WO2016039340A1 - Biaxially stretched sheet and container for packaging - Google Patents
Biaxially stretched sheet and container for packaging Download PDFInfo
- Publication number
- WO2016039340A1 WO2016039340A1 PCT/JP2015/075475 JP2015075475W WO2016039340A1 WO 2016039340 A1 WO2016039340 A1 WO 2016039340A1 JP 2015075475 W JP2015075475 W JP 2015075475W WO 2016039340 A1 WO2016039340 A1 WO 2016039340A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- biaxially stretched
- stretched sheet
- sheet
- acrylonitrile
- main body
- Prior art date
Links
- 238000004806 packaging method and process Methods 0.000 title claims description 27
- 229920001893 acrylonitrile styrene Polymers 0.000 claims abstract description 23
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims abstract description 23
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 18
- 229920001577 copolymer Polymers 0.000 claims abstract description 17
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000013305 food Nutrition 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- -1 polypropylene Polymers 0.000 description 37
- 239000003921 oil Substances 0.000 description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 23
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 239000000178 monomer Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 15
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 14
- 238000000465 moulding Methods 0.000 description 12
- 230000002087 whitening effect Effects 0.000 description 11
- 239000004793 Polystyrene Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920005990 polystyrene resin Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000003856 thermoforming Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 3
- FCKXGFANXSHGAW-DTXPUJKBSA-N (2s)-n,n'-bis[(2s)-1-(2-chloro-4-nitroanilino)-1-oxo-3-phenylpropan-2-yl]-2-hydroxybutanediamide Chemical compound C([C@H](NC(=O)C[C@H](O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(=O)NC=1C(=CC(=CC=1)[N+]([O-])=O)Cl)C(=O)NC=1C(=CC(=CC=1)[N+]([O-])=O)Cl)C1=CC=CC=C1 FCKXGFANXSHGAW-DTXPUJKBSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 230000013011 mating Effects 0.000 description 3
- 235000010746 mayonnaise Nutrition 0.000 description 3
- 239000008268 mayonnaise Substances 0.000 description 3
- GLPXGXQOVMEKIJ-UHFFFAOYSA-N octadecan-1-amine;octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC[NH3+].CCCCCCCCCCCCCCCCCC([O-])=O GLPXGXQOVMEKIJ-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- BQARUDWASOOSRH-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-yl hydrogen carbonate Chemical compound CC(C)(C)OOC(C)(C)OC(O)=O BQARUDWASOOSRH-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- SPVZSOCLAVDNBA-UHFFFAOYSA-N octadecan-1-amine octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCN.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O SPVZSOCLAVDNBA-UHFFFAOYSA-N 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000004846 water-soluble epoxy resin Substances 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- VNFXPOAMRORRJJ-UHFFFAOYSA-N (4-octylphenyl) 2-hydroxybenzoate Chemical compound C1=CC(CCCCCCCC)=CC=C1OC(=O)C1=CC=CC=C1O VNFXPOAMRORRJJ-UHFFFAOYSA-N 0.000 description 1
- VEKMQTKVEVZPET-UHFFFAOYSA-N 1,1-bis(2,3-ditert-butyl-4-methylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1C(C)(C)C)C)C(O)(C(CO)(CO)CO)C1=C(C(=C(C=C1)C)C(C)(C)C)C(C)(C)C VEKMQTKVEVZPET-UHFFFAOYSA-N 0.000 description 1
- KMHAFDJFHSEAHT-UHFFFAOYSA-N 1,1-bis(2,3-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C=1C(=C(C=CC1)C(O)(C(CO)(CO)CO)C1=C(C(=CC=C1)C(C)(C)C)C(C)(C)C)C(C)(C)C KMHAFDJFHSEAHT-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical compound CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- OCSIKZYSDOXRPA-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-3-octadecylhenicosane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(CCCCCCCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC OCSIKZYSDOXRPA-UHFFFAOYSA-N 0.000 description 1
- YYFJBFQNTPRKOS-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)hexadecane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(CCCCCCCCCCCC)C(O)C(CO)(CO)CO YYFJBFQNTPRKOS-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- JLZIIHMTTRXXIN-UHFFFAOYSA-N 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JLZIIHMTTRXXIN-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 1
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 description 1
- WXHVQMGINBSVAY-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 WXHVQMGINBSVAY-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- KLIZOTJVECGYSJ-UHFFFAOYSA-N 2-[2-[3-(benzotriazol-2-yl)-5-(2-phenylpropan-2-yl)phenyl]propan-2-yl]phenol Chemical compound C=1C(N2N=C3C=CC=CC3=N2)=CC(C(C)(C)C=2C(=CC=CC=2)O)=CC=1C(C)(C)C1=CC=CC=C1 KLIZOTJVECGYSJ-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- BXCRLBBIZJSWNS-UHFFFAOYSA-N 2-hydroxyethyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCCO BXCRLBBIZJSWNS-UHFFFAOYSA-N 0.000 description 1
- LWZNQGJGMBRAII-UHFFFAOYSA-N 2-methylhexyl prop-2-enoate Chemical compound CCCCC(C)COC(=O)C=C LWZNQGJGMBRAII-UHFFFAOYSA-N 0.000 description 1
- LVFFZQQWIZURIO-UHFFFAOYSA-N 2-phenylbutanedioic acid Chemical compound OC(=O)CC(C(O)=O)C1=CC=CC=C1 LVFFZQQWIZURIO-UHFFFAOYSA-N 0.000 description 1
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- QRLSTWVLSWCGBT-UHFFFAOYSA-N 4-((4,6-bis(octylthio)-1,3,5-triazin-2-yl)amino)-2,6-di-tert-butylphenol Chemical compound CCCCCCCCSC1=NC(SCCCCCCCC)=NC(NC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=N1 QRLSTWVLSWCGBT-UHFFFAOYSA-N 0.000 description 1
- KTFGFGGLCMGYTP-UHFFFAOYSA-N 4-Anilino-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)NC1=CC=CC=C1 KTFGFGGLCMGYTP-UHFFFAOYSA-N 0.000 description 1
- STEYNUVPFMIUOY-UHFFFAOYSA-N 4-Hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CC(O)CC(C)(C)N1CCO STEYNUVPFMIUOY-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- ZAAQJFLUOUQAOG-UHFFFAOYSA-N 4-benzyl-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=CC=CC=2)=C1 ZAAQJFLUOUQAOG-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000936 Agarose Polymers 0.000 description 1
- 229920008790 Amorphous Polyethylene terephthalate Polymers 0.000 description 1
- 240000000662 Anethum graveolens Species 0.000 description 1
- CFLUVFXTJIEQTE-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCC(=O)OCC(O)COCC(O)COC(=O)CCCCCCCCCCCCCCCCC Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)COCC(O)COC(=O)CCCCCCCCCCCCCCCCC CFLUVFXTJIEQTE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- CGBXSWXZXBQCMR-UHFFFAOYSA-N Glycerol 1-hexadecanoate Chemical compound OCC(O)CO.CCCCCCCCCCCCCCCC(O)=O CGBXSWXZXBQCMR-UHFFFAOYSA-N 0.000 description 1
- 229920002527 Glycogen Polymers 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920002000 Xyloglucan Polymers 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- JHSNLCCMZMGXLK-UHFFFAOYSA-N [3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]-2-hydroxypropyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)COCC(O)COCC(O)CO JHSNLCCMZMGXLK-UHFFFAOYSA-N 0.000 description 1
- NYRCVROJUVSTOQ-UHFFFAOYSA-N [4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C NYRCVROJUVSTOQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- XKKUASDWWBYSDY-UHFFFAOYSA-N di(nonoxy)-(8-phenyloctyl)phosphane Chemical compound C(CCCCCCCC)OP(OCCCCCCCCC)CCCCCCCCC1=CC=CC=C1 XKKUASDWWBYSDY-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- ZPJYGYOBASXMHY-UHFFFAOYSA-N docosanoic acid;octadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCN.CCCCCCCCCCCCCCCCCCCCCC(O)=O ZPJYGYOBASXMHY-UHFFFAOYSA-N 0.000 description 1
- HWGUOODPQIXVKG-UHFFFAOYSA-N dodecan-1-amine;octadecanoic acid Chemical compound CCCCCCCCCCCC[NH3+].CCCCCCCCCCCCCCCCCC([O-])=O HWGUOODPQIXVKG-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- HARQWLDROVMFJE-UHFFFAOYSA-N ethyl 3,3-bis(tert-butylperoxy)butanoate Chemical compound CCOC(=O)CC(C)(OOC(C)(C)C)OOC(C)(C)C HARQWLDROVMFJE-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229940096919 glycogen Drugs 0.000 description 1
- 229920000669 heparin Polymers 0.000 description 1
- 229960002897 heparin Drugs 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
- 229960003160 hyaluronic acid Drugs 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 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
- NWAHZAIDMVNENC-UHFFFAOYSA-N octahydro-1h-4,7-methanoinden-5-yl methacrylate Chemical compound C12CCCC2C2CC(OC(=O)C(=C)C)C1C2 NWAHZAIDMVNENC-UHFFFAOYSA-N 0.000 description 1
- QADJHAOXTKCYFT-UHFFFAOYSA-N octyl 3-(3-octoxy-3-oxopropyl)sulfanylpropanoate Chemical compound CCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCC QADJHAOXTKCYFT-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229960000292 pectin Drugs 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 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
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 229940100515 sorbitan Drugs 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- MZHULIWXRDLGRR-UHFFFAOYSA-N tridecyl 3-(3-oxo-3-tridecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCC MZHULIWXRDLGRR-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/054—Forming anti-misting or drip-proofing coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D43/00—Lids or covers for rigid or semi-rigid containers
- B65D43/14—Non-removable lids or covers
- B65D43/16—Non-removable lids or covers hinged for upward or downward movement
- B65D43/162—Non-removable lids or covers hinged for upward or downward movement the container, the lid and the hinge being made of one piece
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/056—Forming hydrophilic coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2025/00—Use of polymers of vinyl-aromatic compounds or derivatives thereof as moulding material
- B29K2025/04—Polymers of styrene
- B29K2025/08—Copolymers of styrene, e.g. AS or SAN, i.e. acrylonitrile styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/18—Polymers of nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
- C08J2325/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/18—Homopolymers or copolymers of nitriles
- C08J2333/20—Homopolymers or copolymers of acrylonitrile
Definitions
- the present invention relates to a biaxially stretched sheet and a packaging container.
- the biaxially stretched polystyrene resin sheet is excellent in transparency and has high rigidity. Therefore, it is thermoformed and widely used in the food packaging container field.
- the polystyrene resin has lower oil resistance than the olefin resin, and the oil resistance is further lowered due to the biaxial stretching.
- the sheet surface is whitened.
- a joint part that connects a lid part called a hinge and a main body part since the joint part is stressed, it is easy to cause cracks due to oil adhesion.
- the sauces used for filling foods are whitened and perforated when heated in a microwave oven, so an OPP film is sandwiched between the food and the lid.
- the countermeasure is taken so that the lid does not touch the lid.
- polystyrene-based sheets which are highly oil-resistant resins
- polypropylene sheets have low transparency and poor visibility of contents.
- the polyethylene terephthalate sheet has low heat resistance and low rigidity, there are problems such as remarkable deformation when used at 60 ° C. or higher. From these facts, it can be said that the polystyrene-based sheet is a sheet suitable for food packaging containers having transparency, rigidity, and heat resistance, but improvement in oil resistance has been particularly demanded.
- Patent Document 1 a styrene-based biaxially stretched styrene-based copolymer mainly composed of a copolymer with styrene containing 4 to 20% by weight of any one component of acrylic acid, methacrylic acid, or maleic anhydride.
- the sheet shows practical heat resistance of 100 ° C. or higher and that whitening does not occur even when in contact with food oil at that temperature.
- Patent Documents 2, 3, and 4 only the surface layer is relaxed by performing multi-layer coextrusion using a resin having a low Vicat softening point on the surface layer and biaxial stretching at a stretching temperature suitable for the core layer. A technique for improving oil resistance by producing a sheet with reduced stress is shown.
- oil and polystyrene sheet are laminated by laminating a film made of an oil-resistant resin such as polypropylene, acrylic resin, and amorphous polyethylene terephthalate resin on the food contact surface of a polystyrene biaxially stretched sheet.
- an oil-resistant resin such as polypropylene, acrylic resin, and amorphous polyethylene terephthalate resin
- the oil resistance improvement method which does not make a direct contact with is shown.
- Patent Document 7 shows improvement in oil resistance by a sheet obtained from an acrylonitrile homopolymer which is a resin having higher oil resistance than polystyrene and a copolymer containing 90% by mass or more of an acrylonitrile component.
- Patent Documents 2 to 6 it is impossible to increase the material cost and processing cost due to film lamination, and it is impossible to recycle into a transparent product because the film is an incompatible polymer. Further, at the time of thermoforming, since resins having different softening points are molded at the same temperature, there are problems such as appearance defects and molding distortion remaining.
- thermoforming is difficult due to higher resin strength compared to polystyrene resin, or after dissolving in DMSO solvent and producing a cast film, DMSO solvent is replaced with water in a water tank.
- DMSO solvent is replaced with water in a water tank.
- the productivity is low, and it is difficult to manage the residual solvent and water absorption of the resin, and the sheet properties are likely to fluctuate. .
- the present invention uses an acrylonitrile-styrene copolymer, and biaxially stretched styrene with excellent balance of transparency, rigidity, practical strength, heat resistance, whitening resistance under oil contact conditions, chemical resistance, and shrink resistance. It is an object to provide a system sheet and a packaging container.
- the present invention is as follows. (1) A biaxially stretched sheet obtained by biaxially stretching an acrylonitrile-styrene copolymer, wherein the content of acrylonitrile units in the copolymer is 10 to 40% by mass, and the weight average molecular weight of the copolymer is 100,000 to 250,000, polydispersity is 2.0 to 2.5, biaxial stretching sheet magnification of biaxial stretching sheet is 4 to 10 times, and maximum orientation relaxation stress in MD direction and TD direction is 0, respectively.
- a packaging container comprising the biaxially stretched sheet according to (1) or (2) and comprising a main body, a lid, and a hinge that connects the main body and the lid to each other.
- the biaxially stretched sheet according to (2) is formed, and includes a main body portion, a lid portion, and a hinge portion that connects the main body portion and the lid portion to each other.
- a packaging container that is an object contact surface.
- an acrylonitrile-styrene copolymer is used, and a biaxial shaft having excellent balance of transparency, rigidity, practical strength, heat resistance, whitening resistance under oil contact conditions, chemical resistance, and shrink resistance.
- a stretched styrenic sheet and a packaging container are provided.
- FIG. 1 It is a perspective view which shows one Embodiment of the container for packaging. It is a side view of the packaging container of FIG.
- the acrylonitrile-styrene copolymer of this embodiment includes an acrylonitrile monomer unit (acrylonitrile unit) and a styrene monomer unit (styrene unit), and is obtained, for example, by bulk continuous polymerization.
- the content of acrylonitrile monomer units in the acrylonitrile-styrene copolymer is 10 to 40% by mass, preferably 18 to 32% by mass, based on the total amount of monomer units constituting the copolymer.
- the content of the acrylonitrile monomer unit exceeds 40% by mass, the hue, appearance, and sheet-forming property are inferior.
- the content of the acrylonitrile monomer unit is less than 10% by mass, oil resistance, Appearance and strength are inferior.
- acrylonitrile-based monomer unit examples include units such as acrylonitrile and methacrylonitrile, with acrylonitrile units being preferred. These acrylonitrile monomer units may be used alone or in combination of two or more.
- styrene monomer unit examples include units such as styrene, ⁇ -methyl styrene, p-methyl styrene, o-methyl styrene, m-methyl styrene, ethyl styrene, and pt-butyl styrene. Styrene units are preferred. These styrenic monomer units may be used alone or in combination of two or more. The content of styrene monomer units in the acrylonitrile-styrene copolymer may be, for example, 60 to 90% by mass based on the total amount of monomer units constituting the copolymer.
- the acrylonitrile-styrene copolymer may contain a copolymerizable vinyl monomer unit as necessary.
- the vinyl monomer unit include acrylic acid, methacrylic acid, maleic anhydride, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, dicyclopentanyl methacrylate, and isobornyl methacrylate.
- Examples include units such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, and decyl acrylate.
- Content of a vinyl-type monomer unit may be less than 10 mass parts with respect to a total of 100 mass parts of a styrene-type monomer unit and an acrylonitrile-type monomer unit.
- the acrylonitrile-styrene copolymer may contain a known reinforcing rubber such as butadiene rubber, styrene-butadiene rubber, methyl methacrylate-butadiene-styrene rubber, ethylene-propylene rubber, etc., if necessary.
- the content of the reinforcing rubber is preferably less than 10 parts by mass with respect to 100 parts by mass in total of the styrene monomer unit and the acrylonitrile monomer unit. When the content of the rubber component is 10 parts by mass or more, the transparency is undesirably lowered.
- the acrylonitrile-styrene copolymer can be obtained by polymerizing an acrylonitrile monomer and a styrene monomer. Although it does not specifically limit as a polymerization method, Bulky continuous polymerization is preferable for odor reduction.
- a solvent such as ethylbenzene, toluene and methyl ethyl ketone is added in an amount of 10 to 40 parts by mass with respect to a total of 100 parts by mass of the styrene monomer and the acrylonitrile monomer.
- the polymerization method is preferred.
- t-butyl peroxybenzoate t-butyl peroxy-2-ethylhexanoate
- 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane 1,1-bis (T-butylperoxy) -cyclohexane
- 2,2-bis (4,4-di-butylperoxycyclohexyl) propane t-butylperoxyisopropyl monocarbonate
- di-t-butyl peroxide dicumyl peroxide
- a known organic peroxide such as ethyl-3,3-di- (t-butylperoxy) butyrate
- a known molecular weight modifier such as dodecyl mercaptan or n-dodecyl mercaptan may be added.
- the polymerization temperature is preferably 80 to 170 ° C, more preferably 100 to 160 ° C.
- the polystyrene-reduced weight average molecular weight of the acrylonitrile-styrene copolymer measured by the SEC method is preferably 100,000 to 250,000, and more preferably 150,000 to 200,000. If the weight average molecular weight is less than 100,000, the strength of the sheet and the folding resistance are reduced due to the strength reduction of the resin. When the weight average molecular weight is 250,000 or more, a decrease in sheet film formability and container moldability is observed due to an increase in viscosity.
- the SEC measurement was performed under the following conditions.
- an ultraviolet absorber In the acrylonitrile-styrene copolymer, an ultraviolet absorber, a light stabilizer, and an antioxidant can be used alone or in combination.
- ultraviolet absorbers examples include 2- (5′-methyl-2′-hydroxyphenyl) benzotriazole, 2- (5′-t-butyl-2′-hydroxyphenyl) benzotriazole, 2- [2′-hydroxy- 3 ′, 5′-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] benzotriazole, 2- (3 ′, 5′-di-t-butyl-2′-hydroxyphenyl) benzotriazole, 2- (3′- t-butyl-5′-methyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3 ′, 5′-di-t-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3 ′, 5′-di-t-amyl-2′-hydroxyphenyl) benzotriazole, 2- [3 ′-(3 ′′, 4 ′′, 5 ′′, 6 ′′ -tetrahydrophthalimi Domethyl) -5′-
- Salicylic acid ultraviolet absorbers 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, cyanoacrylate ultraviolet absorbers such as ethyl-2-cyano-3,3′-diphenyl acrylate, rutile titanium oxide, Anatase type titanium oxide, and titanium oxide UV stabilizers such as titanium oxide treated with surface treatment agents such as alumina, silica, silane coupling agent and titanium coupling agent.
- Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, dimethyl succinate, 1 -(2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, 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 ]] And 1- [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionyl Car
- Antioxidants include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy -3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2-thiobis (4-methyl-6-tert-butylphenol) and 1,3,5-trimethyl-2,4,6-tris Phenolic antioxidants such as (3,5-di-t-butyl-4-hydroxybenzyl) benzene, ditridecyl-3,3′-thiodipropionate, dill Such as ril-3,3′-
- Sulfur-based antioxidant trisnonylphenyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, (tridecyl) pentaerythritol diphosphite, bis ( Octadecyl) pentaerythritol diphosphite, bis (di-t-butylphenyl) pentaerythritol diphosphite, bis (di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, dinonylphenyloctylphosphonite, Tetrakis (2,4-di-t-butylphenyl) 1,4 Phenylene-di-phosphonite, tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylene-di-phosphonite
- Acrylonitrile-styrene copolymers include lubricants, plasticizers, colorants, antistatic agents, flame retardants, additives such as mineral oil, reinforcing fibers such as glass fibers, carbon fibers and aramid fibers, talc, silica depending on the application. Further, fillers such as mica and calcium carbonate may be blended within a range that does not impair the object of the present invention.
- the biaxially stretched sheet of this embodiment is formed by biaxially stretching an acrylonitrile-styrene copolymer.
- a method for producing a biaxially stretched sheet for example, an acrylonitrile-styrene copolymer is melt-kneaded with an extruder, extruded from a die (particularly a T die), and then stretched sequentially or simultaneously in a biaxial direction. is there.
- the thickness of a biaxially stretched sheet is not specifically limited, Usually, 0.05 mm or more and less than 0.6 mm, Preferably it is 0.1 mm or more and less than 0.5 mm.
- the surface magnification indicated by A ⁇ B is It is preferably 4 to 10 times. In this plane magnification, both the MD draw ratio and the TD draw ratio are preferably 1.5 to 3.5 times. If any of A, B, and A ⁇ B is outside the above range, thickness unevenness occurs in the sheet, and in a container obtained by hot plate forming the sheet, the buckling strength may decrease, which is not preferable. . More preferably, the surface magnification is 4 to 8 times, and the MD draw ratio and TD draw ratio are 2.0 to 3.0 times, respectively.
- Y represents the length [mm] of the straight line drawn on MD and TD with respect to the test piece of the biaxially stretched sheet before heating
- Z is the sheet measured according to JIS K7206. The length [mm] of the straight line after the test piece is left to shrink for 60 minutes in an oven having a temperature 30 ° C. higher than the Vicat softening point temperature is shown.
- a and b are 0.2 MPa to 0.6 MPa, respectively.
- of the difference between the relaxation stress and the maximum orientation relaxation stress in the TD direction is 0.3 MPa or less, preferably, a and b are 0.3 MPa to 0.5 MPa, and
- a and b are less than 0.2 MPa, the sheet strength is lowered and the folding resistance is inferior.
- the biaxially stretched sheet may contain a sulfur compound derived from a chain transfer agent or an antioxidant, and the content of this sulfur component (sulfur content) is preferably 100 to 300 ppm.
- sulfur content is less than 100 ppm, the amount of chain transfer agent or antioxidant used is limited, and it is difficult to obtain a copolymer having a desired molecular weight.
- sulfur content is 300 ppm or more, an odor derived from a sulfur compound is generated during thermoforming, and the working environment is lowered.
- the sulfur content can be measured by ICP-MS (Inductively Coupled Plasma Mass Spectrometer).
- the content of the volatile substance in the biaxially stretched sheet is preferably 200 to 2000 ppm.
- Volatile substances mean volatile substances defined by the Food Sanitation Law. Specific examples of the volatile substance include styrene, toluene, ethylbenzene, n-propylbenzene, isopropylbenzene, and acrylonitrile.
- the content of the volatile substance is the total amount of these volatile components. Content of a volatile substance is adjusted by changing the temperature or adjustment time of the devolatilization process at the time of superposition
- the content of the volatile substance is less than 200 ppm, it is not preferable because it is necessary to set the temperature so as to cause decomposition or discoloration of the resin, and it is not preferable because the adjustment time extension needs to significantly reduce the productivity.
- the content of the volatile substance exceeds 2000 ppm, the working environment is deteriorated such that an odor is generated at the time of thermoforming like the sulfur content.
- the content of volatile substances can be measured by gas chromatography.
- the acrylonitrile-styrene copolymer biaxially stretched sheet is made into an antioxidant, a lubricant, a release agent, a plasticizer, as necessary, at the time of melt kneading or raw material production for forming a sheet, as long as the object of the present invention is not impaired.
- Known additives such as agents, pigments, dyes, foaming agents, foaming nucleating agents, inorganic fillers and antistatic agents can be contained.
- Oil resistance can be enhanced by applying a hydrophilic antifogging agent to the sheet surface that comes into contact with food, that is, by further providing an antifogging agent layer on at least one surface of the biaxially oriented sheet.
- Anti-fogging agents include nonionic surfactants such as sucrose fatty acid esters, sorbitan monostearate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan fatty acid ester surfactants such as sorbitan monomontanate, glycerin Glycerin fatty acid ester surfactants such as monolaurate, glycerin monopalmitate, glycerin monostearate, diglycerin distearate, triglycerin monostearate, tetraglycerin monomontanate, polyethylene glycol monopalmitate, polyethylene glycol mono Polyethylene glycol surfactants such as stearate, alkylene oxide adducts of alkylphenols, esters of sorbitan / glycerin condensates and organic acids; polyoxy Tylene (2 mol) stearylamine, polyoxyethylene (2 mol) laurylamine, polyoxyethylene alkylamine compounds such as polyoxy
- antifogging agents include polyvinyl alcohol and copolymers thereof (eg, acrylamide, copolymers with polyvinylpyrrolidone), polyvinylpyrrolidone and copolymers thereof (eg, copolymers with vinyl acetate), cellulose Derivatives (hydroxymethylcellulose, hydroxyethylcellulose, etc.), starch derivatives, gelatin, gum arabic, casein, xanthan gum, glycogen, chitin, chitosan, agarose, carrageenan, heparin, hyaluronic acid, pectin, xyloglucan, polyethylene oxide, polypropylene oxide, water-soluble Water-soluble epoxy resin, water-soluble epoxy resin, water-soluble phenol resin, water-soluble urea resin, water-soluble melamine resin, water-soluble amino resin, water-soluble polyamide resin, water-soluble acrylic resin, water-soluble Polycarboxylic acid salts, water soluble polyester resins, water-soluble polyurethane
- the method of coating the antifogging agent on the biaxially stretched sheet is not particularly limited, and a method of coating using a roll coater, a knife coater, a gravure roll coater or the like can be simply mentioned. Moreover, spraying, immersion, etc. are also employable.
- the water contact angle after application of the antifogging agent that is, the water contact angle on the surface of the antifogging agent layer of the biaxially stretched sheet is preferably 5 to 15 °.
- the water contact angle is less than 5 °, the surface becomes sticky, and there are problems such as poor appearance during molding and easy adhesion of dust.
- the water contact angle is 15 ° or more, the lipophilicity becomes high and the effect as a protective film cannot be obtained.
- the water contact angle can be measured according to JIS R 3257.
- FIG. 1 is a perspective view showing an embodiment of a packaging container
- FIG. 2 is a side view of the packaging container.
- the packaging container 1 includes a main body 2 that can accommodate contents, a lid 3, and a hinge 4 that connects the main body 2 and the lid 3 to each other.
- the packaging container 1 is formed by molding the above-described biaxially stretched sheet.
- the lid 3 can be opened and closed as shown in FIGS. For example, when the main body 2 and the lid 3 are fitted to each other, the lid 3 is closed (FIG. 2B).
- the surface of the anti-fogging agent layer becomes the content contact surface (the surface of the anti-fogging agent layer is disposed inside the main body 2 and the lid 3). Is preferred.
- the radius of curvature of the hinge portion 4 when the lid portion 3 is closed (FIG. 2B) (when the hinge portion 4 is viewed from the direction in which the hinge portion 4 extends (in the side view of FIG. 2B))
- the radius of curvature of the portion 4 is preferably 2 to 10 mm.
- the curvature radius of the hinge part 4 in a state where the lid part 3 is closed is less than 2 mm, the distortion of the hinge part 4 increases and the sheet is likely to be whitened.
- the radius of curvature of the hinge part 4 in a state where the lid part 3 is closed exceeds 10 mm, a fitting failure occurs when the lid part 3 is closed due to a shape defect or thinning of the hinge part 4. Moreover, it becomes a cause by which a crack generate
- the packaging container 1 can be suitably used for food packaging applications, that is, for the purpose of using food as contents (the main body 2 stores food).
- the materials used for the biaxially stretched sheet are publicly sanitary and stable, such as those registered in the Food Additives Official Statement and the Polyolefin Hygiene Council Positive List. It is preferable to use a material that is recognized for its properties.
- the molding machine to be used is desirably a type of molding machine that can set the time during which the sheet is pressed against the hot plate, the time for forming by pressure air, the time lag for switching from sheet pressure welding to pressure forming, the molding cycle, and the like.
- Example 1 Using an acrylonitrile-styrene copolymer (a) with a sheet extruder (T-die width 500 mm, ⁇ 40 mm extruder (manufactured by Tanabe Plastic Machinery Co., Ltd.)), an unstretched sheet having a thickness of 1.2 mm at an extrusion temperature of 230 ° C. Obtained.
- This sheet is preheated to 140 ° C. with a batch-type biaxial stretching machine (Toyo Seiki), and the strain rate is 0.1 / sec and the MD direction is 2.4 times and the TD direction is 2.4 times (the surface magnification is 5.8 times).
- sucrose laurate ester Rosmar A (Daiichi Kogyo Seiyaku Co., Ltd.) was applied with a bar coater and dried in an oven at 105 ° C. for 1 minute.
- the water contact angle on the work surface was 10 ° C.
- the biaxially oriented sheet had a sulfur content of 100 ppm and a volatile substance content of 1000 ppm.
- the obtained sheet was measured and evaluated by the following methods. The results are shown in Table 2.
- the biaxially stretched sheet was crushed, and about 0.5 g of the biaxially stretched sheet was precisely weighed, dissolved in 50 ml of tetrahydrofuran, 1 ml of diethylbenzene standard solution was added, diluted with tetrahydrofuran to a constant volume of 20 ml, and measured with a gas chromatograph.
- the thickness is measured using a microgauge at the intersection 25 points when the biaxially stretched sheet is made into a grid shape at intervals of 50 mm in the MD direction and the TD direction, and the average thickness and its standard deviation ⁇ are calculated. With respect to the thickness unevenness, the standard deviation ⁇ was evaluated according to the following criteria to evaluate the film forming property. ⁇ : ⁇ is less than 0.03 mm ⁇ : ⁇ is 0.03 mm or more and less than 0.07 mm ⁇ : ⁇ is 0.07 mm or more
- ⁇ No change
- ⁇ Slight whitening
- ⁇ Significant whitening, perforation
- Examples 2 to 28> In the same manner as in Example 1, sheets were prepared and evaluated using the resins and stretching conditions described in Tables 2 and 3. The results are shown in Tables 2 and 3.
- the sheets shown in the examples are both good and well-balanced, but the sheets shown in the comparative examples have some characteristics such as sheet strength, folding resistance, and oil resistance.
- the sheet is insufficient and has low practicality.
- the biaxially stretched sheet of the present invention has excellent balance of transparency, rigidity, practical strength, heat resistance, whitening resistance under chemical contact with oil, chemical resistance, shrinkage resistance, and packaging for packaging foods, etc. It can be suitably used as a container for use.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Wrappers (AREA)
- Laminated Bodies (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
Abstract
Description
(1) アクリロニトリル-スチレン共重合体を二軸延伸してなる二軸延伸シートであって、共重合体におけるアクリロニトリル単位の含有量が10~40質量%であり、共重合体の重量平均分子量が10万~25万、多分散度が2.0~2.5であり、二軸延伸シートの二軸延伸の面倍率が4~10倍、MD方向及びTD方向の最大配向緩和応力がそれぞれ0.2~0.6MPa、MD方向の最大配向緩和応力(a)とTD方向の最大配向緩和応力(b)との差の絶対値(|a-b|)が0.3MPa以下であり、二軸延伸シートにおける硫黄含有量が100~300ppm、揮発性物質の含有量が200~2000ppmである、二軸延伸シート。
(2) 二軸延伸シートの少なくとも一方の表面に防曇剤層が更に設けられ、防曇剤層の表面における水接触角が5~15°である、(1)に記載の二軸延伸シート。
(3) (1)又は(2)に記載の二軸延伸シートを成形してなり、本体部と、蓋部と、本体部及び蓋部を互いに連結するヒンジ部とを備える、包装用容器。
(4) (2)に記載の二軸延伸シートを成形してなり、本体部と、蓋部と、本体部及び蓋部を互いに連結するヒンジ部とを備え、防曇剤層の表面が内容物接触面である、包装用容器。
(5) 本体部が食品を収容する本体部であり、蓋部が閉じた状態でのヒンジ部の曲率半径が2~10mmである、(3)又は(4)に記載の包装用容器。 That is, the present invention is as follows.
(1) A biaxially stretched sheet obtained by biaxially stretching an acrylonitrile-styrene copolymer, wherein the content of acrylonitrile units in the copolymer is 10 to 40% by mass, and the weight average molecular weight of the copolymer is 100,000 to 250,000, polydispersity is 2.0 to 2.5, biaxial stretching sheet magnification of biaxial stretching sheet is 4 to 10 times, and maximum orientation relaxation stress in MD direction and TD direction is 0, respectively. 0.2 to 0.6 MPa, the absolute value (| ab−) of the difference between the maximum orientation relaxation stress (a) in the MD direction and the maximum orientation relaxation stress (b) in the TD direction is 0.3 MPa or less, A biaxially stretched sheet having a sulfur content of 100 to 300 ppm and a volatile material content of 200 to 2000 ppm in the axially stretched sheet.
(2) The biaxially stretched sheet according to (1), wherein an antifogging agent layer is further provided on at least one surface of the biaxially stretched sheet, and the water contact angle on the surface of the antifogging agent layer is 5 to 15 °. .
(3) A packaging container comprising the biaxially stretched sheet according to (1) or (2) and comprising a main body, a lid, and a hinge that connects the main body and the lid to each other.
(4) The biaxially stretched sheet according to (2) is formed, and includes a main body portion, a lid portion, and a hinge portion that connects the main body portion and the lid portion to each other. A packaging container that is an object contact surface.
(5) The packaging container according to (3) or (4), wherein the main body part is a main body part for containing food, and the curvature radius of the hinge part in a state where the lid part is closed is 2 to 10 mm.
なお、SEC測定は、以下のような条件で実施した。
装置:昭和電工社製Shodex「SYSTEM-21」
カラム:PLgel MIXED-B
温度:40℃
溶媒:テトラヒドロフラン
流量:1.0ml/分
検出:RI
濃度:0.2質量%
注入量:100μl
検量線:標準ポリスチレン(Polymer Laboratories製)を用い、溶離時間と溶出量との関係を分子量と変換して各種平均分子量(重量平均分子量、数平均分子量等)を求めた。 The polydispersity (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is preferably 2.0 to 2.5, and preferably 2.1 to 2.5. Is more preferable. If the polydispersity is less than 2.0, it is necessary to change the polymerization method and equipment, and the productivity of the resin is lowered. When the polydispersity is 2.5 or more, processability and oil resistance are lowered due to a decrease in strength due to an increase in low molecular weight components and an increase in viscosity due to an increase in high molecular weight components.
The SEC measurement was performed under the following conditions.
Apparatus: Shodex “SYSTEM-21” manufactured by Showa Denko KK
Column: PLgel MIXED-B
Temperature: 40 ° C
Solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Detection: RI
Concentration: 0.2% by mass
Injection volume: 100 μl
Calibration curve: Standard polystyrene (manufactured by Polymer Laboratories) was used, and the relationship between elution time and elution amount was converted to molecular weight to obtain various average molecular weights (weight average molecular weight, number average molecular weight, etc.).
容積約20Lの完全混合型攪拌槽である第一反応器と容積約40Lの攪拌機付塔式プラグフロー型反応器である第二反応器を直列に接続し、さらに予熱器を付した脱揮槽を2基直列に接続して構成した。アクリロニトリル10質量%、スチレン90質量%で構成する単量体溶液85質量部に対し、エチルベンゼン15質量部、t-ブチルパーオキシイソプロピルモノカーボネート0.01質量部、t-ドデシルメルカプタン0.25質量部を混合し原料溶液とした。この原料溶液を毎時6.0kgで125℃に制御した第一反応器に導入した。第一反応器より連続的に反応液を抜き出し、この反応液を流れの方向に向かって125℃から160℃の勾配がつくように調整した第二反応器に導入した。次に予熱器で160℃に加温した後67kPaに減圧した第一脱揮槽に導入し、さらに予熱器で230℃に加温した後1.3kPaに減圧した第二脱揮槽に導入し残存単量体と溶剤を除去した。これをストランド状に押出し切断することによりペレット形状のアクリロニトリル-スチレン系共重合体(AS-1)を得た。(AS-1)の組成は、表1に記載のとおり、アクリロニトリル単位10質量%、スチレン単位90質量%であり、重量平均分子量は150000、多分散度2.3であった。 Experimental Example 1 {Production of acrylonitrile-styrene copolymer (AS-1)}
A devolatilizing tank in which a first reactor which is a fully mixed stirring tank having a capacity of about 20 L and a second reactor which is a tower-type plug flow reactor with a stirring capacity of about 40 L are connected in series, and a preheater is further attached. Two units were connected in series. 15 parts by mass of ethylbenzene, 0.01 parts by mass of t-butylperoxyisopropyl monocarbonate, 0.25 parts by mass of t-dodecyl mercaptan with respect to 85 parts by mass of a monomer solution composed of 10% by mass of acrylonitrile and 90% by mass of styrene Were mixed to obtain a raw material solution. This raw material solution was introduced into a first reactor controlled at 125 ° C. at 6.0 kg per hour. The reaction solution was continuously withdrawn from the first reactor, and this reaction solution was introduced into a second reactor adjusted to have a gradient from 125 ° C. to 160 ° C. in the flow direction. Next, after heating to 160 ° C. with a preheater, it was introduced into the first devolatilization tank reduced to 67 kPa, and further heated to 230 ° C. with a preheater and then introduced into the second devolatilization tank reduced to 1.3 kPa. Residual monomer and solvent were removed. This was extruded and cut into strands to obtain pellet-shaped acrylonitrile-styrene copolymer (AS-1). As shown in Table 1, the composition of (AS-1) was 10% by mass of acrylonitrile units, 90% by mass of styrene units, the weight average molecular weight was 150,000, and the polydispersity was 2.3.
実験例1の各種原料仕込み量を調整し、表1に記載のアクリロニトリル-スチレン樹脂(AS-2~21)を得た。 Experimental Examples 2 to 21 {Production of acrylonitrile-styrene copolymer (AS-2 to 21)}
The amounts of various raw materials charged in Experimental Example 1 were adjusted to obtain acrylonitrile-styrene resins (AS-2 to 21) shown in Table 1.
アクリロニトリル-スチレン共重合体(a)をシート押出機(Tダイ幅500mm、φ40mmのエキストルーダー(田辺プラスチック機械社製))を用い、押出温度230℃で、厚さ1.2mmの未延伸シートを得た。このシートをバッチ式二軸延伸機(東洋精機)にて、140℃に予熱し、歪み速度0.1/secでMD方向2.4倍、TD方向2.4倍(面倍率5.8倍)に延伸し、厚さ0.21mmの二軸延伸シートを得た。さらに、バーコーターにて1%ショ糖ラウリン酸エステル(リケマールA(第一工業製薬株式会社製)を5g/m2塗工し、105℃のオーブンにて1分間乾燥させた。乾燥後の塗工表面の水接触角は10度であった。この二軸延伸シートの硫黄含有量は100ppm、揮発性物質含有量は1000ppmであった。 <Example 1>
Using an acrylonitrile-styrene copolymer (a) with a sheet extruder (T-die width 500 mm, φ40 mm extruder (manufactured by Tanabe Plastic Machinery Co., Ltd.)), an unstretched sheet having a thickness of 1.2 mm at an extrusion temperature of 230 ° C. Obtained. This sheet is preheated to 140 ° C. with a batch-type biaxial stretching machine (Toyo Seiki), and the strain rate is 0.1 / sec and the MD direction is 2.4 times and the TD direction is 2.4 times (the surface magnification is 5.8 times). ) To obtain a biaxially stretched sheet having a thickness of 0.21 mm. Furthermore, 5 g /
二軸延伸シートの試験片に対して、MDおよびTDに100mmの直線Yを引き、JIS K7206に準拠して測定したシートのビカット軟化点温度より30℃高い温度のオーブンに、上記試験片を60分間静置し収縮させた後の、上記直線の長さZ[mm]を測定し、次式すなわち、延伸倍率=Y/Z、単位[倍]によって算出した。 [Stretch ratio]
For a test piece of a biaxially stretched sheet, a straight line Y of 100 mm was drawn on MD and TD, and the test piece was placed in an oven having a temperature 30 ° C. higher than the Vicat softening point temperature of the sheet measured in accordance with JIS K7206. The length Z [mm] of the straight line after being allowed to stand and contract for a minute was measured and calculated by the following formula, that is, draw ratio = Y / Z, unit [times].
二軸延伸シートから20mm×200mm×0.2mmの試験片を得た。その試験片の両端を固定し、130℃のオイルバスに浸漬した後、荷重が最大となった時の応力値を算出した。その時のMD方向の応力値を最大配向緩和応力aとし、TD方向の応力値を最大緩和応力bとし、|a-b|を求めた。 [Maximum orientation relaxation stress (shrink resistance)]
A test piece of 20 mm × 200 mm × 0.2 mm was obtained from the biaxially stretched sheet. Both ends of the test piece were fixed, immersed in a 130 ° C. oil bath, and then the stress value when the load reached the maximum was calculated. At that time, the stress value in the MD direction was defined as the maximum orientation relaxation stress a, the stress value in the TD direction was defined as the maximum relaxation stress b, and | ab− was obtained.
ICP-MS(誘導結合プラズマ質量分析装置)にて測定した。 [Sulfur content]
Measurement was performed by ICP-MS (inductively coupled plasma mass spectrometer).
二軸延伸シートを破砕し、その約0.5gを精秤し、テトラヒドロフラン50mlに溶解し、ジエチルベンゼン標準液1mlを加え、テトラヒドロフランで薄めて20mlに定容し、ガスクロマトグラフにて測定した。 [Volatile substance content]
The biaxially stretched sheet was crushed, and about 0.5 g of the biaxially stretched sheet was precisely weighed, dissolved in 50 ml of tetrahydrofuran, 1 ml of diethylbenzene standard solution was added, diluted with tetrahydrofuran to a constant volume of 20 ml, and measured with a gas chromatograph.
JIS R 3257に準じて、接触角計DM-701(協和界面化学)にて、試験液に蒸留水を用い、滴下量2μL、滴下後から30秒後の接触角を測定した。 [Water contact angle]
According to JIS R 3257, the contact angle was measured with a contact angle meter DM-701 (Kyowa Interface Chemistry) using distilled water as the test solution, the drop amount being 2 μL, and the contact angle 30 seconds after the drop.
重合に使用した各単量体について、共重合体中の未反応単量体をガスクロマトグラフィーにて算出し、以下の式に基づいて実際に単量体が重合した割合(重合
率)を求め、樹脂の生産性を評価した。
重合率(%)=重合体質量÷(重合体質量+未反応単量体の質量)×100
○:重合率90.0%~100%
△:重合率80.0%以上90.0%未満
×:重合率80%未満 [Resin productivity]
For each monomer used in the polymerization, the unreacted monomer in the copolymer was calculated by gas chromatography, and the ratio (polymerization rate) in which the monomer was actually polymerized was determined based on the following formula. Resin productivity was evaluated.
Polymerization rate (%) = polymer mass ÷ (polymer mass + unreacted monomer mass) × 100
○: Polymerization rate 90.0% to 100%
Δ: Polymerization rate 80.0% or more and less than 90.0% ×: Polymerization rate less than 80%
二軸延伸シートをMD方向及びTD方向に50mm間隔で格子状にした時の交点25点についてマイクロゲージを用いて厚さを測定し、平均厚さとその標準偏差σを算出し、厚さについては数値で、厚さムラについては標準偏差σを下記基準で評価し、製膜性の評価とした。
○:σが0.03mm未満
△:σが0.03mm以上、0.07mm未満
×:σが0.07mm以上 (Sheet film formability)
The thickness is measured using a microgauge at the intersection 25 points when the biaxially stretched sheet is made into a grid shape at intervals of 50 mm in the MD direction and the TD direction, and the average thickness and its standard deviation σ are calculated. With respect to the thickness unevenness, the standard deviation σ was evaluated according to the following criteria to evaluate the film forming property.
○: σ is less than 0.03 mm Δ: σ is 0.03 mm or more and less than 0.07 mm ×: σ is 0.07 mm or more
JIS K-6251に準拠し、二軸延伸シートを1号型テストピース形状にカットし、島津製作所AGS-100D型引張試験機を用い、引張速度500mm/minにて測定し、評価した。
○:60MPa超え
△:40~60MPa
×:40MPa未満 [Sheet strength]
In accordance with JIS K-6251, the biaxially stretched sheet was cut into a No. 1 type test piece shape, and measured and evaluated at a tensile speed of 500 mm / min using a Shimadzu AGS-100D type tensile tester.
○: Over 60 MPa Δ: 40 to 60 MPa
X: Less than 40 MPa
ASTM D2176に準じて、シート押出方向(縦方向)とそれに垂直な方向(横方向)の耐折曲げ強さを測定した。縦横の平均値を求め評価した。
○:10回以上
△:5回以上、10回未満
×:5回未満 [Folding resistance]
In accordance with ASTM D2176, the bending strength in the sheet extrusion direction (longitudinal direction) and the direction perpendicular thereto (lateral direction) was measured. An average value in the vertical and horizontal directions was obtained and evaluated.
○: 10 times or more △: 5 times or more and less than 10 times ×: less than 5 times
JIS K-7361-1に準じ、ヘーズメーターNDH5000(日本電色社)により測定した。測定には上記にて作製した二軸延伸シート0.21mm厚を用いた。
○:1.0%未満
△:1.0~2.0%
×:2.0%超え 〔transparency〕
According to JIS K-7361-1, it was measured with a haze meter NDH5000 (Nippon Denshoku). The biaxially stretched sheet 0.21 mm thickness produced above was used for the measurement.
○: Less than 1.0% △: 1.0-2.0%
×: Over 2.0%
厚さ0.21mmの延伸シートを10枚重ね、分光測色計CM-2500d(コニカミノルタ)のSCI測定(正反射光込み)より得られたb値を評価した。
○:3未満
△:3~5
×:5超え [Hue]
Ten stretched sheets having a thickness of 0.21 mm were stacked, and the b value obtained by SCI measurement (including specular reflection light) of a spectrocolorimeter CM-2500d (Konica Minolta) was evaluated.
○: Less than 3 △: 3-5
×: Over 5
熱板成型機HPT-400A(脇坂エンジニアリング製)にて、熱板温度135℃、加熱時間2.0秒の条件で、嵌合フードパック(本体部寸法 縦130×横110×深さ28mm、蓋部寸法 縦130×横110×高さ25mm、ヒンジ部の曲率半径3mm)を成形し外観を評価した。また、成形品の蓋を閉めた際の嵌合状態を評価した。
○:良好
△:軽微な白化、軽微なレインドロップ
×:著しい白化、著しいレインドロップ、形状不良、嵌合不良(ずれ、はずれ、ゆがみ)(製品化できない) [Formability]
With a hot plate molding machine HPT-400A (manufactured by Wakisaka Engineering Co., Ltd.), with a hot plate temperature of 135 ° C and a heating time of 2.0 seconds, the fitting hood pack (main body dimensions 130 x 110 x 28 mm depth, lid Part dimensions 130 × 110 × 25 mm in height and the radius of curvature of the
○: Good △: Slight whitening, light raindrop ×: Significant whitening, remarkable raindrop, shape defect, poor fitting (deviation, disengagement, distortion) (cannot be commercialized)
熱板成型機HPT-400A(脇坂エンジニアリング製)にて、熱板温度135℃、加熱時間2.0秒の条件で嵌合フードパックを10枚成形した後の熱板成型機周辺の雰囲気の臭いを官能評価した。
○:特異的な臭いはしない
△:わずかに異臭を感じる
×:鼻につくほどの臭いを感じる [Odor when molding containers]
Odor of the atmosphere around the hot plate molding machine after forming 10 mating food packs on a hot plate molding machine HPT-400A (manufactured by Wakisaka Engineering) at a hot plate temperature of 135 ° C and a heating time of 2.0 seconds Sensory evaluation.
○: No specific odor △: Slightly off-flavor ×: Smelly enough to get on the nose
熱板成型機HPT-400A(脇坂エンジニアリング製)にてヒンジ部を有する嵌合フードパックを成形し、サラダ油(日清製油社製)、マヨネーズ(味の素社製)の試験液をしみ込ませたガーゼ10×10mmをヒンジ部に貼り付け、60℃オーブンにて24時間静置し、付着部の表面観察を行った。
○:変化無し
△:わずかに白化あり
×:著しい白化、穴空きあり [Oil resistance (chemical resistance)]
A gauze 10 in which a mating food pack having a hinge portion is formed by a hot plate molding machine HPT-400A (manufactured by Wakisaka Engineering Co., Ltd.) and impregnated with a test solution of salad oil (manufactured by Nisshin Oil Co., Ltd.) and mayonnaise (manufactured by Ajinomoto Co., Inc.) × 10 mm was attached to the hinge part, and allowed to stand in a 60 ° C. oven for 24 hours, and the surface of the adhered part was observed.
○: No change △: Slight whitening ×: Significant whitening, perforation
嵌合フードパック蓋部の内側中央に2×2cmでマヨネーズを付け、容器本体に水100gを入れ、蓋容器をかぶせて1500Wの電子レンジで30分間加熱した後、マヨネーズ付着部分の様子を目視で評価した。
○:変化なし
△:容器がわずかに変形
×:白化あり、穴あきあり、容器が著しく変形(製品化できない) [Range resistance]
Put the mayonnaise at 2 × 2 cm in the center of the inside of the lid of the mating hood pack, put 100 g of water into the container body, cover the lid container and heat for 30 minutes in a 1500 W microwave oven, then visually check the mayonnaise adhering part evaluated.
○: No change △: Slightly deformed container ×: Whitening, perforated, container deformed significantly (cannot be commercialized)
実施例1と同様の方法で、表2、表3に記載の樹脂、延伸条件にてシートを作成し、評価を行った。結果は表2、表3に示した。 <Examples 2 to 28>
In the same manner as in Example 1, sheets were prepared and evaluated using the resins and stretching conditions described in Tables 2 and 3. The results are shown in Tables 2 and 3.
実施例1と同様の方法で、表4、表5に記載の樹脂、延伸条件にてシートを作成し、評価を行った。結果は表4、表5に示した。 <Comparative Examples 1 to 17>
In the same manner as in Example 1, a sheet was prepared using the resins described in Tables 4 and 5 and stretching conditions, and evaluated. The results are shown in Tables 4 and 5.
Claims (5)
- アクリロニトリル-スチレン共重合体を二軸延伸してなる二軸延伸シートであって、
前記共重合体におけるアクリロニトリル単位の含有量が10~40質量%であり、
前記共重合体の重量平均分子量が10万~25万、多分散度が2.0~2.5であり、
前記二軸延伸シートの二軸延伸の面倍率が4~10倍、MD方向及びTD方向の最大配向緩和応力がそれぞれ0.2~0.6MPa、MD方向の最大配向緩和応力(a)とTD方向の最大配向緩和応力(b)との差の絶対値(|a-b|)が0.3MPa以下であり、
前記二軸延伸シートにおける硫黄含有量が100~300ppm、揮発性物質の含有量が200~2000ppmである、二軸延伸シート。 A biaxially stretched sheet obtained by biaxially stretching an acrylonitrile-styrene copolymer,
The acrylonitrile unit content in the copolymer is 10 to 40% by mass,
The copolymer has a weight average molecular weight of 100,000 to 250,000 and a polydispersity of 2.0 to 2.5.
The biaxially stretched sheet has a surface magnification of 4 to 10 times, the maximum orientation relaxation stress in the MD direction and the TD direction is 0.2 to 0.6 MPa, the maximum orientation relaxation stress (a) in the MD direction and TD, respectively. The absolute value (| ab−) of the difference from the maximum orientation relaxation stress (b) in the direction is 0.3 MPa or less,
A biaxially stretched sheet having a sulfur content of 100 to 300 ppm and a volatile substance content of 200 to 2000 ppm in the biaxially stretched sheet. - 前記二軸延伸シートの少なくとも一方の表面に防曇剤層が更に設けられ、前記防曇剤層の表面における水接触角が5~15°である、請求項1に記載の二軸延伸シート。 The biaxially stretched sheet according to claim 1, wherein an antifogging agent layer is further provided on at least one surface of the biaxially stretched sheet, and a water contact angle on the surface of the antifogging agent layer is 5 to 15 °.
- 請求項1又は2に記載の二軸延伸シートを成形してなり、
本体部と、蓋部と、前記本体部及び前記蓋部を互いに連結するヒンジ部とを備える、包装用容器。 The biaxially stretched sheet according to claim 1 or 2 is formed,
A packaging container comprising a main body part, a lid part, and a hinge part that connects the main body part and the lid part to each other. - 請求項2に記載の二軸延伸シートを成形してなり、
本体部と、蓋部と、前記本体部及び前記蓋部を互いに連結するヒンジ部とを備え、
前記防曇剤層の表面が内容物接触面である、包装用容器。 The biaxially stretched sheet according to claim 2 is molded,
A main body, a lid, and a hinge that connects the main body and the lid to each other;
A packaging container, wherein a surface of the antifogging agent layer is a content contact surface. - 前記本体部が食品を収容する本体部であり、
前記蓋部が閉じた状態での前記ヒンジ部の曲率半径が2~10mmである、請求項3又は4に記載の包装用容器。 The main body is a main body for containing food;
The packaging container according to claim 3 or 4, wherein a radius of curvature of the hinge portion when the lid portion is closed is 2 to 10 mm.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020167033975A KR102390734B1 (en) | 2014-09-08 | 2015-09-08 | Biaxially stretched sheet and container for packaging |
JP2016547451A JP6190541B2 (en) | 2014-09-08 | 2015-09-08 | Biaxially stretched sheet and packaging container |
CN201580040360.7A CN106573410B (en) | 2014-09-08 | 2015-09-08 | Biaxial stretch-formed sheet material and container for packing |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-182752 | 2014-09-08 | ||
JP2014182751 | 2014-09-08 | ||
JP2014182752 | 2014-09-08 | ||
JP2014-182751 | 2014-09-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016039340A1 true WO2016039340A1 (en) | 2016-03-17 |
Family
ID=55459085
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/075475 WO2016039340A1 (en) | 2014-09-08 | 2015-09-08 | Biaxially stretched sheet and container for packaging |
PCT/JP2015/075476 WO2016039341A1 (en) | 2014-09-08 | 2015-09-08 | Biaxially stretched sheet and container for packaging |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/075476 WO2016039341A1 (en) | 2014-09-08 | 2015-09-08 | Biaxially stretched sheet and container for packaging |
Country Status (5)
Country | Link |
---|---|
JP (2) | JP6190541B2 (en) |
KR (2) | KR102258974B1 (en) |
CN (2) | CN106573410B (en) |
TW (2) | TWI622485B (en) |
WO (2) | WO2016039340A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018083908A (en) * | 2016-11-25 | 2018-05-31 | デンカ株式会社 | Styrenic oriented sheet and package, and method for producing the same |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018048319A (en) * | 2016-09-14 | 2018-03-29 | デンカ株式会社 | Stretched sheet, packaging container, and methods of manufacturing the same |
JP7019353B2 (en) * | 2016-09-14 | 2022-02-15 | デンカ株式会社 | Stretched sheets and packaging containers, and their manufacturing methods |
JP6741035B2 (en) * | 2018-03-15 | 2020-08-19 | 三菱ケミカル株式会社 | Biaxially stretched polystyrene resin sheet and molded product |
CN112477210B (en) * | 2020-12-01 | 2022-09-06 | 漳州职业技术学院 | Preparation and preservation method of longan preservative film |
CN112590181B (en) * | 2020-12-01 | 2023-02-10 | 漳州职业技术学院 | Preparation and production system of agricultural product fresh-keeping composite film |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH107817A (en) * | 1996-06-21 | 1998-01-13 | Daicel Chem Ind Ltd | As resin-based biaxially stretched sheet and thermally formed product |
JP2000281809A (en) * | 1999-04-01 | 2000-10-10 | Daicel Chem Ind Ltd | Bi-axially stretched styrene-based resin sheet |
JP2001026619A (en) * | 1999-07-14 | 2001-01-30 | Denki Kagaku Kogyo Kk | Styrene-based resin, preparation thereof, and food packing vessel |
JP2001105489A (en) * | 1999-10-06 | 2001-04-17 | Daicel Chem Ind Ltd | Styrene resin sheet and method of manufacturing the same |
JP2001164011A (en) * | 1999-12-08 | 2001-06-19 | Denki Kagaku Kogyo Kk | Antifogging styrene-based transparent resin sheet and molded product thereof |
JP2002212233A (en) * | 2001-01-15 | 2002-07-31 | Denki Kagaku Kogyo Kk | Poly(meth)acryl/styrene resin, and sheet and food package container made thereof |
JP2003012734A (en) * | 2001-06-28 | 2003-01-15 | Denki Kagaku Kogyo Kk | Styrenic copolymer and its biaxially oriented sheet and container |
JP2004067955A (en) * | 2002-08-09 | 2004-03-04 | Denki Kagaku Kogyo Kk | Anticlouding styrene type transparent resin sheet and its formed product |
JP2005170031A (en) * | 2003-11-20 | 2005-06-30 | Mitsubishi Chemicals Corp | Anti-fogging resin sheet and anti-fogging container for wrapping foodstuff using it |
JP2006045368A (en) * | 2004-08-05 | 2006-02-16 | Tosoh Corp | Transparent resin composition and optical film |
JP2010185087A (en) * | 1999-07-27 | 2010-08-26 | Daicel Chem Ind Ltd | Synthetic resin sheet |
JP2014087955A (en) * | 2012-10-30 | 2014-05-15 | Denki Kagaku Kogyo Kk | Biaxially stretched sheet and container |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4812072B1 (en) | 1969-09-22 | 1973-04-18 | ||
EP0107281A3 (en) | 1982-09-30 | 1988-03-16 | Mobil Oil Corporation | A method of shaping polyacrylonitrile film |
JPS6225031A (en) | 1985-07-26 | 1987-02-03 | Asahi Chem Ind Co Ltd | Heat-resistive sheet of biaxially oriented styrene base |
JP2005035208A (en) | 2003-07-17 | 2005-02-10 | Denki Kagaku Kogyo Kk | Oilproof polystyrene-based laminate sheet and container |
JP4217591B2 (en) | 2003-12-01 | 2009-02-04 | 株式会社トクヤマ | MULTILAYER FILM, LAMINATE, AND THERMOFORMED CONTAINER |
JP4053022B2 (en) | 2004-06-08 | 2008-02-27 | 電気化学工業株式会社 | Polystyrene-based biaxially stretched laminated sheet, molded body and container |
KR100672862B1 (en) * | 2005-05-26 | 2007-01-22 | 광 석 서 | Method For Producing Highly thermoformable colored polymer film |
JP2007277428A (en) | 2006-04-07 | 2007-10-25 | Asahi Kasei Chemicals Corp | Oil resistant film, and molded container using the same |
-
2015
- 2015-09-08 CN CN201580040360.7A patent/CN106573410B/en active Active
- 2015-09-08 JP JP2016547451A patent/JP6190541B2/en active Active
- 2015-09-08 KR KR1020167033976A patent/KR102258974B1/en active IP Right Grant
- 2015-09-08 TW TW104129736A patent/TWI622485B/en active
- 2015-09-08 WO PCT/JP2015/075475 patent/WO2016039340A1/en active Application Filing
- 2015-09-08 WO PCT/JP2015/075476 patent/WO2016039341A1/en active Application Filing
- 2015-09-08 CN CN201580040372.XA patent/CN106573411B/en active Active
- 2015-09-08 TW TW104129735A patent/TWI622484B/en active
- 2015-09-08 KR KR1020167033975A patent/KR102390734B1/en active IP Right Grant
- 2015-09-08 JP JP2016547452A patent/JP6190542B2/en active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH107817A (en) * | 1996-06-21 | 1998-01-13 | Daicel Chem Ind Ltd | As resin-based biaxially stretched sheet and thermally formed product |
JP2000281809A (en) * | 1999-04-01 | 2000-10-10 | Daicel Chem Ind Ltd | Bi-axially stretched styrene-based resin sheet |
JP2001026619A (en) * | 1999-07-14 | 2001-01-30 | Denki Kagaku Kogyo Kk | Styrene-based resin, preparation thereof, and food packing vessel |
JP2010185087A (en) * | 1999-07-27 | 2010-08-26 | Daicel Chem Ind Ltd | Synthetic resin sheet |
JP2001105489A (en) * | 1999-10-06 | 2001-04-17 | Daicel Chem Ind Ltd | Styrene resin sheet and method of manufacturing the same |
JP2001164011A (en) * | 1999-12-08 | 2001-06-19 | Denki Kagaku Kogyo Kk | Antifogging styrene-based transparent resin sheet and molded product thereof |
JP2002212233A (en) * | 2001-01-15 | 2002-07-31 | Denki Kagaku Kogyo Kk | Poly(meth)acryl/styrene resin, and sheet and food package container made thereof |
JP2003012734A (en) * | 2001-06-28 | 2003-01-15 | Denki Kagaku Kogyo Kk | Styrenic copolymer and its biaxially oriented sheet and container |
JP2004067955A (en) * | 2002-08-09 | 2004-03-04 | Denki Kagaku Kogyo Kk | Anticlouding styrene type transparent resin sheet and its formed product |
JP2005170031A (en) * | 2003-11-20 | 2005-06-30 | Mitsubishi Chemicals Corp | Anti-fogging resin sheet and anti-fogging container for wrapping foodstuff using it |
JP2006045368A (en) * | 2004-08-05 | 2006-02-16 | Tosoh Corp | Transparent resin composition and optical film |
JP2014087955A (en) * | 2012-10-30 | 2014-05-15 | Denki Kagaku Kogyo Kk | Biaxially stretched sheet and container |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018083908A (en) * | 2016-11-25 | 2018-05-31 | デンカ株式会社 | Styrenic oriented sheet and package, and method for producing the same |
Also Published As
Publication number | Publication date |
---|---|
JPWO2016039341A1 (en) | 2017-04-27 |
CN106573410A (en) | 2017-04-19 |
TWI622485B (en) | 2018-05-01 |
WO2016039341A1 (en) | 2016-03-17 |
CN106573410B (en) | 2019-10-29 |
TWI622484B (en) | 2018-05-01 |
TW201618934A (en) | 2016-06-01 |
CN106573411B (en) | 2019-10-18 |
KR20170053594A (en) | 2017-05-16 |
KR102258974B1 (en) | 2021-06-02 |
TW201618933A (en) | 2016-06-01 |
CN106573411A (en) | 2017-04-19 |
JP6190541B2 (en) | 2017-08-30 |
KR102390734B1 (en) | 2022-04-26 |
JP6190542B2 (en) | 2017-08-30 |
JPWO2016039340A1 (en) | 2017-04-27 |
KR20170052528A (en) | 2017-05-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6190542B2 (en) | Biaxially stretched sheet and packaging container | |
JP6148411B2 (en) | Styrene biaxially stretched sheet, biaxially stretched sheet with anti-fogging agent layer, packaging container, and cooking method | |
TWI697507B (en) | Biaxially stretched sheet and its formed product | |
JP2018203837A (en) | Styrenic resin composition, stretched sheet and molding | |
JPH06279546A (en) | Stretched styrene resin sheet | |
WO2018012373A1 (en) | Biaxially stretched sheet and shaped article of same | |
JP2018012530A (en) | Biaxially stretched sheet and package | |
JP4582765B2 (en) | Polystyrene-based biaxially stretched sheet and method for producing the same | |
JP6393125B2 (en) | Fitting container using styrene biaxially stretched sheet | |
JP2016158962A (en) | Container for heating in microwave oven, using styrene-based biaxial oriented sheet, and cooking method | |
JP6775622B2 (en) | Biaxially stretched sheet and molded product | |
JP6776386B2 (en) | Biaxially stretched sheet and molded product | |
JP2006273914A (en) | Bioriented styrene-based resin sheet and formed product | |
JP2019210437A (en) | Styrene-based copolymer and its compact, sheet | |
JP2016175393A (en) | Biaxially stretched sheet and molded article | |
JP2016175394A (en) | Biaxially stretched sheet and molded article | |
WO2020218447A1 (en) | Laminated film | |
JP7177776B2 (en) | Laminate and its manufacturing method | |
JP2005248002A (en) | Heat-resistant styrene resin stretched sheet | |
JP2023061603A (en) | Biaxially stretched sheet and package container | |
JP2010031142A (en) | Styrene-based resin film, laminate sheet and molded article using the same | |
JP2016060192A (en) | Biaxially oriented styrenic resin laminated sheet, molded article, and food packaging container | |
JP2019048949A (en) | Styrenic copolymer and method for producing the same, and molding |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15839530 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016547451 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20167033975 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15839530 Country of ref document: EP Kind code of ref document: A1 |