ｍｍ、総高さ９７０ｍｍ、胴体肉厚３．６ｍｍの標準的なクローズドタイプのものを成形した。
なお、層比率は容器の厚み比率を観察しながら押し出し機のスクリュー回転数を調整し最外層が１０％、第２層が４０％、第３層が３％、第４層が１％、第５層が３％、最内層が４３％となるようにした。
（３）使用樹脂
各層に使用した樹脂は以下の通りである。
最外層：エチレン系重合体（ＰＥ−１）
第２層：エチレン系重合体（ＰＥ−１）１０重量部、接着性樹脂（ＭＡＰＥ）６重量部、バリア性樹脂（ＥＶＯＨ）１重量部、エチレン系重合体（ＰＥ−２）４１重量部の樹脂組成物
第３層：接着性樹脂（ＭＡＰＥ）
第４層：バリア性樹脂（ＥＶＯＨ）
第５層：接着性樹脂（ＭＡＰＥ）
最内層：エチレン系重合体（ＰＥ−２）
上記の結果、成形加工性、座屈強度（剛性）、落下衝撃性（耐衝撃性）、溶媒透過防止性、低溶出性、ガスバリア性、耐久性に優れた多層中空容器が得られた。
Example 1
A 200 L drum was molded with the following contents, and the performance was evaluated. The results are shown in Table 1.
(1) Used molding machine A large-scale multi-layer blow molding machine (NB150, manufactured by Nippon Steel Works) was used, and the extruder screw and the layer configuration were molded under the following conditions.
Outermost layer (first layer from outside) 90mmφ, L / D22
Second layer (second layer from outside) 120mmφ, L / D28
Third layer (third layer from the outside) 50mmφ, L / D22
4th layer (4th layer from the outside) 50mmφ, L / D28
5th layer (5th layer from the outside) 50mmφ, L / D22
Innermost layer (sixth layer from the outside) system 120mmφ, L / D241
(2) Molding conditions Five types and six-layer multilayer drums having a drum weight of 10 kg and a capacity of 200 L were molded under the conditions of a molding temperature of 210 ° C., a blow mold cooling temperature of 20 ° C., and a cooling time of 180 seconds. The drum was molded in a standard closed type having a body outer diameter of 580 mm, a total height of 970 mm, and a body thickness of 3.6 mm.
It should be noted that the layer ratio is 10% for the outermost layer, 40% for the second layer, 3% for the third layer, 1% for the fourth layer, The 5 layers were 3% and the innermost layer was 43%.
(3) Resin used The resin used for each layer is as follows.
Outermost layer: ethylene polymer (PE-1)
Second layer: 10 parts by weight of ethylene polymer (PE-1), 6 parts by weight of adhesive resin (MAPE), 1 part by weight of barrier resin (EVOH), 41 parts by weight of ethylene polymer (PE-2) Resin composition Third layer: Adhesive resin (MAPE)
Fourth layer: barrier resin (EVOH)
Fifth layer: Adhesive resin (MAPE)
Innermost layer: ethylene polymer (PE-2)
As a result, a multilayer hollow container excellent in moldability, buckling strength (rigidity), drop impact property (impact resistance), solvent permeation prevention property, low elution property, gas barrier property, and durability was obtained.
（実施例２）
最外層が１０％、第２層が４０％、第３層が３％、第４層が３％、第５層が３％、最内層が４１％となるようにした以外は実施例１と同様に行なった。結果を表１に示す。
成形加工性、座屈強度（剛性）、落下衝撃性（耐衝撃性）、溶媒透過防止性、低溶出性、ガスバリア性、耐久性に優れた多層中空容器が得られた。
(Example 2)
Example 1 except that the outermost layer is 10%, the second layer is 40%, the third layer is 3%, the fourth layer is 3%, the fifth layer is 3%, and the innermost layer is 41%. The same was done. The results are shown in Table 1.
A multilayer hollow container excellent in molding processability, buckling strength (rigidity), drop impact property (impact resistance), solvent permeation prevention property, low elution property, gas barrier property, and durability was obtained.
（実施例３）
最外層が１０％、第２層が４０％、第３層が３％、第４層が５％、第５層が３％、最内層が３９％となるようにした以外は実施例１と同様に行なった。結果を表１に示す。
成形加工性、座屈強度（剛性）、落下衝撃性（耐衝撃性）、溶媒透過防止性、低溶出性、ガスバリア性、耐久性に優れた多層中空容器が得られた。
(Example 3)
Example 1 except that the outermost layer is 10%, the second layer is 40%, the third layer is 3%, the fourth layer is 5%, the fifth layer is 3%, and the innermost layer is 39%. The same was done. The results are shown in Table 1.
A multilayer hollow container excellent in molding processability, buckling strength (rigidity), drop impact property (impact resistance), solvent permeation prevention property, low elution property, gas barrier property, and durability was obtained.
（比較例１）
第２層、第３層、第４層、第５層及び最内層に、最外層と同じ樹脂（ＰＥ−１）を使用した以外は実施例１と同様に行なった。結果を表１に示す。容器の溶媒透過防止性が低かった。
(Comparative Example 1)
It carried out similarly to Example 1 except having used the same resin (PE-1) as an outermost layer for the 2nd layer, the 3rd layer, the 4th layer, the 5th layer, and the innermost layer. The results are shown in Table 1. The solvent permeation prevention property of the container was low.
（比較例２）
最内層の樹脂として、エチレン系重合体（ＰＥ−３）を使用した以外は実施例２と同様に行なった。結果を表１に示す。容器の大型容器耐久性が低かった。
(Comparative Example 2)
The same operation as in Example 2 was performed except that an ethylene polymer (PE-3) was used as the innermost layer resin. The results are shown in Table 1. The durability of the large container was low.
（実施例４）
以下の内容で４５０ｍｌボトルを成形し、性能を評価した。結果を表２に示す。
（１）使用成形機
５種６層の小型多層ブロー成形機（ベクム社製）を用い、押し出し機スクリューと層構成は以下の条件で成形した。
最外層（外側から１層目）系４０ｍｍφ、Ｌ／Ｄ２２
第２層（外側から２層目）系４０ｍｍφ、Ｌ／Ｄ２２
第３層（外側から３層目）系２０ｍｍφ、Ｌ／Ｄ２０
第４層（外側から４層目）系２０ｍｍφ、Ｌ／Ｄ２０
第５層（外側から５層目）系２０ｍｍφ、Ｌ／Ｄ２０
最内層（外側から６層目）系４０ｍｍφ、Ｌ／Ｄ２２
（２）成形条件
成形温度２１０℃、ブロー金型冷却温度２０℃、冷却時間３０秒の条件にてボトル重量３０ｇ、容量４５０ｃｃの多層ボトルを成形した。なお、層比率は容器の厚み比率を観察しながら押し出し機のスクリュー回転数を調整し最外層が１０％、第２層が３０％、第３層が１０％、第４層が１０％、第５層が１０％、最内層が３０％となるようにした。
（３）使用樹脂
各層に使用した樹脂は以下の通りである。
最外層：エチレン系重合体（ＰＥ−１）
第２層：エチレン系重合体（ＰＥ−１）１０重量部、接着性樹脂（ＭＡＰＥ）６重量部、バリア性樹脂（ＥＶＯＨ）１重量部、エチレン系重合体（ＰＥ−２）４１重量部の樹脂組成物
第３層：接着性樹脂（ＭＡＰＥ）
第４層：バリア性樹脂（ＥＶＯＨ）
第５層：接着性樹脂（ＭＡＰＥ）
最内層：エチレン系重合体（ＰＥ−２）
上記の結果、成形加工性、座屈強度（剛性）、落下衝撃性（耐衝撃性）、溶媒透過防止性、低溶出性、ガスバリア性、耐久性に優れた多層中空容器が得られた。
Example 4
A 450 ml bottle was molded with the following contents, and the performance was evaluated. The results are shown in Table 2.
(1) Used molding machine Using 5 types and 6 layers of small multilayer blow molding machine (manufactured by Becum), the extruder screw and layer structure were molded under the following conditions.
Outermost layer (first layer from outside) 40mmφ, L / D22
Second layer (second layer from outside) 40mmφ, L / D22
Third layer (third layer from the outside) system 20mmφ, L / D20
Fourth layer (fourth layer from the outside) system 20 mmφ, L / D20
5th layer (5th layer from the outside) system 20mmφ, L / D20
Innermost layer (sixth layer from outside) 40mmφ, L / D22
(2) Molding conditions A multilayer bottle having a bottle weight of 30 g and a capacity of 450 cc was molded under the conditions of a molding temperature of 210 ° C., a blow mold cooling temperature of 20 ° C., and a cooling time of 30 seconds. The layer ratio was adjusted by adjusting the screw speed of the extruder while observing the thickness ratio of the container. The outermost layer was 10%, the second layer was 30%, the third layer was 10%, the fourth layer was 10%, The 5 layers were 10% and the innermost layer was 30%.
(3) Resin used The resin used for each layer is as follows.
Outermost layer: ethylene polymer (PE-1)
Second layer: 10 parts by weight of ethylene polymer (PE-1), 6 parts by weight of adhesive resin (MAPE), 1 part by weight of barrier resin (EVOH), 41 parts by weight of ethylene polymer (PE-2) Resin composition Third layer: Adhesive resin (MAPE)
Fourth layer: barrier resin (EVOH)
Fifth layer: Adhesive resin (MAPE)
Innermost layer: ethylene polymer (PE-2)
As a result, a multilayer hollow container excellent in moldability, buckling strength (rigidity), drop impact property (impact resistance), solvent permeation prevention property, low elution property, gas barrier property, and durability was obtained.
（実施例５）
最外層が１０％、第２層が２５％、第３層が１０％、第４層が２０％、第５層が１０％、最内層が２５％となるようにした以外は実施例４と同様に行なった。結果を表２に示す。成形加工性、座屈強度（剛性）、落下衝撃性（耐衝撃性）、溶媒透過防止性、低溶出性、ガスバリア性、耐久性に優れた多層中空容器が得られた。
(Example 5)
Example 4 except that the outermost layer is 10%, the second layer is 25%, the third layer is 10%, the fourth layer is 20%, the fifth layer is 10%, and the innermost layer is 25%. The same was done. The results are shown in Table 2. A multilayer hollow container excellent in molding processability, buckling strength (rigidity), drop impact property (impact resistance), solvent permeation prevention property, low elution property, gas barrier property, and durability was obtained.
（比較例３）
第２層、第３層、第４層、第５層及び最内層に、最外層と同じ樹脂（ＰＥ−１）を使用した以外は実施例４と同様に行なった。結果を表２に示す。容器の溶媒透過防止性、ガスバリア性が低かった。
(Comparative Example 3)
It carried out similarly to Example 4 except having used the same resin (PE-1) as an outermost layer for the 2nd layer, the 3rd layer, the 4th layer, the 5th layer, and the innermost layer. The results are shown in Table 2. The solvent permeation prevention property and gas barrier property of the container were low.
（比較例４）
最内層の樹脂として、エチレン系重合体（ＰＥ−３）を使用した以外は実施例５と同様に行なった。結果を表２に示す。容器のボトルＥＳＣＲ（耐久性）が低かった。
(Comparative Example 4)
The same operation as in Example 5 was performed except that an ethylene polymer (PE-3) was used as the innermost layer resin. The results are shown in Table 2. The bottle ESCR (durability) of the container was low.
本発明の多層中空容器を用いることにより、成形加工性、剛性、耐衝撃性等の機械強度、透過防止性、クリーン性及び耐久性に優れるコンテナ容器、特に大型ブロー成形クリーン容器を好適に得られる。 By using the multilayer hollow container of the present invention, a container container excellent in mechanical strength such as molding processability, rigidity, impact resistance, permeation prevention, cleanliness and durability, particularly a large blow molded clean container can be suitably obtained. .
Claims (5)
最外層が下記特性（１）〜（３）の条件を満足するエチレン系重合体からなり、最内層が下記特性（１）〜（３）の条件を満足し、鉄及びアルミニウム含有量が各々１０重量ｐｐｍ以下、鉄及びアルミニウム以外の金属の合計含有量が３００重量ｐｐｍ以下であり、且つステアリン酸カルシウム以外の添加剤を含まないエチレン系重合体からなり、層厚みの構成比が最外層１０〜３０％、バリ回収層３０〜６０％、接着層１〜１５％、バリア層１〜１５％、最内層２０〜５０％（ただし、全ての層厚み構成比の合計が１００％）であることで、透過防止性及び容器内容液への金属溶出量が少ないことを特徴とする多層中空容器。
特性（１）温度１９０℃、荷重２１．６ｋｇのメルトフローレートが０．０１〜１００ｇ／１０分
特性（２）密度が０．９４１ｇ／ｃｍ３以上０．９８０ｇ／ｃｍ３以下
特性（３）オルゼン曲げ剛性が６００ＭＰａ以上１３００ＭＰａ以下 A multilayer hollow container laminated in order of the outermost layer, the burr recovery layer, the adhesive layer, the barrier layer and the innermost layer from the outside ,
The outermost layer is made of an ethylene polymer that satisfies the conditions of the following characteristics (1) to (3), the innermost layer satisfies the conditions of the following characteristics (1) to (3), and the iron and aluminum contents are 10 respectively. The total content of metals other than weight ppm and metals other than iron and aluminum is 300 ppm by weight or less, and is composed of an ethylene-based polymer that does not contain additives other than calcium stearate. %, Burr recovery layer 30 to 60%, adhesive layer 1 to 15%, barrier layer 1 to 15%, innermost layer 20 to 50% (however, the total of all layer thickness components is 100%) A multilayer hollow container characterized in that the permeation preventing property and the amount of metal elution into the container liquid are small.
Characteristic (1) Temperature 190 ° C., melt flow rate of load 21.6 kg is 0.01 to 100 g / 10 min. Characteristic (2) Density is 0.941 g / cm 3 or more and 0.980 g / cm 3 or less Characteristic (3) Olsen bending rigidity Is 600 MPa to 1300 MPa
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005350412A JP4922606B2 (en) | 2005-12-05 | 2005-12-05 | Multi-layer hollow container |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005350412A JP4922606B2 (en) | 2005-12-05 | 2005-12-05 | Multi-layer hollow container |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007152712A JP2007152712A (en) | 2007-06-21 |
| JP4922606B2 true JP4922606B2 (en) | 2012-04-25 |
Family
ID=38237668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005350412A Expired - Fee Related JP4922606B2 (en) | 2005-12-05 | 2005-12-05 | Multi-layer hollow container |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4922606B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5017002B2 (en) * | 2007-07-06 | 2012-09-05 | 日本ポリエチレン株式会社 | Multilayer blow molded article and method for producing the same |
| JP5179915B2 (en) * | 2008-03-26 | 2013-04-10 | 大阪瓦斯株式会社 | Resin tank and manufacturing method thereof |
| JP5755081B2 (en) * | 2011-08-22 | 2015-07-29 | 株式会社クレハ | Synthetic resin blow molded container with annular recess |
| CN110770137B (en) * | 2017-07-18 | 2021-08-03 | 富士胶片株式会社 | Container, method for manufacturing container, and chemical liquid container |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4008295B2 (en) * | 2001-06-25 | 2007-11-14 | 日本ポリオレフィン株式会社 | Adhesive resin composition, multilayer laminate structure using the same, and container |
| JP2003096133A (en) * | 2001-09-21 | 2003-04-03 | Japan Polychem Corp | Polyethylene resin for high-purity chemical container |
| JP2004136522A (en) * | 2002-10-17 | 2004-05-13 | Japan Polychem Corp | Blow-molded article |
| JP4564876B2 (en) * | 2004-04-06 | 2010-10-20 | 日本ポリエチレン株式会社 | Polyethylene resin for container lid |
-
2005
- 2005-12-05 JP JP2005350412A patent/JP4922606B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007152712A (en) | 2007-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2081990B1 (en) | Barrier film for food packaging | |
| US20050142373A1 (en) | Oxygen-absorbing resin composition and laminate | |
| JP5204967B2 (en) | Polyethylene resin for injection molded plastic fuel tank and injection molded fuel tank using the same | |
| JP2008518848A (en) | Barrier multilayer container | |
| US20050186373A1 (en) | Multilayer sheets and films composed of polypropylene and cyclic olefin copolymer | |
| US20100130692A1 (en) | Ethylene-based polymer compositions, methods of making the same, and articles prepared therefrom | |
| JP4912882B2 (en) | Multilayer pellets comprising an ethylene-vinyl alcohol copolymer resin composition | |
| JP4922606B2 (en) | Multi-layer hollow container | |
| US20050186376A1 (en) | Multilayer sheets and films composed of PCTFE and cyclic olefin copolymer | |
| JP2009161615A (en) | Polyethylene resin, blow molded product using it, and its usage | |
| JP5925632B2 (en) | Resin laminate containing plant-derived polyethylene and resin multilayer container | |
| KR100843592B1 (en) | Multi-layer container having barrier property | |
| JP5883234B2 (en) | Resin multilayer container with collection layer | |
| JPH0496946A (en) | Polyethylene-based resin composition | |
| JP5997879B2 (en) | Resin multilayer container | |
| JP3805386B2 (en) | Fuel container and fuel transfer pipe | |
| JP5679572B2 (en) | Resin multilayer container | |
| JP2004136522A (en) | Blow-molded article | |
| JP2014043018A (en) | Resin laminate and multilayer container made of resin containing plant-derived ethylene resin | |
| JP5824244B2 (en) | Resin multilayer container with collection layer | |
| CN108546352A (en) | Rotational molding polyethylene composition | |
| JP7356296B2 (en) | Resin composition and multilayer structure using the same | |
| JP2008279662A (en) | Multilayered bottle | |
| JP2022007521A (en) | Resin composition, molding, laminate, pipe, pipe for hot water circulation, heat insulation multilayer pipe, and pipe for fuel | |
| JP4734841B2 (en) | Multi-layer plastic container |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080911 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20101117 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20101130 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110128 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110607 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110728 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120117 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120206 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4922606 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150210 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150210 Year of fee payment: 3 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150210 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150210 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |