JPH02248438A - Thermoplastic resin foam and its production - Google Patents
Thermoplastic resin foam and its productionInfo
- Publication number
- JPH02248438A JPH02248438A JP6937589A JP6937589A JPH02248438A JP H02248438 A JPH02248438 A JP H02248438A JP 6937589 A JP6937589 A JP 6937589A JP 6937589 A JP6937589 A JP 6937589A JP H02248438 A JPH02248438 A JP H02248438A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- temperature
- foam
- styrene
- polymer
- 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
- 239000006260 foam Substances 0.000 title claims abstract description 37
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 62
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 30
- 238000002844 melting Methods 0.000 claims abstract description 16
- 230000008018 melting Effects 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 229920001169 thermoplastic Polymers 0.000 claims abstract 2
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract 2
- 238000010097 foam moulding Methods 0.000 claims description 11
- 239000011342 resin composition Substances 0.000 claims description 11
- 230000009477 glass transition Effects 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 13
- 238000000465 moulding Methods 0.000 abstract description 12
- 238000010438 heat treatment Methods 0.000 abstract description 9
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 abstract description 6
- -1 polyethylene Polymers 0.000 description 54
- 239000004793 Polystyrene Substances 0.000 description 32
- 229920002223 polystyrene Polymers 0.000 description 32
- 238000005187 foaming Methods 0.000 description 29
- 229920001971 elastomer Polymers 0.000 description 20
- 239000008188 pellet Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 239000005060 rubber Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000306 component Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 241000156978 Erebia Species 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 229920006248 expandable polystyrene Polymers 0.000 description 5
- 239000004088 foaming agent Substances 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical group ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 4
- 235000019399 azodicarbonamide Nutrition 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 3
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 150000003440 styrenes Polymers 0.000 description 3
- 125000003011 styrenyl group Polymers [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004156 Azodicarbonamide Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- 229920006328 Styrofoam Polymers 0.000 description 2
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- ALIFPGGMJDWMJH-UHFFFAOYSA-N n-phenyldiazenylaniline Chemical compound C=1C=CC=CC=1NN=NC1=CC=CC=C1 ALIFPGGMJDWMJH-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920003197 poly( p-chlorostyrene) Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000008261 styrofoam Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- CZGWDPMDAIPURF-UHFFFAOYSA-N (4,6-dihydrazinyl-1,3,5-triazin-2-yl)hydrazine Chemical compound NNC1=NC(NN)=NC(NN)=N1 CZGWDPMDAIPURF-UHFFFAOYSA-N 0.000 description 1
- ULUZGMIUTMRARO-UHFFFAOYSA-N (carbamoylamino)urea Chemical compound NC(=O)NNC(N)=O ULUZGMIUTMRARO-UHFFFAOYSA-N 0.000 description 1
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-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(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 1
- DMYOHQBLOZMDLP-UHFFFAOYSA-N 1-[2-(2-hydroxy-3-piperidin-1-ylpropoxy)phenyl]-3-phenylpropan-1-one Chemical compound C1CCCCN1CC(O)COC1=CC=CC=C1C(=O)CCC1=CC=CC=C1 DMYOHQBLOZMDLP-UHFFFAOYSA-N 0.000 description 1
- XLHCFNYXQWSNAX-UHFFFAOYSA-N 1-n,4-n-dimethyl-1-n,4-n-dinitrobenzene-1,4-dicarboxamide Chemical compound [O-][N+](=O)N(C)C(=O)C1=CC=C(C(=O)N(C)[N+]([O-])=O)C=C1 XLHCFNYXQWSNAX-UHFFFAOYSA-N 0.000 description 1
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 1
- ZGWSIKBJQLBUPK-UHFFFAOYSA-N 2-(carbamoylcarbamoyl)benzoic acid Chemical compound NC(=O)NC(=O)C1=CC=CC=C1C(O)=O ZGWSIKBJQLBUPK-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
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 229920001079 Thiokol (polymer) Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- VRFNYSYURHAPFL-UHFFFAOYSA-N [(4-methylphenyl)sulfonylamino]urea Chemical compound CC1=CC=C(S(=O)(=O)NNC(N)=O)C=C1 VRFNYSYURHAPFL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- VQXINLNPICQTLR-UHFFFAOYSA-N carbonyl diazide Chemical compound [N-]=[N+]=NC(=O)N=[N+]=[N-] VQXINLNPICQTLR-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- WEBPLNHGJRPWKC-UHFFFAOYSA-N dioxazinane Chemical compound C1CNOOC1 WEBPLNHGJRPWKC-UHFFFAOYSA-N 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012533 medium component Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 229920012128 methyl methacrylate acrylonitrile butadiene styrene Polymers 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920001620 poly(3-methyl styrene) Polymers 0.000 description 1
- 229920001627 poly(4-methyl styrene) Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001608 poly(methyl styrenes) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- WEHDCBONCFYXKK-UHFFFAOYSA-N tert-butyl 3-(4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)OC(=O)CCC1=CC=C(O)C=C1 WEHDCBONCFYXKK-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は熱可塑性樹脂発泡体とその製造方法に関し、詳
しくは主としてシンジオタクチック構造を有するスチレ
ン系重合体を素材として用いてなる耐熱性のすぐれた熱
可塑性樹脂発泡体ならびにその効率のよい製造方法に関
する。[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a thermoplastic resin foam and a method for producing the same, and more specifically, it relates to a thermoplastic resin foam and a method for producing the same. This invention relates to an excellent thermoplastic resin foam and an efficient manufacturing method thereof.
〔従来の技術及び発明が解決しようとする課題〕従来か
ら、アタクチック構造のスチレン系重合体やポリエチレ
ン、ポリプロピレン等のオレフィン系重合体の発泡体は
広く知られており、特にアタクチック構造のスチレン系
重合体の発泡体は、発泡スチロールとして各種用途に幅
広く利用されている。[Prior art and problems to be solved by the invention] Foams of styrene polymers with an atactic structure and olefin polymers such as polyethylene and polypropylene have been widely known. The combined foam is widely used as Styrofoam for various purposes.
しかし、この発泡スチロールや発泡ポリエチレン等は、
低発泡体は合成木材として建材に使用され、また高発泡
体は断熱材として使用されているが、耐熱性において未
だ不充分である。特に、発泡スチロールの場合、ガラス
転移温度である１００℃を越えると熱変形し、また発泡
ポリエチレンの場合は、１３５℃を越えると熱変形する
という欠点があワた。However, this styrofoam, foamed polyethylene, etc.
Low foam materials are used as synthetic wood for building materials, and high foam materials are used as heat insulating materials, but their heat resistance is still insufficient. In particular, foamed polystyrene suffers from thermal deformation when the glass transition temperature exceeds 100°C, and foamed polyethylene suffers from thermal deformation when the temperature exceeds 135°C.
ところで、本発明者らのグループは、先般、シンジオタ
クテイシテイ−の高いスチレン系重合体を開発すること
に成功し、さらにこのスチレン系重合体に他の成分を配
合した組成物を開発した（特開昭６２−１０４８１８号
公報、同６２−２５７９４８号公報、同６２−２５７９
５０号公報）。By the way, the group of the present inventors has recently succeeded in developing a styrenic polymer with high syndiotacticity, and has also developed a composition in which this styrenic polymer is blended with other components ( JP-A No. 62-104818, JP-A No. 62-257948, JP-A No. 62-2579
Publication No. 50).
本発明者らは、このシンジオタクチック構造を有するス
チレン系重合体あるいはその組成物が、アタクチック構
造のスチレン系重合体やその組成物に比べて、機械的強
度や耐熱性等にすぐれたものであることに着目して、鋭
意研究を続けた。The present inventors have discovered that this styrenic polymer having a syndiotactic structure or its composition has superior mechanical strength, heat resistance, etc. compared to a styrenic polymer having an atactic structure or its composition. He focused on one thing and continued his research.
その結果、このシンジオタクチック構造のスチレン系重
合体あるいはこれを含む組成物を、発泡剤の存在下で特
定の温度範囲にて加熱発泡することによって、従来の発
泡スチロールに比べて著しく耐熱性のすぐれた発泡体が
得られることを見出した０本発明はこのような知見に基
いて完成したものである。As a result, by heating and foaming this syndiotactic styrenic polymer or a composition containing it in the presence of a blowing agent at a specific temperature range, we have found that it has significantly better heat resistance than conventional styrene foam. The present invention was completed based on this finding.
すなわち、本発明は主としてシンジオタクチック構造を
有するスチレン系重合体あるいは該スチレン系重合体を
含有する熱可塑性樹脂組成物からなり、発泡倍率が１．
２〜８０倍でありかつ結晶化度が２０％以上である熱可
塑性樹脂発泡体を提供するものである。また主としてシ
ンジオタクチック構造を有するスチレン系重合体あるい
は該スチレン系重合体を含有する熱可塑性樹脂組成物を
、発泡剤の存在下ガラス転移温度以上かつ融点より５０
℃高い温度以下の温度で発泡成形することによって、上
記の熱可塑性樹脂発泡体を製造する方法をも提供するも
のである。That is, the present invention mainly consists of a styrenic polymer having a syndiotactic structure or a thermoplastic resin composition containing the styrenic polymer, and has an expansion ratio of 1.
The object of the present invention is to provide a thermoplastic resin foam having a crystallinity of 2 to 80 times as much as 20% or more. Furthermore, a styrenic polymer mainly having a syndiotactic structure or a thermoplastic resin composition containing the styrenic polymer is heated at a temperature higher than the glass transition temperature and 50° below the melting point in the presence of a blowing agent.
The present invention also provides a method for producing the above-mentioned thermoplastic resin foam by foam molding at a temperature lower than or equal to a temperature higher than 10°C.
本発明では、樹脂発泡体のベース素材として、主として
シンジオタクチック構造を有するスチレン系重合体ある
いは該スチレン系重合体を含有する熱可塑性樹脂組成物
を用いる。ここでスチレン系重合体の主としてシンジオ
タクチック構造とは、立体化学構造が主としてシンジオ
タクチック構造、即ち炭素−炭素結合から形成される主
鎖に対して側鎖であるフェニル基や置換フェニル基が交
互に反対方向に位置する立体構造を有するものであり、
そのタフティシティ−は同位体炭素による核磁気共鳴法
（℃−ＮＭＲ法）により定量される。In the present invention, a styrenic polymer having a syndiotactic structure or a thermoplastic resin composition containing the styrene polymer is mainly used as the base material of the resin foam. Here, the mainly syndiotactic structure of a styrenic polymer means that the stereochemical structure is mainly syndiotactic, that is, the main chain formed from carbon-carbon bonds has a phenyl group or substituted phenyl group as a side chain. It has a three-dimensional structure that is alternately located in opposite directions,
The toughness is determined by nuclear magnetic resonance method (° C.-NMR method) using carbon isotope.
１３Ｃ−ＮＭＲ法により測定されるタフティシティ−は
、連続する複数個の構成単位の存在割合、例えば２ｍ−
の場合はダイアンド、３個の場合はトリアンド、５個の
場合はペンタッドによって示すことができるが、本発明
に言う主としてシンジオタクチック構造を有するスチレ
ン系重合体とは、通常はダイアツドで７５％以上、好ま
しくは８５％以上、若しくはペンタッド（ラセミペンタ
ッド）で３０％以上、好ましくは５０％以上のシンジオ
タクテイシテイ−を有するポリスチレン、ポリ（アルキ
ルスチレン）、ポリ（ハロゲン化スチレン）、ポリ（ア
ルコキシスチレン）、ポリ（ビニル安息香酸エステル）
およびこれらの混合物、あるいはこれらを主成分とする
共重合体を指体する。Toughness measured by 13C-NMR is the proportion of consecutive constituent units, for example 2m-
In the case of , it can be indicated by diand, in case of 3, it can be indicated by triand, and in case of 5, it can be indicated by pentad, but the styrenic polymer having mainly syndiotactic structure as referred to in the present invention is usually 75% or more diand. , preferably 85% or more, or polystyrene, poly(alkyl styrene), poly(halogenated styrene), poly(alkoxy styrene), poly(vinyl benzoate)
and mixtures thereof, or copolymers containing these as main components.
なお、ここでポリ（アルキルスチレン）としては、ポリ
（メチルスチレン）、ポリ（エチルスチレン）。Note that poly(alkylstyrene) here includes poly(methylstyrene) and poly(ethylstyrene).
ポリ（イソプロピルスチレン）、ポリ（ターシャリ−ブ
チルスチレン）などがあり、ポリ（ハロゲン化スチレン
）としては、ポリ（クロロスチレン）。Poly(isopropylstyrene), poly(tertiary-butylstyrene), etc. Poly(halogenated styrene) includes poly(chlorostyrene).
ポリ（ブロモスチレン）、ポリ（フルオロスチレン）な
どがある、また、ポリ（アルコキシスチレン）としては
、ポリ（メトキシスチレン）、ポリ゛（エトキシスチレ
ン）などがある、これらのうち特に好ましいスチレン系
重合体としては、ポリスチレン、ポリ（ｐ−メチルスチ
レン）、ポリ（ｍ−メチルスチレン）、ポリ（ｐ−ター
シャリ−ブチルスチレン）、ポリ（ｐ−クロロスチレン
）、ポリ（ｍ−クロロスチレン）、ポリ（ｐ−フルオロ
スチレン）、更にはスチレンとｐ−メチルスチレンとの
共重合体をあげることができる。Examples of poly(bromostyrene) and poly(fluorostyrene) include poly(alkoxystyrene) such as poly(methoxystyrene) and poly(ethoxystyrene). Particularly preferred styrenic polymers among these include poly(methoxystyrene) and poly(ethoxystyrene). Polystyrene, poly(p-methylstyrene), poly(m-methylstyrene), poly(p-tert-butylstyrene), poly(p-chlorostyrene), poly(m-chlorostyrene), poly(p-chlorostyrene), -fluorostyrene), as well as copolymers of styrene and p-methylstyrene.
また、本発明に用いるスチレン系重合体は、分子量につ
いては制限はないが、重量平均分子量が１０．０００以
上のものが好ましく、とりわけ５０．０００以上のもの
が最適である。さらに、分子量分布についてもその広狭
は制約がなく、様々なものを充当することが可能である
。このような主としてシンジオタクチック構造を有する
スチレン系重合体は、例えば不活性炭化水素溶媒中また
は溶媒の不存在下に、チタン化合物、及び水とトリアル
キルアルミニウムの縮合生成物を触媒として、スチレン
系単量体（上記スチレン系重合体に対応する単量体）を
重合することにより製造することができる（特開昭６２
−１８７７０８号公報）。Furthermore, the molecular weight of the styrenic polymer used in the present invention is not limited, but those having a weight average molecular weight of 10,000 or more are preferred, and those of 50,000 or more are particularly optimal. Further, there is no restriction on the width or narrowness of the molecular weight distribution, and various types can be used. Such styrenic polymers having a mainly syndiotactic structure can be produced by using a titanium compound and a condensation product of water and trialkylaluminum as catalysts, for example, in an inert hydrocarbon solvent or in the absence of a solvent. It can be produced by polymerizing monomers (monomers corresponding to the above-mentioned styrene polymers) (Japanese Patent Laid-Open No. 62
-187708).
本発明における発泡体のベース素材は、上述の如きシン
ジオタクチック構造のスチレン系重合体であるが、この
スチレン系重合体に必要に応じて他の成分を加えた熱可
塑性樹脂組成物を充当することもできる。ここで、上記
スチレン系重合体と併用することのできる成分は、ゴム
状重合体や上記スチレン系重合体以外の熱可塑性樹脂な
どがあり、さらには滑剤、酸化安定剤、無機充填材、紫
外線吸収剤、熱安定剤、難燃剤、帯電防止剤１着色剤等
の各種添加剤をあげることもできる。The base material of the foam in the present invention is a styrene polymer with a syndiotactic structure as described above, and a thermoplastic resin composition prepared by adding other components to this styrene polymer as necessary is used. You can also do that. Here, components that can be used in combination with the above styrene polymer include rubber-like polymers and thermoplastic resins other than the above styrene polymer, as well as lubricants, oxidation stabilizers, inorganic fillers, and ultraviolet absorbers. Various additives such as additives, heat stabilizers, flame retardants, antistatic agents, and colorants can also be mentioned.
ここで、ゴム状重合体としては、様々なものが使用可能
であるが、最も好適なものはスチレン系化合物をその一
成分として含むゴム状共重合体で、例えば、スチレン−
ブタジェンブロック共重合体のブタジェン部分を一部あ
るいは完全に水素化したゴム（ＳＥＢＳ）、スチレン−
ブタジェン共重合体ゴム（ＳＢＲ）、アクリル酸メチル
−ブタジェン−スチレン共重合体ゴム、アクリロニトリ
ル−ブタジェン−スチレン共重合体ゴム（ＡＢＳゴム）
、アクリロニトリル−アルキルアクリレート−ブタジェ
ン−スチレン共重合体ゴム（ＡＡＢＳ）。Here, various rubber-like polymers can be used, but the most suitable one is a rubber-like copolymer containing a styrene compound as one of its components, such as a styrene-based copolymer.
Rubber (SEBS) in which the butadiene portion of a butadiene block copolymer is partially or completely hydrogenated, styrene-
Butadiene copolymer rubber (SBR), methyl acrylate-butadiene-styrene copolymer rubber, acrylonitrile-butadiene-styrene copolymer rubber (ABS rubber)
, acrylonitrile-alkyl acrylate-butadiene-styrene copolymer rubber (AABS).
メタクリル酸メチル−アルキルアクリレート−スチレン
共重合体ゴム（ＭＡＳ）、メタクリル酸メチル−アルキ
ルアクリレート−ブタジェン−スチレン共重合体ゴム（
ＭＡＢＳ）などが挙げられ、これらはいずれもスチレン
単位を有するため、上述の主としてシンジオタクチック
構造を有するスチレン系重合体に対する分散性が良好で
あり、その結果、物性の改善効果が著しい、さらに用い
ることのできるゴム状重合体の他の例としては、天然ゴ
ム、ポリブタジェン、ポリイソプレン、ポリイソブチレ
ン、ネオプレン、エチレン−プロピレン共重合体ゴム、
ポリスルフィドゴム、チオコールゴム、アクリルゴム、
ウレタンゴム、シリコーンゴム、エピクロルヒドリンゴ
ム、ポリエーテルエステルゴム、ポリエステルエステル
ゴムなどが挙げられる。Methyl methacrylate-alkyl acrylate-styrene copolymer rubber (MAS), methyl methacrylate-alkyl acrylate-butadiene-styrene copolymer rubber (
MABS), etc., and since these all have styrene units, they have good dispersibility in the above-mentioned styrenic polymers mainly having a syndiotactic structure, and as a result, they have a remarkable effect of improving physical properties. Other examples of rubbery polymers that can be used include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, ethylene-propylene copolymer rubber,
polysulfide rubber, thiokol rubber, acrylic rubber,
Examples include urethane rubber, silicone rubber, epichlorohydrin rubber, polyether ester rubber, and polyester ester rubber.
また、上記スチレン系重合体以外の熱可塑性樹脂として
は、製造すべき発泡体の用途等により様々なものを選定
することができるが、例えばアタクチック構造のポリス
チレン、アイソタクチック構造のポリスチレン、ＡＳ樹
脂、ＡＢＳ樹脂などのスチレン系重合体をはじめ、ポリ
エステル（ポリエチレンテレフタレートなど）、ポリカ
ーボネート、ポリエーテル′（ポリフェニレンオキサイ
ド。In addition, various thermoplastic resins other than the above-mentioned styrene polymers can be selected depending on the use of the foam to be manufactured, such as polystyrene with an atactic structure, polystyrene with an isotactic structure, and AS resin. , styrenic polymers such as ABS resin, polyester (polyethylene terephthalate, etc.), polycarbonate, polyether' (polyphenylene oxide).
ポリスルホン、ポリエーテルスルホンなど）、ポリアミ
ド、ポリオキシメチレンなどの縮合系重合体、ポリアク
リル酸、ポリアクリル酸エステル。(polysulfone, polyethersulfone, etc.), condensation polymers such as polyamide, polyoxymethylene, polyacrylic acid, polyacrylic acid ester.
ポリメチルメタクリレートなどのアクリル系重合体、ポ
リエチレン、ポリプロピレン、ポリブテン。Acrylic polymers such as polymethyl methacrylate, polyethylene, polypropylene, and polybutene.
ポリ４−メチルペンテン−１，エチレン−プロピレン共
重合体などのポリオレフィン、あるいはポリ塩化ビニル
、ポリ塩化ビニリデン、ポリ弗化ビニリデンなどの含ハ
ロゲン化合物重合体などがあげられる。これらの中で、
アククチツク構造のポリスチレン、アイソタクチック構
造のポリスチレン、ポリフェニレンエーテル（ポリフェ
ニレンオキサイド）あるいはこれらの混合物、またはこ
れらを主体とする共重合体等が、シンジオタクチック構
造のスチレン系重合体と相溶性が良好であり、また発泡
体の製造が容易であることから特に好ましい。即ち、上
記の好適な熱可塑性樹脂を用いると、溶融粘度、結晶化
速度を調整することができるとともに、配合量９種類９
分子量等を適宜選定することにより、従来の非品性樹脂
（アタクチックボリスチレン、ポリ塩化ビニルなど）お
よび結晶性樹脂（ポリエチレン、ポリプロピレンなど）
の発泡に用いられている発泡成形法を柔軟に適用するこ
とができる。Examples include polyolefins such as poly-4-methylpentene-1 and ethylene-propylene copolymers, and halogen-containing compound polymers such as polyvinyl chloride, polyvinylidene chloride, and polyvinylidene fluoride. Among these,
Polystyrene with an active structure, polystyrene with an isotactic structure, polyphenylene ether (polyphenylene oxide), a mixture thereof, or a copolymer mainly composed of these, has good compatibility with a styrenic polymer with a syndiotactic structure. It is particularly preferred because it is easy to produce a foam. That is, by using the above-mentioned suitable thermoplastic resin, the melt viscosity and crystallization rate can be adjusted, and the blending amount can be adjusted to 9 types.
By appropriately selecting molecular weight etc., conventional non-grade resins (atactic polystyrene, polyvinyl chloride, etc.) and crystalline resins (polyethylene, polypropylene, etc.)
The foam molding method used for foaming can be applied flexibly.
なお、これらのゴム状重合体や熱可塑性樹脂を使用する
場合に、その使用量については、特に制限はないが、前
記シンジオタクチック構造のスチレン系重合体１００重
量部あたり、ゴム状重合体を１００重量部以下、好まし
くは５〜７０重量部程度とし、また前述の熱可塑性樹脂
は１０００重量部以下、好ましくは１〜２００重量部の
範囲で適宜選定すればよい。When using these rubbery polymers and thermoplastic resins, there is no particular restriction on the amount used, but the amount of rubbery polymer per 100 parts by weight of the styrene polymer with the syndiotactic structure is The amount of the thermoplastic resin may be selected appropriately within the range of 100 parts by weight or less, preferably from 5 to 70 parts by weight, and 1000 parts by weight or less, preferably from 1 to 200 parts by weight.
本発明の樹脂発泡体は、上述のシンジオタクチック構造
のスチレン系重合体あるいはこれとゴム状重合体や他の
熱可塑性樹脂等からなる熱可塑性樹脂組成物をベース素
材としてなるものであり、さらにその発泡倍率は１．２
〜８０倍、好ましくは１．２〜６０倍であって、しかも
結晶化度が２０％以上、好ましくは２５〜８０％である
ことに特徴がある。ここで、発泡倍率が１．２倍より小
さいと発泡体としての特性である軽量性、断熱性等が充
分でないばかりでなく、不均一に気泡が存在することに
なり、従来の成形品に（らぺ、力学物性、外観が悪化し
好ましくない。また、発泡倍率が８０倍より大きいと、
発泡倍率の増加に伴う力学物性の低下により、実用に供
しえなくなる。また、結晶化度が２０％未満であると、
耐熱性がガラス転移温度付近となり、特性の向上が見ら
れない。The resin foam of the present invention is made of the above-mentioned syndiotactic structure styrene polymer or a thermoplastic resin composition consisting of this, a rubbery polymer, other thermoplastic resin, etc. as a base material, and further Its foaming ratio is 1.2
~80 times, preferably 1.2 to 60 times, and is characterized by a crystallinity of 20% or more, preferably 25 to 80%. Here, if the foaming ratio is smaller than 1.2 times, not only will the characteristics of the foam, such as lightness and heat insulation, not be sufficient, but the air bubbles will be unevenly present, and conventional molded products ( It is undesirable because the foam, mechanical properties, and appearance deteriorate.Also, if the expansion ratio is greater than 80 times,
Due to the decrease in mechanical properties as the expansion ratio increases, it becomes impossible to put it into practical use. In addition, when the crystallinity is less than 20%,
The heat resistance is close to the glass transition temperature, and no improvement in properties is observed.
また、本発明の樹脂発泡体は上記の如き特性を有するも
のであれば、他に制限はないが、密度は０．０１３〜０
．８４ ｇ ／ａｍ’の範囲で、融点が１６０〜３３０
℃のものが特に好ましい。Further, the resin foam of the present invention has no other limitations as long as it has the above characteristics, but the density is 0.013 to 0.
．． 84 g/am', melting point 160-330
℃ is particularly preferred.
このような特徴を持つ樹脂発泡体は各種の製造方法があ
るが、次の如き方法にて効率よく製造することができる
。Although there are various methods for producing a resin foam having such characteristics, it can be efficiently produced by the following method.
すなわち、上述のシンジオタクチック構造のスチレン系
重合体あるいはこれとゴム状重合体や他の熱可塑性樹脂
等からなる熱可塑性樹脂組成物を、発泡剤の存在下でガ
ラス転移温度（Ｔｇ）以上、融点（Ｔｍ）より５０°Ｃ
高い温度以下に加熱して発泡成形する。ここで発泡剤は
、加熱、即ち加熱発泡に先立ってベース素材と混合させ
てもよく、また加熱発泡時に混合させてもよい、加熱発
泡に先立って発泡剤を混合させる方法としては、例えば
スチレン系モノマーを重合してシンジオタクチック構造
のスチレン系重合体を製造する際に発泡剤を混合させて
おく方法、ベース素材である重合体パウダーに含浸させ
る方法、重合体ペレットに含浸させる方法、あるいは重
合体パウダーや重合体ペレットとトライブレンドする方
法など様々な方法があげられる。ここで、発泡剤を含浸
させる方法を用いる場合は、他の樹脂とのブレンドによ
り、含浸性を向上させることができる。特に、均一な発
泡体を得るためにアタクチックポリスチレンのような相
溶性でかつ溶媒等の流体状発泡剤への含浸性の良い熱可
塑性樹脂をブレンドすることは有効である。また、加熱
発泡時に発泡剤を混合させる方法としては、重合体パウ
ダーや重合体ペレットとトライブレンドする方法以外に
、例えば成形機の押出スクリューの途中から、プロピレ
ン、塩化メチル、フレオンガス等の常温気体発泡剤を吹
き込む方法など各種各様の方法がある。That is, the above-mentioned styrenic polymer having a syndiotactic structure or a thermoplastic resin composition consisting of the same, a rubbery polymer, other thermoplastic resin, etc. is heated to a temperature higher than the glass transition temperature (Tg) in the presence of a blowing agent. 50°C above melting point (Tm)
Foam molding is performed by heating below a high temperature. Here, the foaming agent may be mixed with the base material prior to heating, that is, heating and foaming, or may be mixed during heating and foaming. There are two methods: mixing a blowing agent when polymerizing monomers to produce a styrenic polymer with a syndiotactic structure, impregnating it into the polymer powder that is the base material, impregnating it into polymer pellets, or impregnating it into polymer pellets. There are various methods such as tri-blending with combined powder and polymer pellets. Here, when using a method of impregnating a foaming agent, the impregnating property can be improved by blending with other resins. In particular, in order to obtain a uniform foam, it is effective to blend a thermoplastic resin, such as atactic polystyrene, which is compatible and has good impregnability with a fluid blowing agent such as a solvent. In addition, as a method of mixing a blowing agent during heating and foaming, in addition to the method of tri-blending with polymer powder or polymer pellets, for example, from the middle of the extrusion screw of a molding machine, room temperature gas foaming of propylene, methyl chloride, Freon gas, etc. There are various methods such as injecting a chemical.
なお、本発明では、上記の加熱発泡によって発泡性のス
チレン系重合体あるいは樹脂組成物を得、これをさらに
各種成形法によって発泡成形体としてもよいが、発泡と
成形を同時に進行させる加熱発泡成形によって発泡成形
体を製造してもよい。In addition, in the present invention, a foamable styrenic polymer or resin composition may be obtained by the above heat foaming, and this may be further formed into a foam molded product by various molding methods, but heat foam molding in which foaming and molding are performed simultaneously A foamed molded article may be manufactured by.
成形あるいは加熱発泡成形の方法は、公知の方法を適宜
採用すればよいが、例えば融着成形、押出発泡成形、射
出発泡成形などが利用できる。As the method of molding or heat foam molding, any known method may be appropriately adopted, and for example, fusion molding, extrusion foam molding, injection foam molding, etc. can be used.
本発明の方法では、発泡成形にあたり、押出発泡、射出
発泡成形においては結晶化温度以上、融点より５０℃高
い温度以下が好ましく、スチし・ン系重合体がシンジオ
タクチックポリスチレンであって、他の樹脂やゴム成分
を含まない場合、２００〜３２０℃が好ましい。In the method of the present invention, in extrusion foam molding and injection foam molding, the temperature is preferably higher than the crystallization temperature and lower than 50°C higher than the melting point, and the styrene-based polymer is syndiotactic polystyrene and other 200 to 320°C is preferable when the resin or rubber component is not included.
ここで、成形温度が結晶化温度以下では、結晶化による
弾性率の増加により充分な発泡倍率が得られなかったり
、均一な発泡体が得られないなどの不都合が生ずる。ま
た、融点より５０°Ｃ高い温度を超えると分解が著しく
、力学物性の低下や外観の悪化が著しい。Here, if the molding temperature is below the crystallization temperature, disadvantages such as an insufficient expansion ratio cannot be obtained due to an increase in elastic modulus due to crystallization, and a uniform foam cannot be obtained. Moreover, if the temperature exceeds 50° C. higher than the melting point, decomposition will be significant, resulting in significant deterioration of mechanical properties and appearance.
また、比較的非晶のビーズ、シートより発泡させる加熱
発泡（ビーズ発泡タイプの方法）においては、ガラス転
移温度以上、融点より２０℃高い温度で行なうことが好
ましく、例えばスチレン系重合体がシンジオタクチック
ポリスチレンであって、アタクチックポリスチレンとの
混合物の場合、９０゛Ｃ〜２９０℃が好ましい。ここで
、ガラス転移温度以下では、分子運動が凍結しており、
発泡が困難であり、また融点より２０゛Ｃ高い温度を超
えるもとの成形材料が互いに融は合い、ビーズ発泡法の
特徴を生かせなくなる。In addition, in heat foaming (bead foaming type method) in which relatively amorphous beads or sheets are foamed, it is preferable to carry out at a temperature higher than the glass transition temperature and 20°C higher than the melting point. In the case of a mixture of atactic polystyrene and atactic polystyrene, the temperature is preferably 90°C to 290°C. Here, below the glass transition temperature, molecular motion is frozen,
It is difficult to foam, and the original molding materials at temperatures exceeding 20°C above the melting point melt together, making it impossible to take advantage of the characteristics of the bead foaming method.
本発明において使用する発泡剤としては、特に制限はな
く、一般の揮発性発泡剤や分解性発泡剤の中から一種あ
るいは二種以上を適宜組み合わせて選定すればよい。ま
た、発泡剤を用いるにあたっては、発泡促進剤９発泡遅
延剤９発泡核剤等の発泡助剤を併用することもできる。The blowing agent used in the present invention is not particularly limited, and may be selected from among general volatile blowing agents and decomposable blowing agents, or a suitable combination of two or more thereof. Moreover, when using a foaming agent, foaming aids such as a foaming accelerator, a foaming retardant, and a foaming nucleating agent can also be used together.
上述の揮発性発泡剤としては、常温、常圧においてシン
ジオタクチック構造のスチレン系重合体を溶解あるいは
膨潤させず、しかも沸点が用いるベース素材の加熱成形
温度（例えばシンジオタクチックポリスチレン単独では
９０℃〜３２０°Ｃ）以下の流体であれば広範に使用で
きる０例えば常温で液体の揮発性発泡剤には、炭化水素
類、アルコール類、エステル類、エーテル類、ケトン類
。The volatile blowing agent mentioned above does not dissolve or swell the syndiotactic styrenic polymer at room temperature and pressure, and has a boiling point that is below the heating molding temperature of the base material used (for example, 90°C for syndiotactic polystyrene alone). For example, volatile blowing agents that are liquid at room temperature include hydrocarbons, alcohols, esters, ethers, and ketones.
ハロゲン化炭素類等があげられ、好ましくは炭素数５〜
１４の飽和炭化水素類、具体的にはへキサン、ヘプタン
、オクタン、デカン等があげられる。Examples include halogenated carbons, preferably 5 to 5 carbon atoms.
14 saturated hydrocarbons, specifically hexane, heptane, octane, decane, etc.
これらの液体の揮発性発泡剤としては、溶解度パラメー
ター（Ｐｏｌｙｍｅｒ Ｈａｎｄ Ｂｏｏｋ、 ＢＲＡ
ＮＤＲＵＰ＋ＩＭＰＩＥＲＧＵＴｈＭ集）δ： １０
（ｃａｔ／Ｃ４） ””以下が沸点。Volatile blowing agents for these liquids have solubility parameters (Polymer Hand Book, BRA
NDRUP+IMPIERGU ThM collection) δ: 10
(cat/C4) "" or lower is the boiling point.
溶解性から考慮すると好ましい。It is preferable from the viewpoint of solubility.
また、常温で気体の揮発性発泡剤としては、プロパン、
塩化メチル、フロンガス（フレオン１２など）を例示す
ることができる。In addition, volatile blowing agents that are gaseous at room temperature include propane,
Examples include methyl chloride and chlorofluorocarbon gas (Freon 12, etc.).
一方、分解性発泡剤は、室温で安定であり、その分解温
度が、用いるベース素材の加熱成形温度（ガラス転移温
度以上、融点より５０°Ｃ高い温度）以下であって、分
解した際に窒素ガス等のガスを発生するものであれば、
各種のものが使用可能である。この分解性発泡剤は、無
機発泡剤と有機発泡剤とに分類でき、ここで無機発泡剤
としては、重炭酸ナトリウム、炭酸アンモニウム、重炭
酸アンモニウム、アジド化合物（ＣａＮ、、ＢａＮ、な
ど）。On the other hand, decomposable blowing agents are stable at room temperature, have a decomposition temperature below the thermoforming temperature of the base material used (a temperature above the glass transition temperature, 50°C higher than the melting point), and when decomposed, nitrogen If it generates gas such as gas,
Various types can be used. The degradable blowing agents can be classified into inorganic blowing agents and organic blowing agents, and the inorganic blowing agents include sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, azide compounds (CaN, BaN, etc.).
亜硝酸アンモニウム等があり、また有機発泡剤としては
、ヒドラジン−ベンジル縮合物、有機カルボニルアジド
、アゾビスアルキルホスホネート。Examples include ammonium nitrite, and organic blowing agents include hydrazine-benzyl condensate, organic carbonyl azide, and azobisalkylphosphonate.
テトラヒドロジオキサジン等が使用でき、具体的にはア
ゾジカルボンアミド（ＡＤＣＡ）、アゾビスホルムアミ
ド（ＡＢＦＡ）、アゾビスイソブチロニトリル（ＡＺＤ
Ｎ）、 ジアゾアミノベンゼン（ＤＡＢ）、Ｎ、Ｎ’
−ジニトロソペンタメチレンテトラミン（ＤＰＴ）、Ｎ
、Ｎ’−ジメチル−Ｎ、Ｎ’−ジニトロテレフタルアミ
ド（ＤＭＤＮＴＡ）、ベンゼンスルホニルヒドラジド（
ＢＳＨ）。Tetrahydrodioxazine etc. can be used, specifically azodicarbonamide (ADCA), azobisformamide (ABFA), azobisisobutyronitrile (AZD).
N), diazoaminobenzene (DAB), N, N'
- dinitrosopentamethylenetetramine (DPT), N
, N'-dimethyl-N,N'-dinitroterephthalamide (DMDNTA), benzenesulfonyl hydrazide (
BSH).
ｐ−トルエンスルホニルヒドラジド（ＴＳＨ）。p-Toluenesulfonyl hydrazide (TSH).
ｐ’ 、ｐ’−オキシビスベンゼンスルホニルヒドラジ
ド（ＤＢＳＨ）、ｐ−トルエンスルホニル゛セミカルバ
ジド、オキザリルヒドラジド、ニトログアニジン、ヒド
ラゾジカルボンアミド、バリウムアゾジカルボキシレー
ト、トリヒドラジノトリアジンなどがあげられる。p', p'-oxybisbenzenesulfonyl hydrazide (DBSH), p-toluenesulfonyl semicarbazide, oxalyl hydrazide, nitroguanidine, hydrazodicarbonamide, barium azodicarboxylate, trihydrazinotriazine, and the like.
本発明では、このような発泡剤をベース素材に混合して
加熱発泡させ−るが、この際に加える発泡剤の量は、製
造すべき発泡体の種類や発泡率等により異なり、状況に
応じて適宜選定することとなるが、通常はシンジオタク
チック構造のスチレン系重合体１００重量部あたり、０
．０５〜５０重量部、好ましくは０．１〜３５重量部と
すればよい。In the present invention, such a blowing agent is mixed with the base material and foamed by heating, but the amount of blowing agent added at this time varies depending on the type of foam to be manufactured, the foaming rate, etc., and may vary depending on the situation. However, usually 0 parts per 100 parts by weight of the syndiotactic styrene polymer.
．． The amount may be 0.05 to 50 parts by weight, preferably 0.1 to 35 parts by weight.
また、前述した如（、必要に応じて発泡助剤を加えるこ
ともできるが、このうち発泡促進作用を示す発泡助剤と
しては、発泡剤が重炭酸ナトリウムのときはクエン酸、
発泡剤がＤＰＴのときは尿素と脂肪酸アンモニウムの組
み合わせ、あるいはフタル酸モノウレイドが有効であり
、発泡剤が０ＢＳＨのときはホウ酸塩が有効である。そ
の他所型により公知の発泡促進剤を用い得る０発泡核剤
として作用する発泡助剤は、発泡体の発泡を微細かつ均
一にすることを目的として加えるものであり、ステアリ
ン酸マグネシウム等の金属セッケンやシリカ、タルク等
の無機物質を用いればよい。In addition, as mentioned above, foaming aids can be added as needed; among these, foaming aids that promote foaming include citric acid, when the foaming agent is sodium bicarbonate,
When the blowing agent is DPT, a combination of urea and fatty acid ammonium or phthalic acid monoureide is effective, and when the blowing agent is 0BSH, borate is effective. In addition, a known foaming accelerator may be used depending on the type of foaming agent.The foaming auxiliary agent that acts as a foaming nucleating agent is added for the purpose of making the foaming of the foam fine and uniform. Inorganic substances such as silica, talc, etc. may be used.
また、本発明の発泡体の成形形状は特に制限なく種々の
ものが可能である。具体的には、ビーズ。Moreover, the molded shape of the foam of the present invention is not particularly limited, and various shapes are possible. Specifically, beads.
シート、カップ、トレイ、棒状やその他三次元成形体が
含まれる。Includes sheets, cups, trays, rods, and other three-dimensional molded objects.
次に、本発明を実施例および比較例によりさらに詳しく
説明する。Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
参考例１（主としてシンジオタクチック構造を有するポ
リスチレンの製造）
反応容器に、反応溶媒としてトルエン２１と触媒成分と
してテトラエトキシチタン５ミリモルおよびメチルアル
ミノキサンをアルミニウム原子として５００ミリモル入
れ、５０℃においてスチレン１５１を加え、４時間重合
反応を行った。Reference Example 1 (Production of polystyrene mainly having a syndiotactic structure) Toluene 21 as a reaction solvent, 5 mmol of tetraethoxytitanium as a catalyst component, and 500 mmol of methylaluminoxane as an aluminum atom were placed in a reaction vessel, and styrene 151 was added at 50°C. In addition, a polymerization reaction was carried out for 4 hours.
反応終了後、生成物を塩酸とメタノールとの混合液で洗
浄して、触媒成分を分解除去した０次いで乾燥すること
により、スチレン系重合体（ポリスチレン）２．５ｋｇ
を得た。次に、この重合体を、メチルエチルケトンを溶
媒としてソックスレー抽出し、抽出残分９５重量％を得
た。この抽出残分の重量平均分子量はｓｏｏ、ｏｏｏで
あった。また、この重合体はＩＳＣ−ＮＭＲによる分析
（溶媒＝１．２−ジクロロベンゼン）から、シンジオタ
クチック構造に基因する１ ４５．３５ｐｐｍに吸収が
認められ、そのピーク面積から算出したラセミペンタッ
ドでのシンジオタクテイシテイ−は９６％であった。After the reaction, the product was washed with a mixture of hydrochloric acid and methanol to decompose and remove the catalyst component.Then, the product was dried to produce 2.5 kg of styrene polymer (polystyrene).
I got it. Next, this polymer was subjected to Soxhlet extraction using methyl ethyl ketone as a solvent to obtain an extraction residue of 95% by weight. The weight average molecular weight of this extraction residue was soo, ooo. In addition, this polymer was analyzed by ISC-NMR (solvent = 1,2-dichlorobenzene), and absorption was observed at 145.35 ppm due to the syndiotactic structure, which was calculated from the peak area of racemic pentad. The syndiotactic rate was 96%.
実施例１
参考例１によって得られたポリスチレンパウダー５００
重量部を、ヘキサン４０重量部とメタノール６０重量部
との混合液中に２４時間、２５°Ｃで放置して、該混合
液からなる揮発性液体を含浸させた。この液体含浸ポリ
スチレンパウダー３ｇを、融着ブレス成形用金型（１０
ｃｍＸ １０ＣＩＩＸ０．３１容量〕に入れ、２９０℃
で３分間保持したところ、発泡体が得られた。この発泡
体の密度を水置換法によって求め、また、次式によって
定義される有効発泡率を求めた。さらに熱的性質を調べ
るために、Ｄｉｆｆｅｒｅｎｔｉａｌ Ｓｃａｎｎｉｎ
ｇ Ｃａｌｏｒｉｍｅｔｅｒ（ＤＳＣ）測定を行ない、
溶融温度及び結晶化度を調べた。これらの結果を第１表
に示す。Example 1 Polystyrene powder 500 obtained according to Reference Example 1
Part by weight was left in a mixed solution of 40 parts by weight of hexane and 60 parts by weight of methanol at 25° C. for 24 hours to impregnate the volatile liquid consisting of the mixed solution. 3 g of this liquid-impregnated polystyrene powder was poured into a mold for fusion press molding (10
cm
When the mixture was held for 3 minutes, a foam was obtained. The density of this foam was determined by the water displacement method, and the effective foaming rate defined by the following formula was determined. In order to further investigate the thermal properties, Differential Scannin
g Perform Calorimeter (DSC) measurement,
Melting temperature and crystallinity were investigated. These results are shown in Table 1.
ρＯ
ρ。二 発泡処理を施さない場合の成形体の密度（ｇ／
ｃｄ）
ρ ： 発泡成形体の密度（ｇ ／ｄ）実施例２
参考例１によって得られたポリスチレンパウダー１００
重量部に対し、発泡核剤としてタルク（商品名：ＦＦＲ
，平均粒径０．６μｍ、浅田製粉■製）１重量部、酸化
防止剤としてビス（２，４−ジ−ｔ−ブチルフェニル）
ペンタエリスリトールジホスファイト（商品名： ＰＥ
Ｐ−２４，アデカ・アーガス社製）０．７重量部および
テトラキス〔メチレン（３，５−ジ−ｔ−ブチル−４−
ヒドロキシハイドロシンナメート）〕メタン（商品名：
ＡＯ−６０，７デカ・アーガス社製）０．１重量部を加
え、単軸押出機にて、ペレット化した。ρO ρ. (2) Density of the molded product without foaming treatment (g/
cd) ρ: Density (g/d) of foamed molded product Example 2 Polystyrene powder 100 obtained according to Reference Example 1
Talc (product name: FFR) is added as a foaming nucleating agent to the weight part.
, average particle size 0.6 μm, manufactured by Asada Seifun ■) 1 part by weight, bis(2,4-di-t-butylphenyl) as an antioxidant
Pentaerythritol diphosphite (product name: PE
P-24, manufactured by Adeka Argus) and 0.7 parts by weight of tetrakis [methylene (3,5-di-t-butyl-4-
Hydroxyhydrocinnamate)] Methane (Product name:
0.1 part by weight of AO-60.7 (manufactured by Deca Argus) was added and pelletized using a single screw extruder.
次に、このペレットをオートクレーブ中に入れ、デカン
４００重量部を加え、１７４℃に加熱し、４８時間沸騰
、撹拌を行った後、風乾させ、発泡性ポリスチレンペレ
ットを得た。このペレットを、Ｔ−ダイを取り付けた押
出成形機により２９０℃でシート状に押出成形した。こ
のシートを実施例１と同様に密度、溶融温度を調べた。Next, this pellet was placed in an autoclave, 400 parts by weight of decane was added thereto, heated to 174°C, boiled and stirred for 48 hours, and then air-dried to obtain expandable polystyrene pellets. This pellet was extruded into a sheet at 290° C. using an extrusion molding machine equipped with a T-die. The density and melting temperature of this sheet were examined in the same manner as in Example 1.
これらの結果を第１表に示す。These results are shown in Table 1.
実施例３
実施例２によって得られた発泡性ポリスチレンペレット
を用い、ミニマット射出成形機（住友重機■製）によっ
て、樹脂温度３００℃、金型温度１６０℃にて成形し、
ＪＩＳ−１号（１／２）型の引張試験片を得た。この試
験片の密度、融解温度を調べた。結果を第１表に示す。Example 3 The expandable polystyrene pellets obtained in Example 2 were molded using a minimat injection molding machine (manufactured by Sumitomo Heavy Industries ■) at a resin temperature of 300°C and a mold temperature of 160°C.
A JIS-1 (1/2) type tensile test piece was obtained. The density and melting temperature of this test piece were investigated. The results are shown in Table 1.
実施例４
参考例１によって得られたポリスチレンパウダ−４０重
量部に対し、アククチツク構造のポリスチレン（商品名
：出光スチロール ＵＳ−３００゜出光石油化学■製）
４０重量部、５ＥＢＳゴム（商品名：Ｃ−１６５２，シ
ェル化学■製）２０重量部１発発泡剤としてステアリン
酸マグネシウム０．５重量部、酸化防止剤としてビス（
２，４−ジ−ｔ−ブチルフェニル）ペンタエリスリトー
ルジホスファイト（商品名： ＰＥＰ−２４，アデカ・
アーガス社製）０．７重量部およびテトラキス〔メチレ
ン（３，５−ジ−ｔ−ブチル−４−ヒドロキシハイドロ
シンナメート）〕メタン（商品名：ＡＯ−６０，アデカ
・アーガス社製）０．１重量部を加え、２９０℃にて単
軸押出機によってペレット化した。Example 4 40 parts by weight of the polystyrene powder obtained in Reference Example 1 was mixed with polystyrene having an active structure (trade name: Idemitsu Styrene US-300゜manufactured by Idemitsu Petrochemical ■).
40 parts by weight, 5 EBS rubber (product name: C-1652, manufactured by Shell Chemical ■) 20 parts by weight 1 0.5 parts by weight of magnesium stearate as a blowing agent, bis(
2,4-di-t-butylphenyl) pentaerythritol diphosphite (trade name: PEP-24, ADEKA
0.7 parts by weight (manufactured by Argus) and 0.1 part by weight of tetrakis[methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane (trade name: AO-60, manufactured by Adeka Argus) Parts by weight were added and pelletized using a single screw extruder at 290°C.
このペレット１００重量部に対し、アゾシカ−ボンアミ
ド５重量部をトライブレンドし、この混合物を実施例２
と同様に押出シート成形を行った。To 100 parts by weight of this pellet, 5 parts by weight of Azocica-bonamide was triblended, and this mixture was used in Example 2.
Extrusion sheet molding was performed in the same manner.
結果を第１表に示す。The results are shown in Table 1.
実施例５
実施例１によって得られた液体含浸ポリスチレンパウダ
ー１００重量部に対し、さらに発泡剤として、重炭酸ナ
トリウム０．４重量部９尭泡助剤としてクエン酸０．２
重量部をトライブレンドして、実施例１と同様に融着プ
レス成形を行った。Example 5 To 100 parts by weight of the liquid-impregnated polystyrene powder obtained in Example 1, 0.4 parts by weight of sodium bicarbonate was added as a blowing agent, and 0.2 parts by weight of citric acid was added as a foaming aid.
Parts by weight were triblended and fusion press molding was performed in the same manner as in Example 1.
結果を第１表に示す。The results are shown in Table 1.
実施例６
参考例１によって得られたポリスチレンパウダーを、単
軸押出機でペレット化するに際し、ホッパ一部分を密閉
耐圧構造に改良し、ポリスチレンパウダーとともに、プ
ロピレンガスを、１０ｋｇ重／ｃ＋ｊで圧送し、プロピ
レンガスを含浸した発泡性ポリスチレンペレットを得た
。この発泡性ポリスチレンペレットを実施例１と同様に
融着プレス成形を行った。結果を第１表に示す。Example 6 When the polystyrene powder obtained in Reference Example 1 was pelletized using a single-screw extruder, a part of the hopper was improved to have a sealed pressure-resistant structure, and propylene gas was pumped together with the polystyrene powder at a rate of 10 kg/c+j. Expandable polystyrene pellets impregnated with propylene gas were obtained. This expandable polystyrene pellet was subjected to fusion press molding in the same manner as in Example 1. The results are shown in Table 1.
参考例２（主としてシンジオタクチック構造を有するポ
リスチレンの製造）
反応容器に、反応溶媒としてヘキサンＩＩ１．！：Ｍ媒
成分としてテトラエトキシチタン０．７５ミリモルおよ
びメチルアルミノキサンをアルミニウム原子として７５
ミリモル入れ、５０ ℃においてスチレン５Ｉ！、を加
え、２時間重合反応を行った。Reference Example 2 (Production of polystyrene mainly having a syndiotactic structure) Hexane II1. ! : 0.75 mmol of tetraethoxytitanium as the M medium component and 75 mmol of methylaluminoxane as an aluminum atom.
Add mmol of styrene 5I at 50 °C! , and a polymerization reaction was carried out for 2 hours.
反応終了後、生成物を塩酸とメタノールとの混合液で洗
浄して、触媒成分を分解除去した０次いで乾燥すること
により、スチレン系重合体（ポリスチレン）１０８ｇを
得た。次に、この重合体を、メチルエチルケトンを溶媒
としてソックスレー抽出し、抽出残分９５重量％を得た
。この抽出残分の重量平均分子量は４２０，０００、数
平均分子量は１９６，０００．融点は２７０℃であった
。After the reaction was completed, the product was washed with a mixture of hydrochloric acid and methanol to decompose and remove the catalyst component, and then dried to obtain 108 g of a styrene polymer (polystyrene). Next, this polymer was subjected to Soxhlet extraction using methyl ethyl ketone as a solvent to obtain an extraction residue of 95% by weight. The weight average molecular weight of this extraction residue was 420,000, and the number average molecular weight was 196,000. The melting point was 270°C.
また、この重合体は℃−ＮＭＲによる分析（溶媒：１．
２−ジクロロベンゼン）から、シンジオタクチック構造
に基因する１４５．３５ｐｐｍに吸収が認められ、その
ピーク面積から算出したラセミペンタッドでのシンジオ
タクテイシテイ−は９５％であった。Further, this polymer was analyzed by C-NMR (solvent: 1.
2-dichlorobenzene), absorption was observed at 145.35 ppm due to the syndiotactic structure, and the syndiotacticity in racemic pentad calculated from the peak area was 95%.
実施例７
参考例２で得られたポリスチレンを、ヘキサンに浸漬し
、次いで風乾してヘキサン含浸のポリスチレンパウダー
を得た。Example 7 The polystyrene obtained in Reference Example 2 was immersed in hexane and then air-dried to obtain hexane-impregnated polystyrene powder.
このようにして得たヘキサン含浸ポリスチレンパウダー
を、実施例３と同様に射出成形を行った。The hexane-impregnated polystyrene powder thus obtained was injection molded in the same manner as in Example 3.
結果を第１表に示す。The results are shown in Table 1.
比較例１
参考例１によって得られたポリスチレンパウダー１００
重量部に、酸化防止剤としてビス（２゜４−ジ−ｔ−ブ
チルフェニル）ペンタエリスリトールジホスファイト（
商品名： ＰＥＰ−２４，７デカ・アーガス社製）０．
７重量部およびテトラキス〔メチレン（３，５−ジー、
ｔ−ブチル−４−ヒドロキシハイドロシンナメート）〕
メタン（商品名：ＡＯ−６０，７デ；ｈ ・７−ガス社
製）０．１重量部を加え、単軸押出機でペレタイズした
。このペレットを実施例３と同様に射出成形を行った。Comparative Example 1 Polystyrene powder 100 obtained according to Reference Example 1
Bis(2°4-di-t-butylphenyl)pentaerythritol diphosphite (2°4-di-t-butylphenyl) pentaerythritol diphosphite (
Product name: PEP-24,7 (manufactured by Deca Argus) 0.
7 parts by weight and tetrakis [methylene (3,5-di,
t-butyl-4-hydroxyhydrocinnamate)]
0.1 part by weight of methane (trade name: AO-60.7DE; manufactured by 7-Gas Co., Ltd.) was added, and the mixture was pelletized using a single screw extruder. This pellet was injection molded in the same manner as in Example 3.
結果を第１表に示す。The results are shown in Table 1.
比較例２
ポリスチレンペレットの代わりに、ポリエチレンペレッ
ト（商品名：出光ポリエチレン５４０ Ｅ。Comparative Example 2 Polyethylene pellets (trade name: Idemitsu Polyethylene 540 E) were used instead of polystyrene pellets.
出光石油化学■製）を用いたこと以外は、実施例２と同
様の操作を行った。結果を第１表に示す。The same operation as in Example 2 was carried out, except that Idemitsu Petrochemical Co., Ltd.) was used. The results are shown in Table 1.
比較例３
ポリスチレンペレットの代わりに、アタクチック構造の
ポリスチレンペレット（商品名；出光スチロールＵＳ−
３００．出光石油化学■製）を用いたこと以外は、実施
例２と同様の操作を行った。Comparative Example 3 Instead of polystyrene pellets, polystyrene pellets with atactic structure (trade name: Idemitsu Styrene US-
300. The same operation as in Example 2 was carried out, except that Idemitsu Petrochemical Co., Ltd.) was used.
結果を第１表に示す。The results are shown in Table 1.
実施例８
参考例１で得られたポリスチレンパウダーを８０℃のシ
クロヘキサン中で攪拌、風乾した。このパウダーにアタ
クチックポリスチレン（実施例４で用いたものと同じ）
を混合し、単軸、ベント無しの押出機にて押出した。こ
の時、先端に内径０．５鵬のキャピラリーを取り付け、
押出後ただちに水中で急冷し、カットした。得られたベ
レット小片は、直径０．３ｍ、長さ０．７ｍの円筒状で
、アタクチックポリスチレンを１０ｗｔ％、シクロヘキ
サンを３ｗｔ％含み、結晶化度は３％であった。Example 8 The polystyrene powder obtained in Reference Example 1 was stirred in 80° C. cyclohexane and air-dried. Add atactic polystyrene (same as used in Example 4) to this powder.
were mixed and extruded using a single-screw extruder without a vent. At this time, attach a capillary with an inner diameter of 0.5 mm to the tip,
Immediately after extrusion, it was quenched in water and cut. The obtained pellet pieces had a cylindrical shape with a diameter of 0.3 m and a length of 0.7 m, contained 10 wt% of atactic polystyrene, 3 wt% of cyclohexane, and had a crystallinity of 3%.
この小片を１４０℃のオープン中に２分間入れたところ
発泡ビーズが得られた。結果を第１表に示す。When this small piece was placed in an open oven at 140° C. for 2 minutes, foamed beads were obtained. The results are shown in Table 1.
本発明によれば、所望の発泡率を有する耐熱性にすぐれ
た熱可塑性樹脂発泡体を容易に得ることができる。また
この熱可塑性樹脂発泡体は、耐熱性を必要とする建材、
断熱材１食品包装材、緩衝材等に幅広くかつ有効に利用
することができる。According to the present invention, a thermoplastic resin foam having a desired expansion rate and excellent heat resistance can be easily obtained. This thermoplastic resin foam can also be used for building materials that require heat resistance.
Thermal insulation material 1 can be widely and effectively used in food packaging materials, cushioning materials, etc.
手続補正書（自発） 平成２年６月８日Procedural amendment (voluntary) June 8, 1990
Claims (4)
ン系重合体あるいは該スチレン系重合体を含有する熱可
塑性樹脂組成物からなり、発泡倍率が１．２〜８０倍で
ありかつ結晶化度が２０％以上である熱可塑性樹脂発泡
体。(1) Mainly composed of a styrenic polymer having a syndiotactic structure or a thermoplastic resin composition containing the styrene polymer, with an expansion ratio of 1.2 to 80 times and a crystallinity of 20% or more Thermoplastic foam.
ン系重合体あるいは該スチレン系重合体を含有する熱可
塑性樹脂組成物を、発泡剤の存在下ガラス転移温度以上
かつ融点より５０℃高い温度以下の温度で発泡成形する
ことを特徴とする請求項１記載の熱可塑性樹脂発泡体の
製造方法。(2) A styrenic polymer mainly having a syndiotactic structure or a thermoplastic resin composition containing the styrenic polymer is heated in the presence of a blowing agent at a temperature higher than the glass transition temperature and lower than a temperature 50°C higher than the melting point. 2. The method for producing a thermoplastic resin foam according to claim 1, comprising foam molding.
ン系重合体あるいは該スチレン系重合体を含有する熱可
塑性樹脂組成物を、発泡剤の存在下結晶化温度以上かつ
融点より５０℃高い温度以下の温度で押出発泡成形する
ことを特徴とする請求項１記載の熱可塑性樹脂発泡体の
製造方法。(3) A styrenic polymer mainly having a syndiotactic structure or a thermoplastic resin composition containing the styrenic polymer is heated in the presence of a blowing agent at a temperature higher than the crystallization temperature and lower than a temperature 50°C higher than the melting point. 2. The method for producing a thermoplastic resin foam according to claim 1, comprising extrusion foam molding.
ン系重合体あるいは該スチレン系重合体を含有する熱可
塑性樹脂組成物を、発泡剤の存在下ガラス転移温度以上
かつ融点より２０℃高い温度以下の温度で加熱発泡成形
することを特徴とする請求項１記載の熱可塑性樹脂発泡
体の製造方法。(4) A styrenic polymer mainly having a syndiotactic structure or a thermoplastic resin composition containing the styrenic polymer is heated in the presence of a blowing agent at a temperature higher than the glass transition temperature and lower than a temperature 20°C higher than the melting point. 2. The method for producing a thermoplastic resin foam according to claim 1, wherein the thermoplastic resin foam is heated and foamed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6937589A JPH07119307B2 (en) | 1989-03-23 | 1989-03-23 | Thermoplastic foam and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6937589A JPH07119307B2 (en) | 1989-03-23 | 1989-03-23 | Thermoplastic foam and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02248438A true JPH02248438A (en) | 1990-10-04 |
| JPH07119307B2 JPH07119307B2 (en) | 1995-12-20 |
Family
ID=13400751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6937589A Expired - Fee Related JPH07119307B2 (en) | 1989-03-23 | 1989-03-23 | Thermoplastic foam and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07119307B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5889069A (en) * | 1997-07-15 | 1999-03-30 | The Dow Chemical Company | High temperature syndiotactic styrene polymer foam |
| JP2005112882A (en) * | 2003-10-02 | 2005-04-28 | Jsp Corp | Foamable styrene polymer particle, foamed styrene polymer particle, foamed styrene polymer particle molded article, and production method of foamed styrene polymer particle |
-
1989
- 1989-03-23 JP JP6937589A patent/JPH07119307B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5889069A (en) * | 1997-07-15 | 1999-03-30 | The Dow Chemical Company | High temperature syndiotactic styrene polymer foam |
| US6051621A (en) * | 1997-07-15 | 2000-04-18 | The Dow Chemical Company | High temperature syndiotactic styrene polymer foam |
| JP2005112882A (en) * | 2003-10-02 | 2005-04-28 | Jsp Corp | Foamable styrene polymer particle, foamed styrene polymer particle, foamed styrene polymer particle molded article, and production method of foamed styrene polymer particle |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07119307B2 (en) | 1995-12-20 |
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