CN104271666A - 嵌段共聚物组合物及片材 - Google Patents
嵌段共聚物组合物及片材 Download PDFInfo
- Publication number
- CN104271666A CN104271666A CN201380024337.XA CN201380024337A CN104271666A CN 104271666 A CN104271666 A CN 104271666A CN 201380024337 A CN201380024337 A CN 201380024337A CN 104271666 A CN104271666 A CN 104271666A
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- CN
- China
- Prior art keywords
- block copolymer
- copolymer composition
- molecular weight
- quality
- vinyl aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 141
- 239000000203 mixture Substances 0.000 title claims abstract description 112
- -1 vinyl aromatic hydrocarbon Chemical class 0.000 claims abstract description 72
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 61
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims description 94
- 239000001993 wax Substances 0.000 claims description 37
- 239000004215 Carbon black (E152) Substances 0.000 claims description 23
- 229930195733 hydrocarbon Natural products 0.000 claims description 23
- 150000002430 hydrocarbons Chemical class 0.000 claims description 23
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 239000000314 lubricant Substances 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 11
- 239000004200 microcrystalline wax Substances 0.000 claims description 10
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 10
- 150000003857 carboxamides Chemical class 0.000 claims description 8
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 8
- 229940075507 glyceryl monostearate Drugs 0.000 claims description 8
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 claims description 8
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 235000013361 beverage Nutrition 0.000 abstract description 4
- 235000013305 food Nutrition 0.000 abstract description 4
- 150000001993 dienes Chemical class 0.000 abstract 3
- 239000002932 luster Substances 0.000 abstract 1
- 239000005022 packaging material Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 50
- 229920001577 copolymer Polymers 0.000 description 49
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 29
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 17
- 239000000178 monomer Substances 0.000 description 15
- 239000004793 Polystyrene Substances 0.000 description 13
- 229920002223 polystyrene Polymers 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 238000000465 moulding Methods 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000006866 deterioration Effects 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 238000009740 moulding (composite fabrication) Methods 0.000 description 7
- 230000035939 shock Effects 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 238000003856 thermoforming Methods 0.000 description 5
- 238000007666 vacuum forming Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 150000002900 organolithium compounds Chemical class 0.000 description 4
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- 238000007493 shaping process Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 241000779819 Syncarpia glomulifera Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229920005601 base polymer Polymers 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920005669 high impact polystyrene Polymers 0.000 description 3
- 239000004797 high-impact polystyrene Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000001739 pinus spp. Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229940036248 turpentine Drugs 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
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- 229920000573 polyethylene Polymers 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-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
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- DBWWINQJTZYDFK-UHFFFAOYSA-N 2-ethenyl-1,4-dimethylbenzene Chemical compound CC1=CC=C(C)C(C=C)=C1 DBWWINQJTZYDFK-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-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
- CUWJKUDBPCMCIZ-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCC.C(CC)(=O)O Chemical compound CCCCCCCCCCCCCCCCCC.C(CC)(=O)O CUWJKUDBPCMCIZ-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VWLHWLSRQJQWRG-UHFFFAOYSA-O Edrophonum Chemical compound CC[N+](C)(C)C1=CC=CC(O)=C1 VWLHWLSRQJQWRG-UHFFFAOYSA-O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
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- 238000005452 bending Methods 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical compound CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 239000012530 fluid Substances 0.000 description 1
- 125000005908 glyceryl ester group Chemical group 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical class CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 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
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
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- 229920002545 silicone oil Polymers 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- 239000002562 thickening agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明提供一种嵌段共聚物组合物,所述嵌段共聚物组合物适合于食品容器、饮料容器、工业用容器、泡罩包装等各种包装材料,具有优良的透明性、光泽、强度、刚性、成型加工性,也具有优良的防粘连性能、防堆叠性能,即便在混合乙烯基芳香族烃类聚合物使用的情况下,前述特性也优良、物性平衡良好。一种嵌段共聚物组合物,其为乙烯基芳香族烃与共轭二烯的嵌段共聚物组合物,其中,在分子量150000~300000的范围具有分子量峰、并具有递变链段的嵌段共聚物成分(I)的共轭二烯含有率为10~20质量%,在分子量50000~140000的范围具有分子量峰、并具有递变链段的嵌段共聚物成分(II)的共轭二烯含量为30~50质量%,嵌段共聚物组合物中的嵌段共聚物成分(I)与嵌段共聚物成分(II)的分子量峰面积比(I)/(II)为20/80~80/20。
Description
技术领域
本发明涉及嵌段共聚物组合物及片材。
背景技术
由乙烯基芳香族烃与共轭二烯形成的嵌段共聚物被广泛用于食品容器、饮料容器、工业用容器(※包括各种托盘)、泡罩包装(blister pack)等各种包装材料。对包装材料多有设计性的需求,且必须能够清楚地看到内容物,故要求包装材料的原料具有优良的透明性、光泽。另一方面,由乙烯基芳香族烃与共轭二烯形成的嵌段共聚物有时混合乙烯基芳香族烃类聚合物而用于包装材料,所以此种树脂组合物也必须有良好的透明性。对于此课题,专利文献1~2中记载有使用具有特定聚合物构造的由乙烯基芳香族烃与共轭二烯形成的嵌段共聚物对解决课题有效的内容。
进而,在包装材料用途中,也必须要有能承受实际使用的强度(拉伸强度、耐冲击强度),以赋予这些物性为目的,有使用共轭二烯含有率高的嵌段共聚物的手段。但是,在随机地使用共轭二烯的含有率高的嵌段共聚物的情况下,会变得缺乏与乙烯基芳香族烃类聚合物的相容性,而难以确保良好的透明性、光泽。
另一方面,作为包装材料的一般制造方法,有将材料熔融混炼并成型为片材后,进行真空成型、压空成型、加压成型等热成型,制成各种成型体的方法。这些制造工艺有如下形式:成型为片材,卷取成卷状态并保管后,再自辊将片材抽出并进行热成型,由此得到成型品的离线(off line)形式;以及经片材成型后,不经由卷状态下的保管而直接进行热成型得到成型品的在线(in line)形式。在离线形式中,因以片材彼此接触的卷状态长时间保管,所以在使用由乙烯基芳香族烃与共轭二烯形成的嵌段共聚物的情况下,容易产生片材彼此粘接无法剥下的现象(以下,简称为“粘连”)。由于一旦发生粘连不良,就无法用于随后的热成型等,故期望赋予防粘连性能。关于此课题,专利文献3~5中记载有在该嵌段共聚物中使用烃系蜡作为有效防止粘连的手段的内容。
然而,根据由乙烯基芳香族烃与共轭二烯形成的嵌段共聚物的构造,即使随机地选定烃系蜡进行使用,有时也会未展现充分的防粘连效果,故要求使用适合所使用的聚合物的烃系蜡。
另外,在成型为包装材料后,在经过以将成型品彼此重叠的状态进行保管的过程的情况下,再次将其彼此分离进行使用时,有时发生成型品的接触面彼此卡住的现象(以下,简称为“堆叠”)。此现象在使用由乙烯基芳香族烃与共轭二烯形成的嵌段共聚物的情况下容易发生,特别是包装材料的沟槽越深,或包装材料的形状越复杂,成型品彼此的接触面积越增加,分离变得越困难,因此需要优良的防堆叠性能。近年来,由于形状复杂的包装材料增加,故对材料期望实现更优良的防堆叠性能。
现有技术文献
专利文献
专利文献1:日本特许第4787480号公报
专利文献2:日本特开2006-143944号公报
专利文献3:日本特许第1958261号公报
专利文献4:日本特开2005-139326号公报
专利文献5:日本特许第4812946号公报
发明内容
[发明所要解决的课题]
本发明的目的在于提供适合各种形状的食品容器、饮料容器、工业用容器、泡罩包装等各种包装材料(※包括各种托盘)的、具有优良的透明性、光泽、强度、刚性、成型加工性的材料,以及具有更优良的防粘连性能与防堆叠性能、且即便在混合乙烯基芳香族烃类聚合物而使用的情况下前述特性也优良的、物性平衡良好的材料。
[用于解决课题的手段]
本发明是一种嵌段共聚物组合物,其为由乙烯基芳香族烃与共轭二烯形成的嵌段共聚物组合物,其中,在分子量150000~300000的范围有分子量峰(peak)、且含有递变链段(tapered block)的嵌段共聚物成分(I)中的共轭二烯含有率为10~20质量%;在分子量50000~140000的范围有分子量峰,且含有递变链段的嵌段共聚物成分(II)中的共轭二烯含有率为30~50质量%;分子量峰的面积比(I)/(II)为20/80~80/20;更优选一种嵌段共聚物组合物,其中,嵌段共聚物成分(I)在分子量180000~290000的范围具有分子量峰,且含有递变链段,并且共轭二烯的含有率为10~15质量%,而嵌段共聚物成分(II)在分子量60000~100000的范围具有分子量峰,且含有递变链段,并且共轭二烯含有率为30~40质量%,进而,分子量峰的面积比(I)/(II)为40/60~60/40。另外,本发明是一种嵌段共聚物组合物,其中,嵌段共聚物成分(I)含有分子量80000~150000的乙烯基芳香族烃的聚合链段部分,前述嵌段共聚物成分(II)含有分子量5000~40000的乙烯基芳香族烃的聚合链段部分。进而,本发明是一种嵌段共聚物组合物,在嵌段共聚物组合物中,单独含有总量0.03~1.0质量%的烃系蜡,或含有总量0.03~1.0质量%的、烃系蜡与选自硬脂酸十八烷基酯、硬脂酸单甘油酯、芥酸酰胺、二十二碳酰胺中的至少1种以上;优选前述烃系蜡为熔点60~120℃的微晶蜡、或合成蜡、或微晶蜡与合成蜡的混合物中的任一种,并在嵌段共聚物组合物中含有0.03~0.5质量%;更优选前述烃系蜡的熔点为80~110℃;一种嵌段共聚物组合物,其中,前述选自硬脂酸十八烷基酯、硬脂酸单甘油酯、芥酸酰胺、二十二碳酰胺的润滑剂的总量相对于嵌段共聚物组合物为0.03~0.5质量%。此外,本发明是前述嵌段共聚物组合物与乙烯基芳香族烃类聚合物以30/70~100/0的质量比混合而成的树脂组合物、使用前述材料的片材、及其容器。
[发明效果]
通过使用本发明的嵌段共聚物组合物,无论是在单独使用该嵌段共聚物组合物的情况下,还是混合该嵌段共聚物组合物与乙烯基芳香族烃类聚合物进行使用的情况下,均可实现优良的透明性、光泽、强度、刚性、成型加工性。进而,除了前述特性以外,在片材及成型品的使用方面,也能实现更优良的防粘连性能与防堆叠性能,使各种形状的包装材料的制造及使用变容易。
具体实施方式
本发明的嵌段共聚物组合物以由乙烯基芳香族烃与共轭二烯形成的嵌段共聚物作为构成要素。
作为本发明的嵌段共聚物中所使用的乙烯基芳香族烃,可列举出例如:苯乙烯、邻甲基苯乙烯、对甲基苯乙烯、对叔丁基苯乙烯、2,4-二甲基苯乙烯、2,5-二甲基苯乙烯、α-甲基苯乙烯、乙烯基萘、乙烯基蒽等,其中优选为苯乙烯。
作为本发明的嵌段共聚物中所使用的共轭二烯,可列举出:1,3-丁二烯、2-甲基-1,3-丁二烯(异戊二烯)、2,3-二甲基-1,3-丁二烯、1,3-戊二烯、1,3-己二烯等,其中优选为1,3-丁二烯、异戊二烯。
本发明的嵌段共聚物可通过如下方法制造:在经过脱水的有机溶剂中,以有机锂化合物作为引发剂,视需要使无规化剂共存,将乙烯基芳香族烃及共轭二烯的单体加以聚合。作为有机溶剂,可使用丁烷、戊烷、己烷、异戊烷、庚烷、辛烷、异辛烷等脂肪族烃,环己烷、甲基环己烷、乙基环己烷等脂环式烃,或苯、甲苯、乙基苯、二甲苯等芳香族烃等,其中优选为环己烷。
有机锂化合物是于分子中键合了1个以上锂原子的化合物,例如可以使用:乙基锂、正丙基锂、正丁基锂、仲丁基锂、叔丁基锂等单官能有机锂化合物,除此以外,也可使用六亚甲基二锂、丁二烯基二锂、异戊二烯基二锂等多官能有机锂化合物,其中优选为正丁基锂。
作为无规化剂,主要是使用四氢呋喃(THF),此外还可使用醚类、胺类、硫醚类、磷酰胺、烷基苯磺酸盐、钾或钠的醇盐等。醚类可列举出例如:二甲基醚、二乙基醚、二苯基醚、二乙二醇二甲基醚、二乙二醇二丁基醚等。胺类除了叔胺、例如三甲胺、三乙胺、四甲基乙二胺以外,也可使用内环状胺等。除此之外,可使用三苯基膦、六甲基磷酰胺、烷基苯磺酸钾(或钠)、丁醇钾(或钠)等作为无规化剂。
相对于全部投料单体100质量份,这些无规化剂的添加量在10质量份以下,优选为0.001~8质量份。添加时间可在聚合反应开始前,也可在聚合过程中。另外,也可视需要而追加添加。
如此进行而得到的嵌段共聚物溶液,通过添加足以使活性末端惰性化的量的水、醇、二氧化碳等聚合停止剂来将嵌段共聚物惰性化。作为自此嵌段共聚物溶液回收嵌段共聚物的方法,可使用将此溶液投入甲醇等不良溶剂使其析出的方法、通过加热辊等使溶剂蒸发而使其析出的方法(滚筒烘干机法)、通过浓缩器将溶液浓缩后由排气式挤出机将溶剂除去的方法、将溶液分散于水中并通过吹入水蒸汽将溶剂加热除去的方法(蒸汽汽提法)等任意方法。
在将多种嵌段共聚物混合制成嵌段共聚物组合物的情况下,作为其混合方法,可列举出:在将经除去溶剂的嵌段共聚物彼此掺和后,投入挤出机,一边使其熔融一边混炼、混合的方法;在将除去溶剂前的嵌段共聚物的溶液彼此掺和后,除去溶剂而得到混合物的方法;在1个反应容器中能够聚合多种嵌段共聚物的方法;本发明的嵌段共聚物组合物可使用前述的任一种混合方法。
本发明的嵌段共聚物组合物视需要可含有各种添加剂。作为主要的添加剂,可列举出:增塑剂、抗氧化剂、耐候剂、润滑剂、抗静电剂、防雾剂、颜料等。
作为增塑剂,可使用总称为液体石蜡的石蜡油、液态石蜡(Nujol)、矿物油、矿油精(mineral spirit)、矿质松节油、白油、石油溶剂(white spirit)、白矿油、石油精、矿油精(mineral thinner)、石油精(petroleum spirit)、水性石蜡、白矿物油等。
作为抗氧化剂,可列举出例如:丙烯酸-2-叔丁基-6-(3-叔丁基-2-羟基-5-甲基苄基)-4-甲基苯酯、丙烯酸-2-[1-(2-羟基-3,5-二叔戊基苯基)乙基]-4,6-二-叔戊基苯酯、丙酸正十八烷基-3-(4-羟基-3,5-二叔丁基苯基)酯等酚系抗氧化剂,亚磷酸-2,2’-亚甲基双(4,6-二叔丁基苯基)辛酯、亚磷酸三(2,4-二叔丁基苯基)酯等磷系抗氧化剂等例子。
作为耐候剂,可列举出例如:2-(2-羟基-3-叔丁基-5-甲基苯基)-5-氯苯并三唑等苯并三唑类紫外线吸收剂、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯等受阻胺型耐候剂等例子。进而,前述的白油、硅油等也可作为耐候剂添加。
作为润滑剂,除了脂肪酸、脂肪酸酯、脂肪酸酰胺、丙三醇脂肪酸酯(甘油酯)、山梨醇酐脂肪酸酯、季戊四醇脂肪酸酯、蔗糖脂肪酸酯、丙二醇脂肪酸酯等以外,作为烃系蜡可列举出聚乙烯蜡、费托蜡(Fischer-Tropsch wax)等合成蜡,石蜡、微晶蜡等天然蜡。
作为抗静电剂,除了二壬基萘磺酸等阴离子表面活性剂、季铵化合物等阳离子表面活性剂以外,可列举出两性离子表面活性剂、非离子表面活性剂等。作为抗静电剂的使用方法,可使用混入树脂内部的形态和涂布于成型后的成型品表面的形态中的任一种。抗静电剂可以在不损害防粘连性能、防堆叠性能的范围内使用。
作为防雾剂,可列举出:甘油脂肪酸酯、聚甘油脂肪酸酯、山梨醇酐脂肪酸酯及其环氧乙烷加成物等多元醇的脂肪酸酯。作为防雾剂的使用方法,可列举出:混入树脂内部的形态和成型后涂布于成型品表面的形态等。防雾剂可以在不损害防粘连性能、防堆叠性能的范围内使用。
本发明的嵌段共聚物组合物视需要可含有填充材料。作为通过添加填充材料而得到的效果,主要可列出:高强度化、高刚性化、赋予防粘连性能、赋予防堆叠性能、赋予润滑性、隔热化、导电化、绝缘化、降低成本、着色等,可根据目的使用无机填充材料、有机填充材料、或两者。
作为填充材料,可列举出:高抗冲聚苯乙烯(HIPS)、乙烯基芳香族烃-(甲基)丙烯酸酯及/或(甲基)丙烯酸共聚物的交联微珠、乙烯基芳香族烃共聚物的交联微珠等有机物填充材料、二氧化硅微珠、石英微珠等无机物填充材料。为了得到良好的透明性,优选使用HIPS、乙烯基芳香族烃-(甲基)丙烯酸酯及/或(甲基)丙烯酸共聚物的交联微珠、乙烯基芳香族烃共聚物的交联微珠。相对于100质量份的树脂组合物,其配混比在10质量份以下,优选为0.05~5质量份,更优选为0.1~3质量份。这些物质可以在不损害各种成型品的外观的范围内使用。
本发明的嵌段共聚物组合物必须有结构不同的嵌段共聚物成分(I)与嵌段共聚物成分(II)。本发明的嵌段共聚物组合物含有:在以凝胶渗透色谱法测定所得到的分子量分布中,在分子量150000~300000的范围具有分子量峰的嵌段共聚物成分(I)。该嵌段共聚物成分(I)的分子量峰若低于150000,则会造成流动性变得过高,成型加工性降低,除此之外,在将乙烯基芳香族烃的聚合链段导入该嵌段共聚物中的情况下,聚合链段的分子量降低,导致与乙烯基芳香族烃类聚合物混合使用时的透明性恶化。若高于300000,则会造成流动性变得过低,成型加工性降低。嵌段共聚物成分(I)的更优选分子量范围为180000~290000。
嵌段共聚物成分(I)中的共轭二烯含有率优选为10~20质量%,更优选为10~15质量%。在小于10质量%时,除了造成强度过度降低以外,在与共轭二烯含有率高的嵌段共聚物成分混合时,还会导致相容性降低、透明性恶化。若大于20质量%,则除了造成刚性过度降低以外,在与乙烯基芳香族烃类聚合物混合使用时,还会导致相容性降低、透明性恶化。
嵌段共聚物成分中的共轭二烯的含量可以由公知的通常的卤素加成法得到。作为通常的卤素加成法的例子,可举出如下的方法:在能将该试料完全溶解的溶剂中使其溶解后,添加过量的氯化碘/四氯化碳溶液使其充分反应,以硫代硫酸钠/乙醇溶液滴定未反应的氯化碘,由得到的双键量算出共轭二烯含量。
本发明的嵌段共聚物组合物含有:在分子量50000~140000的范围具有分子量峰的嵌段共聚物成分(II)。该嵌段共聚物成分(II)的分子量峰若低于50000,则会导致强度过低,若大于140000,则会导致流动性降低、透明性恶化。嵌段共聚物成分(II)的更优选分子量范围为60000~100000。
嵌段共聚物成分(II)的共轭二烯含有率优选为30~50质量%,更优选为30~40质量%。在小于30质量%时,因会造成强度过度降低而不优选。若大于50质量%,除了透明性降低以外,还会导致与嵌段共聚物成分(I)的相容性降低、透明性恶化。
本发明的嵌段共聚物组合物含有:前述嵌段共聚物成分(I)与嵌段共聚物成分(II)。嵌段共聚物成分(I)的刚性及与乙烯基芳香族烃类聚合物的相容性优良,嵌段共聚物成分(II)的增强性优良。嵌段共聚物成分(I)与嵌段共聚物成分(II)的存在比(质量比)与凝胶渗透色谱法的分子量峰的面积比大致一致,这些嵌段共聚物成分(I)与(II)的分子量峰的面积比(I)/(II)优选为20/80~80/20,更优选为40/60~60/40。嵌段共聚物成分(I)的峰面积比若低于20,或嵌段共聚物成分(II)的峰面积比若高于80,则除了造成刚性过度降低以外,还会导致与乙烯基芳香族烃类聚合物的相容性降低、透明性恶化。嵌段共聚物成分(I)的峰面积比若高于80,或嵌段共聚物成分(II)的峰面积比若低于20,则会造成强度过度降低。
前述嵌段共聚物成分(I)中的乙烯基芳香族烃的聚合链段的分子量优选为80000~150000。若低于80000,则与乙烯基芳香族烃类共聚物的相容性会降低,若高于150000,则与嵌段共聚物成分(II)的相容性会降低,任一情况均会导致透明性恶化。
前述乙烯基芳香族烃的聚合链段优选乙烯基芳香族烃含有率为90质量%以上。若低于90质量%,则与乙烯基芳香族烃类聚合物的相容性会降低,透明性会恶化。更优选范围是95质量%以上,进一步优选为100质量%。
作为掌握乙烯基芳香族烃的聚合链段的存在的手段之一,可举出如下方法:依据文献(I.M.KOLTHOFF,et al.,Journal of Polymer Science,Volume 1,429(1946)中记载的方法),由将该嵌段共聚物进行锇酸分解而得到的成分的分子量来判断。
前述嵌段共聚物成分(II)中的乙烯基芳香族烃的聚合链段部分的分子量优选为5000~40000。在低于5000的情况或高于40000的情况中的任一种情况下,均可能导致强度降低而不优选。
本发明的嵌段共聚物组合物所含有的嵌段共聚物成分(I)及嵌段共聚物成分(II)分别含有乙烯基芳香族烃与共轭二烯的组成比自链段一边末端往另一边末端变化的递变链段。各嵌段共聚物组合物中的主要的递变链段整体中的单体质量比(乙烯基芳香族烃/乙烯基芳香族烃)没有特别受到限制,优选较为相近,更优选等值。各嵌段共聚物组合物的单体质量比的差异若变大,则相容性会恶化,容易导致透明性降低。
递变链段能通过在该链段形成时,将乙烯基芳香族烃与共轭二烯两单体一次性添加到聚合活性末端而得到。递变链段的组成比的变化(梯度)可通过一次性添加时进料的乙烯基芳香族烃与共轭二烯的质量比、无规化剂的添加等来调整。
本发明的嵌段共聚物为了实现前述结构上的特点,可采用下面列举的结构中的任一种。
(a)A-C
(b)C-A
(c)A-C-A
(d)A-B-C
(e)B-C-A
(f)A-B-C-A
(g)A-C-C
(h)C-C-A
(i)A-C-C-A
(j)A-B-C-B-C-A
(k)A-B-C-C-A
(l)A-C-B-C-A
(m)A-C-X
(n)A-C-A-X
(o)A-B-C-X
(p)A-B-C-A-X
此处,A是乙烯基芳香族烃的聚合链段,B是共轭二烯的聚合链段,C是乙烯基芳香族烃与共轭二烯的共聚链段,表示乙烯基芳香族烃与共轭二烯的组成比从该链段的一末端到另一边的末端连续地单调改变的递变链段。另外,X表示偶联中心。本发明的嵌段共聚物成分(I)、(II)可采用的结构的组合优选为以下中的任一种。
(1)(I)A-C-A、(II)A-C
(2)(I)A-C-A、(II)C-A
(3)(I)A-B-C-A、(II)A-B-C
(4)(I)A-B-C-A、(II)B-C-A
(5)(I)A-C-C-A、(II)A-C-C
(6)(I)A-C-C-A、(II)C-C-A
(7)(I)A-B-C-C-A、(II)A-B-C
(8)(I)A-B-C-C-A、(II)C-A
(9)(I)A-B-C-C-A、(II)C-C-A
(10)(I)A-C-B-C-A、(II)A-C
(11)(I)A-C-B-C-A、(II)B-C-A
(12)(I)A-C-X、(II)A-C
(13)(I)A-C-A-X、(II)A-C-A
(14)(I)A-B-C-X、(II)A-B-C
(15)(I)A-B-C-A-X、(II)A-B-C-A
本发明的嵌段共聚物组合物的维卡软化点温度没有特别受到限制,优选依据ISO306(JIS K7206)、以10N负重所测定的维卡软化点温度为60~100℃。若低于60℃,则除了嵌段共聚物组合物单体容易粘连以外,还会导致成型加工性降低,故不优选。若高于100℃,则除了会造成嵌段共聚物组合物的强度过度降低以外,还会变成高温成型而导致成型加工性降低,故不优选。维卡软化点温度的更优选范围是70~90℃。
本发明的嵌段共聚物组合物的弯曲强度没有特别受到限制,在依据ISO178(JIS K7171)、以试验速度2mm/min测定时的试验片能承受的最大弯曲应力(弯曲强度)为20~60MPa。若低于20MPa,则会造成刚性过度降低,导致对片材进行热成型时的成型加工性降低,若高于60MPa,因会导致成型品的柔软性降低、强度降低,故不优选。弯曲强度的更优选范围是30~50MPa。
本发明的嵌段共聚物组合物的雾度值没有特别受到限制,依据ISO14782(JIS K7136)测定的雾度值优选为7以下。若高于7,则在将乙烯基芳香族类烃混合在嵌段共聚物组合物中的情况下,会造成透明性显著降低而不优选。雾度值的更优选范围是5以下。
本发明的嵌段共聚物组合物的光泽没有特别受到限制,优选依据JISK7105所测定的光泽值为150以上。若低于150,因会导致宏观上的光泽感降低、透明性恶化、设计性降低,故不优选。光泽值的更优选范围是160以上。
为了有效赋予各种包装材料中所需要的防粘连性能及防堆叠性能,本发明的嵌段共聚物组合物可单独使用烃系蜡,或组合使用烃系蜡与选自硬脂酸十八烷基酯、硬脂酸单甘油酯、芥酸酰胺、二十二碳酰胺中的润滑剂。前述烃系蜡以外的润滑剂可单独使用,也可组合使用2种以上。作为上述润滑剂的添加量,在嵌段共聚物组合物中,总添加量优选为0.03~1.0质量%,更优选烃系蜡为0.03~0.5质量%,选自硬脂酸十八烷基酯、硬脂酸单甘油酯、芥酸酰胺、二十二碳酰胺中的润滑剂的总量为0.03~0.5质量%。若低于0.03质量%,则无法充分展现防粘连性能、防堆叠性能、或其两者,若高于0.5质量%,则润滑剂向成型品表面的渗出容易变得过量,使外观不良的危险性变高。
作为烃系蜡,主要可举出前述的聚乙烯蜡、费托蜡等合成蜡,以及石蜡、微晶蜡等天然蜡。优选为石蜡、微晶蜡、合成蜡,更优选为微晶蜡、合成蜡或其混合物。
为了有效地得到优良的防粘连性能,本发明的嵌段共聚物组合物优选含有烃系蜡。更优选熔点为60~120℃的微晶蜡、合成蜡、微晶蜡与合成蜡的混合物中的任一种,进一步优选前述烃系蜡的熔点为80~110℃。若熔点低于60℃,则得不到充分的防粘连性能,若高于120℃,则润滑剂向成型品表面的移动性降低,故不优选。
为了有效地得到优良的防堆叠性能,本发明的嵌段共聚物组合物优选使用选自硬脂酸单甘油酯、硬脂酸十八烷基酯、芥酸酰胺、二十二碳酰胺中的至少1种以上润滑剂。因前述的烃系蜡也能得到一定的防堆叠性能,所以能用于通用形状的包装材料用途,但在沟槽深或形状复杂的包装材料等特殊用途上,成型品彼此的接触面积增加且要求高防堆叠性能,因而变得难以适用。更优选将前述烃系蜡与选自硬脂酸单甘油酯、硬脂酸十八烷基酯、芥酸酰胺、二十二碳酰胺中的至少1种以上润滑剂组合使用。
进而,本发明的嵌段共聚物组合物可以在不损害防粘连性能、防堆叠性能、外观的范围内,出于赋予抗静电性能、及提升成型品彼此的分离性能的目的而视需要使用前述的抗静电剂。作为抗静电剂的添加量,在嵌段共聚物组合物中优选含有0.03~3质量%。若小于0.03质量%,则得不到充分的抗静电性能,而若高于3质量%,则抗静电剂的渗出会变得过多,容易导致外观恶化,故不优选。
由此得到的嵌段共聚物组合物可以视需要混合乙烯基芳香族烃类聚合物而使用,能混合的嵌段共聚物组合物/乙烯基芳香族烃类聚合物的质量比为30/70~100/0。该嵌段共聚物组合物的质量比若低于30,则会造成强度过度降低,无法供实用。
作为能与本发明的嵌段共聚物组合物混合的乙烯基芳香族烃类聚合物,可列举出:乙烯基芳香族烃聚合物、乙烯基芳香族烃与丙烯酸酯的共聚物、乙烯基芳香族烃与甲基丙烯酸甲酯的共聚物等,作为代表性的物质,可列举出:聚苯乙烯、苯乙烯/丙烯酸正丁酯共聚物、苯乙烯/甲基丙烯酸甲酯共聚物。其中,尤其作为一般的物质,可举出聚苯乙烯。
本发明的嵌段共聚物组合物无论是单独还是作为与乙烯基芳香族烃类聚合物的混合物,均适宜用于各种成型品。作为成型品的制造方法,可举出:将用公知的T模流延法、使用环状模的吹胀法、流延法、压延法等制成的片材,用公知的真空成型法、压空成型法、加压成型法、热板成型法等热成型法来制成各种成型品的方法;或用公知的注塑成型法来制成各种成型品的方法。此外,在将成型品重叠保管的用途中也能使用。
使用本发明的由嵌段共聚物组合物与乙烯基芳香族烃类聚合物形成的树脂组合物的片材的厚度没有特别受到限定,一般可在0.05mm~5mm的范围使用。厚度若低于0.05mm,则会造成该片材的刚性、强度过度降低,若高于5mm,则将该片材热成型为各种成型品会变困难,无法供实用。更优选的厚度为0.1mm~1.5mm。
对于本发明的由嵌段共聚物组合物与乙烯基芳香族烃类聚合物形成的树脂组合物,主要考虑包装材料所必须的强度、刚性、成本等的平衡来选择乙烯基芳香族烃类聚合物的添加量。作为不依赖于乙烯基芳香族烃类聚合物的添加量而重视的物性,可举出雾度值、光泽等。
作为使用本发明的树脂组合物的片材的雾度值的优选范围的例子,0.6mm厚的片材的雾度值优选为7%以下,更优选为5%以下。雾度值若高于7%,则宏观上的透明感显著降低,设计性降低,故不优选。
进而,作为使用本发明的树脂组合物的片材的光泽值的优选范围的例子,0.6mm厚的片材的光泽值优选为150以上,更优选为160以上。光泽值若低于150,则会导致宏观上的光泽感降低、透明性恶化、设计性降低,故不优选。
作为片材的强度的指标,可举出使用拉伸试验机的拉伸伸长率。作为使用本发明的树脂组合物的片材的拉伸伸长率的优选范围的例子,0.6mm厚的片材的以拉伸速度10mm/min测定的、片材在生产方向上的拉伸伸长率优选为20%以上。若低于20%,则片材会缺乏强度,难以供实用。前述拉伸伸长率的更优选范围为50%以上。
作为片材的刚性的指标,可举出以与前述拉伸伸长率的测定同样地得到的拉伸弹性模量。作为使用本发明的树脂组合物的片材的拉伸弹性模量的优选范围的例子,0.6mm厚的片材的以拉伸速度10mm/min测定的、片材在生产方向上的拉伸弹性模量优选为500~2500MPa,更优选为1000~2000MPa。若低于500MPa,则会造成片材的刚性、玻璃化转变温度过度降低,导致成型加工性降低。若高于2500MPa,则会造成片材强度过度降低,难以供实用。
作为使用本发明的树脂组合物的片材的冲击强度的优选范围的例子,对于0.6mm厚的片材,依据ASTM D-3420,使用半径10mm的冲击子得到的冲击强度优选为2~10kJ/m。若低于2kJ/m,则会造成冲击强度过度降低,若高于10kJ/m,则会造成片材的刚性过度降低,并导致成型加工性降低。冲击强度的更优选范围为2~7kJ/m。
实施例
以下,基于实施例更详细说明本发明,但本发明不受这些实施例所限定。
参考例1~15的嵌段共聚物(A)~(O)的制法
[参考例1]嵌段共聚物(A)的制法
(1)于反应容器中进料490kg的环己烷。
(2)在内温30℃下一边搅拌,一边添加1640mL的正丁基锂(10质量%环己烷溶液),添加12.0kg的苯乙烯单体,加以升温使其聚合。
(3)在内温50℃下,添加36.5kg的丁二烯单体与49.6kg的苯乙烯单体,在内温未大幅超过80℃的范围内加以升温使其聚合。
(4)在内温60℃下,添加111.9kg的苯乙烯单体,加以聚合。
(5)在内温75℃下,添加将33.7g的环氧化大豆油(ADEKACORPORATION制ADK CIZER O-130P)以5L的环己烷稀释而成的溶液,使其反应,结束聚合。
[参考例2]嵌段共聚物(B)的制法
(1)于反应容器中进料250kg的环己烷。
(2)在内温30℃下一边搅拌,一边添加750mL的正丁基锂(10质量%环己烷溶液),再添加34.0kg的苯乙烯单体,加以升温使其聚合。
(3)在内温40℃下,添加12.0kg的丁二烯单体,加以聚合。
(4)在内温50℃下,添加54.0kg的苯乙烯单体,结束聚合。
参考例4(嵌段共聚物(D))、参考例11(嵌段共聚物(K))是参考参考例2的制法制作的。各原料的进料量记载于表1。
[参考例3]嵌段共聚物(C)的制法
(1)在反应容器中进料518kg的环己烷。
(2)在内温30℃下一边搅拌,一边添加1360mL的正丁基锂(10质量%环己烷溶液),再添加9.1kg的苯乙烯单体,加以升温使其聚合。
(3)在内温65℃下,添加3.6kg的丁二烯单体,加以升温使其聚合。
(4)在内温40℃下,一次性添加27.3kg的丁二烯单体与23.3kg的苯乙烯单体,在内温未大幅超过80℃的范围内,加以升温使其聚合。
(5)在内温40℃下,添加118.7kg的苯乙烯单体,结束聚合。
参考例7(嵌段共聚物(G))、参考例8(嵌段共聚物(H))是参考参考例3的制法制作的。各原料的进料量记于表1。
[参考例5]嵌段共聚物(E)的制法
(1)在反应容器中进料367.5kg的环己烷。
(2)在内温30℃下一边搅拌,一边添加780mL的正丁基锂(10质量%环己烷溶液),添加5.5kg的苯乙烯单体,加以升温使其聚合。
(3)在内温40℃下,一次性添加16.9kg的丁二烯单体与22.8kg的苯乙烯单体,在内温未大幅超过70℃的范围内,加以升温使其聚合。
(4)在内温40℃下,添加112.3kg的苯乙烯单体,结束聚合。
[参考例6]嵌段共聚物(F)的制法
(1)于反应容器中进料450kg的环己烷。
(2)在内温30℃下一边搅拌,一边添加990mL的正丁基锂(10质量%环己烷溶液),再添加3.6kg的苯乙烯单体,加以升温使其聚合。
(3)一边将内温保持在80℃,一边分别以96.7kg/h、10.0kg/h的恒定添加速度同时添加总量156.6kg的苯乙烯单体、及总量16.2kg的丁二烯单体这二者,在添加结束后,亦将此状态保持足够的时间。
(4)让内温为78℃,添加3.6kg的苯乙烯单体,结束聚合。
[参考例9]嵌段共聚物(I)的制法
(1)于反应容器中进料259kg的环己烷。
(2)在内温30℃下一边搅拌,一边添加2020mL的正丁基锂(10质量%环己烷溶液),添加9.1kg的苯乙烯单体,加以升温使其聚合。
(3)在内温60℃下,添加2.7kg的丁二烯单体,使其聚合。
(4)在内温40℃下,一次性添加42.8kg的丁二烯单体与36.4kg的苯乙烯单体,在内温未大幅超过70℃的范围内升温,结束聚合。
参考例15(嵌段共聚物(O))是参考参考例9的制法制作的。各原料的进料量记载于表1。
[参考例10]嵌段共聚物(J)的制法
(1)于反应容器中进料270kg的环己烷。
(2)在内温30℃下一边搅拌,一边添加3980mL的正丁基锂(10质量%环己烷溶液),再添加22.0kg的苯乙烯单体,加以升温使其聚合。
(3)在内温40℃下,一次性添加45.0kg的丁二烯单体与33.0kg的苯乙烯单体,在内温未大幅超过65℃的范围内升温,结束聚合。
参考例12(嵌段共聚物(L))、参考例13(嵌段共聚物(M))、参考例14(嵌段共聚物(N))是参考参考例10的制法制作的。各原料的进料量记载于表1。
将如此进行而得到的嵌段共聚物A~O在构造方面的特征示于表1。关于表1中的嵌段共聚物的构造,A1及A2表示聚苯乙烯链段,B表示聚丁二烯链段,C表示由苯乙烯与丁二烯形成的递变链段,Cr表示由苯乙烯与丁二烯形成的无规链段,X表示偶联中心。各嵌段共聚物的分子量、嵌段共聚物中的共轭二烯的比率、乙烯基芳香族烃的聚合链段部分的分子量依据后述方法测定。
[表1]
[分子量的测定]
嵌段共聚物的分子量用下述GPC测定装置及条件进行测定。
装置名:高速GPC装置HLC-8220(东曹株式会社制)
色谱柱:将3支PL gel MIXED-B串联
温度:40℃
检测:差示折射率
溶剂:四氢呋喃
浓度:2质量%
标准曲线:使用标准聚苯乙烯(PL CORPORATION制)制作,测定以聚苯乙烯换算值计在分子量70000~150000的范围与150000~350000的范围有分子量峰的主要成分的峰值分子量。另外对于重均分子量,也依照相同测定条件测定,以聚苯乙烯换算值测定。
[共轭二烯含有比率的测定]
嵌段共聚物中的共轭二烯的含有质量%的测定是依下述方法进行测定的。
(1)将0.1g的试料溶解于氯仿50mL。
(2)添加25mL的氯化碘/四氯化碳溶液并充分混合后,在暗处放置1小时。
(3)添加75mL的2.5%碘化钾溶液,充分混合。
(4)一边充分搅拌,一边添加20%硫代硫酸钠/乙醇溶液直至溶液颜色变成淡黄色程度。
(5)加入约0.5mL的1%淀粉指示剂,再以20%硫代硫酸钠/乙醇溶液滴定至变成无色。
(6)滴定结束后,计测消耗掉的硫代硫酸钠/乙醇溶液量a[mL]。
为了实施基于空白测定的校正,单独以氯仿实施(1)~(6)的操作,测定消耗掉的硫代硫酸钠/乙醇溶液量b[mL]。
共轭二烯的含有率依据下式由测定值算出。
共轭二烯的含有率(%)=[(b-a)×0.1×c×27/1000]/W×100
c:20%硫代硫酸钠/乙醇溶液的滴定度
W:试料量[g]
[乙烯基芳香族烃的聚合链段部分的分子量测定]
对于嵌段共聚物中的乙烯基芳香族烃的聚合链段部分的分子量,根据前述的锇酸分解法,通过GPC测定装置测定所得到的乙烯基芳香族烃链段成分。另外,关于低分子量成分,通过使用低分子量色谱柱的GPC测定装置测定。
前述嵌段共聚物(A)~(O)是在聚合后,以聚合液的状态将2种以上溶液掺和后,使用直脱式的挤出机除去溶剂,得到嵌段共聚物组合物。嵌段共聚物组合物的一般物性归纳于表2及表3。嵌段共聚物组合物中的共轭二烯的比率依据前述方法测定,雾度值、产生拉伸破裂的应变、弯曲弹性模量、维卡软化点温度、弯曲强度依据以下方法测定。
[维卡软化点温度的测定]
嵌段共聚物组合物的维卡软化点温度是使用148 HDA Heat DistortionTester(安田精机制作所株式会社制),依据ISO306(JIS K7206),以10N负重来测定的。
[弯曲强度的测定]
嵌段共聚物组合物的弯曲强度是使用BENDOGRAPH II(东洋精机株式会社制),依据ISO178(JIS K7171),测定以试验速度2mm/min测定时试验片所能承受的最大弯曲应力(弯曲强度)。
[伸长率(产生拉伸破裂的应变)的测定]
嵌段共聚物组合物的伸长率(产生拉伸破裂的应变)是使用拉伸试验机(TSE Co.Ltd.制),依据ISO527-2(JIS K7161、7162)进行测定的。
[雾度值的测定]
嵌段共聚物组合物的雾度值是使用Haze Meter NDH300A(日本电色工业株式会社制),依据ISO14782(JIS K7136)进行测定的。
[光泽的测定]
片材的光泽是使用Gloss Meter VG2000(日本电色工业株式会社制),依据ISO2813(JIS Z8741),测定入射角60°时的光泽值。
[表2]
[表3]
接下来,对表2及表3的嵌段共聚物组合物,将各嵌段共聚物组合物与聚苯乙烯(东洋苯乙烯株式会社制TOYO Styrol GP级名:G200C)充分进行颗粒掺和后,使用TANABE PLASTICS MACHINERY CO.,LTD制片材挤出机(螺杆直径:40mm、螺杆构成:全螺纹型),一边以200℃加以熔融混合,一边自模唇间隙0.65mm的T型模挤出成片状。挤出的片材以施加过镜面加工的50℃的双辊进行牵引并冷却,以生产速度0.9m/min收集平均厚度0.60mm的片材。将相对于嵌段共聚物组合物与聚苯乙烯的混合比(嵌段共聚物组合物的质量%/聚苯乙烯的质量%)的片材物性测定结果一并归纳于表2及表3。片材的拉伸弹性模量、伸长率、片材冲击度、雾度值、光泽是依据以下方法测定的。
[拉伸弹性模量、伸长率的评价]
片材的拉伸弹性模量是使用TENSILON万能试验机RTG-1210(A&DCo.Ltd.制),以片材的生产方向(以下简称为MD。)与拉伸方向一致的方式,冲切成哑铃状,以拉伸速度10mm/min、卡盘间距离50mm进行测定。另外,片材的伸长率(到破裂为止的伸长率)是在前述拉伸弹性模量的测定时一并测定的。
[片材冲击度的评价]
片材冲击度(片材冲击强度)是使用冲击试验机(TESTER SANGYO Co.Ltd.制),依据ASTM D-3420,进行使用直径10mm的冲击子的冲压来测定的。
[雾度值的评价]
片材的雾度值是使用Haze Meter NDH2000(日本电色工业株式会社制),依据ISO14782(JIS K7136)测定的。
[光泽的评价]
片材的光泽是使用Gloss Meter VG2000(日本电色工业株式会社制),依据ISO2813(JIS Z8741),测定入射角60°的光泽值。
接下来,将任意润滑剂混合在前述嵌段共聚物组合物中,制作记载于表4的实施例5~10与记载于表5的比较例6~10的嵌段共聚物组合物。将前述嵌段共聚物组合物与聚苯乙烯(东洋苯乙烯株式会社制TOYO Styrol GP级名:G200C)以混合比(嵌段共聚物组合物的质量%/聚苯乙烯的质量%)为70质量%/30质量%充分进行颗粒掺和,使用TANABE PLASTICS MACHINERYCO.,LTD制片材挤出机(螺杆直径:40mm,螺杆构成:全螺杆型),一边以200℃加以熔融混合,一边自模唇间隙0.65mm的T型模挤出成片状。挤出的片材以施加过镜面加工的50℃的双辊进行牵引并冷却,以生产速度1.9m/min制作平均厚度0.30mm的片材。制成的片材的防粘连性能如下评价。
[防粘连性能的评价]
制作平均厚度0.30mm的片材后,5分钟连续卷取到直径90mm的纸管上成为卷状。使用相同方法,各制作2支卷,在23℃的环境下与40℃的环境下分别保管1支。在前述的规定温度环境下保管24小时后取出,依据以下基准评价自卷将片材剥下时的剥离性,结果示于表4及表5。
良:能容易地将片材剥离,且剥离片材的外观无异常。
可:虽然能将片材剥离,但伴随着剥离时的阻力感或剥离时的异响。
差:片材粘连,剥离时伴随着伤痕或破裂等外观异常。
接下来,在制作实施例5~10、比较例6~12的嵌段共聚物组合物后,将前述嵌段共聚物组合物与聚苯乙烯(东洋苯乙烯株式会社制TOYO Styrol GP级名:G200C)以混合比(嵌段共聚物组合物的质量%/聚苯乙烯的质量%)为60质量%/40质量%充分进行颗粒掺和,使用TANABE PLASTICS MACHINERYCO.,LTD制片材挤出机(螺杆直径:40mm、螺杆构成:全螺杆型),一边以200℃加以熔融混合,一边自模唇间隙0.65mm的T型模挤出成片状。挤出的片材以施加过镜面加工的50℃的双辊进行牵引并冷却,以生产速度0.9m/min制成平均厚度0.60mm的片材。制成的片材以浅野研究所株式会社制作的研究开发用压空真空成型机,使用托盘深度19mm的零件托盘用模具,于110℃真空成型。制成的成型品的防堆叠性能如下进行评价。
[防堆叠性能的评价]
作为防堆叠性能的评价,将真空成型的托盘在5片重叠的状态下,于23℃的环境下保管24小时,测定人为地将以自身重量而重叠的托盘各自分离所需要的时间[秒]。接下来,对成型后在23℃的环境下保管7天的零件托盘的分离秒数,依据以下基准判定防堆叠性能的优劣。测定结果示于表4及表5。
良:分离秒数为7秒以下
可:分离秒数为10秒以下
差:分离秒数为11秒以上
[表4]
[表5]
由表2、表3的结果可知,通过使用本发明的嵌段共聚物组合物,可平衡良好地展现透明性、光泽、刚性、强度、成型加工性,除此以外,在制成与乙烯基芳香族烃聚合物的树脂组合物的情况下,也不会引起透明性、光泽的明显降低,能适宜地使用。此外,由表4、表5的结果可知,通过使用特定的润滑剂,可实现更优良的防粘连性能与防堆叠性能。藉此,通过使用本发明的嵌段共聚物组合物,使各种形状的包装材料的制造及使用变容易。
[产业上的可利用性]
本发明的嵌段共聚物组合物是适合各种形状的各种包装材料的制造及使用的材料,使用此材料的片材可用于食品容器、饮料容器、工业用容器、泡罩包装等。此外,也适宜用于如实施注塑成型、异型挤出的用途。
Claims (13)
1.一种嵌段共聚物组合物,其特征在于,其为由乙烯基芳香族烃与共轭二烯形成的嵌段共聚物组合物,在分子量150000~300000的范围具有分子量峰、且含有递变链段的嵌段共聚物成分(I)中的共轭二烯的含有率为10~20质量%;在分子量50000~140000的范围具有分子量峰、且含有递变链段的嵌段共聚物成分(II)中的共轭二烯含有率为30~50质量%;且嵌段共聚物组合物中的嵌段共聚物成分(I)与嵌段共聚物成分(II)的分子量峰面积之比(I)/(II)为20/80~80/20。
2.如权利要求1所述的嵌段共聚物组合物,其特征在于,嵌段共聚物成分(I)在分子量180000~290000的范围具有分子量峰,且共轭二烯的含有率为10~15质量%,嵌段共聚物成分(II)在分子量60000~100000的范围具有分子量峰,且共轭二烯含有率为30~40质量%,嵌段共聚物组合物中的嵌段共聚物成分(I)与嵌段共聚物成分(II)的分子量峰的面积比(I)/(II)为40/60~60/40。
3.如权利要求1或2所述的嵌段共聚物组合物,其特征在于,嵌段共聚物成分(I)包含满足分子量80000~150000的范围的乙烯基芳香族烃的聚合链段部分,嵌段共聚物成分(II)包含满足5000~40000的分子量范围的乙烯基芳香族烃的聚合链段部分。
4.如权利要求1至3中任一项所述的嵌段共聚物组合物,其特征在于,在嵌段共聚物组合物中,单独含有总量0.03~1.0质量%的烃系蜡,或含有总量0.03~1.0质量%的、烃系蜡与选自硬脂酸十八烷基酯、硬脂酸单甘油酯、芥酸酰胺、二十二碳酰胺中的至少一种以上。
5.如权利要求4所述的嵌段共聚物组合物,其特征在于,烃系蜡是熔点60~120℃的微晶蜡、合成蜡、微晶蜡与合成蜡的混合物中的任一种,且在嵌段共聚物组合物中,含有0.03~0.5质量%。
6.如权利要求5所述的嵌段共聚物组合物,其特征在于,烃系蜡的熔点为80~110℃。
7.如权利要求4至6中任一项所述的嵌段共聚物组合物,其特征在于,在嵌段共聚物组合物中,含有总量0.03~0.5质量%的选自硬脂酸十八烷基酯、硬脂酸单甘油酯、芥酸酰胺、二十二碳酰胺的润滑剂。
8.一种树脂组合物,其是将权利要求1至7中的任一项所述的嵌段共聚物组合物与乙烯基芳香族烃类聚合物以30/70~100/0的质量比混合而成的。
9.一种片材,其使用了权利要求1至7中的任一项所述的嵌段共聚物组合物。
10.一种片材,其使用了权利要求8所述的树脂组合物。
11.一种容器,其使用了权利要求1至7中的任一项所述的嵌段共聚物组合物。
12.一种容器,其使用了权利要求8所述的树脂组合物。
13.一种容器,其使用了权利要求9或10所述的片材。
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SG11201407159PA (en) | 2014-12-30 |
KR20150012273A (ko) | 2015-02-03 |
EP2848650B1 (en) | 2017-11-08 |
TW201350514A (zh) | 2013-12-16 |
EP2848650A1 (en) | 2015-03-18 |
EP2848650B2 (en) | 2020-05-27 |
WO2013168679A1 (ja) | 2013-11-14 |
IN2014DN10034A (zh) | 2015-08-14 |
US9732215B2 (en) | 2017-08-15 |
JPWO2013168679A1 (ja) | 2016-01-07 |
US20150152257A1 (en) | 2015-06-04 |
MX362954B (es) | 2019-02-27 |
CN104271666B (zh) | 2018-11-13 |
MX2014013421A (es) | 2015-04-14 |
KR102036541B1 (ko) | 2019-10-25 |
EP2848650A4 (en) | 2015-12-30 |
TWI617590B (zh) | 2018-03-11 |
JP6099637B2 (ja) | 2017-03-22 |
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