JP4671161B2 - Oxygen-absorbing resin composition - Google Patents
Oxygen-absorbing resin composition Download PDFInfo
- Publication number
- JP4671161B2 JP4671161B2 JP2004046697A JP2004046697A JP4671161B2 JP 4671161 B2 JP4671161 B2 JP 4671161B2 JP 2004046697 A JP2004046697 A JP 2004046697A JP 2004046697 A JP2004046697 A JP 2004046697A JP 4671161 B2 JP4671161 B2 JP 4671161B2
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- copolymer
- resin composition
- resin
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000011342 resin composition Substances 0.000 title claims description 54
- 229920005989 resin Polymers 0.000 claims description 61
- 239000011347 resin Substances 0.000 claims description 61
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 54
- 229910052760 oxygen Inorganic materials 0.000 claims description 54
- 239000001301 oxygen Substances 0.000 claims description 54
- 229920001577 copolymer Polymers 0.000 claims description 47
- -1 polyethylene Polymers 0.000 claims description 28
- 239000004698 Polyethylene Substances 0.000 claims description 27
- 229920000573 polyethylene Polymers 0.000 claims description 27
- 229910052723 transition metal Inorganic materials 0.000 claims description 13
- 150000003624 transition metals Chemical class 0.000 claims description 12
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- 150000001993 dienes Chemical class 0.000 claims description 11
- 229920005992 thermoplastic resin Polymers 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 34
- 239000005020 polyethylene terephthalate Substances 0.000 description 34
- 239000010410 layer Substances 0.000 description 31
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 27
- 230000004888 barrier function Effects 0.000 description 24
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 17
- 239000008188 pellet Substances 0.000 description 15
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 10
- 230000006866 deterioration Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 238000004806 packaging method and process Methods 0.000 description 9
- 229920001684 low density polyethylene Polymers 0.000 description 8
- 239000004702 low-density polyethylene Substances 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000001954 sterilising effect Effects 0.000 description 6
- 238000004659 sterilization and disinfection Methods 0.000 description 6
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical class CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 5
- 229920001903 high density polyethylene Polymers 0.000 description 5
- 239000004700 high-density polyethylene Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920001179 medium density polyethylene Polymers 0.000 description 5
- 239000004701 medium-density polyethylene Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 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
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 239000004840 adhesive resin Substances 0.000 description 3
- 229920006223 adhesive resin Polymers 0.000 description 3
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- MHPUGCYGQWGLJL-UHFFFAOYSA-N 5-methyl-hexanoic acid Chemical compound CC(C)CCCC(O)=O MHPUGCYGQWGLJL-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 235000013365 dairy product Nutrition 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 229920005679 linear ultra low density polyethylene Polymers 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- SFTGRPFSYZGXQW-GQCTYLIASA-N (4e)-3-methylhexa-1,4-diene Chemical compound C\C=C\C(C)C=C SFTGRPFSYZGXQW-GQCTYLIASA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- GCORITRBZMICMI-CMDGGOBGSA-N (e)-dodec-4-enoic acid Chemical compound CCCCCCC\C=C\CCC(O)=O GCORITRBZMICMI-CMDGGOBGSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- FERWUCFAQLAGDE-UHFFFAOYSA-N 1,3-bis(2-hydroxyphenyl)propane-1,3-dione Chemical compound OC1=CC=CC=C1C(=O)CC(=O)C1=CC=CC=C1O FERWUCFAQLAGDE-UHFFFAOYSA-N 0.000 description 1
- DNXKZJFMYKDQNL-UHFFFAOYSA-N 1,3-bis(4-chlorophenyl)propane-1,3-dione Chemical compound C1=CC(Cl)=CC=C1C(=O)CC(=O)C1=CC=C(Cl)C=C1 DNXKZJFMYKDQNL-UHFFFAOYSA-N 0.000 description 1
- XKFZOWRFWMXGQG-UHFFFAOYSA-N 1,3-bis(4-methylphenyl)propane-1,3-dione Chemical compound C1=CC(C)=CC=C1C(=O)CC(=O)C1=CC=C(C)C=C1 XKFZOWRFWMXGQG-UHFFFAOYSA-N 0.000 description 1
- HIMLFYUFZYQSDE-UHFFFAOYSA-N 1,3-dicyclohexylpropane-1,3-dione Chemical compound C1CCCCC1C(=O)CC(=O)C1CCCCC1 HIMLFYUFZYQSDE-UHFFFAOYSA-N 0.000 description 1
- LIKQHVGPOUBDTG-UHFFFAOYSA-N 1,4-diphenylbutane-1,3-dione Chemical compound C=1C=CC=CC=1CC(=O)CC(=O)C1=CC=CC=C1 LIKQHVGPOUBDTG-UHFFFAOYSA-N 0.000 description 1
- TYNRJXSHXIDFKH-UHFFFAOYSA-N 1-(4-chlorophenyl)-3-phenylpropane-1,3-dione Chemical compound C1=CC(Cl)=CC=C1C(=O)CC(=O)C1=CC=CC=C1 TYNRJXSHXIDFKH-UHFFFAOYSA-N 0.000 description 1
- LRQGFQDEQPZDQC-UHFFFAOYSA-N 1-Phenyl-1,3-eicosanedione Chemical compound CCCCCCCCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 LRQGFQDEQPZDQC-UHFFFAOYSA-N 0.000 description 1
- BKUAQOCVPRDREL-UHFFFAOYSA-N 1-Phenyl-1,3-octadecanedione Chemical compound CCCCCCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 BKUAQOCVPRDREL-UHFFFAOYSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- PPWUTZVGSFPZOC-UHFFFAOYSA-N 1-methyl-2,3,3a,4-tetrahydro-1h-indene Chemical compound C1C=CC=C2C(C)CCC21 PPWUTZVGSFPZOC-UHFFFAOYSA-N 0.000 description 1
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- VGYZKPWMARHMDW-UHFFFAOYSA-N 1-phenyltetradecane-1,3-dione Chemical compound CCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 VGYZKPWMARHMDW-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-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
- DOMHCBYZLIWUHE-UHFFFAOYSA-N 2-(chloromethyl)-3-prop-1-en-2-ylbicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(C(=C)C)C2CCl DOMHCBYZLIWUHE-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
- BSELJBOMYPMBNL-UHFFFAOYSA-N 2-acetyl-3,4-dihydro-2h-naphthalen-1-one Chemical compound C1=CC=C2C(=O)C(C(=O)C)CCC2=C1 BSELJBOMYPMBNL-UHFFFAOYSA-N 0.000 description 1
- OEKATORRSPXJHE-UHFFFAOYSA-N 2-acetylcyclohexan-1-one Chemical compound CC(=O)C1CCCCC1=O OEKATORRSPXJHE-UHFFFAOYSA-N 0.000 description 1
- CTUQBZGKHZPYJF-UHFFFAOYSA-N 2-benzoyl-1,3-diphenylpropane-1,3-dione Chemical compound C=1C=CC=CC=1C(=O)C(C(=O)C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 CTUQBZGKHZPYJF-UHFFFAOYSA-N 0.000 description 1
- HUCQLDZSDDSFKF-UHFFFAOYSA-N 2-benzoyl-3,4-dihydro-2h-naphthalen-1-one Chemical compound C1CC2=CC=CC=C2C(=O)C1C(=O)C1=CC=CC=C1 HUCQLDZSDDSFKF-UHFFFAOYSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical class CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- NVHGRUYAFQFUJE-UHFFFAOYSA-N 2-octadecanoyl-3,4-dihydro-2h-naphthalen-1-one Chemical compound C1=CC=C2C(=O)C(C(=O)CCCCCCCCCCCCCCCCC)CCC2=C1 NVHGRUYAFQFUJE-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethyl-hexanoic acid Chemical compound OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- AHZPYLAZRVPKIB-UHFFFAOYSA-N 4,5-dimethylhexa-1,4-diene Chemical compound CC(C)=C(C)CC=C AHZPYLAZRVPKIB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 1
- KLAWFKRMCIXRFS-UHFFFAOYSA-N 5-ethenylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C=C)CC1C=C2 KLAWFKRMCIXRFS-UHFFFAOYSA-N 0.000 description 1
- VSQLAQKFRFTMNS-UHFFFAOYSA-N 5-methylhexa-1,4-diene Chemical compound CC(C)=CCC=C VSQLAQKFRFTMNS-UHFFFAOYSA-N 0.000 description 1
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 1
- UGJBFMMPNVKBPX-UHFFFAOYSA-N 5-propan-2-ylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C(C)C)CC1C=C2 UGJBFMMPNVKBPX-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 1
- UCKITPBQPGXDHV-UHFFFAOYSA-N 7-methylocta-1,6-diene Chemical compound CC(C)=CCCCC=C UCKITPBQPGXDHV-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 1
- GCORITRBZMICMI-UHFFFAOYSA-N Linderic acid Natural products CCCCCCCC=CCCC(O)=O GCORITRBZMICMI-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920003354 Modic® Polymers 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 235000006468 Thea sinensis Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004708 Very-low-density polyethylene Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 101150059062 apln gene Proteins 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
- 235000021342 arachidonic acid Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000008452 baby food Nutrition 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 235000012174 carbonated soft drink Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- KDMCQAXHWIEEDE-UHFFFAOYSA-L cobalt(2+);7,7-dimethyloctanoate Chemical compound [Co+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O KDMCQAXHWIEEDE-UHFFFAOYSA-L 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008162 cooking oil Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229940013688 formic acid Drugs 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229920001112 grafted polyolefin Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 235000009569 green tea Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- ZBRRLVWJAPULGW-UHFFFAOYSA-N henicosane-2,4-dione Chemical compound CCCCCCCCCCCCCCCCCC(=O)CC(C)=O ZBRRLVWJAPULGW-UHFFFAOYSA-N 0.000 description 1
- ILPNRWUGFSPGAA-UHFFFAOYSA-N heptane-2,4-dione Chemical compound CCCC(=O)CC(C)=O ILPNRWUGFSPGAA-UHFFFAOYSA-N 0.000 description 1
- WYKDTBMIJGOJAN-UHFFFAOYSA-N heptatriacontane-18,20-dione Chemical compound CCCCCCCCCCCCCCCCCC(=O)CC(=O)CCCCCCCCCCCCCCCCC WYKDTBMIJGOJAN-UHFFFAOYSA-N 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 235000015094 jam Nutrition 0.000 description 1
- 235000008960 ketchup Nutrition 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 235000013622 meat product Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229960002969 oleic acid Drugs 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 235000020333 oolong tea Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 235000014101 wine Nutrition 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、酸素存在下で劣化を起こしやすい内容品、特に飲料、食品、及び医薬品等の包装材に用いられる酸素吸収性樹脂組成物に関する。 The present invention relates to an oxygen-absorbing resin composition that is used in packaging materials such as beverages, foods, and pharmaceuticals that are susceptible to deterioration in the presence of oxygen.
従来、包装容器としては、金属缶、ガラスビン、各種プラスチック容器等が使用されている。プラスチック容器は、軽量であり、耐衝撃性にもある程度優れているという利点を有しているが、容器壁を透過する酸素による内容物の変質、フレーバー低下等の問題を有している。特に、金属缶やガラスビンでは容器壁を通しての酸素透過がゼロであり、容器内に残留する酸素のみが問題となるのに対して、プラスチック容器の場合には、器壁を通して無視し得ないオーダーの酸素が透過し、内容品の保存性の点で問題となっている。
これを防止するために、プラスチック容器では、エチレン−ビニルアルコール共重合体等のガス遮断性を有する樹脂の層を少なくとも１層有する多層構造体が提案されている（例えば、特許文献１参照。）。
また、ポリマーから成り酸素捕集特性を有する組成物又は該組成物の層を含有する包装用障壁において、組成物が酸化可能有機成分の金属触媒酸化により酸素を捕集することを特徴とする包装用障壁が提案されており、酸化可能有機成分として、ポリアミド、特にキシリレン基含有ポリアミドが使用されている（例えば、特許文献２参照。）。
上記ガスバリヤー性に優れた樹脂、例えばエチレン−ビニルアルコール共重合体（ＥＶＯＨ）は、低湿度条件下ではきわめて優れた酸素遮断性を示すものの、高湿度条件下では酸素に対する透過性が極めて大きくなるという問題を有している。さらに、内容物の保存性の向上を目的として、上記ガスバリヤー性樹脂は湯殺菌、ボイル殺菌、レトルト殺菌等の加熱殺菌包装技法と組み合わせて用いられる場合が多い。従って、この加熱殺菌時に、ＥＶＯＨは高湿度条件下に置かれるため、酸素透過性の大きい状態になるばかりでなく、ＥＶＯＨが有する保水性のために、殺菌終了後も酸素透過性の大きい状態が続き、所定のガスバリヤー性が得られない。
Conventionally, metal cans, glass bottles, various plastic containers, and the like are used as packaging containers. The plastic container is advantageous in that it is light in weight and excellent in impact resistance to some extent, but it has problems such as deterioration of contents due to oxygen permeating through the container wall and lowering of flavor. In particular, oxygen permeation through the container wall is zero in metal cans and glass bottles, and only the oxygen remaining in the container becomes a problem, whereas in the case of plastic containers, it cannot be ignored through the container wall. Oxygen permeates, which is a problem in terms of storage stability of the contents.
In order to prevent this, as a plastic container, a multilayer structure having at least one resin layer having gas barrier properties such as an ethylene-vinyl alcohol copolymer has been proposed (for example, see Patent Document 1). .
Also, a packaging comprising a polymer having oxygen scavenging properties or a packaging barrier containing a layer of the composition, wherein the composition collects oxygen by metal-catalyzed oxidation of an oxidizable organic component Barriers have been proposed, and polyamides, particularly xylylene group-containing polyamides, are used as oxidizable organic components (see, for example, Patent Document 2).
Resins with excellent gas barrier properties, such as ethylene-vinyl alcohol copolymer (EVOH), exhibit extremely good oxygen barrier properties under low humidity conditions, but extremely high permeability to oxygen under high humidity conditions. Has the problem. Furthermore, the gas barrier resin is often used in combination with a heat sterilization packaging technique such as hot water sterilization, boil sterilization, or retort sterilization for the purpose of improving the storage stability of the contents. Therefore, during this heat sterilization, EVOH is placed under a high humidity condition, so that not only the oxygen permeability becomes high, but also the water permeability of EVOH has a high oxygen permeability even after the end of sterilization. Subsequently, a predetermined gas barrier property cannot be obtained.
しかしながら、上記酸素吸収性樹脂組成物は、成形中に樹脂の酸化劣化によって着色するという問題が生じ、外観上好ましくない。また、より優れた耐熱性を有する酸素吸収性樹脂組成物に対する要求がある。
本発明の目的は、上記酸素吸収性樹脂組成物において、酸素吸収性能に優れ、かつ成形中の樹脂の酸化劣化を抑制して、成形時に着色を生じない酸素吸収性樹脂組成物を提供することである。
また、本発明の他の目的は、耐熱性に優れた酸素吸収性樹脂組成物を提供することである。
However, the oxygen-absorbing resin composition has a problem of coloring due to oxidative degradation of the resin during molding, which is not preferable in appearance. There is also a need for an oxygen-absorbing resin composition having better heat resistance.
An object of the present invention is to provide an oxygen-absorbing resin composition that is excellent in oxygen-absorbing performance in the above-described oxygen-absorbing resin composition and that suppresses oxidative deterioration of the resin during molding and does not cause coloring during molding. It is.
Another object of the present invention is to provide an oxygen-absorbing resin composition having excellent heat resistance.
本発明は、水添スチレン−ジエン共重合体（Ａ）、分子構造にエチレン構造を有する熱可塑性樹脂（Ｂ）及び遷移金属触媒（Ｃ）を含み、共重合体（Ａ）がトリガーとなって熱可塑性樹脂（Ｂ）の酸化が進行することによって酸素を吸収する酸素吸収性樹脂組成物を提供する。ここで、共重合体（Ａ）は、ジエン由来の炭素−炭素二重結合を１×１０-5〜１×１０-2ｅｑ／ｇの範囲で含有するのがよい。 The present invention includes a hydrogenated styrene-diene copolymer (A), a thermoplastic resin (B) having an ethylene structure in the molecular structure, and a transition metal catalyst (C), and the copolymer (A) is a trigger. Provided is an oxygen-absorbing resin composition that absorbs oxygen when oxidation of a thermoplastic resin (B) proceeds. Here, the copolymer (A) preferably contains a diene-derived carbon-carbon double bond in a range of 1 × 10 −5 to 1 × 10 −2 eq / g.
本発明の酸素吸収性樹脂組成物を用いることにより、酸素吸収性能に優れ、かつ成形中の樹脂の酸化劣化を抑制することができる。また、耐熱性に優れた酸素吸収性樹脂組成物を提供することができる。 By using the oxygen-absorbing resin composition of the present invention, the oxygen-absorbing performance is excellent, and the oxidative deterioration of the resin during molding can be suppressed. Moreover, the oxygen-absorbing resin composition excellent in heat resistance can be provided.
本発明の酸素吸収性樹脂組成物は、水添スチレン−ジエン共重合体（Ａ）、分子構造にエチレン構造を有する熱可塑性樹脂（Ｂ）及び遷移金属触媒（Ｃ）を含み、共重合体（Ａ）がトリガーとなって熱可塑性樹脂（Ｂ）の酸化が進行することによって酸素を吸収するものである。
水添スチレン−ジエン共重合体（Ａ）としては、スチレン−ジエン共重合体を水素化することによって得ることができる。例えば、旭化成ケミカルズ（株）からタフテックＰ２０００というグレード名の樹脂として入手ができる。この樹脂は、スチレン−ジエン共重合体におけるビニル−ポリブタジエン相が水素添加されている。水添スチレン−ジエン共重合体（Ａ）を用いることにより、耐熱性に優れた酸素吸収性樹脂組成物を提供することができる。
The oxygen-absorbing resin composition of the present invention comprises a hydrogenated styrene-diene copolymer (A), a thermoplastic resin (B) having an ethylene structure in the molecular structure, and a transition metal catalyst (C). A) is triggered by the oxidation of the thermoplastic resin (B) to absorb oxygen.
The hydrogenated styrene-diene copolymer (A) can be obtained by hydrogenating the styrene-diene copolymer. For example, it can be obtained from Asahi Kasei Chemicals Corporation as a resin having a grade name of Tuftec P2000. In this resin, the vinyl-polybutadiene phase in the styrene-diene copolymer is hydrogenated. By using the hydrogenated styrene-diene copolymer (A), an oxygen-absorbing resin composition having excellent heat resistance can be provided.
スチレン−ジエン共重合体としては、鎖状又は環状の共役又は非共役ジエンから誘導された単位を含む樹脂が好ましい。これらの樹脂は単独で用いてもよく、また二種以上の樹脂のブレンド物の形態で用いることもできる。
鎖状又は環状の共役又は非共役ジエンの単量体としては、例えばブタジエン、イソプレン等の共役ジエン；１，４−ヘキサジエン、３−メチル−１，４−ヘキサジエン、４−メチル−１，４−ヘキサジエン、５−メチル−１，４−ヘキサジエン、４，５−ジメチル−１，４−ヘキサジエン、７−メチル−１，６−オクタジエン等の鎖状非共役ジエン；メチルテトラヒドロインデン、５−エチリデン−２−ノルボルネン、５−メチレン−２−ノルボルネン、５−イソプロピリデン−２−ノルボルネン、５−ビニリデン−２−ノルボルネン、６−クロロメチル−５−イソプロペニル−２−ノルボルネン、ジシクロペンタジエン等の環状非共役ジエンが挙げられる。
As the styrene-diene copolymer, a resin containing a unit derived from a linear or cyclic conjugated or non-conjugated diene is preferable. These resins may be used alone or in the form of a blend of two or more resins.
Examples of the monomer of the chain or cyclic conjugated or non-conjugated diene include conjugated dienes such as butadiene and isoprene; 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4- Chain non-conjugated dienes such as hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene; methyltetrahydroindene, 5-ethylidene-2 -Cyclic non-conjugated such as norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, dicyclopentadiene Examples include dienes.
具体的な共重合体（Ａ）としては、水添スチレン−ブタジエン共重合体、水添スチレン−イソプレン共重合体等が挙げられる。
このうち、熱可塑性樹脂（Ｂ）に対するトリガー効果が顕著であること、酸素吸収後の酸化副生物の量が少ないことから、共重合体（Ａ）としてはジエンから誘導された単位がＣ1-4の直鎖アルキル鎖である分岐部分を有する共重合体が好ましく、具体的には水添スチレン−ブタジエン共重合体、特に水添スチレン−ブタジエン−スチレントリブロック共重合体が好ましい。
また、成形中の熱安定性、及び熱可塑性樹脂（Ｂ）に対するトリガー効果が顕著である点から、共重合体（Ａ）は、ジエン由来の炭素−炭素二重結合を１×１０-5〜１×１０-2ｅｑ／ｇの範囲で含有するのが好ましい。より好ましくは、１×１０-4〜１×１０-2ｅｑ／ｇである。さらに好ましくは、１×１０-4〜５×１０-3ｅｑ／ｇである。そこで、（Ａ）（Ｂ）及び（Ｃ）を配合した酸素吸収性樹脂組成物としては、炭素−炭素二重結合を２×１０-6〜１×１０-4ｅｑ／ｇの範囲で含有するのが好ましい。より好ましくは、１×１０-5〜５×１０-5ｅｑ／ｇである。
Specific examples of the copolymer (A) include a hydrogenated styrene-butadiene copolymer and a hydrogenated styrene-isoprene copolymer.
Among these, since the trigger effect on the thermoplastic resin (B) is remarkable and the amount of oxidation by-products after oxygen absorption is small, the unit derived from diene as the copolymer (A) is C 1- A copolymer having a branched portion that is a linear alkyl chain of 4 is preferable, and specifically, a hydrogenated styrene-butadiene copolymer, particularly a hydrogenated styrene-butadiene-styrene triblock copolymer is preferable.
In addition, the copolymer (A) has a diene-derived carbon-carbon double bond of 1 × 10 −5 to 1 in that the thermal stability during molding and the trigger effect on the thermoplastic resin (B) are remarkable. It is preferably contained in the range of 1 × 10 −2 eq / g. More preferably, it is 1 × 10 −4 to 1 × 10 −2 eq / g. More preferably, it is 1 * 10 < -4 > -5 * 10 < -3 > eq / g. Therefore, the oxygen-absorbing resin composition containing (A), (B), and (C) contains a carbon-carbon double bond in a range of 2 × 10 −6 to 1 × 10 −4 eq / g. Is preferred. More preferably, it is 1 × 10 −5 to 5 × 10 −5 eq / g.
前記樹脂（Ｂ）としては、例えば、低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、線状低密度ポリエチレン、線状超低密度ポリエチレン等のポリエチレン、アイソタクティック又はシンジオタクテイクスポリプロピレン等のポリプロピレン、エチレン−プロピレン共重合体、ポリブテン−１、エチレン−ブテン−１共重合体、エチレン−プロピレン−ブテン−１共重合体、エチレン−酢酸ビニル共重合体、エチレン−ビニルアルコール共重合体等のエチレン系共重合体、プロピレン−ブテン−１共重合体等のプロピレン系共重合体、イオン架橋オレフィン共重合体或いはこれらのブレンド物等が挙げられる。好ましくは、樹脂（Ｂ）はポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体、エチレン系共重合体及びプロピレン系共重合体である。
また、上記樹脂をベースポリマーとし、不飽和カルボン酸又はこれらの誘導体でグラフト変性された酸変性オレフィン系樹脂を分子構造にエチレン構造を有する熱可塑性樹脂（Ｂ）として用いることもできる。
Examples of the resin (B) include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polyethylene such as linear ultra low density polyethylene, polypropylene such as isotactic or syndiotactic polypropylene, Ethylene-based copolymers such as ethylene-propylene copolymer, polybutene-1, ethylene-butene-1 copolymer, ethylene-propylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer Examples thereof include a copolymer, a propylene-based copolymer such as a propylene-butene-1 copolymer, an ion-crosslinked olefin copolymer, or a blend thereof. Preferably, the resin (B) is polyethylene, polypropylene, an ethylene-propylene copolymer, an ethylene copolymer, and a propylene copolymer.
Further, an acid-modified olefin resin graft-modified with an unsaturated carboxylic acid or a derivative thereof using the above resin as a base polymer can be used as the thermoplastic resin (B) having an ethylene structure in the molecular structure.
遷移金属触媒としては、鉄、コバルト、ニッケル等の周期律表第VIII族金属成分が好ましいが、他に銅、銀等の第Ｉ族金属：錫、チタン、ジルコニウム等の第IV族金属、バナジウムの第V族、クロム等VI族、マンガン等のVII族の金属成分を挙げることができる。これらの金属成分の内でもコバルト成分は、酸素吸収速度が大きく、本発明の目的に特に適したものである。
遷移金属触媒は、上記遷移金属の低価数の無機酸塩或いは有機酸塩或いは錯塩の形で一般に使用される。
無機酸塩としては、塩化物などのハライド、硫酸塩等のイオウのオキシ酸塩、硝酸塩などの窒素のオキシ酸塩、リン酸塩などのリンオキシ酸塩、ケイ酸塩等が挙げられる。
一方有機酸塩としては、カルボン酸塩、スルホン酸塩、ホスホン酸塩などが挙げられるが、カルボン酸塩が本発明の目的に好適であり、その具体例としては、酢酸、プロピオン酸、イソプロピオン酸、ブタン酸、イソブタン酸、ペンタン酸、イソペンタン酸、ヘキサン酸、ヘプタン酸、イソヘプタン酸、オクタン酸、２−エチルヘキサン酸、ノナン酸、３，５，５−トリメチルヘキサン酸、デカン酸、ネオデカン酸、ウンデカン酸、ラウリン酸、ミリスチン酸、パルミチン酸、マーガリン酸、ステアリン酸、アラキン酸、リンデル酸、ツズ酸、ペトロセリン酸、オレイン酸、リノール酸、リノレン酸、アラキドン酸、ギ酸、シュウ酸、スルファミン酸、ナフテン酸等の遷移金属塩が挙げられる。
The transition metal catalyst is preferably a Group VIII metal component of the periodic table such as iron, cobalt and nickel, but also a Group I metal such as copper and silver: Group IV metals such as tin, titanium and zirconium, vanadium Group V, Group VI such as chromium, and Group VII metal components such as manganese. Among these metal components, the cobalt component has a high oxygen absorption rate and is particularly suitable for the purpose of the present invention.
The transition metal catalyst is generally used in the form of a low-valent inorganic acid salt, organic acid salt or complex salt of the transition metal.
Examples of inorganic acid salts include halides such as chlorides, sulfur oxyacid salts such as sulfates, nitrogen oxyacid salts such as nitrates, phosphorus oxyacid salts such as phosphates, and silicates.
On the other hand, examples of the organic acid salt include a carboxylate, a sulfonate, and a phosphonate. The carboxylate is suitable for the purpose of the present invention, and specific examples thereof include acetic acid, propionic acid, and isopropion. Acid, butanoic acid, isobutanoic acid, pentanoic acid, isopentanoic acid, hexanoic acid, heptanoic acid, isoheptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, 3,5,5-trimethylhexanoic acid, decanoic acid, neodecanoic acid , Undecanoic acid, Lauric acid, Myristic acid, Palmitic acid, Margaric acid, Stearic acid, Arachic acid, Linderic acid, Tuzic acid, Petroceric acid, Oleic acid, Linoleic acid, Linolenic acid, Arachidonic acid, Formic acid, Oxalic acid, Sulfamine Examples thereof include transition metal salts such as acid and naphthenic acid.
一方、遷移金属の錯体としては、β−ジケトンまたはβ−ケト酸エステルとの錯体が使用され、β−ジケトンまたはβ−ケト酸エステルとしては、例えば、アセチルアセトン、アセト酢酸エチル、１，３−シクロヘキサジオン、メチレンビス−１，３ーシクロヘキサジオン、２−ベンジル−１，３−シクロヘキサジオン、アセチルテトラロン、パルミトイルテトラロン、ステアロイルテトラロン、ベンゾイルテトラロン、２−アセチルシクロヘキサノン、２−ベンゾイルシクロヘキサノン、２−アセチル−１，３−シクロヘキサンジオン、ベンゾイル−ｐ−クロルベンゾイルメタン、ビス（４−メチルベンゾイル）メタン、ビス（２−ヒドロキシベンゾイル）メタン、ベンゾイルアセトン、トリベンゾイルメタン、ジアセチルベンゾイルメタン、ステアロイルベンゾイルメタン、パルミトイルベンゾイルメタン、ラウロイルベンゾイルメタン、ジベンゾイルメタン、ビス（４−クロルベンゾイル）メタン、ビス（メチレン−３，４−ジオキシベンゾイル）メタン、ベンゾイルアセチルフェニルメタン、ステアロイル（４−メトキシベンゾイル）メタン、ブタノイルアセトン、ジステアロイルメタン、アセチルアセトン、ステアロイルアセトン、ビス（シクロヘキサノイル）−メタン及びジピバロイルメタン等を用いることができる。 On the other hand, as the transition metal complex, a complex with β-diketone or β-keto acid ester is used, and examples of β-diketone or β-keto acid ester include acetylacetone, ethyl acetoacetate, 1,3-cyclohexane. Sadione, methylenebis-1,3-cyclohexadione, 2-benzyl-1,3-cyclohexadione, acetyltetralone, palmitoyltetralone, stearoyltetralone, benzoyltetralone, 2-acetylcyclohexanone, 2-benzoylcyclohexanone 2-acetyl-1,3-cyclohexanedione, benzoyl-p-chlorobenzoylmethane, bis (4-methylbenzoyl) methane, bis (2-hydroxybenzoyl) methane, benzoylacetone, tribenzoylmethane, diacetylbenzoylmethane Stearoylbenzoylmethane, palmitoylbenzoylmethane, lauroylbenzoylmethane, dibenzoylmethane, bis (4-chlorobenzoyl) methane, bis (methylene-3,4-dioxybenzoyl) methane, benzoylacetylphenylmethane, stearoyl (4-methoxybenzoyl) ) Methane, butanoylacetone, distearoylmethane, acetylacetone, stearoylacetone, bis (cyclohexanoyl) -methane, dipivaloylmethane, and the like can be used.
ＥＶＯＨ等のガスバリヤー性樹脂に共重合体（Ａ）を配合する酸素吸収性樹脂組成物の場合には、共重合体（Ａ）が有する不飽和結合の数、即ち、共重合体（Ａ）の添加量により、前記組成物の酸素吸収量が決定する。共重合体（Ａ）の配合量を多くすれば酸素吸収量も多くなるが、基材樹脂の酸素バリヤー性が低下し、透明性が低下するといった問題が生じる。そのため、その配合量には限界があり、酸素吸収量も限定される。
一方、本発明の酸素吸収性樹脂組成物は、共重合体（Ａ）がトリガーとなって樹脂（Ｂ）の酸化が進行することによって酸素を吸収するため、ＥＶＯＨ等のガスバリヤー性樹脂をベースとする酸素吸収性樹脂組成物に比べ、はるかに多量の酸素を吸収することができる。また、長期にわたり酸素を有効に吸収でき、汎用樹脂に酸素を吸収させることができるため、コスト面でも有利である。
In the case of an oxygen-absorbing resin composition in which the copolymer (A) is blended with a gas barrier resin such as EVOH, the number of unsaturated bonds of the copolymer (A), that is, the copolymer (A) The amount of oxygen absorbed by the composition is determined by the amount added. If the amount of the copolymer (A) is increased, the amount of oxygen absorbed also increases, but there arises a problem that the oxygen barrier property of the base resin is lowered and the transparency is lowered. Therefore, there is a limit to the amount of the compound, and the oxygen absorption amount is also limited.
On the other hand, the oxygen-absorbing resin composition of the present invention is based on a gas barrier resin such as EVOH because it absorbs oxygen by the copolymer (A) as a trigger and the oxidation of the resin (B) proceeds. As compared with the oxygen-absorbing resin composition, a much larger amount of oxygen can be absorbed. Moreover, since oxygen can be effectively absorbed over a long period of time and oxygen can be absorbed by a general-purpose resin, it is advantageous in terms of cost.
本発明の酸素吸収性樹脂組成物において、前記共重合体（Ａ）の配合量は前記共重合体（Ａ）と前記樹脂（Ｂ）の合計重量に対して２．５〜１０重量％の範囲である。前記樹脂（Ａ）の配合量がこの範囲内であれば、前記樹脂（Ａ）のトリガー効果が効率よく発現し、成形中の酸化劣化を抑制することができる。好ましくは、４〜８重量％である。
本発明の酸素吸収性樹脂組成物において、遷移金属触媒は、酸素吸収性樹脂組成物合計重量に対して、遷移金属量として１０〜１０００ｐｐｍ、特に５０〜５００ｐｐｍの量で含有されていることが好ましい。遷移金属触媒の量が上記範囲内であれば、良好なガスバリヤー性を得ることができ、酸素吸収性樹脂組成物の混練成形時における劣化傾向を抑制することができる。
さらに、本発明の酸素吸収性樹脂組成物は、２０００ｐｐｍ以下のリン系酸化防止剤を含有していることが好ましい。リン系酸化防止剤を添加することによって、本発明の酸素吸収性樹脂組成物の高い酸素吸収性能を維持しつつ、成形時の酸化劣化をさらに抑制することができる。より好ましくは、本発明の酸素吸収性樹脂組成物は３００〜１５００ｐｐｍのリン系酸化防止剤を含有する。
In the oxygen-absorbing resin composition of the present invention, the amount of the copolymer (A) is in the range of 2.5 to 10% by weight with respect to the total weight of the copolymer (A) and the resin (B). It is. If the blending amount of the resin (A) is within this range, the trigger effect of the resin (A) can be expressed efficiently, and oxidative deterioration during molding can be suppressed. Preferably, it is 4 to 8% by weight.
In the oxygen-absorbing resin composition of the present invention, the transition metal catalyst is preferably contained in an amount of 10 to 1000 ppm, particularly 50 to 500 ppm as the amount of transition metal with respect to the total weight of the oxygen-absorbing resin composition. . If the amount of the transition metal catalyst is within the above range, good gas barrier properties can be obtained, and deterioration tendency during kneading and molding of the oxygen-absorbing resin composition can be suppressed.
Furthermore, the oxygen-absorbing resin composition of the present invention preferably contains 2000 ppm or less of a phosphorus-based antioxidant. By adding a phosphorus antioxidant, it is possible to further suppress oxidative deterioration during molding while maintaining the high oxygen absorption performance of the oxygen-absorbing resin composition of the present invention. More preferably, the oxygen-absorbing resin composition of the present invention contains 300 to 1500 ppm of a phosphorus-based antioxidant.
酸素吸収性樹脂組成物の配合には、種々の手段を用いることができるが、サイドフィードを備えた二軸押出機を用いる方法が好適である。二軸押出機による混連に際しては、酸素吸収性樹脂組成物の劣化を最小限とするため、非酸化的雰囲気で実施するのが良い。また、滞留時間を短く、成形温度もできるだけ低温とすることが、酸素吸収性樹脂組成物の性能維持において極めて重要である。 Various means can be used for blending the oxygen-absorbing resin composition, but a method using a twin screw extruder equipped with a side feed is preferred. When mixing with a twin-screw extruder, it is preferable to carry out in a non-oxidizing atmosphere in order to minimize the deterioration of the oxygen-absorbing resin composition. In addition, it is extremely important to maintain the performance of the oxygen-absorbing resin composition that the residence time is short and the molding temperature is as low as possible.
本発明で用いる酸素吸収性樹脂組成物には、一般に必要ではないが、所望によりそれ自体公知の活性化剤を配合することができる。活性化剤の適当な例は、これに限定されないが、ポリエチレングリコール、ポリプロピレングリコール、エチレン・メタクリル酸共重合体、各種アイオノマー等の水酸基及び／又はカルボキシル基含有重合体である。
本発明に用いる酸素吸収性樹脂組成物には、充填剤、着色剤、耐熱安定剤、耐候安定剤、リン系酸化防止剤以外の酸化防止剤、老化防止剤、光安定剤、紫外線吸収剤、帯電防止剤、金属セッケンやワックス等の滑剤、改質用樹脂乃至ゴム、等の公知の樹脂配合剤を、それ自体公知の処方に従って配合できる。
例えば、滑剤を配合することにより、スクリューへの樹脂の食い込みが改善される。滑剤としては、ステアリン酸マグネシウム、ステアリン酸カルシウム等の金属石ケン、流動、天然または合成パラフィン、マイクロワックス、ポリエチレンワックス、塩素化ポリエチレンワックス等の炭化水素系のもの、ステアリン酸、ラウリン酸等の脂肪酸系のもの、ステアリン酸アミド、バルミチン酸アミド、オレイン酸アミド、エシル酸アミド、メチレンビスステアロアミド、エチレンビスステアロアミド等の脂肪酸モノアミド系またはビスアミド系のもの、ブチルステアレート、硬化ヒマシ油、エチレングリコールモノステアレート等のエステル系のもの、セチルアルコール、ステアリルアルコール等のアルコール系のもの、およびそれらの混合系が一般に用いられる。
In general, the oxygen-absorbing resin composition used in the present invention is not necessary, but an activator known per se can be blended if desired. Suitable examples of activators include, but are not limited to, polymers containing hydroxyl and / or carboxyl groups such as polyethylene glycol, polypropylene glycol, ethylene / methacrylic acid copolymers, various ionomers and the like.
The oxygen-absorbing resin composition used in the present invention includes a filler, a colorant, a heat stabilizer, a weather stabilizer, an antioxidant other than a phosphorus antioxidant, an anti-aging agent, a light stabilizer, an ultraviolet absorber, Known resin compounding agents such as antistatic agents, lubricants such as metal soaps and waxes, and modifying resins or rubbers can be blended according to a formulation known per se.
For example, by incorporating a lubricant, the bite of the resin into the screw is improved. Lubricants include metal soaps such as magnesium stearate and calcium stearate, hydrocarbons such as fluid, natural or synthetic paraffin, micro wax, polyethylene wax and chlorinated polyethylene wax, and fatty acid systems such as stearic acid and lauric acid. Fatty acid monoamides or bisamides such as stearic acid amide, valmitic acid amide, oleic acid amide, esylic acid amide, methylene bisstearamide, ethylene bisstearamide, butyl stearate, hydrogenated castor oil, ethylene An ester type such as glycol monostearate, an alcohol type such as cetyl alcohol and stearyl alcohol, and a mixed system thereof are generally used.
本発明の酸素吸収性組成物は、粉末、粒状又はシート等の形状で、密封包装体内の酸素吸収に使用することができる。また、ライナー、ガスケット用又は被覆形成用の樹脂やゴム中に配合して、包装体内の残留酸素吸収に用いることができる。さらに、フィルム、シートの形で包装材料として、また、カップ、トレイ、ボトル、チューブ容器等のキャップ形で包装容器として包装体の製造に用いることができる。
本発明の酸素吸収性樹脂組成物は、これを含む少なくとも一層（以下、酸素吸収性層という。）と、他の樹脂の層からなる多層構造体の形で使用することが好ましい。なお、酸素吸収性樹脂組成物を含む層とは、上記の酸素吸収性樹脂組成物のみからなる層、及び他の樹脂等を基材とし酸素吸収性樹脂組成物を配合してなる層の両者の場合を含む。
多層構造体を構成する、酸素吸収性層以外の樹脂層は、熱可塑性樹脂又は熱硬化性樹脂から、その使用態様や要求される機能により適宜選択できる。例えば、オレフィン系樹脂、熱可塑性ポリエステル樹脂、酸素バリヤー性樹脂等が挙げられる。
オレフィン樹脂としては、低密度ポリエチレン（ＬＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）、線状低密度ポリエチレン（ＬＬＤＰＥ）、線状超低密度ポリエチレン（ＬＶＬＤＰＥ）等のポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、エチレン−プロピレン共重合体、ポリブテン−１、エチレン−ブテン−１共重合体、プロピレン−ブテン−１共重合体、エチレン−プロピレン−ブテン−１共重合体、エチレン−酢酸ビニル共重合体、イオン架橋オレフィン共重合体（アイオノマー）或いはこれらのブレンド物等が挙げられる。
The oxygen-absorbing composition of the present invention can be used for oxygen absorption in a sealed package in the form of powder, granules or sheets. Moreover, it can mix | blend with resin and rubber | gum for liners, gaskets, or coating formation, and can be used for residual oxygen absorption in a package. Furthermore, it can be used for the production of a package as a packaging material in the form of a film or sheet, and as a packaging container in the form of a cap such as a cup, tray, bottle, tube container or the like.
The oxygen-absorbing resin composition of the present invention is preferably used in the form of a multilayer structure comprising at least one layer containing this (hereinafter referred to as oxygen-absorbing layer) and another resin layer. The layer containing the oxygen-absorbing resin composition is both a layer made of only the above-mentioned oxygen-absorbing resin composition and a layer formed by blending the oxygen-absorbing resin composition with another resin as a base material. Including the case.
The resin layer other than the oxygen-absorbing layer constituting the multilayer structure can be appropriately selected from a thermoplastic resin or a thermosetting resin depending on its use mode or required function. For example, an olefin resin, a thermoplastic polyester resin, an oxygen barrier resin, and the like can be given.
Examples of the olefin resin include polyethylene (PE) such as low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), and linear very low density polyethylene (LVLDPE). , Polypropylene (PP), ethylene-propylene copolymer, polybutene-1, ethylene-butene-1 copolymer, propylene-butene-1 copolymer, ethylene-propylene-butene-1 copolymer, ethylene-vinyl acetate Examples thereof include copolymers, ion-crosslinked olefin copolymers (ionomers), and blends thereof.
また、熱可塑性ポリエステル樹脂としては、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリグリコール酸を主体とするポリエステル樹脂、或いはこれらの共重合ポリエステル、更にはこれらのブレンド物等が挙げられる。
酸素バリヤー性樹脂としては、エチレン−ビニルアルコール共重合体（ＥＶＯＨ）を挙げることができる。例えば、エチレン含有量が２０〜６０モル％、好ましくは、２５〜５０モル％であるエチレン−酢酸ビニル共重合体を、ケン化度が９６モル％以上、好ましくは、９９モル％以上となるようにケン化して得られる共重合体ケン化物が使用される。
このエチレンビニルアルコール共重合体ケン化物は、フィルムを形成することができる分子量を有する。一般に、フェノール：水の重量比で８５：１５の混合溶媒中３０℃で測定して０．０１ｄｌ／ｇ以上、好ましくは、０．０５ｄｌ／ｇ以上の粘度を有する。
酸素バリヤー性樹脂の他の例としては、ポリメタキシリデンアジパミド（ＭＸＤ６）等のポリアミド樹脂、環状オレフィン系共重合体（ＣＯＣ）、特にエチレンと環状オレフィンとの共重合体、特に、三井化学社製のＡＰＥＬ等を用いることができる。
The thermoplastic polyester resin includes polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), a polyester resin mainly composed of polyglycolic acid, or a copolymer polyester thereof, and further Examples include blends.
Examples of the oxygen barrier resin include an ethylene-vinyl alcohol copolymer (EVOH). For example, an ethylene-vinyl acetate copolymer having an ethylene content of 20 to 60 mol%, preferably 25 to 50 mol%, has a saponification degree of 96 mol% or more, preferably 99 mol% or more. A saponified copolymer obtained by saponification is used.
This saponified ethylene vinyl alcohol copolymer has a molecular weight capable of forming a film. Generally, it has a viscosity of 0.01 dl / g or more, preferably 0.05 dl / g or more, measured at 30 ° C. in a mixed solvent of phenol: water in a weight ratio of 85:15.
Other examples of oxygen barrier resins include polyamide resins such as polymetaxylidene adipamide (MXD6), cyclic olefin copolymers (COC), particularly copolymers of ethylene and cyclic olefins, particularly Mitsui APEL manufactured by Kagaku Co., Ltd. can be used.
上記多層構造体の構造は、使用態様、要求される機能により適宜選択できる。
例えば、酸素吸収性層をＯＡＲとして表して、次の構造がある。
二層構造：ＰＥＴ／ＯＡＲ、ＰＥ／ＯＡＲ、ＯＰＰ／ＯＡＲ、
三層構造：ＰＥ／ＯＡＲ／ＰＥＴ、ＰＥＴ／ＯＡＲ／ＰＥＴ、ＰＥ／ＯＡＲ／ＯＰＰ、ＥＶＯＨ／ＯＡＲ／ＰＥＴ、ＰＥ／ＯＡＲ／ＣＯＣ、
四層構造：ＰＥ／ＰＥＴ／ＯＡＲ／ＰＥＴ、ＰＥ／ＯＡＲ／ＥＶＯＨ／ＰＥＴ、ＰＥＴ／ＯＡＲ／ＥＶＯＨ／ＰＥＴ、ＰＥ／ＯＡＲ／ＥＶＯＨ／ＣＯＣ、ＰＥ／ＯＡＲ／ＥＶＯＨ／ＰＥ、
五層構造：ＰＥＴ／ＯＡＲ／ＰＥＴ／ＯＡＲ／ＰＥＴ、ＰＥ／ＰＥＴ／ＯＡＲ／ＥＶＯＨ／ＰＥＴ、ＰＥＴ／ＯＡＲ／ＥＶＯＨ／ＣＯＣ／ＰＥＴ、ＰＥＴ／ＯＡＲ／ＰＥＴ／ＣＯＣ／ＰＥＴ、ＰＥ／ＯＡＲ／ＥＶＯＨ／ＣＯＣ／ＰＥＴ、ＰＥ／ＥＶＯＨ／ＯＡＲ／ＥＶＯＨ／ＰＥ
六層構造：ＰＥＴ／ＯＡＲ／ＰＥＴ／ＯＡＲ／ＥＶＯＨ／ＰＥＴ、ＰＥ／ＰＥＴ／ＯＡＲ／ＣＯＣ／ＥＶＯＨ／ＰＥＴ、ＰＥＴ／ＯＡＲ／ＥＶＯＨ／ＰＥＴ／ＣＯＣ／ＰＥＴ、ＰＥ／ＥＶＯＨ／ＯＡＲ／ＰＥ／ＥＶＯＨ／ＰＥ
七層構造：ＰＥＴ／ＯＡＲ／ＣＯＣ／ＰＥＴ／ＥＶＯＨ／ＯＡＲ／ＰＥＴ、
尚、ＰＥとは、低密度ポリエチレン（ＬＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）、線状低密度ポリエチレン（ＬＬＤＰＥ）、線状超低密度ポリエチレン（ＬＶＬＤＰＥ）を意味する。
これらの構造で、酸素バリヤー層を少なくとも一層有している構造が、酸素吸収層の寿命を向上することができるため好ましい。
The structure of the multilayer structure can be appropriately selected depending on the use mode and the required function.
For example, the oxygen absorbing layer is expressed as OAR and has the following structure.
Two-layer structure: PET / OAR, PE / OAR, OPP / OAR,
Three-layer structure: PE / OAR / PET, PET / OAR / PET, PE / OAR / OPP, EVOH / OAR / PET, PE / OAR / COC,
Four-layer structure: PE / PET / OAR / PET, PE / OAR / EVOH / PET, PET / OAR / EVOH / PET, PE / OAR / EVOH / COC, PE / OAR / EVOH / PE,
Five-layer structure: PET / OAR / PET / OAR / PET, PE / PET / OAR / EVOH / PET, PET / OAR / EVOH / COC / PET, PET / OAR / PET / COC / PET, PE / OAR / EVOH / COC / PET, PE / EVOH / OAR / EVOH / PE
Six-layer structure: PET / OAR / PET / OAR / EVOH / PET, PE / PET / OAR / COC / EVOH / PET, PET / OAR / EVOH / PET / COC / PET, PE / EVOH / OAR / PE / EVOH / PE
Seven-layer structure: PET / OAR / COC / PET / EVOH / OAR / PET,
PE means low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), and linear ultra-low density polyethylene (LVLDPE).
In these structures, a structure having at least one oxygen barrier layer is preferable because the life of the oxygen absorbing layer can be improved.
上記積層体の製造に当たって、各樹脂層間に必要により接着剤樹脂を介在させることもできる。
このような接着剤樹脂としては、カルボン酸、カルボン酸無水物、カルボン酸塩、カルボン酸アミド、カルボン酸エステル等に基づくカルボニル（−ＣＯ−）基を主鎖又は側鎖に、１〜７００ミリイクイバレント（ｍｅｑ）／１００ｇ樹脂、特に１０〜５００（ｍｅｑ）／１００ｇ樹脂の濃度で含有する熱可塑性樹脂が挙げられる。接着剤樹脂の適当な例は、エチレン−アクリル酸共重合体、イオン架橋オレフィン共重合体、無水マレイン酸グラフトポリエチレン、無水マレイン酸グラフトポリプロピレン、アクリル酸グラフトポリオレフフィン、エチレン−酢酸ビニル共重合体、共重合ポリエステル、共重合熱可塑性等の１種又は２種以上の組み合わせである。これらの樹脂は、同時押出或いはサンドイッチラミネーション等による積層に有用である。
In manufacturing the laminate, an adhesive resin may be interposed between the resin layers as necessary.
As such an adhesive resin, a carbonyl (—CO—) group based on a carboxylic acid, a carboxylic acid anhydride, a carboxylate, a carboxylic acid amide, a carboxylic acid ester or the like is used in a main chain or a side chain of 1 to 700 mm. Examples include thermoplastic (meq) / 100 g resin, particularly thermoplastic resin contained at a concentration of 10 to 500 (meq) / 100 g resin. Suitable examples of the adhesive resin include ethylene-acrylic acid copolymer, ion-crosslinked olefin copolymer, maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, acrylic acid grafted polyolefin, ethylene-vinyl acetate copolymer. , One or a combination of two or more of copolyester and copolymer thermoplasticity. These resins are useful for lamination by coextrusion or sandwich lamination.
上記多層構造体は、それ自体公知の方法で製造が可能である。例えば、樹脂の種類に応じた数の押出機を用いて、多層多重ダイを用いて通常の押出成形を行えばよい。
また、本発明の多層構造体の製造には、樹脂の種類に応じた数の射出成形機を用いて、共射出法や逐次射出法により多層射出成形体を製造することができる。
更に、本発明の多層構造体を用いたフィルムやシートの製造には、押出コート法や、サンドイッチラミネーションを用いることができ、また、予め形成されたフィルムのドライラミネーションによって多層フィルムあるいはシートを製造することもできる。
The multilayer structure can be produced by a method known per se. For example, ordinary extrusion molding may be performed using a multilayer multiple die using the number of extruders corresponding to the type of resin.
In the production of the multilayer structure of the present invention, a multilayer injection molded article can be produced by a co-injection method or a sequential injection method using a number of injection molding machines corresponding to the type of resin.
Furthermore, for the production of a film or sheet using the multilayer structure of the present invention, an extrusion coating method or sandwich lamination can be used, and a multilayer film or sheet is produced by dry lamination of a film formed in advance. You can also.
フィルム等の包装材料は、種々の形態の包装袋として用いることができ、その製袋は、それ自体公知の製袋法で行うことができ、三方或いは四方シールの通常のパウチ類、ガセット付パウチ類、スタンディングパウチ類、ピロー包装袋などが挙げられるが、この例に限定されない。
本発明の多層構造体を用いた包装容器は、酸素による内容物の香味低下を防止できる容器として有用である。
充填できる内容物としては、飲料ではビール、ワイン、フルーツジュース、炭酸ソフトドリンク、ウーロン茶、緑茶等、食品では果物、ナッツ、野菜、肉製品、幼児食品、コーヒー、ジャム、マヨネーズ、ケチャップ、食用油、ドレッシング、ソース類、佃煮類、乳製品等、その他では医薬品、化粧品、ガソリン等、酸素存在下で劣化を起こしやすい内容品などが挙げられるが、これらの例に限定されない。
上記包装容器は、さらに外装体によって包装した包装体としてもよい。
次に、実施例及び比較例を示して本発明を説明する。
Packaging materials such as film can be used as packaging bags of various forms, and the bags can be produced by a known bag making method. Ordinary pouches with three- or four-side seals, pouches with gussets. , Standing pouches, pillow packaging bags, and the like, but are not limited to this example.
The packaging container using the multilayer structure of the present invention is useful as a container that can prevent a decrease in flavor of the contents due to oxygen.
Contents that can be filled include beer, wine, fruit juice, carbonated soft drink, oolong tea, green tea for beverages, fruits, nuts, vegetables, meat products, infant foods for food, coffee, jam, mayonnaise, ketchup, cooking oil, Examples include dressings, sauces, boiled dairy products, dairy products, and the like, and other products such as pharmaceuticals, cosmetics, gasoline, etc. that are susceptible to deterioration in the presence of oxygen, but are not limited to these examples.
The said packaging container is good also as a package further packaged by the exterior body.
Next, an Example and a comparative example are shown and this invention is demonstrated.
実施例で用いたスチレン−ジエン共重合体の炭素−炭素二重結合含有量の測定方法や樹脂組成ペレットの作製方法を次に示す。
スチレン−ジエン共重合体の炭素−炭素二重結合含有量の測定方法
重クロロホルムを溶媒に用い、スチレン−ジエン共重合体を１０〜１５ｗｔ％の濃度に溶解し、１３Ｃ−ＮＭＲ測定（ＪＥＯＬ製、ＪＮＭ−ＥＸ２７０）を行いスペクトルより樹脂の構造を同定した。それにより上記含有量は、樹脂１ｇ中に含まれる二重結合のモル数（ｅｑ／ｇ）を計算により求めた。
樹脂組成ペレットの作製方法
低密度ポリエチレン樹脂（ＪＢ２２１Ｒ日本ポリオレフィン（株）製）に、水添スチレン−ブタジエン共重合体樹脂又は水添スチレン−イソプレン共重合体樹脂を種々の重量％で、又、酸化触媒としてネオデカン酸コバルト（ＤＩＣＮＡＴＥ５０００大日本インキ化学工業（株）製）をＣｏ換算で３５０ｐｐｍ配合し、撹拌乾燥機（ダルトン（株）製）を用い５０℃で予備混練後ホッパーに投入した。定量フィーダーにより２軸押出機（ＴＥＭ３５東芝機械（株）製）内に投入し、温度設定２００℃、回転数１００ＲＰＭでストランド状に押出、樹脂組成ペレットを得た。
樹脂組成物の酸素吸収量の測定方法
種々の樹脂組成ペレットを凍結粉砕機で粉砕後定量し、蒸留水１．０ｍｌと共に内容量８５ｍｌの酸素不透過性容器［ハイレトフレックス：ＨＲ７８−８４東洋製罐（株）製ポリプロピレン／スチール箔／ポリプロピレン製カップ状積層容器］に入れ、ポリプロピレン（内層）／アルミ箔／ポリエステル（外層）の蓋材でヒートシールし、５０℃条件下で保存した。この容器内酸素濃度を経時日時においてガスクロマトグラフィー（ＧＣ−８Ａ島津製作所（株）製）を用いて測定し、酸素吸収量（ｃｃ／ｇ）を算出した。
The method for measuring the carbon-carbon double bond content of the styrene-diene copolymer used in the examples and the method for producing the resin composition pellets are shown below.
Method for measuring carbon-carbon double bond content of styrene-diene copolymer Using heavy chloroform as a solvent, styrene-diene copolymer was dissolved at a concentration of 10 to 15 wt%, and 13C-NMR measurement (manufactured by JEOL, JNM-EX270) and the structure of the resin was identified from the spectrum. Thereby, the content was obtained by calculating the number of moles (eq / g) of double bonds contained in 1 g of the resin.
Preparation method of resin composition pellets Low density polyethylene resin (manufactured by JB221R Nippon Polyolefin Co., Ltd.), hydrogenated styrene-butadiene copolymer resin or hydrogenated styrene-isoprene copolymer resin in various weight percentages, and oxidation As a catalyst, cobalt neodecanoate (DICATE5000 Dainippon Ink and Chemicals Co., Ltd.) was blended at 350 ppm in terms of Co, and premixed at 50 ° C. using a stir dryer (Dalton Co., Ltd.) and charged into the hopper. The sample was put into a twin screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd.) with a quantitative feeder, and extruded into a strand shape at a temperature setting of 200 ° C. and a rotation speed of 100 RPM to obtain resin composition pellets.
Measuring method of oxygen absorption amount of resin composition Various resin composition pellets were pulverized with a freeze pulverizer and quantified, and an oxygen-impermeable container having an internal volume of 85 ml together with 1.0 ml of distilled water [Hiletflex: HR78-84 manufactured by Toyo It was put into a polypropylene / steel foil / polypropylene cup-shaped laminated container manufactured by Sakai Co., Ltd.], heat-sealed with a lid of polypropylene (inner layer) / aluminum foil / polyester (outer layer), and stored at 50 ° C. The oxygen concentration in the container was measured using gas chromatography (GC-8A manufactured by Shimadzu Corporation) at the time and date, and the oxygen absorption (cc / g) was calculated.
多層ボトルの作製方法及び酸素バリヤー性評価
内外ポリエチレン層用５０ｍｍ主押出機にＪＢ２２１Ｒ（日本ポリオレフィン（株）製）、接着層用３０ｍｍ副押出機ＡにモディックＬ５２２（三菱化学（株）製）、バリヤー層用３０ｍｍ副押出機ＢにエバールＦ１０１Ｂ（（株）クラレ製）、酸素吸収層用３０ｍｍ副押出機Ｃに種々の樹脂組成ペレットを供給し、温度２１０℃の多層ダイより溶融パリソンを押し出し、公知の溶融ブロー成形法によりノズル径φ４５、内容量１５０ｍｌ、重量１２ｇの円筒形５種６層多層ボトルを作製した。層構成を下記に示す。
外側 ＰＥ層／接着層／バリヤー層／接着層／酸素吸収層／ＰＥ層
重量％ ２０/２．５/５/２．５/１０/６０
多層ボトルの酸素バリヤー性を評価する為、容器内に蒸留水１ｍｌを入れ、窒素雰囲気下で口部をアルミラミネート材で密封し、容器内の初期酸素濃度を０．０２％以下にし、３０℃、８０％ＲＨで保存した。この容器内酸素濃度を経時日時においてガスクロマトグラフィー（ＧＣ−８Ａ島津製作所（株）製）を用いて測定した。
ハンターカラーｂ値の測定方法
上記多層ボトルの胴壁から４０ｍｍ×４０ｍｍの試験片を切り出し、カラーコンピューター（ＳＭ−４スガ試験機（株）製）を用い試験片の裏側に標準白板を置き、反射法によりハンターカラーｂ値を測定した。
Preparation method of multilayer bottle and evaluation of oxygen barrier property JB221R (manufactured by Nippon Polyolefin Co., Ltd.) for 50 mm main extruder for inner and outer polyethylene layers, Modic L522 (manufactured by Mitsubishi Chemical Corporation) for 30 mm sub-extruder A for adhesive layer, barrier Eval F101B (manufactured by Kuraray Co., Ltd.) is supplied to the 30 mm sub-extruder B for the layer, and various resin composition pellets are supplied to the 30 mm sub-extruder C for the oxygen absorbing layer, and the molten parison is extruded from a multilayer die having a temperature of 210 ° C. A cylindrical 5-type 6-layer multilayer bottle having a nozzle diameter of 45, an internal volume of 150 ml, and a weight of 12 g was prepared by the melt blow molding method. The layer structure is shown below.
Outside PE layer / adhesive layer / barrier layer / adhesive layer / oxygen absorbing layer / PE layer% by weight 20 / 2.5 / 5 / 2.5 / 10/60
In order to evaluate the oxygen barrier property of the multilayer bottle, 1 ml of distilled water was put in the container, and the mouth was sealed with an aluminum laminate under a nitrogen atmosphere, the initial oxygen concentration in the container was made 0.02% or less, and 30 ° C. And stored at 80% RH. The oxygen concentration in the container was measured using gas chromatography (GC-8A manufactured by Shimadzu Corporation) at the time and date.
Hunter Color b Value Measurement Method A 40 mm × 40 mm test piece is cut out from the barrel wall of the multilayer bottle, and a standard white plate is placed on the back side of the test piece using a color computer (SM-4 Suga Test Instruments Co., Ltd.), and reflected. Hunter color b value was measured by the method.
［実施例１］
低密度ポリエチレン樹脂（ＪＢ２２１Ｒ日本ポリオレフィン（株）製）に、水添スチレン−イソプレン−スチレントリブロック共重合体樹脂（ハイブラー７１２５（株）クラレ製、この樹脂中の炭素−炭素二重結合含有量は２．０×１０-4ｅｑ／ｇであった）５．０重量％と酸化触媒を配合し、上記方法で樹脂組成ペレットを作製し、樹脂組成物の酸素吸収量（ｃｃ／ｇ）を算出した。その結果を表１に示す。
また、このペレットを用いて、上記方法で多層ボトルを作製し、酸素バリヤー性評価及びハンターカラーｂ値の測定を行った。その結果を表２に示す。
[Example 1]
Low density polyethylene resin (manufactured by JB221R Nippon Polyolefin Co., Ltd.), hydrogenated styrene-isoprene-styrene triblock copolymer resin (manufactured by Kuraray, Hybler 7125 Co., Ltd.), the carbon-carbon double bond content in this resin is 2.0 × 10 −4 eq / g) was blended with 5.0 wt% and an oxidation catalyst, resin composition pellets were prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. did. The results are shown in Table 1.
Moreover, using this pellet, a multilayer bottle was produced by the above method, and oxygen barrier property evaluation and measurement of Hunter color b value were performed. The results are shown in Table 2.
［実施例２］
水添スチレン−イソプレン−スチレントリブロック共重合体樹脂の代わりに水添スチレン−ブタジエン−スチレントリブロック共重合体樹脂（タフテックＰ２０００旭化成ケミカルズ（株）製、この樹脂中の炭素−炭素二重結合含有量は１．９×１０-3ｅｑ／ｇであった）を用いた以外は実施例１と同様に樹脂組成ペレットを作製し、樹脂組成物の酸素吸収量（ｃｃ／ｇ）を算出した。その結果を表１に示す。
また、このペレットを用いて、上記方法で多層ボトルを作製し、酸素バリヤー性評価及びハンターカラーｂ値の測定を行った。その結果を表２に示す。
[Example 2]
Instead of hydrogenated styrene-isoprene-styrene triblock copolymer resin, hydrogenated styrene-butadiene-styrene triblock copolymer resin (Tuftec P2000 Asahi Kasei Chemicals Corporation, containing carbon-carbon double bond in this resin) Resin composition pellets were prepared in the same manner as in Example 1 except that the amount was 1.9 × 10 −3 eq / g), and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
Moreover, using this pellet, a multilayer bottle was produced by the above method, and oxygen barrier property evaluation and measurement of Hunter color b value were performed. The results are shown in Table 2.
［実施例３］
水添スチレン−イソプレン−スチレントリブロック共重合体樹脂の代わりに水添スチレン−ブタジエン−スチレントリブロック共重合体樹脂（タフテックＰ２０００旭化成ケミカルズ（株）製、この樹脂中の炭素−炭素二重結合含有量は１．９×１０-3ｅｑ／ｇであった）２．５重量％と水添スチレン−ブタジエン共重合体樹脂（ダイナロン１３２０Ｐ（株）ＪＳＲ製、この樹脂中の炭素−炭素二重結合含有量は２．４×１０-5ｅｑ／ｇであった）２．５重量％を用いた以外は実施例１と同様に樹脂組成ペレットを作製し、樹脂組成物の酸素吸収量（ｃｃ／ｇ）を算出した。その結果を表１に示す。
また、このペレットを用いて、上記方法で多層ボトルを作製し、酸素バリヤー性評価及びハンターカラーｂ値の測定を行った。その結果を表２に示す。
[Example 3]
Instead of hydrogenated styrene-isoprene-styrene triblock copolymer resin, hydrogenated styrene-butadiene-styrene triblock copolymer resin (Tuftec P2000 Asahi Kasei Chemicals Corporation, containing carbon-carbon double bond in this resin) The amount was 1.9 × 10 −3 eq / g) 2.5% by weight and hydrogenated styrene-butadiene copolymer resin (manufactured by Dynalon 1320P Co., Ltd. JSR, carbon-carbon double bond in this resin) Resin composition pellets were prepared in the same manner as in Example 1 except that 2.5 wt% was used (content was 2.4 × 10 −5 eq / g), and the oxygen absorption amount of the resin composition (cc / g) was calculated. The results are shown in Table 1.
Moreover, using this pellet, a multilayer bottle was produced by the above method, and oxygen barrier property evaluation and measurement of Hunter color b value were performed. The results are shown in Table 2.
［実施例４］
低密度ポリエチレン樹脂（ＪＢ２２１Ｒ日本ポリオレフィン（株）製）に、水添スチレン−イソプレン−スチレントリブロック共重合体樹脂（ハイブラー７１２５（株）クラレ製、この樹脂中の炭素−炭素二重結合含有量は２．０×１０-4ｅｑ／ｇであった）５．０重量％と酸化触媒を配合し、さらにリン系酸化防止剤（アデカスタブ２１１２旭電化工業（株）製）を１０００ｐｐｍ配合し、実施例１と同様に樹脂組成ペレットを作製し、樹脂組成物の酸素吸収量（ｃｃ／ｇ）を算出した。その結果を表１に示す。
また、このペレットを用いて、上記方法で多層ボトルを作製し、酸素バリヤー性評価及びハンターカラーｂ値の測定を行った。その結果を表２に示す。
[Example 4]
Low density polyethylene resin (manufactured by JB221R Nippon Polyolefin Co., Ltd.), hydrogenated styrene-isoprene-styrene triblock copolymer resin (manufactured by Kuraray, Hybler 7125 Co., Ltd.), the carbon-carbon double bond content in this resin is Example 2 was formulated by blending 5.0 wt% (which was 2.0 × 10 -4 eq / g) and an oxidation catalyst, and further adding 1000 ppm of a phosphorus-based antioxidant (Adeka Stub 2112 manufactured by Asahi Denka Kogyo Co., Ltd.). Resin composition pellets were prepared in the same manner as in Example 1, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
Moreover, using this pellet, a multilayer bottle was produced by the above method, and oxygen barrier property evaluation and measurement of Hunter color b value were performed. The results are shown in Table 2.
［比較例１］
水添スチレン−イソプレン−スチレントリブロック共重合体樹脂（ハイブラー７１２５（株）クラレ製）を配合しなかった以外は実施例１と同様に樹脂組成ペレットを作製し、樹脂組成物の酸素吸収量（ｃｃ／ｇ）を算出した。その結果を表１に示す。
また、このペレットを用いて、上記方法で多層ボトルを作製し、酸素バリヤー性評価及びハンターカラーｂ値の測定を行った。その結果を表２に示す。
[Comparative Example 1]
Resin composition pellets were prepared in the same manner as in Example 1 except that a hydrogenated styrene-isoprene-styrene triblock copolymer resin (manufactured by KHIRAY, HIBRAR 7125) was not blended, and the oxygen absorption amount of the resin composition ( cc / g) was calculated. The results are shown in Table 1.
Moreover, using this pellet, a multilayer bottle was produced by the above method, and oxygen barrier property evaluation and measurement of Hunter color b value were performed. The results are shown in Table 2.
Claims (5)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004046697A JP4671161B2 (en) | 2003-07-10 | 2004-02-23 | Oxygen-absorbing resin composition |
| AU2004255626A AU2004255626B2 (en) | 2003-07-10 | 2004-07-01 | Oxygen-absorbing resin composition |
| PCT/JP2004/009705 WO2005005533A1 (en) | 2003-07-10 | 2004-07-01 | Oxygen-absorbing resin composition |
| EP04747174A EP1672019B1 (en) | 2003-07-10 | 2004-07-01 | Oxygen-absorbing resin composition |
| DE602004026206T DE602004026206D1 (en) | 2003-07-10 | 2004-07-01 | |
| AT04747174T ATE461969T1 (en) | 2003-07-10 | 2004-07-01 | OXYGEN ABSORBING RESIN COMPOSITION |
| US11/351,737 US7709567B2 (en) | 2003-07-10 | 2006-02-10 | Oxygen-absorbing resin composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003194839 | 2003-07-10 | ||
| JP2004046697A JP4671161B2 (en) | 2003-07-10 | 2004-02-23 | Oxygen-absorbing resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005042089A JP2005042089A (en) | 2005-02-17 |
| JP4671161B2 true JP4671161B2 (en) | 2011-04-13 |
Family
ID=34277251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004046697A Expired - Lifetime JP4671161B2 (en) | 2003-07-10 | 2004-02-23 | Oxygen-absorbing resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4671161B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4941873B2 (en) * | 2004-02-23 | 2012-05-30 | 東洋製罐株式会社 | Oxygen-absorbing resin composition |
| JP5268014B2 (en) * | 2005-07-19 | 2013-08-21 | 東洋製罐グループホールディングス株式会社 | Pellets for oxygen-absorbing resin composition and oxygen-absorbing resin composition |
| JP4993405B2 (en) * | 2005-08-19 | 2012-08-08 | 東洋製罐株式会社 | Pellets for forming oxygen-absorbing resin articles and method for producing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001106920A (en) * | 1999-03-03 | 2001-04-17 | Kuraray Co Ltd | Resin composition having gas barrier property |
| JP2002155214A (en) * | 2000-09-01 | 2002-05-28 | Kuraray Co Ltd | Resin composition and multilayer container |
-
2004
- 2004-02-23 JP JP2004046697A patent/JP4671161B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001106920A (en) * | 1999-03-03 | 2001-04-17 | Kuraray Co Ltd | Resin composition having gas barrier property |
| JP2002155214A (en) * | 2000-09-01 | 2002-05-28 | Kuraray Co Ltd | Resin composition and multilayer container |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005042089A (en) | 2005-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4314637B2 (en) | Oxygen-absorbing resin composition and laminate | |
| JP5019248B2 (en) | Oxygen-absorbing resin composition | |
| JPWO2005080076A1 (en) | Plastic multilayer structure | |
| JP4406921B2 (en) | Multilayer structure | |
| JP3896875B2 (en) | Resin composition and packaging material excellent in moldability and gas barrier properties | |
| JP2002241608A (en) | Oxygen-absorbing resin composition, packaging material and multi-layered container for package | |
| JP2001039475A (en) | Resin composition, laminate, container and container lid | |
| JP4399860B2 (en) | Multi-layer container | |
| US8232347B2 (en) | Method of making oxygen-absorbing resin composition | |
| JP2006028496A (en) | Odor scavenger resin composition | |
| JP4186592B2 (en) | Resin composition and packaging material excellent in moldability and gas barrier properties | |
| JP4993405B2 (en) | Pellets for forming oxygen-absorbing resin articles and method for producing the same | |
| WO2005005533A1 (en) | Oxygen-absorbing resin composition | |
| JP4671161B2 (en) | Oxygen-absorbing resin composition | |
| JP4389150B2 (en) | Oxygen-absorbing resin composition and multilayer structure using the same | |
| JP5527919B2 (en) | Moisture and oxygen barrier resin composition | |
| JP4186609B2 (en) | Gas barrier material and laminated structure using the same | |
| JP5585795B2 (en) | Oxygen-absorbing resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070115 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100621 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100818 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20101012 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101129 |
|
| 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: 20101227 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4671161 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110109 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140128 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140128 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: 20140128 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140128 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |