JPH01201350A - Production of styrene resin composition and its molding - Google Patents
Production of styrene resin composition and its moldingInfo
- Publication number
- JPH01201350A JPH01201350A JP63023745A JP2374588A JPH01201350A JP H01201350 A JPH01201350 A JP H01201350A JP 63023745 A JP63023745 A JP 63023745A JP 2374588 A JP2374588 A JP 2374588A JP H01201350 A JPH01201350 A JP H01201350A
- Authority
- JP
- Japan
- Prior art keywords
- molding
- resin composition
- weight
- acid
- parts
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 27
- 238000000465 moulding Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 150000007524 organic acids Chemical class 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 229920001890 Novodur Polymers 0.000 claims description 10
- 239000003484 crystal nucleating agent Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 abstract description 16
- 230000008025 crystallization Effects 0.000 abstract description 16
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- -1 poly(vinyl benzoate) Polymers 0.000 description 34
- 238000000034 method Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000156978 Erebia Species 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- JBDSSBMEKXHSJF-UHFFFAOYSA-N cyclopentanecarboxylic acid Chemical compound OC(=O)C1CCCC1 JBDSSBMEKXHSJF-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-N isocaproic acid Chemical compound CC(C)CCC(O)=O FGKJLKRYENPLQH-UHFFFAOYSA-N 0.000 description 2
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 230000000155 isotopic effect Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000028161 membrane depolarization Effects 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003303 reheating Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 150000003440 styrenes Polymers 0.000 description 2
- 125000003011 styrenyl group Polymers [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000007666 vacuum forming Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- WBJWXIQDBDZMAW-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carbonyl chloride Chemical compound C1=CC=CC2=C(C(Cl)=O)C(O)=CC=C21 WBJWXIQDBDZMAW-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 241000981595 Zoysia japonica Species 0.000 description 1
- QEFMKHZCJWQOFY-UHFFFAOYSA-N [Na].CC(C)(C)c1ccc(O)c(c1Cc1c(ccc(O)c1C(C)(C)C)C(C)(C)C)C(C)(C)C Chemical compound [Na].CC(C)(C)c1ccc(O)c(c1Cc1c(ccc(O)c1C(C)(C)C)C(C)(C)C)C(C)(C)C QEFMKHZCJWQOFY-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- PYHXGXCGESYPCW-UHFFFAOYSA-N alpha-phenylbenzeneacetic acid Natural products C=1C=CC=CC=1C(C(=O)O)C1=CC=CC=C1 PYHXGXCGESYPCW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- CSJKPFQJIDMSGF-UHFFFAOYSA-K aluminum;tribenzoate Chemical compound [Al+3].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 CSJKPFQJIDMSGF-UHFFFAOYSA-K 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 1
- GMVARPAQVYKXMQ-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1.OC(=O)C1CCCCC1 GMVARPAQVYKXMQ-UHFFFAOYSA-N 0.000 description 1
- QOXHZZQZTIGPEV-UHFFFAOYSA-K cyclopenta-1,3-diene;titanium(4+);trichloride Chemical compound Cl[Ti+](Cl)Cl.C=1C=C[CH-]C=1 QOXHZZQZTIGPEV-UHFFFAOYSA-K 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920003197 poly( p-chlorostyrene) 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
- 229920001608 poly(methyl styrenes) Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- SNAQARSCIHDMGI-UHFFFAOYSA-M sodium;bis(4-tert-butylphenyl) phosphate Chemical compound [Na+].C1=CC(C(C)(C)C)=CC=C1OP([O-])(=O)OC1=CC=C(C(C)(C)C)C=C1 SNAQARSCIHDMGI-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はスチレン系樹脂組成物と成形品の製造方法に関
し、詳しくはシンジオタクチック構造のスチレン系重合
体に特定の結晶核剤を配合してなるスチレン系樹脂組成
物、ならびにこの組成物を低温で成形してなる耐熱性、
耐溶剤性等の諸物性にすぐれたスチレン系樹脂成形品の
製造方法に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for producing a styrenic resin composition and a molded article. styrenic resin composition, and heat resistance obtained by molding this composition at low temperature,
This invention relates to a method for manufacturing styrene resin molded products with excellent physical properties such as solvent resistance.
〔従来の技術及び発明が解決しようとする課題〕従来か
らラジカル重合法等により製造されるスチレン系重合体
は、その立体構造がアタクチック構造を有しており、種
々の成形法、例えば射出成形、押出成形、中空成形、真
空成形、注入成形などの方法によって、様々な形状のも
のに成形され、家庭電気器具、事務機器、家庭用品、包
装容器。[Prior art and problems to be solved by the invention] Styrenic polymers conventionally produced by radical polymerization methods have an atactic three-dimensional structure, and can be processed by various molding methods, such as injection molding, It is molded into various shapes by extrusion molding, blow molding, vacuum forming, injection molding and other methods, and is used for household appliances, office equipment, household goods, and packaging containers.
玩具、家具１合成紙その他産業資材などとして幅広く用
いられている。It is widely used as toys, furniture, synthetic paper, and other industrial materials.
しかしながら、このようなアタクチック構造のスチレン
系重合体は、結晶化しないため、機械的強度や耐熱性、
耐薬品性に劣るという欠点があった。However, such styrenic polymers with an atactic structure do not crystallize, so they have poor mechanical strength, heat resistance,
It had the disadvantage of poor chemical resistance.
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）。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は、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
、耐熱性、耐溶剤性、電気特性等にすぐれたものである
が、これを素材にして得られる成形品は結晶化させるた
めに高い成形温度が要求されていた。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). This styrenic polymer having a syndiotactic structure or its composition has superior mechanical strength, heat resistance, solvent resistance, electrical properties, etc. compared to a styrenic polymer or its composition having an atactic structure. However, molded products made from this material require high molding temperatures in order to crystallize it.
そこで、本発明者らは上述のシンジオタクチック構造を
有するスチレン系重合体からすぐれた物性の成形品を低
温で効率よく製造すべく鋭意研究を重ねた。Therefore, the present inventors have conducted extensive research in order to efficiently produce molded articles with excellent physical properties at low temperatures from the styrenic polymer having the above-mentioned syndiotactic structure.
その結果、このシンジオタクチック構造のスチレン系重
合体に、有機酸の金属塩や有機リン化合物からなる結晶
核剤を配合した組成物が、結晶化速度が大きく低温での
成形が可能であることを見出した。本発明はかかる知見
に基いて完成したものである。As a result, we found that a composition containing a styrenic polymer with a syndiotactic structure and a crystal nucleating agent consisting of a metal salt of an organic acid or an organic phosphorous compound has a high crystallization rate and can be molded at low temperatures. I found out. The present invention was completed based on this knowledge.
すなわち、本発明は（Ａ）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１００重量部および（Ｂ
）有機酸の金属塩および／または有機リン化合物からな
る結晶核剤０．０１〜１５重量部を主成分とするスチレ
ン系樹脂組成物を提供するものであり、またこのスチレ
ン系樹脂組成物を室温〜２００°Ｃの成形温度で成形す
ることを特徴とするスチレン系樹脂成形品の製造方法を
も提供するものである。That is, the present invention comprises (A) 100 parts by weight of a styrenic polymer mainly having a syndiotactic structure and (B)
) A styrenic resin composition containing 0.01 to 15 parts by weight of a crystal nucleating agent consisting of a metal salt of an organic acid and/or an organic phosphorus compound as a main component, and the styrenic resin composition is heated to room temperature. The present invention also provides a method for manufacturing a styrenic resin molded article, which is characterized by molding at a molding temperature of ~200°C.
本発明の樹脂組成物は、上述の如＜ （Ａ）、 （Ｂ）
成分を主成分とするものであるが、ここで（Ａ）成分で
あるスチレン系重合体における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（１３
ｃ−ＮＭＲ法）により定量される。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２個の場合はダイアツド、
３個の場合はトリアット、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）。The resin composition of the present invention can be prepared as described above (A), (B).
The main component of the styrenic polymer (A) here is a syndiotactic structure in which the stereochemical structure is mainly syndiotactic, that is, formed from carbon-carbon bonds. It has a three-dimensional structure in which phenyl groups and substituted phenyl groups, which are side chains, are located alternately in opposite directions with respect to the main chain, and its toughness is determined by nuclear magnetic resonance method using isotopic carbon (13
c-NMR method). Toughness measured by the 13C-NMR method is determined by the proportion of consecutive constituent units, for example, if there are two units, the toughness is
In the case of 3 atoms, it can be expressed as triat, and in the case of 5 atoms, it can be expressed as pentad, but the styrenic polymer mainly having a syndiotactic structure as referred to in the present invention is usually 75% or more diad, preferably 85%. or more than 30% in pentad (racemic pentad),
Preferably polystyrene or poly(alkylstyrene) having syndiotacticity of 50% or more.
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称
する。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）、
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）、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。Refers to poly(halogenated styrene), poly(alkoxystyrene), poly(vinyl benzoate), mixtures thereof, or copolymers having these as main components. Note that poly(alkylstyrene) here includes poly(methylstyrene), poly(ethylstyrene),
Examples of poly(isopropylstyrene) and poly(tert-butylstyrene) include poly(halogenated styrene) such as poly(chlorostyrene), poly(bromostyrene), and poly(fluorostyrene). (Alkoxystyrene) includes poly(methoxystyrene), poly(ethoxystyrene), etc.
Among these, particularly preferred styrenic polymers are:
polystyrene.
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。Poly(p-methylstyrene), poly(m-methylstyrene), poly(p-tert-butylstyrene), poly(p-chlorostyrene), poly(m-chlorostyrene)
, poly(p-fluorostyrene), and even styrene and p
-Copolymers with methylstyrene can be mentioned.
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ｓｏ、ｏｏｏ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
。ここで、重量平均分子量が１０．０００未満のもので
は、得られる組成物あるいは成形品の熱的性質９機械的
性質が低下し好ましくない。The styrenic polymer used in the present invention is not particularly limited in molecular weight, but preferably has a weight average molecular weight of 10.000 or more, particularly so, ooo or more. Further, there is no restriction on the width or narrowness of the molecular weight distribution, and various types can be used. If the weight average molecular weight is less than 10,000, the thermal properties or mechanical properties of the obtained composition or molded article will deteriorate, which is undesirable.
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）。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 Application Laid-Open No. 1983-1999).
187708).
次に、本発明の樹脂組成物の（Ｂ）成分は、有機酸の金
属塩および有機リン化合物のいずれか一方あるいは両者
からなるものであり、これらの化合物としては各種のも
のがある。ここで有機酸の金属塩としては、例えば安息
香酸、ｐ−（ｔｅｒｔ−ブチル）安息香酸、シクロヘキ
サンカルボン酸（ヘキサヒドロ安息香酸）、アミノ安息
香酸、β−ナフトエ酸、シクロペンタンカルボン酸、コ
ハク酸。Next, component (B) of the resin composition of the present invention consists of either or both of a metal salt of an organic acid and an organic phosphorus compound, and there are various types of these compounds. Examples of metal salts of organic acids include benzoic acid, p-(tert-butyl)benzoic acid, cyclohexanecarboxylic acid (hexahydrobenzoic acid), aminobenzoic acid, β-naphthoic acid, cyclopentanecarboxylic acid, and succinic acid.
ジフェニル酢酸、グルタル酸、イソニコチン酸。Diphenylacetic acid, glutaric acid, isonicotinic acid.
アジピン酸、セバシン酸、フタール酸、イソフタール酸
、ベンゼンスルホン酸、グリコール酸、カプロン酸、イ
ソカプロン酸、フェニル酢酸、桂皮酸、ラウリン酸、ミ
リスチン酸、バルミチン酸。Adipic acid, sebacic acid, phthalic acid, isophthalic acid, benzenesulfonic acid, glycolic acid, caproic acid, isocaproic acid, phenylacetic acid, cinnamic acid, lauric acid, myristic acid, valmitic acid.
ステアリン酸、オレイン酸等の有機酸のナトリウム塩、
カルシウム塩、アルミニウム塩、マグネシウム塩等の金
属塩があげられる。これらのうち特ニＰ （ｔｅｒｔ
−７’チル）安息香酸のアルミニウム塩、シクロヘキ
サンカルボン酸のナトリウム塩。Sodium salts of organic acids such as stearic acid and oleic acid,
Examples include metal salts such as calcium salts, aluminum salts, and magnesium salts. Among these, special P (tert
-7'Til) aluminum salt of benzoic acid, sodium salt of cyclohexanecarboxylic acid.
β−ナフトエ酸のナトリウム塩などが好ましい。Preferred is the sodium salt of β-naphthoic acid.
また、有機リン化合物としては、例えば次の一般式
（式中、Ｒ’は水素原子あるいは炭素数１〜１８のアル
キル基を示し、Ｒ１は炭素数１〜１８のアまた、ＭはＮ
ａ、に、Ｍｇ、ＣａあるいはＡｌを示し、ａはＭの原子
価を示す。）
で表わされる有機リン化合物（ｂｌ）あるいは（式中、
Ｒはメチレン基、エチリデン基、プロピリデン基あるい
はイソプロピリデン基を示し、Ｒ”ＩＦ５はそれぞれ水
素原子あるいは炭素数１〜６のアルキル基を示す。また
、Ｍ、ａは前記と同じである。）
で表わされる有機リン化合物（ｂよ）をあげることがで
きる。In addition, as an organic phosphorus compound, for example, the following general formula (wherein R' represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, R1 represents an atom having 1 to 18 carbon atoms, and M is N
a represents Mg, Ca or Al, and a represents the valence of M. ) or (in the formula,
R represents a methylene group, an ethylidene group, a propylidene group, or an isopropylidene group, and R''IF5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and M and a are the same as above.) The following organic phosphorus compounds (b) can be mentioned.
上記一般式（Ｂ−１）で表わされる有機リン化合物（ｂ
Ｉ）の具体例を化学式で示すと次の如くである。Organic phosphorus compound (b
A specific example of I) is shown as a chemical formula as follows.
一方、一般式（Ｂ−ｎ）で表わされるを機リン化合物（
ｂｚ）についても、式中のＲ，Ｒ’、Ｒ’およびＭの種
類により様々なものがある。そのうちＲ３゜Ｒ４はそれ
ぞれ水素原子あるいは炭素数１〜６のアルキル基を示す
が、このアルキル基としてはメチル基、エチル基、イソ
プロピル基、ｎ−ブチル基、イソブチル基、第２ブチル
基、第３ブチル基。On the other hand, the compound represented by the general formula (B-n) (
There are also various types of bz) depending on the types of R, R', R' and M in the formula. Of these, R3 and R4 each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl groups include methyl, ethyl, isopropyl, n-butyl, isobutyl, sec-butyl, tertiary-butyl, etc. Butyl group.
ｎ−アミル基、第３７ミル基、ヘキシル基などがある。Examples include n-amyl group, 37th mil group, and hexyl group.
この有機リン化合物（ｂよ）の具体例を化学式で示すと
次の如くである。A specific example of this organic phosphorus compound (b) is shown in chemical formula as follows.
本発明では、（Ｂ）成分である有機酸の金属塩や有機リ
ン化合物は、核剤、特に（Ａ）成分である主としてシン
ジオタクチック構造を有するスチレン系重合体が結晶す
る際の結晶核剤として機能するものであり、その配合割
合は、（Ａ）成分１００重量部に対して０．０１〜１５
重量部、好ましくは０．０５〜５重量部である。ここで
、（Ｂ）成分の配合割合が０．０１重量部未満では、樹
脂組成物の結晶化を促進する効果がほとんど期待できず
、また１５重量部を超えると、樹脂組成物あるいはその
成形品の耐熱性、耐薬品性等が著しく低下し、実用に供
しえなくなる。In the present invention, the metal salt of an organic acid or the organic phosphorus compound which is the component (B) is a nucleating agent, especially a crystal nucleating agent when the styrenic polymer having a syndiotactic structure, which is the component (A), crystallizes. The blending ratio is 0.01 to 15 parts by weight per 100 parts by weight of component (A).
Parts by weight, preferably 0.05 to 5 parts by weight. Here, if the blending ratio of component (B) is less than 0.01 parts by weight, almost no effect of promoting crystallization of the resin composition can be expected, and if it exceeds 15 parts by weight, the resin composition or its molded product The heat resistance, chemical resistance, etc. of the product deteriorate significantly, making it impossible to put it into practical use.
本発明の樹脂組成物は、上記（Ａ）、 （Ｂ）両成分を
主成分とするものであるが、さらに、必要に応じて適当
な可塑剤、滑剤さらには熱可塑性樹脂。The resin composition of the present invention mainly contains both components (A) and (B), and further contains a suitable plasticizer, lubricant, and thermoplastic resin, if necessary.
ゴム、酸化防止剤あるいは無機充填材等を適宜配合する
こともできる。Rubber, antioxidants, inorganic fillers, etc. can also be blended as appropriate.
本発明の樹脂組成物を得るには、上記（Ａ）。In order to obtain the resin composition of the present invention, the above (A).
（Ｂ）成分ならびに所望成分を配合し、常温で混合ある
いは溶融混練など様々な方法でブレンドすればよく、そ
の方法は特に制限されない。Component (B) and desired components may be blended together and blended by various methods such as mixing at room temperature or melt-kneading, and the method is not particularly limited.
また、本発明の製造方法では、上述のスチレン系樹脂組
成物を室温〜２００°Ｃ１好ましくは６０〜１６０℃の
金型温度（成形温度）で成形する。Moreover, in the manufacturing method of the present invention, the above-mentioned styrenic resin composition is molded at a mold temperature (molding temperature) of room temperature to 200°C, preferably 60 to 160°C.
なお、成形の際の樹脂組成物の温度は特に制限はないが
、通常は２６０〜３５０°Ｃ程度の温度で加熱溶融して
おくことが好ましい、また、成形の手法としては製造す
べき成形品に応じて、適宜選定すればよいが、特に従来
のアタクチック構造を有するスチレン系重合体の成形加
工に採用されている熱成形法などの種々の成形法、より
具体的にはプレス成形、射出成形、押出成形、中空成形
、真空成形、注入成形、注型成形、流延成形、被覆成形
、紡糸成形、浸漬法、刷毛塗り法、スプレー法などによ
る塗布成形や一軸延伸、二輪（逐次あるいは同時）延伸
などの手法によればよい。The temperature of the resin composition during molding is not particularly limited, but it is usually preferable to heat and melt it at a temperature of about 260 to 350°C. In particular, various molding methods such as thermoforming, which is used in conventional molding of styrenic polymers with an atactic structure, and more specifically press molding and injection molding. , extrusion molding, blow molding, vacuum forming, injection molding, cast molding, casting molding, coating molding, spinning molding, coating molding and uniaxial stretching by dipping method, brush coating method, spray method, etc., two-wheel (sequentially or simultaneously) A method such as stretching may be used.
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、溶媒としてトルエン２２と、触媒成分であ
るシクロペンタジェニルチタントリクロリド１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０．８モル加え、２０”Ｃにおいてスチレン３．６！
を加えて１時間重合反応を行った０反応終了後、生成物
を塩酸−メタノール混合液で洗浄し、触媒成分を分解除
去した。Reference Example 1 (Production of polystyrene mainly having a syndiotactic structure) In a reaction vessel, 22 toluene as a solvent, 1 mmol of cyclopentadienyl titanium trichloride as a catalyst component, and 0.8 mol of methylaluminoxane as an aluminum atom were placed in a reaction vessel. In addition, styrene 3.6 at 20”C!
After the completion of the polymerization reaction for 1 hour, the product was washed with a hydrochloric acid-methanol mixture to decompose and remove the catalyst component.
次いで乾燥して重合体３３０ｇ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。この重合体は重量平均
分子量が２９０，０００、数平均分子量１５８．０００
であり、融点は２７０°Ｃであり、さらに同位体炭素の
核磁気共鳴（１３Ｃ−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９６％のものであった。Then, it was dried to obtain 330 g of a polymer. Next, this polymer was subjected to Soxhlet extraction using methyl ethyl ketone as a solvent to obtain an extraction residue of 95% by weight. This polymer has a weight average molecular weight of 290,000 and a number average molecular weight of 158,000.
It has a melting point of 270°C, and isotopic carbon nuclear magnetic resonance (13C-NMR) analysis (solvent: 1,
Absorption was observed at 145.35 ppm+ due to the syndiotactic structure from 2-dichlorobenzene), and the syndiotacticity in racemic pentad calculated from the peak area was 96%.
実施例１
参考例１で得られたシンジオタクチックポリスチレン１
００重量部に対して、ｐ −（ｔｅｒｔ−ブチル）安息
香酸アルミニウム（商品名： ＰＴＢＢＡ−／Ｍ！、大
日本インキ化学工業■製）０．１重量部を、３００°Ｃ
で溶融混練して樹脂組成物を得た。Example 1 Syndiotactic polystyrene 1 obtained in Reference Example 1
00 parts by weight, 0.1 parts by weight of p-(tert-butyl)aluminum benzoate (trade name: PTBBA-/M!, manufactured by Dainippon Ink & Chemicals) was heated at 300°C.
The mixture was melt-kneaded to obtain a resin composition.
次いで、この樹脂組成物を３００°Ｃで厚さ０．３１に
プレス成形し、氷水中で急冷して透明なプレス板を得た
。Next, this resin composition was press-molded at 300°C to a thickness of 0.31 mm, and rapidly cooled in ice water to obtain a transparent press plate.
続いて、このプレス板を３ｆｆＩ１１×３ｆｌＩ１１の
正方形に切って試料を作成し、この試料を用いて脱偏光
測定を行った。ここで脱偏光測定は、試料を２枚のカバ
ーグラスの間に挟み、３００℃の溶融炉で３分間融解さ
せ、結晶化温度８０℃と１５０℃で結晶化速度を測定す
ることにより行った。Subsequently, this press plate was cut into a square of 3ffI11 x 3flI11 to prepare a sample, and depolarization measurement was performed using this sample. Here, the depolarization measurement was performed by sandwiching the sample between two cover glasses, melting the sample in a melting furnace at 300°C for 3 minutes, and measuring the crystallization rate at crystallization temperatures of 80°C and 150°C.
また、上記樹脂組成物をミニマット成形機（住人重機■
製）を用いて、樹脂組成物温度３００℃。In addition, the above resin composition was molded into a mini mat molding machine (Jyujuki ■).
The temperature of the resin composition was 300°C.
金型温度１２０°Ｃで射出成形してダンベル状の試験片
を作成した。この成形の際の離型性ならびに成形品（ダ
ンベル状試験片）の外観を評価した。Dumbbell-shaped test pieces were prepared by injection molding at a mold temperature of 120°C. The mold releasability during this molding and the appearance of the molded product (dumbbell-shaped test piece) were evaluated.
これらの結果を第１表に示す。These results are shown in Table 1.
実施例２
ＰＴＢＢＡ−ＡＩ！、の量を０．５重量部としたこと以
外は、実施例１と同様の操作を行った。結果を第１表に
示す。Example 2 PTBBA-AI! The same operation as in Example 1 was performed except that the amount of was changed to 0.5 parts by weight. The results are shown in Table 1.
実施例３
ＰＴＢＢＡ−／ｌの量を４．０重量部としたこと以外は
、実施例１と同様の操作を行った。結果を第１表に示す
。Example 3 The same operation as in Example 1 was performed except that the amount of PTBBA-/l was 4.0 parts by weight. The results are shown in Table 1.
実施例４
ＰＴＢＢＡ−／ｌの代わりに、式
で表わされるリン酸ビス（４−ｔ−ブチルフェニル）ナ
トリウム（商品名： ＮＡ−１０，アデカ・アーガス社
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。Example 4 Example 4 except that sodium bis(4-t-butylphenyl) phosphate (trade name: NA-10, manufactured by Adeka Argus) represented by the formula was used instead of PTBBA-/l. The same operation as in 2 was performed. The results are shown in Table 1.
実施例５
ＮＡ−１０の量を４．５重量部としたこと以外は、実施
例４と同様の操作を行った。結果を第１表に示す。Example 5 The same operation as in Example 4 was performed except that the amount of NA-10 was 4.5 parts by weight. The results are shown in Table 1.
実施例６
ＰＴＢＢＡ−Ａｎ！の代わりに、式
で表わされるメチレンビス（２，４−ジ−ｔ−ブチルフ
ェノール）アシッドホスフェートナトリウム（商品名：
ＮＡ−１１，アデカ・アーガス社製）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。Example 6 PTBBA-An! Instead of, sodium methylene bis(2,4-di-t-butylphenol) acid phosphate (trade name:
The same operation as in Example 2 was performed except that NA-11 (manufactured by Adeca Argus) was used. The results are shown in Table 1.
実施例７
ＮＡ−１１の量を４．５重量部としたこと以外は、実施
例６と同様の操作を行った。結果を第１表に示す。Example 7 The same operation as in Example 6 was performed except that the amount of NA-11 was 4.5 parts by weight. The results are shown in Table 1.
比較例１
ＰＴＢＢＡ−Ａｌ２を使用しなかったこと以外は、実施
例１と同様の操作を行った。結果を第１表に示す。Comparative Example 1 The same operation as in Example 1 was performed except that PTBBA-Al2 was not used. The results are shown in Table 1.
比較例２
ＰＴＢＢＡ−Ａｎ！の代わりに、ビス（ベンジリデン）
ソルビトール（商品名：ＥＣ−１，イージー化学社製）
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 2 PTBBA-An! instead of bis(benzylidene)
Sorbitol (product name: EC-1, manufactured by Easy Chemical Co., Ltd.)
The same operation as in Example 2 was performed except that .
結果を第１表に示す。The results are shown in Table 1.
比較例３
ＮＡ−１１の量を１７重量部としたこと以外は、実施例
６と同様の操作を行った。結果を第１表に示す。Comparative Example 3 The same operation as in Example 6 was performed except that the amount of NA-11 was 17 parts by weight. The results are shown in Table 1.
比較例４
ＮＡ−１１の量を０．００５重量部としたこと以外は、
実施例６と同様の操作を行った。結果を第１表に示す。Comparative Example 4 Except that the amount of NA-11 was 0.005 parts by weight,
The same operation as in Example 6 was performed. The results are shown in Table 1.
比較例５
ＰＴＢＢＡ−Ａｎ！の量を０．００５重量部としたこと
以外は、実施例１と同様の操作を行った。Comparative Example 5 PTBBA-An! The same operation as in Example 1 was performed except that the amount of was changed to 0.005 parts by weight.
結果を第１表に示す。The results are shown in Table 1.
比較例６
ＰＴＢＢＡ−Ａｆｆｉの量を１７重量部としたこと以外
は、実施例１と同様の操作を行った。結果を第１表に示
す。Comparative Example 6 The same operation as in Example 1 was performed except that the amount of PTBBA-Affi was 17 parts by weight. 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、反応溶媒としてトルエン２２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°Ｃ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 2 (Manufacture of polystyrene mainly having a syndiotactic structure) A reaction vessel was charged with 22 toluene as a reaction solvent, 5 mmol of tetraethoxytitanium as a catalyst component, and 500 mmol of methylaluminoxane as an aluminum atom, and 151 mmol of styrene was added at 50°C. was added to carry out a polymerization reaction 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。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ｓ ｏ ｏ、ｏ
ｏ ｏであった。また、この重合体は１３ｃｍＮＭＲ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９６％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 components. Then, by drying, 2.5 kg of styrenic 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 is s o o, o
It was o o. In addition, this polymer was analyzed by 13 cm NMR (solvent: 1,2-dichlorobenzene), and an absorption was observed at 145.35 ppm due to the syndiotactic structure. The accuracy was 96%.
実施例８
参考例２で得られたシンジオタクチックポリスチレン１
００重量部に対して、ステアリン酸ナトリウム０．５重
量部を３００°Ｃで溶融混練して樹脂組成物を得た。次
いでこの樹脂組成物を用いて、実施例１と同様の評価を
行った。結果を第１表に示す。Example 8 Syndiotactic polystyrene 1 obtained in Reference Example 2
A resin composition was obtained by melt-kneading 0.5 parts by weight of sodium stearate at 300°C. Next, the same evaluation as in Example 1 was performed using this resin composition. The results are shown in Table 1.
実施例９
ステアリン酸ナトリウムの量を３．０重量部としたこと
以外は、実施例８と同様の操作を行った。Example 9 The same operation as in Example 8 was performed except that the amount of sodium stearate was 3.0 parts by weight.
結果を第１表に示す。The results are shown in Table 1.
実施例１０
ステアリン酸ナトリウムの代わりに、ＮＡ−１０を２重
量部用いたこと以外は、実施例８と同様の操作を行った
。結果を第１表に示す。Example 10 The same operation as in Example 8 was performed except that 2 parts by weight of NA-10 was used instead of sodium stearate. The results are shown in Table 1.
比較例７
ステアリン酸ナトリウムの量を０．００５重量部とした
こと以外は、実施例８と同様の操作を行った。結果を第
１表に示す。Comparative Example 7 The same operation as in Example 8 was performed except that the amount of sodium stearate was 0.005 parts by weight. The results are shown in Table 1.
（以下余白）
＊１ｔ、は結晶化誘導時間（秒）を示す。即ち溶融した
樹脂が結晶化する際に、所定の結晶化温度において結晶
核が生成するまでに要する時間（秒）を示す。(The following is a margin) *1t indicates crystallization induction time (seconds). That is, it indicates the time (seconds) required until crystal nuclei are generated at a predetermined crystallization temperature when a molten resin crystallizes.
＊２ ｔ＋ｚ□−１は半量結晶化時間の逆数（１／
秒）を示す。即ち所定の結晶化温度における到達結晶化
度の半分になる時間の逆数（１／秒）を示す。*2 t+z□-1 is the reciprocal of half crystallization time (1/
seconds). That is, it represents the reciprocal (1/sec) of the time required to reach half of the crystallinity reached at a predetermined crystallization temperature.
＊３ 離型性：Ｏ通常の操作で金型から成形品が離れる
。*3 Mold releasability: O The molded product separates from the mold during normal operation.
× 工具を用いたり、再加熱等の 操作を行わないと金型から成 部品が離れない。× Use tools, reheating, etc. If no operation is performed, the mold will Parts cannot be separated.
＊４ 外ｌｌ： ○ 色ムラ、クレージング、クラ
ンクがない。*4 Outside II: ○ No uneven color, crazing, or crank.
△ 成形品の一部に色ムラ、フレ ージングあるいはクラックが 発生している。△ There are uneven colors and flares in some parts of the molded product. cracking or cracking It has occurred.
本発明によれば、樹脂組成物の結晶化速度が大きいため
、低温の金型で成形が可能であり、得られる成形品は結
晶性が高く、耐熱性、耐溶剤性。According to the present invention, since the resin composition has a high crystallization rate, it can be molded using a low-temperature mold, and the resulting molded product has high crystallinity, heat resistance, and solvent resistance.
耐薬品性等のすぐれたものである。It has excellent chemical resistance.
したがって、本発明の樹脂組成物ならびに得られる成形
品は、一般構造材、電気・電子部品、自動車部品等、さ
らにはフィルム、繊維、シート等に幅広くかつ有効に利
用される。Therefore, the resin composition of the present invention and the molded articles obtained can be widely and effectively used in general structural materials, electric/electronic parts, automobile parts, etc., as well as films, fibers, sheets, etc.
したがって、本発明は工業的な利用価値が極めて高いも
のであり、その有効な利用が期待される。Therefore, the present invention has extremely high industrial utility value, and its effective use is expected.
手続補正書（自発）
平成元年４月１０日
２、発明の名称
スチレン系樹脂組成物と成形品の製造方法３、補正をす
る者
事件との関係 特許出願人
出光興産株式会社
４、代理人
住所 、Ｓ １０５ 東京都港区虎ノ門３−２５−３
芝ロイヤル５０５号
氏名 （７８７３）弁理士 大 谷 保電話（４５
９） １２９１番
６、補正の内容
（１）明細書第１６頁１２行目の「実用に供しえなくな
る。」を「実用に供しえなくなる。また（Ｂ）成分の粒
子径については特に制限はないが、造核効果の点からは
平均粒子径が１００μｍ以下、好ましくは５０μｍ以下
、さらに好ましくは５μｍ以下のものである。」に訂正
する。Procedural amendment (voluntary) April 10, 1989 2. Name of the invention: Method for manufacturing styrenic resin compositions and molded articles 3. Relationship with the case of the person making the amendment Patent applicant Idemitsu Kosan Co., Ltd. 4. Agent Address: S105 3-25-3 Toranomon, Minato-ku, Tokyo
Shiba Royal No. 505 Name (7873) Patent Attorney Tamotsu Otani (45)
9) No. 1291 No. 6, Contents of amendment (1) On page 16, line 12 of the specification, ``It will no longer be of practical use.'' has been replaced with ``It will no longer be of practical use.'' Also, there are no particular restrictions on the particle size of component (B). However, from the viewpoint of nucleation effect, the average particle diameter is 100 μm or less, preferably 50 μm or less, and more preferably 5 μm or less.”
（２）同第１９真３行目のｒｌｏｏ重量部に対して、」
と’ Ｐ （ｔｅｒｔ−ブチ」との間に「平均粒子径
０．５μｍの」を挿入する。(2) For the rloo weight part in the 19th true 3rd line,
Insert "average particle size of 0.5 μm" between and ' P (tert-buti).
（３）同第２０真下から７行目の「で表わされる」と「
リン酸ビス（４−ｔ−プチルフェニ」との間に「平均粒
子径１μｍの」を挿入する。(3) “Represented by” and “
"Average particle size of 1 μm" is inserted between bis(4-t-butylphenylphenylphate) phosphate.
（４）同第２１真下から１１１行目「で表わされる」と
「メチレンビス（２，４−ジーｔ−ブ」との間に「平均
粒子径０．８μｍの」を挿入する。(4) In the 111th line from just below the 21st line, insert ``with an average particle diameter of 0.8 μm'' between ``represented by'' and ``methylenebis(2,4-g-t-b)''.
（５）同第２６頁の第１表及び同第２７頁の脚注を下記
の如く訂正する。(5) Table 1 on page 26 and footnotes on page 27 are corrected as follows.
＊１ｔ、は結晶化誘導時間（秒）を示す。即ち溶融した
樹脂が結晶化する際に、所定の結晶化温度において結晶
核が生成するまでに要する時間（秒）を示す。なお、ｔ
、は短いほど結晶化が速いことを示す。*1t indicates crystallization induction time (seconds). That is, it indicates the time (seconds) required until crystal nuclei are generated at a predetermined crystallization temperature when a molten resin crystallizes. In addition, t
, indicates that the shorter the value, the faster the crystallization.
＊２ ｔｌ／ｌ−’は半量結晶化時間の逆数（１／秒
）を示す。即ち所定の結晶化温度における到達結晶化度
の半分になる時間の逆数（１／秒）を示す。なおｔｌ／
ｌ−’は大きいほど結晶化が速く起こることを示す。*2 tl/l-' indicates the reciprocal of half crystallization time (1/sec). That is, it represents the reciprocal (1/sec) of the time required to reach half of the crystallinity reached at a predetermined crystallization temperature. Furthermore, tl/
The larger l-' indicates that crystallization occurs faster.
＊３ ＃型性：Ｏ通常の操作で金型から成形品が離れる
。*3 # Moldability: O The molded product separates from the mold during normal operation.
× 工具を用いたり、再加熱等の 操作を行わないと金型から成 形孔が離れない。× Use tools, reheating, etc. If no operation is performed, the mold will The shape hole does not separate.
＊４ 外観二 〇 色ムラ、クレージング、クラックが
ない。*4 Appearance 2 〇 No uneven color, crazing, or cracks.
Δ 成形品の一部に色ムラ、フレ ージングあるいはクラックが 発生している。 」Δ There is uneven coloring and flaking in some parts of the molded product. cracking or cracking It has occurred. ”
Claims (2)
スチレン系重合体１００重量部および（Ｂ）有機酸の金
属塩および／または有機リン化合物からなる結晶核剤０
．０１〜１５重量部を主成分とするスチレン系樹脂組成
物。(1) (A) 100 parts by weight of a styrenic polymer mainly having a syndiotactic structure and (B) 0 crystal nucleating agent consisting of a metal salt of an organic acid and/or an organic phosphorus compound
．． A styrenic resin composition containing 01 to 15 parts by weight as a main component.
００℃の成形温度で成形することを特徴とするスチレン
系樹脂成形品の製造方法。(2) The styrenic resin composition according to claim 1 is prepared from room temperature to 2.
A method for producing a styrenic resin molded product, characterized by molding at a molding temperature of 00°C.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63023745A JP2583551B2 (en) | 1988-02-05 | 1988-02-05 | Styrene resin composition and method for producing molded article |
| PCT/JP1988/001040 WO1989003857A1 (en) | 1987-10-20 | 1988-10-12 | Styrenic resin composition and process for producing resin molding |
| AU25463/88A AU605383B2 (en) | 1987-10-20 | 1988-10-12 | Styrenic resin composition |
| KR1019890701125A KR940004093B1 (en) | 1987-10-20 | 1988-10-12 | Styrenic resin composition and process for producing molding products |
| EP88117305A EP0312976B1 (en) | 1987-10-20 | 1988-10-18 | Styrene-based resin composition and process for production of moldings |
| ES88117305T ES2050136T3 (en) | 1987-10-20 | 1988-10-18 | RESIN COMPOSITION BASED ON STYRENE AND PROCEDURE TO PRODUCE MOLDED PARTS. |
| AT88117305T ATE100482T1 (en) | 1987-10-20 | 1988-10-18 | STYRENE BASED RESIN MIX AND METHOD OF MAKING MOLDED PARTS. |
| DE88117305T DE3887260T2 (en) | 1987-10-20 | 1988-10-18 | Styrene-based resin mixture and process for producing molded parts. |
| CA000580559A CA1338991C (en) | 1987-10-20 | 1988-10-19 | Styrene-based resin composition and process for production of moldings |
| FI893010A FI97897C (en) | 1987-10-20 | 1989-06-19 | Styrene-based resin composition and process for making molded pieces |
| US07/810,369 US5322869A (en) | 1987-10-20 | 1991-12-18 | Styrene-based resin composition and process for production of moldings |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63023745A JP2583551B2 (en) | 1988-02-05 | 1988-02-05 | Styrene resin composition and method for producing molded article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01201350A true JPH01201350A (en) | 1989-08-14 |
| JP2583551B2 JP2583551B2 (en) | 1997-02-19 |
Family
ID=12118849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63023745A Expired - Fee Related JP2583551B2 (en) | 1987-10-20 | 1988-02-05 | Styrene resin composition and method for producing molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2583551B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01272607A (en) * | 1988-04-26 | 1989-10-31 | Asahi Chem Ind Co Ltd | Production of syndiotactic polystyrene crystal structure |
| US5270353A (en) * | 1989-02-10 | 1993-12-14 | Idemitsu Kosan Co., Ltd. | Resin composition |
| JP2002113756A (en) * | 2000-10-05 | 2002-04-16 | Idemitsu Petrochem Co Ltd | Method for manufacturing molded body of transparent styrene resin, and molded body of transparent styrene resin |
| CN114106529A (en) * | 2022-01-26 | 2022-03-01 | 广东顺德顺炎新材料股份有限公司 | Deformation-resistant high-performance flame-retardant reinforced PET modified engineering plastic and preparation method thereof |
-
1988
- 1988-02-05 JP JP63023745A patent/JP2583551B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01272607A (en) * | 1988-04-26 | 1989-10-31 | Asahi Chem Ind Co Ltd | Production of syndiotactic polystyrene crystal structure |
| US5270353A (en) * | 1989-02-10 | 1993-12-14 | Idemitsu Kosan Co., Ltd. | Resin composition |
| JP2002113756A (en) * | 2000-10-05 | 2002-04-16 | Idemitsu Petrochem Co Ltd | Method for manufacturing molded body of transparent styrene resin, and molded body of transparent styrene resin |
| JP4629846B2 (en) * | 2000-10-05 | 2011-02-09 | 出光興産株式会社 | Method for producing transparent styrene resin molded body and transparent styrene resin molded body |
| CN114106529A (en) * | 2022-01-26 | 2022-03-01 | 广东顺德顺炎新材料股份有限公司 | Deformation-resistant high-performance flame-retardant reinforced PET modified engineering plastic and preparation method thereof |
| CN114106529B (en) * | 2022-01-26 | 2022-04-19 | 广东顺德顺炎新材料股份有限公司 | Deformation-resistant high-performance flame-retardant reinforced PET modified engineering plastic and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2583551B2 (en) | 1997-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0356857B1 (en) | Stretched moldings of styrene-based polymer compositions and process for producing the same | |
| JP2812971B2 (en) | Extrusion molding material and method for producing molded article | |
| EP0312976B1 (en) | Styrene-based resin composition and process for production of moldings | |
| JP2828982B2 (en) | Film, sheet or tape, and method for producing the same | |
| KR960001620B1 (en) | Styrene-based resin composition and the process for producing | |
| US5698652A (en) | Styrenic polymer and molded article | |
| KR100424085B1 (en) | Flame Retardant Polystyrene Coating Composition and Polystyrene Modified Oily Form | |
| JPS62257950A (en) | Thermoplastic resin composition | |
| US5183871A (en) | Styrene polymer molding material and process for preparing same | |
| JPH01316246A (en) | Styrene resin oriented molded product and its manufacture | |
| JP2597392B2 (en) | Non-woven | |
| JP2790636B2 (en) | Stretched film for food packaging | |
| JPH01182349A (en) | Flame retardant resin composition | |
| JPH01201350A (en) | Production of styrene resin composition and its molding | |
| JP2710324B2 (en) | Styrene-based polymer molded article and method for producing the same | |
| JPH01182350A (en) | Polystyrene based resin composition | |
| JPS62259809A (en) | Manufacture of resinous molded item | |
| JP2636900B2 (en) | Stretched styrene resin molded article and method for producing the same | |
| JPH01182347A (en) | Production of styrene based resin composition and molded product thereof | |
| JP3649257B2 (en) | Styrenic resin sheet / film manufacturing method | |
| JP3574694B2 (en) | Polystyrene resin and molded product thereof | |
| JP2927753B2 (en) | Polystyrene resin composition | |
| JPH0386755A (en) | Polyester resin composition | |
| JPH02258812A (en) | Styrene-based copolymer and production thereof | |
| JPH03114724A (en) | Extrusion molding method for thermoplastic resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |