JPH11302370A - Polycarbonate resin and hollow molded container - Google Patents
Polycarbonate resin and hollow molded containerInfo
- Publication number
- JPH11302370A JPH11302370A JP11686698A JP11686698A JPH11302370A JP H11302370 A JPH11302370 A JP H11302370A JP 11686698 A JP11686698 A JP 11686698A JP 11686698 A JP11686698 A JP 11686698A JP H11302370 A JPH11302370 A JP H11302370A
- Authority
- JP
- Japan
- Prior art keywords
- polycarbonate resin
- methylene chloride
- solution
- hydroxyphenyl
- bis
- 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.)
- Pending
Links
- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 121
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 121
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 229910001868 water Inorganic materials 0.000 claims description 56
- 235000013365 dairy product Nutrition 0.000 claims description 3
- 235000014214 soft drink Nutrition 0.000 claims description 3
- 230000006866 deterioration Effects 0.000 abstract description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 138
- 239000000243 solution Substances 0.000 description 61
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 60
- 238000000034 method Methods 0.000 description 37
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 35
- 239000008188 pellet Substances 0.000 description 27
- 238000003756 stirring Methods 0.000 description 22
- 239000003960 organic solvent Substances 0.000 description 21
- 239000000843 powder Substances 0.000 description 18
- -1 carbonyl halide Chemical class 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 14
- 238000000465 moulding Methods 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 238000010103 injection stretch blow moulding Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000000071 blow moulding Methods 0.000 description 4
- 239000006085 branching agent Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010097 foam moulding Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- GPFJHNSSBHPYJK-UHFFFAOYSA-N (3-methylphenyl) hydrogen carbonate Chemical compound CC1=CC=CC(OC(O)=O)=C1 GPFJHNSSBHPYJK-UHFFFAOYSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- MAQOZOILPAMFSW-UHFFFAOYSA-N 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=C(CC=3C(=CC=C(C)C=3)O)C=C(C)C=2)O)=C1 MAQOZOILPAMFSW-UHFFFAOYSA-N 0.000 description 1
- YQERQEMYOWRTEC-UHFFFAOYSA-N 2,6-bis[(2-hydroxy-5-propan-2-ylphenyl)methyl]-4-propan-2-ylphenol Chemical compound CC(C)C1=CC=C(O)C(CC=2C(=C(CC=3C(=CC=C(C=3)C(C)C)O)C=C(C=2)C(C)C)O)=C1 YQERQEMYOWRTEC-UHFFFAOYSA-N 0.000 description 1
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-UHFFFAOYSA-N 0.000 description 1
- KICYRZIVKKYRFS-UHFFFAOYSA-N 2-(3,5-dihydroxyphenyl)benzene-1,3,5-triol Chemical compound OC1=CC(O)=CC(C=2C(=CC(O)=CC=2O)O)=C1 KICYRZIVKKYRFS-UHFFFAOYSA-N 0.000 description 1
- NFAOATPOYUWEHM-UHFFFAOYSA-N 2-(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=CC=C1O NFAOATPOYUWEHM-UHFFFAOYSA-N 0.000 description 1
- WYMGBMHJCXJUHG-UHFFFAOYSA-N 2-(9H-fluoren-4-yl)phenol Chemical compound Oc1ccccc1-c1cccc2Cc3ccccc3-c12 WYMGBMHJCXJUHG-UHFFFAOYSA-N 0.000 description 1
- KYOZIVFRHLSSKN-UHFFFAOYSA-N 2-[[2-hydroxy-3-[(2-hydroxy-5-methylphenyl)methyl]-5-methylphenyl]methyl]-6-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=C(CC=3C(=C(CC=4C(=CC=C(C)C=4)O)C=C(C)C=3)O)C=C(C)C=2)O)=C1 KYOZIVFRHLSSKN-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- IBNFPRMKLZDANU-UHFFFAOYSA-N 4-(4-hydroxy-3-methylphenyl)sulfanyl-2-methylphenol Chemical compound C1=C(O)C(C)=CC(SC=2C=C(C)C(O)=CC=2)=C1 IBNFPRMKLZDANU-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 1
- CUAWUNQAIYJWQT-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxy-3,5-dimethylphenyl)ethyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C=2C=C(C)C(O)=C(C)C=2)C=2C=C(C)C(O)=C(C)C=2)=C1 CUAWUNQAIYJWQT-UHFFFAOYSA-N 0.000 description 1
- UMPGNGRIGSEMTC-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexyl]phenol Chemical compound C1C(C)CC(C)(C)CC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UMPGNGRIGSEMTC-UHFFFAOYSA-N 0.000 description 1
- UJCYBTZHUJWCMB-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-4-propan-2-ylcyclohexyl]phenol Chemical compound C1CC(C(C)C)CCC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UJCYBTZHUJWCMB-UHFFFAOYSA-N 0.000 description 1
- YMSALPCDWZMQQG-UHFFFAOYSA-N 4-[2-(2,4-dihydroxyphenyl)propan-2-yl]benzene-1,3-diol Chemical compound C=1C=C(O)C=C(O)C=1C(C)(C)C1=CC=C(O)C=C1O YMSALPCDWZMQQG-UHFFFAOYSA-N 0.000 description 1
- WCUDAIJOADOKAW-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)pentan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCC)C1=CC=C(O)C=C1 WCUDAIJOADOKAW-UHFFFAOYSA-N 0.000 description 1
- RQTDWDATSAVLOR-UHFFFAOYSA-N 4-[3,5-bis(4-hydroxyphenyl)phenyl]phenol Chemical compound C1=CC(O)=CC=C1C1=CC(C=2C=CC(O)=CC=2)=CC(C=2C=CC(O)=CC=2)=C1 RQTDWDATSAVLOR-UHFFFAOYSA-N 0.000 description 1
- LIDWAYDGZUAJEG-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)-phenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC(O)=CC=1)C1=CC=CC=C1 LIDWAYDGZUAJEG-UHFFFAOYSA-N 0.000 description 1
- BOCLKUCIZOXUEY-UHFFFAOYSA-N 4-[tris(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 BOCLKUCIZOXUEY-UHFFFAOYSA-N 0.000 description 1
- KNDDEFBFJLKPFE-UHFFFAOYSA-N 4-n-Heptylphenol Chemical compound CCCCCCCC1=CC=C(O)C=C1 KNDDEFBFJLKPFE-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- QJAZTRFWQZDCHC-UHFFFAOYSA-N OC1=C(C=CC=C1C)C1=CC=CC=2CC3=CC=CC=C3C1=2 Chemical compound OC1=C(C=CC=C1C)C1=CC=CC=2CC3=CC=CC=C3C1=2 QJAZTRFWQZDCHC-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 description 1
- MUCRFDZUHPMASM-UHFFFAOYSA-N bis(2-chlorophenyl) carbonate Chemical compound ClC1=CC=CC=C1OC(=O)OC1=CC=CC=C1Cl MUCRFDZUHPMASM-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Containers Having Bodies Formed In One Piece (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
(57)【要約】
【課題】 熱安定性に優れ、且つ耐湿熱劣化性の改善さ
れたポリカーボネート樹脂および該ポリカーボネート樹
脂より形成される中空容器を提供する。
【解決手段】 構造粘性指数が１．３６以上であるポリ
カーボネート樹脂であって、該ポリカーボネート樹脂中
に残存する二価フェノールの量が１０ｐｐｍ以下である
ポリカーボネート樹脂および該ポリカーボネート樹脂よ
り形成された中空成形容器。PROBLEM TO BE SOLVED: To provide a polycarbonate resin excellent in heat stability and improved in resistance to humid heat deterioration and a hollow container formed from the polycarbonate resin. A polycarbonate resin having a structural viscosity index of 1.36 or more, wherein the amount of dihydric phenol remaining in the polycarbonate resin is 10 ppm or less, and a hollow molded container formed from the polycarbonate resin .
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリカーボネート
樹脂および中空成形容器に関する。さらに詳しくは、構
造粘性指数が大きく、樹脂中に残存する二価フェノール
の量が極めて少ないポリカーボネート樹脂および該樹脂
を、ブロー成形、押出成形、圧縮成形、発泡成形等の方
法で成形して得られる熱安定性に優れ、耐湿熱劣化性の
改善されたポリカーボネート樹脂製の中空成形容器に関
する。[0001] The present invention relates to a polycarbonate resin and a hollow molded container. More specifically, it is obtained by molding a polycarbonate resin having a large structural viscosity index and an extremely small amount of dihydric phenol remaining in the resin, and the resin by a method such as blow molding, extrusion molding, compression molding, or foam molding. TECHNICAL FIELD The present invention relates to a hollow molded container made of a polycarbonate resin having excellent heat stability and improved resistance to humid heat deterioration.
【０００２】[0002]
【従来の技術】従来、エンジニアリングプラスチックと
して広く用いられているポリカーボネート樹脂は、透明
性、寸法安定性、耐衝撃性がすぐれているために、中空
成形容器、殊に５ガロンのミネラルウォーター用の中空
容器として用いられている。2. Description of the Related Art Conventionally, polycarbonate resins widely used as engineering plastics are excellent in transparency, dimensional stability, and impact resistance. It is used as a container.
【０００３】また、かかるポリカーボネート樹脂の中
で、中空成形容器を成形する際、溶融時にダレを生じ難
い非ニュートン流動性を示す分岐ポリカーボネート樹脂
（特公昭４４−１７１４９号公報、特公昭４７−２３９
１８号公報、特公昭４９−１６２７７号公報、特公昭６
０−１１７３３号公報参照）や高分子量ポリカーボネー
ト樹脂を汎用のポリカーボネート樹脂にブレンドしたも
の（特開平４−２５３７６６号公報参照）が好ましく使
用されている。[0003] Among such polycarbonate resins, a branched polycarbonate resin exhibiting non-Newtonian fluidity, which is less likely to sag when melted during molding of a hollow molded container (JP-B-44-17149, JP-B-47-239).
No. 18, JP-B-49-16277, JP-B-6-6
0-11733) and those obtained by blending a high-molecular-weight polycarbonate resin with a general-purpose polycarbonate resin (see JP-A-4-253766) are preferably used.
【０００４】ところが、かかるポリカーボネート樹脂を
中空成形容器に押出ブロー成形や延伸ブロー成形等の方
法で成形する際に、熱履歴を受け中空成形容器の色味が
黄色くなる場合がある。また、中空成形容器を回収して
再使用するために、水あるいはアルカリ濃度１〜４重量
％のアルカリ水溶液で、温度６０〜８０℃、洗浄時間２
〜７分の洗浄が行われているが、かかる洗浄を行った中
空成形容器に内容物を充填し、これを取り扱う際に落下
等により強い衝撃を受けると破損するなどの問題があっ
た。However, when such a polycarbonate resin is molded into a hollow molded container by a method such as extrusion blow molding or stretch blow molding, the color of the hollow molded container may become yellow due to heat history. Further, in order to collect and reuse the hollow molded container, the container is washed with water or an alkaline aqueous solution having an alkali concentration of 1 to 4% by weight at a temperature of 60 to 80 ° C and a cleaning time of 2 hours.
Although washing is performed for up to 7 minutes, the hollow molded container that has been washed is filled with the contents, and there is a problem that the container is damaged when it is subjected to a strong impact due to dropping or the like in handling the container.
【０００５】一方、特開平７−１０２０５５号公報、特
公平７−１０３２３５号公報には、熱安定性を改善した
分岐ポリカーボネート樹脂及びその製造方法が提案され
ている。前者は硫黄含有量の低い特殊な分岐剤を用いね
ばならず、後者は分岐点が１カ所のみの特殊な分岐ポリ
カーボネート樹脂であり、容易に合成できるものではな
く汎用性に欠け、両者共に得られる分岐ポリカーボネー
ト樹脂の熱安定性はある程度改善されるものの十分では
なく、また、耐湿熱劣化性も十分でなくその改善が求め
られている。On the other hand, Japanese Patent Application Laid-Open Nos. 7-102055 and 7-103235 propose a branched polycarbonate resin having improved thermal stability and a method for producing the same. The former must use a special branching agent with a low sulfur content, and the latter is a special branched polycarbonate resin having only one branch point, which cannot be easily synthesized and lacks versatility, and both are obtained. Although the thermal stability of the branched polycarbonate resin is improved to some extent, it is not sufficient, and the resistance to deterioration due to heat and humidity is not sufficient, so that improvement is required.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、熱安
定性に優れ、耐湿熱劣化性の改善されたポリカーボネー
ト樹脂及び該樹脂より成形される中空成形容器を提供す
ることにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a polycarbonate resin which is excellent in thermal stability and has improved resistance to moist heat deterioration, and a hollow molded container molded from the resin.
【０００７】本発明者はこの目的を達成せんとして鋭意
研究を重ねた結果、ポリカーボネート樹脂中に残存する
二価フェノールの量を特定量以下としたポリカーボネー
ト樹脂から形成される中空成形容器は、その熱安定性、
耐湿熱劣化性が著しく向上することを見出し、本発明に
到達した。The inventor of the present invention has conducted intensive studies to achieve this object, and as a result, a hollow molded container formed of a polycarbonate resin in which the amount of dihydric phenol remaining in the polycarbonate resin is equal to or less than a specific amount, has been found Stability,
The inventors have found that the resistance to moist heat deterioration is significantly improved, and have reached the present invention.
【０００８】[0008]
【課題を解決するための手段】すなわち、本発明によれ
ば、構造粘性指数が１．３６以上であるポリカーボネー
ト樹脂であって、該ポリカーボネート樹脂中に残存する
二価フェノールの量が１０ｐｐｍ以下であるポリカーボ
ネート樹脂およびかかる樹脂より形成された中空成形容
器が提供される。According to the present invention, there is provided a polycarbonate resin having a structural viscosity index of 1.36 or more, wherein the amount of dihydric phenol remaining in the polycarbonate resin is 10 ppm or less. A polycarbonate resin and a hollow molded container formed from such a resin are provided.
【０００９】ポリカーボネート樹脂の溶融特性は、式Ｑ
＝Ｋ・ＰN［式中、Ｑは溶融樹脂の流動量（ｍＬ／ｓｅ
ｃ）、Ｋは定数、Ｐは圧力（ｋｇ／ｃｍ2）、Ｎは構造
粘性指数］から求められる。Ｎ＝１のときはニュートン
流動性を示し、Ｎが大きくなるほど非ニュートン流動性
が大きくなる。本発明のポリカーボネート樹脂はＮが
１．３６以上であり、好ましくは１．３６〜３．５、よ
り好ましくは１．５〜３．５の値を示すものである。The melting properties of polycarbonate resin are given by the formula
= K · P N [wherein Q is the flow rate of the molten resin (mL / sec)
c) and K are constants, P is pressure (kg / cm 2 ), and N is structural viscosity index]. When N = 1, it indicates Newtonian fluidity, and as N increases, non-Newtonian fluidity increases. The N of the polycarbonate resin of the present invention is 1.36 or more, preferably 1.36 to 3.5, and more preferably 1.5 to 3.5.
【００１０】かかる構造粘性指数を有するポリカーボネ
ート樹脂としては、粘度平均分子量７０，０００〜２０
０，０００の高分子量ポリカーボネート樹脂や分岐ポリ
カーボネート樹脂が挙げられる。また、これらの高分子
量ポリカーボネート樹脂や分岐ポリカーボネート樹脂と
粘度平均分子量１０，０００〜４０，０００の汎用ポリ
カーボネート樹脂とのブレンド品も前記構造粘性指数の
範囲を満足するものであれば好適に使用することができ
る。As a polycarbonate resin having such a structural viscosity index, a viscosity average molecular weight of 70,000 to 20
000 high molecular weight polycarbonate resins and branched polycarbonate resins. Blends of these high molecular weight polycarbonate resins or branched polycarbonate resins with general-purpose polycarbonate resins having a viscosity average molecular weight of 10,000 to 40,000 are also preferably used as long as they satisfy the above range of the structural viscosity index. Can be.
【００１１】本発明で使用されるポリカーボネート樹脂
は、二価フェノールとカーボネート前駆物質を溶液法ま
たは溶融法で反応させて得られるものである。ここで用
いる二価フェノールの代表的な例としては、例えばハイ
ドロキノン、レゾルシノール、４，４’−ビフェノー
ル、１，１−ビス（４−ヒドロキシフェニル）エタン、
２，２−ビス（４−ヒドロキシフェニル）プロパン（通
称ビスフェノールＡ）、２，２−ビス（４−ヒドロキシ
−３−メチルフェニル）プロパン、２，２−ビス（４−
ヒドロキシフェニル）ブタン、１，１−ビス（４−ヒド
ロキシフェニル）−１−フェニルエタン、１，１−ビス
（４−ヒドロキシフェニル）シクロヘキサン、１，１−
ビス（４−ヒドロキシフェニル）−３，３，５−トリメ
チルシクロヘキサン、２，２−ビス（４−ヒドロキシフ
ェニル）ペンタン、４，４’−（ｐ−フェニレンジイソ
ブロピリデン）ジフェノール、４，４’−（ｍ−フェニ
レンジイソプロピリデン）ジフェノール、１，１−ビス
（４−ヒドロキシフェニル）−４−イソプロピルシクロ
ヘキサン、ビス（４−ヒドロキシフェニル）オキシド、
ビス（４−ヒドロキシフェニル）スルフィド、ビス（４
−ヒドロキシフェニル）スルホキシド、ビス（４−ヒド
ロキシフェニル）スルホン、ビス（４−ヒドロキシフェ
ニル）ケトン、ビス（４−ヒドロキシフェニル）エステ
ル、２，２−ビス（３，５−ジブロモ−４−ヒドロキシ
フェニル）プロパン、ビス（３，５−ジブロモ−４−ヒ
ドロキシフェニル）スルホン、ビス（４−ヒドロキシ−
３−メチルフェニル）スルフィド、９，９−ビス（４−
ヒドロキシフェニル）フルオレン、９，９−ビス（４−
ヒドロキシ−３−メチルフェニル）フルオレン等が挙げ
られる。これらは単独で用いても、二種以上併用しても
よい。なかでも２，２−ビス（４−ヒドロキシフェニ
ル）プロパンが好ましい。The polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. Representative examples of the dihydric phenol used here include, for example, hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane,
2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-
Hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-
Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′ -(M-phenylenediisopropylidene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide,
Bis (4-hydroxyphenyl) sulfide, bis (4
-Hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) Propane, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, bis (4-hydroxy-
3-methylphenyl) sulfide, 9,9-bis (4-
(Hydroxyphenyl) fluorene, 9,9-bis (4-
(Hydroxy-3-methylphenyl) fluorene and the like. These may be used alone or in combination of two or more. Among them, 2,2-bis (4-hydroxyphenyl) propane is preferred.
【００１２】カーボネート前駆体としてはカルボニルハ
ライド、カーボネートエステルまたはハロホルメート等
が使用され、具体的にはホスゲン、ジフェニルカーボネ
ートまたは二価フェノールのジハロホルメート等が挙げ
られる。As the carbonate precursor, carbonyl halide, carbonate ester or haloformate is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol and the like.
【００１３】上記二価フェノールとカーボネート前駆体
を溶液法または溶融法によって反応させてポリカーボネ
ート樹脂を製造するに当っては、必要に応じて触媒、末
端停止剤、二価フェノールの酸化防止剤等を使用しても
よい。またポリカーボネート樹脂は芳香族または脂肪族
の二官能性カルボン酸を共重合したポリエステルカーボ
ネート樹脂であってもよく、また、得られたポリカーボ
ネート樹脂の２種以上を混合した混合物であってもよ
い。In producing the polycarbonate resin by reacting the above-mentioned dihydric phenol with the carbonate precursor by a solution method or a melting method, a catalyst, a terminal stopper, an antioxidant for the dihydric phenol and the like may be used, if necessary. May be used. The polycarbonate resin may be a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid, or a mixture of two or more of the obtained polycarbonate resins.
【００１４】溶液法による反応は、通常二価フェノール
とホスゲンとの反応であり、酸結合剤および有機溶媒の
存在下に反応させる。酸結合剤としては、例えば水酸化
ナトリウム、水酸化カリウム等のアルカリ金属水酸化物
またはピリジン等のアミン化合物が用いられる。有機溶
媒としては、例えば塩化メチレン、クロロベンゼン等の
ハロゲン化炭化水素が用いられる。また、反応促進のた
めに例えばトリエチルアミン、テトラ−ｎ−ブチルアン
モニウムブロマイド、テトラ−ｎ−ブチルホスホニウム
ブロマイド等の第三級アミン、第四級アンモニウム化合
物、第四級ホスホニウム化合物等の触媒を用いることが
でき、末端停止剤として、例えばフェノール、ｐ−ｔｅ
ｒｔ−ブチルフェノール、ｐ−クミルフェノールおよび
イソオクチルフェノール等の単官能フェノール類を使用
することができる。その際、反応温度は通常０〜４０
℃、反応時間は１０分〜５時間程度、反応中のｐＨは９
以上に保つのが好ましい。The reaction by the solution method is usually a reaction between dihydric phenol and phosgene, and is carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to promote the reaction, for example, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound may be used. As a terminal stopper, for example, phenol, p-te
Monofunctional phenols such as rt-butylphenol, p-cumylphenol and isooctylphenol can be used. At that time, the reaction temperature is usually 0 to 40.
° C, the reaction time is about 10 minutes to 5 hours, and the pH during the reaction is 9
It is preferable to keep the above.
【００１５】溶融法による反応は、通常二価フェノール
とカーボネートエステルとのエステル交換反応であり、
不活性ガスの存在下に二価フェノールとカーボネートエ
ステルとを加熱しながら混合して、生成するアルコール
またはフェノールを留出させる方法により行われる。反
応温度は生成するアルコールまたはフェノールの沸点等
により異なるが、通常１２０〜３５０℃の範囲である。
反応後期には系を１０〜０．１Ｔｏｒｒ程度に減圧して
生成するアルコールまたはフェノールの留出を容易にさ
せる。反応時間は１〜１０時間程度である。また、重合
速度を速めるために通常エステル化反応、エステル交換
反応に使用される重合触媒を用いることができる。The reaction by the melting method is usually a transesterification reaction between a dihydric phenol and a carbonate ester,
The method is carried out by a method in which a dihydric phenol and a carbonate ester are mixed while heating in the presence of an inert gas to distill off the produced alcohol or phenol. The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, but is usually in the range of 120 to 350 ° C.
In the latter stage of the reaction, the pressure of the system is reduced to about 10 to 0.1 Torr to facilitate the distillation of the alcohol or phenol produced. The reaction time is about 1 to 10 hours. Further, in order to increase the polymerization rate, a polymerization catalyst usually used for an esterification reaction and a transesterification reaction can be used.
【００１６】カーボネートエステルとしては、置換され
ていてもよい炭素数６〜１０のアリール基、アラルキル
基あるいは炭素数１〜４のアルキル基などのエステルが
挙げられる。具体的にはジフェニルカーボネート、ジト
リルカーボネート、ビス（クロロフェニル）カーボネー
ト、ｍ―クレジルカーボネート、ジナフチルカーボネー
ト、ビス（ジフェニル）カーボネート、ジメチルカーボ
ネート、ジエチルカーボネート、ジブチルカーボネート
などが挙げられ、なかでもジフェニルカーボネートが好
ましい。Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms. Specific examples include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and the like. Is preferred.
【００１７】本発明でいうポリカーボネート樹脂の分子
量は、塩化メチレン１００ｍＬにポリカーボネート樹脂
０．７ｇを２０℃で溶解した溶液から求めた比粘度（η
sp）を次式に挿入して求めた粘度平均分子量である。 ηsp／ｃ＝［η］＋０．４５×［η］2ｃ（但し［η］
は極限粘度） ［η］＝１．２３×１０-4Ｍ0.83 ｃ＝０．７The molecular weight of the polycarbonate resin in the present invention is determined by the specific viscosity (η) obtained from a solution of 0.7 g of the polycarbonate resin dissolved in 100 mL of methylene chloride at 20 ° C.
sp ) into the following equation. η sp /c=[η]+0.45×[η] 2 c (where [η]
Is the intrinsic viscosity) [η] = 1.23 × 10 −4 M 0.83 c = 0.7
【００１８】本発明における上記１．３６以上の構造粘
性指数を満足する態様としては、粘度平均分子量１０，
０００〜４０，０００のポリカーボネート樹脂１００重
量部に対して粘度平均分子量７０，０００〜２００，０
００の高分子量ポリカーボネート樹脂５〜２５重量部を
配合したポリカーボネート樹脂を好ましく挙げることが
できる。このブレンドされたポリカーボネート樹脂の粘
度平均分子量は、１３，０００〜５０，０００が好まし
く、１８，０００〜４５，０００がより好ましく、２
０，０００〜４０，０００がさらに好ましい。In the present invention, the structural viscosity index of 1.36 or more may be satisfied.
Viscosities of 100,000 to 40,000 and 100,000 parts by weight of a polycarbonate resin having a viscosity average molecular weight of 70,000 to 200,0.
A preferable example is a polycarbonate resin containing 5 to 25 parts by weight of a high molecular weight polycarbonate resin of No. 00. The viscosity average molecular weight of the blended polycarbonate resin is preferably from 13,000 to 50,000, more preferably from 18,000 to 45,000, and
More preferably, it is in the range of from 000 to 40,000.
【００１９】高分子量ポリカーボネート樹脂は、単独で
は溶融成形に供し得ない７０，０００〜２００，００
０、好ましくは１００，０００〜１６０，０００の粘度
平均分子量を有する。粘度平均分子量７０，０００未満
のものを使用した場合は、溶融特性を改良し、その構造
粘性指数を１．３６以上にし、ドローダウンを防止する
ために配合量を多量にしなければならず、その結果溶融
粘度が過剰に増大し、成形が困難になる場合がある。ま
た、粘度平均分子量２００，０００を越えたものを使用
した場合は、混合時の分散が悪く、成形品の外観が劣る
場合がある。The high-molecular-weight polycarbonate resin cannot be subjected to melt molding by itself and has a molecular weight of 70,000 to 200,000.
It has a viscosity average molecular weight of 0, preferably 100,000 to 160,000. When a material having a viscosity average molecular weight of less than 70,000 is used, the melting properties must be improved, the structural viscosity index must be 1.36 or more, and the blending amount must be large in order to prevent drawdown. As a result, the melt viscosity is excessively increased, and molding may be difficult. If the viscosity average molecular weight exceeds 200,000, the dispersion at the time of mixing is poor, and the appearance of the molded product may be poor.
【００２０】また、本発明の１．３６以上の構造粘性指
数を有するポリカーボネート樹脂において、好ましい態
様である分岐ポリカーボネート樹脂を製造する方法とし
ては、上述した溶液法または溶融法による反応におい
て、三官能以上の多官能性化合物の少なくとも１種以上
を分岐剤として、二価フェノールに対して０．０５〜
３．０モル％程度共重合させる方法によって製造され
る。分岐剤としては、例えばフロログルシン、フロログ
ルシド、４，６−ジメチル−２，４，６−トリス（４−
ヒドロキシフェニル）ヘプテン−２、４，６−ジメチル
−２，４，６−トリス（４−ヒドロキシフェニル）ヘプ
タン、１，３，５−トリス（４−ヒドロキシフェニル）
ベンゼン、１，１，１−トリ（４−ヒドロキシフェニ
ル）エタン、１，１，１−トリス（３，５−ジメチル−
４−ヒドロキシフェニル）エタン、２，２−ビス（４，
４−ビス（４−ヒドロキシフェニル）シクロヘキシル）
プロパン、２，６−ビス（２−ヒドロキシ−５−メチル
ベンジル）−４−メチルフェノール、２，６−ビス（２
−ヒドロキシ−−５−イソプロピルベンジル）−４−イ
ソプロピルフェノール、４−｛４−［１，１−ビス（４
−ヒドロキシフェニル）エチル］ベンゼン｝−α，α−
ジメチルベンジルフェノール、ビス（２−ヒドロキシ−
３−（２−ヒドロキシ−５−メチルベンジル）−５−メ
チルフェニル）メタン、テトラキス（４−ヒドロキシフ
ェニル）メタン、トリス（４−ヒドロキシフェニル）フ
ェニルメタン、トリスフェノール、２，２−ビス（２，
４−ジヒドロキシフェニル）プロパン、ビス（２，４−
ジヒドロキシフェニル）ケトン、１，４−ビス（４，４
−ジヒドロキシトリフェニルメチル）ベンゼン、トリメ
リット酸、ピロメリット酸、ベンゾフェノンテトラカル
ボン酸およびこれらの酸クロライド等が挙げられる。な
かでも１，１，１−トリス（４−ヒドロキシフェニル）
エタンが好ましい。In the polycarbonate resin having a structural viscosity index of 1.36 or more according to the present invention, a preferred embodiment of the method for producing a branched polycarbonate resin includes a trifunctional or higher functional resin in the reaction by the solution method or the melting method described above. A branching agent of at least one of the polyfunctional compounds of
It is manufactured by a method of copolymerizing about 3.0 mol%. Examples of the branching agent include phloroglucin, phloroglucid, 4,6-dimethyl-2,4,6-tris (4-
(Hydroxyphenyl) heptene-2,4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl)
Benzene, 1,1,1-tri (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-
4-hydroxyphenyl) ethane, 2,2-bis (4
4-bis (4-hydroxyphenyl) cyclohexyl)
Propane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 2,6-bis (2
-Hydroxy-5-isopropylbenzyl) -4-isopropylphenol, 4- {4- [1,1-bis (4
-Hydroxyphenyl) ethyl] benzene} -α, α-
Dimethylbenzylphenol, bis (2-hydroxy-
3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl) methane, tetrakis (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) phenylmethane, trisphenol, 2,2-bis (2,
4-dihydroxyphenyl) propane, bis (2,4-
Dihydroxyphenyl) ketone, 1,4-bis (4,4
-Dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof. Above all, 1,1,1-tris (4-hydroxyphenyl)
Ethane is preferred.
【００２１】分岐ポリカーボネート樹脂の粘度平均分子
量は、１０，０００〜４０，０００が好ましく、１５，
０００〜３５，０００がより好ましく、２０，０００〜
３０，０００がさらに好ましい。粘度平均分子量が１
０，０００未満のものを使用した場合は、ブロー成形時
の膨らみ性が不均一となり易く、偏肉の多い成形品とな
ることがある。粘度平均分子量が４０，０００を越える
ものを使用した場合は、溶融粘度が過剰に増大し、成形
が困難になる場合がある。The viscosity average molecular weight of the branched polycarbonate resin is preferably from 10,000 to 40,000,
000-35,000 are more preferable, and 20,000-
30,000 is more preferred. Viscosity average molecular weight of 1
If less than 000 is used, the swelling property during blow molding is likely to be non-uniform, and the molded product may have many uneven thicknesses. When a resin having a viscosity average molecular weight of more than 40,000 is used, the melt viscosity may be excessively increased, and molding may be difficult.
【００２２】また、１．３６以上の構造粘性指数を有す
る範囲内で、かかる分岐ポリカーボネート樹脂に、分岐
剤を共重合していない線状のポリカーボネート樹脂を混
合してもよい。Further, within the range having a structural viscosity index of 1.36 or more, a linear polycarbonate resin not copolymerized with a branching agent may be mixed with such a branched polycarbonate resin.
【００２３】本発明においては、高分子量ポリカーボネ
ート樹脂に比べ、分岐ポリカーボネート樹脂は粘度が低
く、製造、精製の方法が容易で、工程も煩雑でなく生産
性にも優れるためより好ましく採用される。In the present invention, the branched polycarbonate resin is more preferably employed because it has a lower viscosity than the high molecular weight polycarbonate resin, is easy to produce and purify, has a simple process, and is excellent in productivity.
【００２４】本発明において、ポリカーボネート樹脂中
に残存する二価フェノールの量は１０ｐｐｍ以下であ
り、８ｐｐｍ以下がより好ましい。二価フェノールの残
存量が１０ｐｐｍを越えると、熱安定性に劣り、耐湿熱
性が十分でなく、該ポリカーボネート樹脂より形成され
た中空成形容器の機械的強度が低下し好ましくない。In the present invention, the amount of the dihydric phenol remaining in the polycarbonate resin is at most 10 ppm, more preferably at most 8 ppm. If the residual amount of the dihydric phenol exceeds 10 ppm, the thermal stability is poor, the wet heat resistance is not sufficient, and the mechanical strength of the hollow molded container formed from the polycarbonate resin is undesirably reduced.
【００２５】本発明においてポリカーボネート樹脂中に
残存する二価フェノールの量を１０ｐｐｍ以下とする方
法としては、ポリカーボネート樹脂の有機溶媒溶液とア
ルカリ水溶液とを混合、攪拌し、有機溶媒溶液中の二価
フェノールをアルカリ水溶液へ抽出する方法が好ましく
採用できる。In the present invention, the amount of the dihydric phenol remaining in the polycarbonate resin is adjusted to 10 ppm or less by mixing an organic solvent solution of the polycarbonate resin with an aqueous alkali solution, stirring the mixture, and stirring the dihydric phenol in the organic solvent solution. Can be preferably employed to extract the compound into an aqueous alkali solution.
【００２６】かかるポリカーボネート樹脂の有機溶媒溶
液は、溶液法においては、反応終了後の有機相をそのま
まあるいは適当な濃度に調整して使用することができ、
溶融法においては得られたポリカーボネート樹脂を有機
溶媒に溶解して使用することができる。有機溶媒溶液中
のポリカーボネート樹脂の濃度は、５〜３５重量％が好
ましく、５〜２０重量％がより好ましい。この濃度範囲
のポリカーボネート樹脂の有機溶媒溶液を使用すると、
二価フェノールの抽出が効率的に行われ、二価フェノー
ルの量が低減されたポリカーボネート樹脂を得られ易く
好ましい。有機溶媒としては、例えば塩化メチレン、ク
ロロベンゼン等のハロゲン化炭化水素が好ましく、特に
塩化メチレンが好ましく用いられる。In the solution method, such an organic solvent solution of the polycarbonate resin can be used as it is or after adjusting the organic phase after the reaction to an appropriate concentration.
In the melting method, the obtained polycarbonate resin can be used by dissolving it in an organic solvent. The concentration of the polycarbonate resin in the organic solvent solution is preferably from 5 to 35% by weight, more preferably from 5 to 20% by weight. When using an organic solvent solution of a polycarbonate resin in this concentration range,
It is preferable because the extraction of dihydric phenol is performed efficiently and a polycarbonate resin having a reduced amount of dihydric phenol can be easily obtained. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are preferable, and methylene chloride is particularly preferably used.
【００２７】また、アルカリ水溶液としては、水酸化ナ
トリウム水溶液が好ましく用いられ、好ましくは０．１
〜５重量％濃度、より好ましくは０．３〜４重量％濃度
の水酸化ナトリウム水溶液が用いられる。かかる濃度範
囲の水酸化ナトリウム水溶液を用いると、二価フェノー
ルの抽出が効率的に行われ、二価フェノールの量が低減
されたポリカーボネート樹脂を得られ易く好ましい。ま
た、使用される水酸化ナトリウム水溶液と有機溶媒溶液
との割合は、水酸化ナトリウム水溶液／有機溶媒溶液
（容量比）で表して０．１〜１０の範囲が好ましく、
０．２〜２の範囲がより好ましい。かかる容量比でポリ
カーボネート樹脂の有機溶媒溶液とアルカリ水溶液とを
混合、攪拌すると、二価フェノールの抽出が効率的に行
われ、二価フェノールの量が低減されたポリカーボネー
ト樹脂を得られ易く好ましい。As the alkaline aqueous solution, an aqueous sodium hydroxide solution is preferably used, and preferably 0.1% aqueous solution.
An aqueous solution of sodium hydroxide having a concentration of -5% by weight, more preferably 0.3-4% by weight is used. The use of an aqueous solution of sodium hydroxide in such a concentration range is preferable because the extraction of dihydric phenol is performed efficiently and a polycarbonate resin with a reduced amount of dihydric phenol can be easily obtained. Further, the ratio of the aqueous sodium hydroxide solution and the organic solvent solution used is preferably in the range of 0.1 to 10 in terms of aqueous sodium hydroxide solution / organic solvent solution (volume ratio),
The range of 0.2 to 2 is more preferable. Mixing and stirring an organic solvent solution of a polycarbonate resin and an aqueous alkali solution at such a volume ratio is preferable because a dihydric phenol can be efficiently extracted and a polycarbonate resin having a reduced amount of the dihydric phenol can be easily obtained.
【００２８】ポリカーボネート樹脂の有機溶媒溶液とア
ルカリ水溶液とを混合、攪拌する方法としては、例え
ば、攪拌翼を回転することにより攪拌を行う方式（槽の
中心軸と攪拌軸とを一致させるもの、攪拌軸を傾斜させ
るもの、槽の側壁に攪拌軸を設けるもの等）、槽を揺動
させることにより攪拌を行う方式、ポンプにより槽内の
液を循環させる方式等が用いられる。混合攪拌した後、
静置して有機溶媒溶液相とアルカリ水溶液相を分液さ
せ、有機溶媒相を取り出すことができる。As a method of mixing and stirring an organic solvent solution of a polycarbonate resin and an aqueous alkali solution, for example, a method of stirring by rotating a stirring blade (a method in which the center axis of the tank is aligned with the stirring axis, a stirring method) A method in which the shaft is inclined, a method in which a stirring shaft is provided on the side wall of the tank, a method in which stirring is performed by swinging the tank, a method in which the liquid in the tank is circulated by a pump, and the like are used. After mixing and stirring,
The organic solvent solution phase and the alkaline aqueous solution phase are separated by standing, and the organic solvent phase can be taken out.
【００２９】また、ポリカーボネート樹脂の有機溶媒溶
液とアルカリ水溶液とを混合、攪拌し、二価フェノール
の抽出が行われた有機溶媒溶液相を取り出す他の方法と
して、遠心抽出装置を用いる方法が採用される。かかる
遠心抽出装置のなかで、分散相の形成と、遠心分離処理
を同一装置で連続して行える交流遠心抽出装置が好まし
く、具体的には、（株）日立製作所製ウルトレックスＥ
Ｐ−０２や川崎エンジニアリング（株）製ＫＣＣ遠心抽
出機等の多孔板付遠心抽出機が挙げられる。また、好ま
しくは３００Ｇ以上、より好ましくは７００Ｇ以上の遠
心力によって、遠心抽出処理を行うことが好ましい。As another method of mixing and stirring an organic solvent solution of a polycarbonate resin and an aqueous alkali solution and extracting a phase of the organic solvent solution from which dihydric phenol has been extracted, a method using a centrifugal extraction device has been adopted. You. Among such centrifugal extraction devices, an AC centrifugal extraction device capable of continuously forming a dispersed phase and performing a centrifugal separation process using the same device is preferable. Specifically, Ultrex E manufactured by Hitachi, Ltd. is preferred.
A centrifugal extractor with a perforated plate such as P-02 or KCC centrifugal extractor manufactured by Kawasaki Engineering Co., Ltd. may be used. Further, it is preferable that the centrifugal extraction process is performed with a centrifugal force of preferably 300 G or more, more preferably 700 G or more.
【００３０】アルカリ水溶液で処理したポリカーボネー
ト樹脂の有機溶媒溶液は、次いで、塩酸と混合攪拌した
後、水洗を繰り返して水溶性不純物を除去する。かくし
て得られるポリカーボネート樹脂の有機溶媒溶液は、通
常、粉粒化されて、ペレット化される。The organic solvent solution of the polycarbonate resin treated with the aqueous alkali solution is then mixed and stirred with hydrochloric acid, and then repeatedly washed with water to remove water-soluble impurities. The organic solvent solution of the polycarbonate resin thus obtained is usually pulverized and granulated.
【００３１】本発明では、殊に溶液法において溶剤とし
て好適に使用される塩化メチレンが、得られるポリカー
ボネート樹脂中に残存しないことが好ましく、具体的に
はポリカーボネート樹脂中に残存する塩化メチレンの量
が好ましくは５ｐｐｍ以下、より好ましくは１ｐｐｍ以
下であることが望ましい。塩化メチレンの量がかかる範
囲内であると、本発明のポリカーボネート樹脂から成形
品を継続して成形した場合に成形金型の鏡面を腐食する
ことがなく好ましい。In the present invention, in particular, it is preferable that methylene chloride, which is suitably used as a solvent in the solution method, does not remain in the obtained polycarbonate resin, and specifically, the amount of methylene chloride remaining in the polycarbonate resin is reduced. It is preferably at most 5 ppm, more preferably at most 1 ppm. When the amount of methylene chloride is within the above range, it is preferable that the mirror surface of the molding die is not corroded when the molded article is continuously molded from the polycarbonate resin of the present invention.
【００３２】塩化メチレンの量を低減する方法として
は、ポリカーボネート樹脂の塩化メチレン溶液を粉粒化
する工程において、例えばポリカーボネート樹脂の塩化
メチレン溶液と固形化溶媒とを剪断力付与作用を有する
攪拌下に供給し、加熱攪拌してポリカーボネート樹脂粉
粒体を得る方法、ポリカーボネート樹脂の塩化メチレン
溶液と固形化溶媒とを予め混合したものあるいはポリカ
ーボネート樹脂の塩化メチレン溶液と固形化溶媒とをそ
れぞれ別々に、造粒槽中の温水に供給して有機溶媒を除
去する粉粒化方法が用いられる。ポリカーボネート樹脂
の塩化メチレン溶液と固形化溶媒とをそれぞれ別々に、
造粒槽中の温水に供給して有機溶媒を除去する粉粒化方
法は、得られるポリカーボネート樹脂粉粒体の比表面積
を所定の範囲に制御し易く、また、ポリカーボネート樹
脂の塩化メチレン溶液と固形化溶媒との混合装置が不要
であり、好ましく採用される。ポリカーボネート樹脂の
塩化メチレン溶液を造粒槽に供給するにあたって、かか
る溶液を滴下あるいは噴霧しても良い。As a method of reducing the amount of methylene chloride, in the step of pulverizing a methylene chloride solution of a polycarbonate resin, for example, a methylene chloride solution of a polycarbonate resin and a solidifying solvent are stirred under a shearing force imparting action. A method of supplying and heating and stirring to obtain a polycarbonate resin powder, a premixed solution of a methylene chloride solution of a polycarbonate resin and a solidification solvent, or a method of separately preparing a methylene chloride solution of a polycarbonate resin and a solidification solvent separately. A pulverization method is used in which the organic solvent is removed by supplying hot water in a granulation tank. Separately the methylene chloride solution of the polycarbonate resin and the solidified solvent, respectively,
The granulation method of removing the organic solvent by supplying to hot water in a granulation tank is easy to control the specific surface area of the obtained polycarbonate resin granules within a predetermined range. A mixing device with a chlorinated solvent is not required and is preferably employed. When supplying the methylene chloride solution of the polycarbonate resin to the granulation tank, the solution may be dropped or sprayed.
【００３３】かかる固形化溶媒としては、ヘプタン、ヘ
キサン、シクロヘキサン、酢酸エチル、ベンゼン、トル
エン、アセトン等が挙げられ、ヘプタン、ヘキサン、酢
酸エチルが好ましく、特にヘプタンが好ましい。固形化
溶媒の使用量は、ポリカーボネート樹脂に対する重量比
で０．５〜１．３の範囲が好ましく、０．７〜１．２の
範囲がより好ましい。この範囲では、得られるポリカー
ボネート樹脂粉粒体の粘着性が小さく互いにくっついた
塊となり難く、また、破砕強度が大きくなり微粉になり
難く好ましい。Examples of such a solidifying solvent include heptane, hexane, cyclohexane, ethyl acetate, benzene, toluene, acetone and the like. Heptane, hexane and ethyl acetate are preferred, and heptane is particularly preferred. The amount of the solidifying solvent used is preferably in the range of 0.5 to 1.3, more preferably 0.7 to 1.2, by weight ratio to the polycarbonate resin. In this range, the obtained polycarbonate resin particles are less likely to form clumps that are small in stickiness and hardly adhere to each other, and that the crushing strength is high and the powder is less likely to become fine powder.
【００３４】造粒時の温水の温度は４０℃〜７０℃が好
ましく、４２℃〜５０℃がより好ましい。また、温水の
量は、ポリカーボネート樹脂に対して重量比で１．０〜
２０の範囲が好ましい。The temperature of the hot water during granulation is preferably from 40 to 70 ° C., more preferably from 42 to 50 ° C. In addition, the amount of warm water is 1.0 to 1.0 by weight with respect to the polycarbonate resin.
A range of 20 is preferred.
【００３５】造粒槽における攪拌は上記温度を維持しな
がら加熱雰囲気下、粒子径を小さくするために剪断力を
持つものが好ましく採用され、このような作用を有する
攪拌翼としてはパドル翼、ヘリカル翼、ニーダー等が挙
げられ、具体的には神鋼パンテック（株）製フルゾー
ン、住友重機（株）製マックスブレンド等の攪拌効率の
良い攪拌翼が好ましく使用される。得られるポリカーボ
ネート樹脂粉粒体は、通常、次いで粉砕し、乾燥され
る。粉砕は湿式粉砕機を用いることが好ましく、スーパ
ークリーンミル、ハンマーミル、グローミル、ホモミッ
クラインミル等が好ましく用いられる。乾燥には熱風乾
燥機、スチーム乾燥機等が好ましく用いられるがいずれ
も防爆タイプが望ましい。かくして得られたポリカーボ
ネート樹脂粉粒体は、好ましくは少なくとも１カ所以上
のベント口を有する押出機を用いて溶融混練しペレット
化される。押出機は一軸でも二軸でもよいが、二軸押出
機が好ましい。The stirring in the granulating tank is preferably carried out in a heating atmosphere while maintaining the above-mentioned temperature and having a shearing force in order to reduce the particle diameter. Paddle blades, helical stirring blades, etc. Examples thereof include a blade and a kneader, and specifically, a stirring blade having high stirring efficiency such as a full zone manufactured by Shinko Pantech Co., Ltd. and a Max Blend manufactured by Sumitomo Heavy Industries, Ltd. is preferably used. The obtained polycarbonate resin particles are then usually ground and dried. For the pulverization, a wet pulverizer is preferably used, and a super clean mill, a hammer mill, a glow mill, a homomic line mill or the like is preferably used. Hot air dryers, steam dryers and the like are preferably used for drying, but explosion-proof types are preferred. The polycarbonate resin particles thus obtained are preferably melt-kneaded and pelletized using an extruder having at least one vent port. The extruder may be single-screw or twin-screw, but a twin-screw extruder is preferred.
【００３６】また、塩化メチレンの量を低減する他の方
法として、ポリカーボネート樹脂粉粒体を押出機でペレ
ット化する際、ベント付き二軸押出機を用いてベント部
を通過する前に、ポリカーボネート樹脂に不活性物質を
添加し、この不活性物質をベント部で脱気する。ベント
付き押出機としてはベント部が二カ所以上設けられてい
る多段ベント付き押出機が好ましく、ベント数と不活性
物質の注入箇所を共に２ヵ所以上設けたものが好まし
い。不活性物質としては、水、窒素、炭酸ガスおよびヘ
プタン、ヘキサン、シクロヘキサン等の低沸点炭化水素
類が挙げられ、なかでも水、窒素、炭酸ガス、ヘプタン
が好ましく、特に水が好ましい。不活性物質の添加量は
ポリカーボネート樹脂粉粒体に対して０．２〜４重量％
が好ましく、この範囲の量の不活性物質を添加すると、
脱気効果が優れ、塩化メチレンが低減され易く好まし
い。As another method for reducing the amount of methylene chloride, when the polycarbonate resin particles are pelletized by an extruder, the polycarbonate resin particles are passed through a vent using a vented twin-screw extruder. And an inert substance is degassed at the vent. As the extruder with a vent, an extruder with a multi-stage vent having two or more vent portions is preferable, and an extruder having two or more vents and two or more inert substance injection locations is preferable. Examples of the inert substance include water, nitrogen, carbon dioxide, and low-boiling hydrocarbons such as heptane, hexane, and cyclohexane. Among them, water, nitrogen, carbon dioxide, and heptane are preferable, and water is particularly preferable. The amount of the inert substance added is 0.2 to 4% by weight based on the polycarbonate resin powder.
Is preferable, and when an amount of the inert substance in this range is added,
The deaeration effect is excellent, and methylene chloride is easily reduced, which is preferable.
【００３７】本発明において得られるポリカーボネート
樹脂には、本発明の目的を損なわない範囲で、さらに光
安定剤、着色剤、帯電防止剤、難燃剤、充填剤、滑剤等
の添加剤を加えることができる。また、他の熱可塑性樹
脂を少割合添加することもできる。また、本発明におい
て得られるポリカーボネート樹脂は、ブロー成形、押出
成形、圧縮成形、発泡成形等の溶融時に非ニュートン流
動性の要求される成形分野に好ましく用いられ、ボト
ル、カップ等の中空成形容器、照明グローブ、複写機の
パネル、ＯＡ機器のパネル、住宅用異形押出、自動車天
井裏張り等に好適に用いられ、特に中空成形容器として
好ましく用いられる。The polycarbonate resin obtained in the present invention may further contain additives such as a light stabilizer, a coloring agent, an antistatic agent, a flame retardant, a filler, a lubricant and the like within a range not to impair the object of the present invention. it can. In addition, other thermoplastic resins can be added in a small proportion. Further, the polycarbonate resin obtained in the present invention is preferably used in the molding field where non-Newtonian fluidity is required at the time of melting such as blow molding, extrusion molding, compression molding, foam molding, and the like, and bottles, hollow molded containers such as cups, It is suitably used for lighting gloves, panels for copiers, panels for OA equipment, profile extrusion for houses, car linings, etc., and is particularly preferably used as a hollow molded container.
【００３８】上述したように、本発明において得られた
ポリカーボネート樹脂ペレットは、中空成形容器として
好ましく使用される。該中空成形容器の成形には、先ず
第一の金型でプレフォームを射出成形し、次いで第二の
金型で所定温度に加熱しながら空気あるいは不活性ガス
を用いてブロー成形される方法が好ましく採用される。
プレフォームの加熱温度はポリカーボネート樹脂の二次
転移温度より３０℃以上高く、ポリカーボネート樹脂の
融点程度までの範囲が好ましい。空気あるいは不活性ガ
スの吹き込み圧力は中空容器を偏肉なく均一に成形でき
る圧力であればよく、２ｋｇｆ／ｃｍ2〜８ｋｇｆ／ｃ
ｍ2程度が好ましい。As described above, the polycarbonate resin pellets obtained in the present invention are preferably used as a hollow molded container. For molding the hollow molded container, first, a preform is injection-molded in a first mold, and then blow molded using air or an inert gas while heating to a predetermined temperature in a second mold. It is preferably adopted.
The heating temperature of the preform is 30 ° C. or more higher than the secondary transition temperature of the polycarbonate resin, and is preferably in a range up to the melting point of the polycarbonate resin. The blowing pressure of the air or the inert gas may be any pressure that can uniformly mold the hollow container without uneven thickness, from 2 kgf / cm 2 to 8 kgf / c.
m 2 is preferable.
【００３９】本発明のポリカーボネート樹脂より好適に
形成される中空成形容器としては、乳製品、清涼飲料
水、水等のボトル、カップなどが挙げられ、好ましくは
乳製品ボトル、清涼飲料水ボトル、水ボトルであり、特
に好ましくは水ボトルである。かかる中空成形容器の厚
みは、０．０７〜１０ｍｍであり、好ましくは０．０７
〜５ｍｍであり、より好ましくは０．１〜２ｍｍであ
る。この範囲の厚みは、外部圧力により変形し難く、製
品全体の重量も重くなり過ぎず適当であり好ましい。こ
こで云う厚みは、胴部の厚みであり、一般に口栓部や底
部のコーナーでは、この胴部の厚みより厚くなってい
る。Examples of the hollow molded container suitably formed from the polycarbonate resin of the present invention include dairy products, soft drinks, water bottles, cups and the like, and preferably dairy product bottles, soft drink bottles, water It is a bottle, particularly preferably a water bottle. The thickness of such a hollow molded container is 0.07 to 10 mm, preferably 0.07 to 10 mm.
To 5 mm, more preferably 0.1 to 2 mm. A thickness in this range is suitable and preferable because it is not easily deformed by external pressure and the weight of the whole product does not become too heavy. The thickness referred to here is the thickness of the trunk portion, and is generally thicker at the plug portion and the bottom corner than the thickness of the trunk portion.
【００４０】また、かかる本発明の中空成形容器には、
その外側または内側にポリエチレンテレフタレート樹
脂、ポリブチレンテレフタレート樹脂、ポリエチレンナ
フタレート樹脂、ポリブチレンナフタレート樹脂等のポ
リエステル樹脂、アクリル樹脂、ポリエチレン樹脂、ポ
リプロピレン樹脂等のポリオレフィン樹脂、ポリアミド
樹脂等の熱可塑性樹脂層を設けてもよく、その外側に擦
過防止のハードコート層、印刷層を設けてもよい。Further, the hollow molded container of the present invention includes:
A thermoplastic resin layer such as a polyester resin such as a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polyethylene naphthalate resin, a polybutylene naphthalate resin, a polyolefin resin such as an acrylic resin, a polyethylene resin and a polypropylene resin, and a polyamide resin on the outside or inside thereof. May be provided, and a hard coat layer and a printing layer for preventing abrasion may be provided on the outside.
【００４１】[0041]
【発明の実施の形態】以下に実施例を挙げて本発明をさ
らに説明する。なお実施例中の部は重量部であり、％は
重量％である。なお、評価は下記の方法によった。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be further described below with reference to examples. Parts in Examples are parts by weight, and% is% by weight. The evaluation was based on the following method.
【００４２】（１）粘度平均分子量：ポリカーボネート
樹脂０．７ｇを塩化メチレン１００ｍｌに溶解し、２０
℃にて測定した。(1) Viscosity average molecular weight: 0.7 g of a polycarbonate resin was dissolved in 100 ml of methylene chloride,
Measured at ° C.
【００４３】（２）ＭＦＲ：ＪＩＳ Ｋ ７２１０に準
拠し温度２８０℃、荷重２．１６ｋｇｆにて測定した。(2) MFR: MFR was measured at a temperature of 280 ° C. and a load of 2.16 kgf according to JIS K7210.
【００４４】（３）構造粘性指数：構造粘性指数Ｎは、
ポリカーボネート樹脂ペレットを高化式フローテスター
（島津製作所（株）製）のシリンダーに入れ、温度を２
８０℃に一定にして、加えた圧力Ｐ（１００〜１８０ｋ
ｇ／ｃｍ2）とそれぞれの溶融樹脂の流出量Ｑ（ｍＬ／
ｓｅｃ）を測定し、それぞれの値を両対数グラフにプロ
ットして得られる回帰直線の勾配から求めた。(3) Structural viscosity index: The structural viscosity index N is
Put the polycarbonate resin pellets into the cylinder of the Koka type flow tester (manufactured by Shimadzu Corporation) and set the temperature to 2
The pressure P (100 to 180 k
g / cm 2 ) and the flow rate Q (mL / mL) of each molten resin.
sec) was measured, and each value was determined from the slope of a regression line obtained by plotting the values on a log-log graph.
【００４５】（４）二価フェノール（ビスフェノール
Ａ）の残存量：ポリカーボネート樹脂３ｇを塩化メチレ
ン３０ｍｌに溶解し攪拌下にアセトニトリル２７０ｍｌ
を滴下後、３０ｍｌまで濃縮し、析出物を濾過後、アセ
トニトリルを加え５０ｍｌに定容し、水／アセトニトリ
ル系グラジエント溶離液を用いたＨＰＬＣにて２７０ｎ
ｍの波長で測定した。(4) Residual amount of dihydric phenol (bisphenol A): 3 g of polycarbonate resin was dissolved in 30 ml of methylene chloride, and 270 ml of acetonitrile was stirred.
Was added dropwise, the mixture was concentrated to 30 ml, and the precipitate was filtered. Acetonitrile was added to make the volume constant to 50 ml, and 270 n by HPLC using a water / acetonitrile gradient eluent.
It was measured at a wavelength of m.
【００４６】（５）塩化メチレンの残存量：ヘッドスペ
ース法（２５０℃、２時間）により、ＦＩＤ−ＧＣにて
測定した。(5) Residual amount of methylene chloride: measured by FID-GC according to the headspace method (250 ° C., 2 hours).
【００４７】（６）熱安定性：試料ペレットを１２０℃
で５時間乾燥した後射出成形機（住友重機（株）製ＳＧ
−１５０）を用い、シリンダー温度３４０℃で１０分間
滞留させたものとさせないものの試験片（縦７０ｍｍ、
横５０ｍｍ、厚み２ｍｍ）をそれぞれ作成し、その色相
の変化（△Ｅ）を測定した。色相の変化は、ＪＩＳ Ｚ
−８７３０に従い、色差計（日本電色（株）製モデルＺ
−１００１ＤＰ）を用いて、それぞれのＬ、ａ、ｂ値を
測定して、次式により算出した。(6) Thermal stability: The sample pellet was heated at 120 ° C.
After drying for 5 hours with an injection molding machine (SG manufactured by Sumitomo Heavy Industries, Ltd.)
-150), a test piece (70 mm long,
(Width 50 mm, thickness 2 mm), respectively, and the change in hue (ΔE) thereof was measured. Hue changes are based on JIS Z
Color difference meter (Model Z manufactured by Nippon Denshoku Co., Ltd.)
-100DP), the respective L, a, and b values were measured and calculated by the following equation.
【００４８】[0048]
【数１】 (Equation 1)
【００４９】（７）湿熱劣化性：試料ペレットを１２０
℃で５時間乾燥した後射出成形機（住友重機（株）製Ｓ
Ｇ−１５０）を用いシリンダー温度３００℃で試験片
（縦７０ｍｍ、横５０ｍｍ、厚み２ｍｍ）を成形し、９
５℃の熱水中に２４時間浸漬した後、取り出した試験片
１０枚を顕微鏡にて観察し発生したボイド数を試験片１
枚当たりの数で示した。(7) Degradation by wet heat: 120
After drying at 5 ° C for 5 hours, the injection molding machine (Sumitomo Heavy Industries, Ltd. S
G-150) to form a test piece (70 mm long, 50 mm wide, 2 mm thick) at a cylinder temperature of 300 ° C.
After being immersed in hot water at 5 ° C. for 24 hours, 10 test pieces taken out were observed with a microscope, and the number of voids generated was measured for test piece 1.
The number was shown per sheet.
【００５０】（８）中空容器落下テスト：１．３ｍｍ厚
の５ガロンの水ボトルを２１０℃で射出延伸ブロー成形
し、９５℃の熱水中に２４時間浸漬した後、水を満たし
て６ｍの高さから地上に落下させ、破壊状況を観察し
た。完全に破壊した場合を×、ひび割れ程度を△、割れ
なかった場合を○とした。(8) Hollow container drop test: A 5-gallon water bottle having a thickness of 1.3 mm was injection-stretched blow-molded at 210 ° C., immersed in hot water at 95 ° C. for 24 hours, and then filled with water and filled with 6 m water. It was dropped from the height to the ground and the state of destruction was observed. The case where the sample was completely broken was evaluated as X, the degree of cracking was evaluated as Δ, and the case where no crack occurred was evaluated as 割 れ.
【００５１】［実施例１］温度計、攪拌機、還流冷却器
付き反応器にイオン交換水３６１部、４８％水酸化ナト
リウム水溶液１２４部、ハイドロサルファイト０．２部
を仕込み、攪拌下にビスフェノールＡ１１４部を溶解し
た後、塩化メチレン５０３部を加えて、２０〜２５℃で
ホスゲン６９．３部を約４０分かけて吹き込み反応させ
ポリカーボネートオリゴマーを得た。この反応混合液の
温度を３０℃にした後ｐ−ｔｅｒｔ−ブチルフェノール
３．１５部と１０％水酸化ナトリウム水溶液６ｍｌに溶
解した１，１，１−トリス（４−ヒドロキシフェニル）
エタン１．２２部を加え、攪拌して乳化後、４％水酸化
ナトリウム水溶液２４７部に溶解したビスフェノールＡ
２２．８部を加えて激しく攪拌して高乳化させ、４時間
攪拌して反応を完結させた。反応終了後、塩化メチレン
４００部を加えて希釈して、応を完結させた。反応終了
後、塩化メチレン２４６部を加えて希釈して、分岐ポリ
カーボネート樹脂１４重量％濃度の塩化メチレン溶液と
した後、多孔板付遠心抽出機（川崎エンジニアリング
（株）製ＫＣＣ遠心抽出機）を用いて０．５％水酸化ナ
トリウム水溶液を流量１０００ｍｌ／ｍｉｎ、有機相を
流量１０００ｍｌ／ｍｉｎの速度で供給し、３５００ｒ
ｐｍの条件で処理した後、有機相を塩酸酸性とし、その
後水洗を繰り返し、水相の導電率がイオン交換水と殆ど
同じになったところで塩化メチレンを蒸発して分岐ポリ
カーボネート樹脂パウダーを得た。このパウダーを乾燥
後、トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）
ホスファイトを３００ｐｐｍ、ステアリン酸モノグリセ
ライドを４５０ｐｐｍ加えて、水添箇所とその直後にベ
ント口を設けた二軸押出機にてポリカーボネート樹脂に
対して１重量％のイオン交換水を添加しながらベント口
から１０ｍｍＨｇの減圧度で吸引して押出しペレット化
した。得られたペレットの分子量は２３，０００（比粘
度は０．４１８）、ＭＦＲは４．０ｇ／１０ｍｉｎ、構
造粘性指数は１．８０であった。このペレット中のビス
フェノールＡは６ｐｐｍ、塩化メチレンは０．８ｐｐｍ
であった。得られたペレットを射出成形して試験片を作
成し、熱安定性および湿熱劣化性を評価した。また、水
ボトルを射出延伸ブロー成形し、得られた水ボトルを湿
熱処理し落下テストを行った。これらの結果を表１に示
した。また、水ボトルを約１ヶ月の間に３００，０００
ショット成形した後、金型表面の錆具合を観察したとこ
ろ、鏡面部分に曇りは生じていなかった。Example 1 A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 361 parts of ion-exchanged water, 124 parts of a 48% aqueous sodium hydroxide solution and 0.2 parts of hydrosulfite, and stirred with bisphenol A114. After dissolving the parts, 503 parts of methylene chloride was added, and 69.3 parts of phosgene was blown into the mixture at 20 to 25 ° C. for about 40 minutes to obtain a polycarbonate oligomer. After adjusting the temperature of the reaction mixture to 30 ° C., 3.15 parts of p-tert-butylphenol and 1,1,1-tris (4-hydroxyphenyl) dissolved in 6 ml of a 10% aqueous sodium hydroxide solution were used.
Ethane (1.22 parts) was added, stirred and emulsified, and then bisphenol A dissolved in 247 parts of a 4% aqueous sodium hydroxide solution.
22.8 parts were added, and the mixture was vigorously stirred to highly emulsify, followed by stirring for 4 hours to complete the reaction. After the reaction was completed, 400 parts of methylene chloride was added for dilution to complete the reaction. After the completion of the reaction, 246 parts of methylene chloride was added to dilute the mixture to obtain a methylene chloride solution having a concentration of 14% by weight of the branched polycarbonate resin, and then using a centrifugal extractor with a perforated plate (KCC centrifugal extractor manufactured by Kawasaki Engineering Co., Ltd.). A 0.5% aqueous sodium hydroxide solution is supplied at a flow rate of 1000 ml / min, and the organic phase is supplied at a flow rate of 1000 ml / min.
After treatment under pm conditions, the organic phase was acidified with hydrochloric acid, and then repeatedly washed with water. When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, methylene chloride was evaporated to obtain a branched polycarbonate resin powder. After drying this powder, tris (2,4-di-tert-butylphenyl)
300 ppm of phosphite and 450 ppm of monoglyceride stearate were added, and 1% by weight of ion-exchanged water was added to the polycarbonate resin from the vent port using a twin-screw extruder provided with a vent port immediately after the hydrogenation point. It was extruded into pellets by suction at a reduced pressure of 10 mmHg. The molecular weight of the obtained pellet was 23,000 (specific viscosity was 0.418), the MFR was 4.0 g / 10 min, and the structural viscosity index was 1.80. 6 ppm of bisphenol A and 0.8 ppm of methylene chloride in the pellets
Met. A test piece was prepared by injection molding of the obtained pellet, and the thermal stability and wet heat deterioration were evaluated. Further, the water bottle was subjected to injection stretch blow molding, and the obtained water bottle was subjected to a wet heat treatment and subjected to a drop test. The results are shown in Table 1. Also, water bottles should be 300,000 for about one month.
After the shot molding, the degree of rust on the surface of the mold was observed. As a result, no fogging occurred on the mirror surface.
【００５２】［実施例２］実施例１と同様にして合成し
た分岐ポリカーボネート樹脂１４重量％濃度の塩化メチ
レン溶液を実施例１と同様の多孔板付き遠心抽出機に流
量１０００ｍｌ／ｍｉｎの速度で、１．０％水酸化ナト
リウム水溶液を流量５００ｍｌ／ｍｉｎの速度で供給
し、３５００ｒｐｍの条件で処理した後、実施例１と同
様にして水洗し、分岐ポリカーボネート樹脂の塩化メチ
レン溶液を得た。次に、滴下ノズル、排出口、脱揮口を
備えたジャケット付１００Ｌ攪拌槽に、板状バッフルを
備えたフルゾーン攪拌翼（神鋼パンテック（株）製）を
装着し、イオン交換水８０Ｌと平均粒径０．６ｍｍのビ
スフェノールＡから得られたポリカーボネート樹脂パウ
ダー５ｋｇを仕込み、均一に攪拌しながら４５℃に内温
を保ちつつ、得られた分岐ポリカーボネート樹脂の塩化
メチレン溶液を３．５ｋｇ／ｍｉｎ、ヘプタンを４９０
ｇ／ｍｉｎ、４５℃の温水を２．５ｋｇ／ｍｉｎの速度
で定量供給し造粒した。得られた分岐ポリカーボネート
樹脂粉粒体のスラリーは排出口よりオーバーフローにて
定量的に取り出した。排出された粉粒体スラリーを湿式
粉砕し、１４５℃で３時間乾燥した後、実施例１と同様
にしてイオン交換水を添加しながら押出しペレット化し
た。このペレット中のビスフェノールＡは５ｐｐｍ、塩
化メチレンは０．７ｐｐｍであった。このものを射出成
形して熱安定性および湿熱劣化性を評価した。また、水
ボトルを射出延伸ブロー成形し、得られた水ボトルを湿
熱処理し落下テストを行った。これらの結果を表１に示
した。また、水ボトルを約１ヶ月の間に３００，０００
ショット成形した後、金型表面の錆具合を観察したとこ
ろ、鏡面部分に曇りは生じていなかった。Example 2 A 14% by weight methylene chloride solution of a branched polycarbonate resin synthesized in the same manner as in Example 1 was introduced into a centrifugal extractor with a perforated plate as in Example 1 at a flow rate of 1000 ml / min. A 1.0% aqueous solution of sodium hydroxide was supplied at a flow rate of 500 ml / min, treated at 3500 rpm, and washed in the same manner as in Example 1 to obtain a methylene chloride solution of a branched polycarbonate resin. Next, a full-zone stirring blade (manufactured by Shinko Pantech Co., Ltd.) equipped with a plate-shaped baffle was attached to a 100-L stirring tank equipped with a jacket provided with a dripping nozzle, a discharge port, and a devolatilization port. 5 kg of a polycarbonate resin powder obtained from bisphenol A having a particle size of 0.6 mm was charged, and while maintaining the internal temperature at 45 ° C. while uniformly stirring, a methylene chloride solution of the obtained branched polycarbonate resin was 3.5 kg / min. 490 heptane
g / min, 45 ° C. hot water was supplied at a constant rate of 2.5 kg / min to perform granulation. The slurry of the obtained branched polycarbonate resin particles was quantitatively taken out from the outlet through overflow. The discharged granule slurry was wet-pulverized, dried at 145 ° C. for 3 hours, and extruded into pellets in the same manner as in Example 1 while adding ion-exchanged water. Bisphenol A in this pellet was 5 ppm, and methylene chloride was 0.7 ppm. This was injection molded and evaluated for thermal stability and wet heat deterioration. Further, the water bottle was subjected to injection stretch blow molding, and the obtained water bottle was subjected to a wet heat treatment and subjected to a drop test. The results are shown in Table 1. Also, water bottles should be 300,000 for about one month.
After the shot molding, the degree of rust on the surface of the mold was observed. As a result, no fogging occurred on the mirror surface.
【００５３】［実施例３］実施例１と同様にして合成し
た分岐ポリカーボネート樹脂１４重量％濃度の塩化メチ
レン溶液を実施例１と同様の多孔板付き遠心抽出機に流
量１０００ｍｌ／ｍｉｎの速度で、３．０％水酸化ナト
リウム水溶液を流量３３０ｍｌ／ｍｉｎの速度で供給
し、３５００ｒｐｍの条件で処理した後、実施例１と同
様にして水洗し、分岐ポリカーボネート樹脂の塩化メチ
レン溶液を得た。この溶液から塩化メチレンを蒸発、除
去して、塩化メチレンの含有量が約３０％のポリカーボ
ネートパウダーを得て、このパウダーに分岐ポリカーボ
ネート樹脂に対して１０％のヘプタンを加えて、その
後、溶媒を留去して乾燥しパウダーを得た。このパウダ
ーに実施例１と同様の添加剤を加え、実施例１と同様に
して押出しペレット化した。このペレット中のビスフェ
ノールＡは３ｐｐｍ、塩化メチレンは０．５ｐｐｍであ
った。このものを射出成形して熱安定性および湿熱劣化
性を評価した。また、水ボトルを射出延伸ブロー成形
し、得られた水ボトルを湿熱処理し落下テストを行っ
た。これらの結果を表１に示した。また、水ボトルを約
１ヶ月の間に３００，０００ショット成形した後、金型
表面の錆具合を観察したところ、鏡面部分に曇りは生じ
ていなかった。Example 3 A 14% by weight methylene chloride solution of a branched polycarbonate resin synthesized in the same manner as in Example 1 was introduced into a centrifugal extractor with a perforated plate as in Example 1 at a flow rate of 1000 ml / min. A 3.0% aqueous sodium hydroxide solution was supplied at a flow rate of 330 ml / min, and the mixture was treated under the conditions of 3500 rpm, and then washed with water in the same manner as in Example 1 to obtain a methylene chloride solution of a branched polycarbonate resin. The methylene chloride was evaporated and removed from this solution to obtain a polycarbonate powder having a methylene chloride content of about 30%. To this powder was added 10% heptane based on the branched polycarbonate resin, and then the solvent was distilled off. It was then dried to obtain a powder. The same additives as in Example 1 were added to this powder, and extruded into pellets in the same manner as in Example 1. Bisphenol A in this pellet was 3 ppm, and methylene chloride was 0.5 ppm. This was injection molded and evaluated for thermal stability and wet heat deterioration. Further, the water bottle was subjected to injection stretch blow molding, and the obtained water bottle was subjected to a wet heat treatment and subjected to a drop test. The results are shown in Table 1. After forming the water bottle for 300,000 shots in about one month, the rust condition of the mold surface was observed. As a result, no fogging occurred on the mirror surface.
【００５４】［実施例４］実施例１と同様にして合成し
た分岐ポリカーボネート樹脂１４重量％濃度の塩化メチ
レン溶液を錨翼とパドル翼を二段に取り付けた混合槽に
入れ、これに１．０％水酸化ナトリウム水溶液を塩化メ
チレン溶液と同容量加えて２０分間激しく攪拌した後有
機相を分離し、かかる有機相を実施例１と同様にして水
洗し、パウダー化し、次いで押出ししてペレットを得
た。このペレット中のビスフェノールＡは５ｐｐｍ、塩
化メチレンは０．８ｐｐｍであった。このものを射出成
形して熱安定性および湿熱劣化性を評価した。また、水
ボトルを射出延伸ブロー成形し、得られた水ボトルを湿
熱処理し落下テストを行った。これらの結果を表１に示
した。また、水ボトルを約１ヶ月の間に３００，０００
ショット成形した後、金型表面の錆具合を観察したとこ
ろ、鏡面部分に曇りは生じていなかった。Example 4 A methylene chloride solution having a concentration of 14% by weight of a branched polycarbonate resin synthesized in the same manner as in Example 1 was placed in a mixing tank having two stages of anchor blades and paddle blades. % Aqueous sodium hydroxide solution and the same volume as the methylene chloride solution, and vigorously stirred for 20 minutes. The organic phase was separated, washed with water and powdered as in Example 1, and extruded to obtain pellets. Was. Bisphenol A in this pellet was 5 ppm, and methylene chloride was 0.8 ppm. This was injection molded and evaluated for thermal stability and wet heat deterioration. Further, the water bottle was subjected to injection stretch blow molding, and the obtained water bottle was subjected to a wet heat treatment and subjected to a drop test. The results are shown in Table 1. Also, water bottles should be 300,000 for about one month.
After the shot molding, the degree of rust on the surface of the mold was observed. As a result, no fogging occurred on the mirror surface.
【００５５】［実施例５］実施例１において、１，１，
１−トリス（４−ヒドロキシフェニル）エタンを使用せ
ず、ｐ−ｔｅｒｔ−ブチルフェノール３．１５部を０．
２７部とした以外は実施例１と同様にして、分子量１１
３，０００（比粘度は２．１６１）の線状高分子量ポリ
カーボネート樹脂パウダーＡを得た。[Embodiment 5] In the first embodiment, 1,1,1,
Without using 1-tris (4-hydroxyphenyl) ethane, 3.15 parts of p-tert-butylphenol was added to 0.1.
The same procedure as in Example 1 was carried out except that the amount was 27 parts, and the molecular weight was 11
3,000 (specific viscosity: 2.161) linear high molecular weight polycarbonate resin powder A was obtained.
【００５６】また、実施例１において、１，１，１−ト
リス（４−ヒドロキシフェニル）エタンを使用しないこ
と以外は実施例１と同様にして、分子量２２，６００
（比粘度は０．４１１）の線状ポリカーボネート樹脂パ
ウダーＢを得た。The procedure of Example 1 was repeated, except that 1,1,1-tris (4-hydroxyphenyl) ethane was not used, and the molecular weight was 22,600.
A linear polycarbonate resin powder B having a specific viscosity of 0.411 was obtained.
【００５７】上記線状高分子量ポリカーボネート樹脂パ
ウダーＡ１０部と上記線状ポリカーボネート樹脂パウダ
ーＢ９０部を混合して、ポリカーボネート樹脂パウダー
を得た。このパウダーに実施例１と同様の添加剤を加
え、実施例１と同様にして押出しペレット化した。得ら
れたペレットの分子量は３２，８００（比粘度は０．５
８６）、ＭＦＲは１．９ｇ／１０ｍｉｎ、構造粘性指数
は１．６０であった。このペレット中のビスフェノール
Ａは３ｐｐｍ、塩化メチレンは０．５ｐｐｍであった。
このペレット中のビスフェノールＡは６ｐｐｍ、塩化メ
チレンは０．９ｐｐｍであった。得られたペレットを射
出成形して試験片を作成し、熱安定性および湿熱劣化性
を評価した。また、水ボトルを射出延伸ブロー成形し、
得られた水ボトルを湿熱処理し落下テストを行った。こ
れらの結果を表１に示した。また、水ボトルを約１ヶ月
の間に３００，０００ショット成形した後、金型表面の
錆具合を観察したところ、鏡面部分に曇りは生じていな
かった。10 parts of the above-mentioned linear high molecular weight polycarbonate resin powder A and 90 parts of the above-mentioned linear polycarbonate resin powder B were mixed to obtain a polycarbonate resin powder. The same additives as in Example 1 were added to this powder, and extruded into pellets in the same manner as in Example 1. The molecular weight of the obtained pellet is 32,800 (specific viscosity is 0.5
86), the MFR was 1.9 g / 10 min, and the structural viscosity index was 1.60. Bisphenol A in this pellet was 3 ppm, and methylene chloride was 0.5 ppm.
Bisphenol A in this pellet was 6 ppm, and methylene chloride was 0.9 ppm. A test piece was prepared by injection molding of the obtained pellet, and the thermal stability and wet heat deterioration were evaluated. In addition, water bottles are injection stretch blow molded,
The obtained water bottle was subjected to a wet heat treatment and subjected to a drop test. The results are shown in Table 1. After forming the water bottle for 300,000 shots in about one month, the rust condition of the mold surface was observed. As a result, no fogging occurred on the mirror surface.
【００５８】［実施例６］撹拌機及び蒸留塔を備えた反
応器に２，２−ビス（４−ヒドロキシフェニル）プロパ
ン４９．６部、ジフェニルカーボネート４９．２部、
１，１，１−トリス（４−ヒドロキシフェニル）エタン
０．４部及び触媒として水酸化ナトリウム０．００００
１部とテトラメチルアンモニウムヒドロキシド０．００
１６部を仕込み、窒素置換した。この混合物を１５０℃
まで加熱して撹拌しながら溶解させた。次いで、減圧度
を３０Ｔｏｒｒとして２００℃まで加熱しながら１時間
で大半のフェノールを留去し、更に２７０℃まで温度を
上げ、減圧度を１Ｔｏｒｒとして３時間重合反応を行な
い分岐ポリカーボネート樹脂を得た。この分岐ポリカー
ボネート樹脂を塩化メチレンに溶解して分岐ポリカーボ
ネート樹脂１０重量％濃度の塩化メチレン溶液とし、こ
の溶液を実施例１と同様に遠心抽出機で処理し、パウダ
ー化し、このパウダーに実施例１と同様の添加剤を加
え、実施例１と同様にして押出しペレット化した。得ら
れたペレットの分子量は２４，０００（比粘度は０．４
３６）、ＭＦＲは４．１ｇ／１０ｍｉｎ、構造粘性指数
は１．７９であった。このペレット中のビスフェノール
Ａは７ｐｐｍ、塩化メチレンは０．８ｐｐｍであった。
得られたペレットを射出成形して試験片を作成し、熱安
定性および湿熱劣化性を評価した。また、水ボトルを射
出延伸ブロー成形し、得られた水ボトルを湿熱処理し落
下テストを行った。これらの結果を表１に示した。ま
た、水ボトルを約１ヶ月の間に３００，０００ショット
成形した後、金型表面の錆具合を観察したところ、鏡面
部分に曇りは生じていなかった。Example 6 A reactor equipped with a stirrer and a distillation column was charged with 49.6 parts of 2,2-bis (4-hydroxyphenyl) propane, 49.2 parts of diphenyl carbonate,
0.4 parts of 1,1,1-tris (4-hydroxyphenyl) ethane and 0.0000 sodium hydroxide as a catalyst
1 part and tetramethylammonium hydroxide 0.00
16 parts were charged and replaced with nitrogen. 150 ° C
And dissolved with stirring. Next, while heating to 200 ° C. at a reduced pressure of 30 Torr, most of the phenol was distilled off in 1 hour, the temperature was further raised to 270 ° C., and a polymerization reaction was performed for 3 hours at a reduced pressure of 1 Torr to obtain a branched polycarbonate resin. This branched polycarbonate resin was dissolved in methylene chloride to form a methylene chloride solution having a concentration of 10% by weight of the branched polycarbonate resin, and the solution was treated with a centrifugal extractor in the same manner as in Example 1 to form a powder. The same additives were added, and the mixture was extruded and pelletized in the same manner as in Example 1. The molecular weight of the obtained pellet was 24,000 (specific viscosity was 0.4
36), the MFR was 4.1 g / 10 min, and the structural viscosity index was 1.79. Bisphenol A in this pellet was 7 ppm, and methylene chloride was 0.8 ppm.
A test piece was prepared by injection molding of the obtained pellet, and the thermal stability and wet heat deterioration were evaluated. Further, the water bottle was subjected to injection stretch blow molding, and the obtained water bottle was subjected to a wet heat treatment and subjected to a drop test. The results are shown in Table 1. After forming the water bottle for 300,000 shots in about one month, the rust condition of the mold surface was observed. As a result, no fogging occurred on the mirror surface.
【００５９】［比較例１］実施例１において、反応終了
後のポリカーボネート樹脂の塩化メチレン溶液を水酸化
ナトリウムを用いた遠心抽出機での処理を行わず、塩酸
酸性としてその後水洗し、また、二軸押出機の代わりに
単軸押出機を用いて、イオン交換水は添加せずベントか
らの脱気のみ行った以外は実施例１と同様にしてペレッ
トを得た。このペレット中のビスフェノールＡは１８ｐ
ｐｍ、塩化メチレンは３０ｐｐｍであった。このものを
射出成形して熱安定性および湿熱劣化性を評価した。ま
た、水ボトルを射出延伸ブロー成形し、得られた水ボト
ルを湿熱処理し落下テストを行った。これらの結果を表
１に示した。また、水ボトルを約１ヶ月の間に３０００
０ショット成形した後、金型表面の錆具合を観察したと
ころ、鏡面部分にやや曇りの生じているところが見られ
た。[Comparative Example 1] In Example 1, the methylene chloride solution of the polycarbonate resin after the completion of the reaction was not treated with a centrifugal extractor using sodium hydroxide, but was acidified with hydrochloric acid and then washed with water. Pellets were obtained in the same manner as in Example 1 except that a single screw extruder was used instead of the screw extruder, and only degassing from the vent was performed without adding ion-exchanged water. Bisphenol A in this pellet is 18p
pm and methylene chloride were 30 ppm. This was injection molded and evaluated for thermal stability and wet heat deterioration. Further, the water bottle was subjected to injection stretch blow molding, and the obtained water bottle was subjected to a wet heat treatment and subjected to a drop test. The results are shown in Table 1. In addition, 3000 bottles of water for about one month
After the 0-shot molding, the rust condition of the mold surface was observed, and it was found that the mirror surface portion was slightly fogged.
【００６０】［比較例２］実施例１において、０．５％
水酸化ナトリウム水溶液を０．０５％水酸化ナトリウム
水溶液に代える以外は実施例１と同様にしてペレットを
得た。このペレット中のビスフェノールＡは１５ｐｐ
ｍ、塩化メチレンは２５ｐｐｍであった。このものを射
出成形して熱安定性および湿熱劣化性を評価した。ま
た、水ボトルを射出延伸ブロー成形し、得られた水ボト
ルを湿熱処理し落下テストを行った。これらの結果を表
１に示した。また、水ボトルを約１ヶ月の間に３０００
０ショット成形した後、金型表面の錆具合を観察したと
ころ、鏡面部分にやや曇りの生じているところが見られ
た。[Comparative Example 2] In Example 1, 0.5%
Pellets were obtained in the same manner as in Example 1 except that the aqueous sodium hydroxide solution was replaced with a 0.05% aqueous sodium hydroxide solution. Bisphenol A in this pellet is 15pp
m and methylene chloride were 25 ppm. This was injection molded and evaluated for thermal stability and wet heat deterioration. Further, the water bottle was subjected to injection stretch blow molding, and the obtained water bottle was subjected to a wet heat treatment and subjected to a drop test. The results are shown in Table 1. In addition, 3000 bottles of water for about one month
After the 0-shot molding, the rust condition of the mold surface was observed, and it was found that the mirror surface portion was slightly fogged.
【００６１】［比較例３］実施例１において、０．５％
水酸化ナトリウム水溶液を６％水酸化ナトリウム水溶液
に代え、６％水酸化ナトリウム水溶液の流量を５００ｍ
Ｌ／ｍｉｎとする以外は実施例１と同様にしてペレット
を得た。このペレット中のビスフェノールＡは２６ｐｐ
ｍ、塩化メチレンは０．９ｐｐｍであった。このものを
射出成形して熱安定性および湿熱劣化性を評価した。ま
た、水ボトルを射出延伸ブロー成形し、得られた水ボト
ルを湿熱処理し落下テストを行った。これらの結果を表
１に示した。また、水ボトルを約１ヶ月の間に３０００
０ショット成形した後、金型表面の錆具合を観察したと
ころ、鏡面部分に曇りは生じていなかった。[Comparative Example 3] In Example 1, 0.5%
The aqueous sodium hydroxide solution was replaced with a 6% aqueous sodium hydroxide solution, and the flow rate of the 6% aqueous sodium hydroxide solution was 500 m.
Pellets were obtained in the same manner as in Example 1 except that L / min was used. Bisphenol A in this pellet is 26pp
m and methylene chloride were 0.9 ppm. This was injection molded and evaluated for thermal stability and wet heat deterioration. Further, the water bottle was subjected to injection stretch blow molding, and the obtained water bottle was subjected to a wet heat treatment and subjected to a drop test. The results are shown in Table 1. In addition, 3000 bottles of water for about one month
After the 0-shot molding, the rust condition of the mold surface was observed. As a result, no fogging occurred on the mirror surface.
【００６２】[0062]
【表１】 [Table 1]
【００６３】[0063]
【発明の効果】本発明のポリカーボネート樹脂は、残存
する二価フェノールが著しく少なく、熱安定性に優れ、
且つ湿熱劣化性にも優れたものであり、かかるポリカー
ボネート樹脂は中空成形容器として好適に用いられその
工業的効果は格別のものがある。The polycarbonate resin of the present invention has extremely low residual dihydric phenol, excellent heat stability,
In addition, the polycarbonate resin is excellent in wet heat deterioration property, and such a polycarbonate resin is suitably used as a hollow molded container, and its industrial effect is remarkable.
Claims (3)
カーボネート樹脂であって、該ポリカーボネート樹脂中
に残存する二価フェノールの量が１０ｐｐｍ以下である
ポリカーボネート樹脂。1. A polycarbonate resin having a structural viscosity index of 1.36 or more, wherein the amount of dihydric phenol remaining in the polycarbonate resin is 10 ppm or less.
り形成された中空成形容器。2. A hollow molded container formed from the polycarbonate resin according to claim 1.
水ボトルまたは水ボトルである請求項２記載の中空成形
容器。3. The hollow molded container according to claim 2, wherein the hollow molded container is a dairy product bottle, a soft drink bottle or a water bottle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11686698A JPH11302370A (en) | 1998-04-27 | 1998-04-27 | Polycarbonate resin and hollow molded container |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11686698A JPH11302370A (en) | 1998-04-27 | 1998-04-27 | Polycarbonate resin and hollow molded container |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11302370A true JPH11302370A (en) | 1999-11-02 |
Family
ID=14697578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11686698A Pending JPH11302370A (en) | 1998-04-27 | 1998-04-27 | Polycarbonate resin and hollow molded container |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11302370A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001342248A (en) * | 2000-06-01 | 2001-12-11 | Teijin Ltd | Method for producing aromatic polycarbonate |
| JP2002226571A (en) * | 2001-02-06 | 2002-08-14 | Teijin Ltd | Copolymerized polycarbonate, method for producing the same and resin composition |
| JP2005336332A (en) * | 2004-05-27 | 2005-12-08 | Teijin Chem Ltd | Method for producing branched polycarbonate resin |
| JP2010132929A (en) * | 2002-04-22 | 2010-06-17 | Mitsubishi Chemicals Corp | Method of producing aromatic polycarbonate composition |
| US8030400B2 (en) | 2006-08-01 | 2011-10-04 | Sabic Innovative Plastics Ip B.V. | Thermoplastic polycarbonate compositions with improved chemical and scratch resistance |
| JP2012006998A (en) * | 2010-06-22 | 2012-01-12 | Teijin Chem Ltd | Polycarbonate resin-made hollow container having carbon film coating thereon |
| WO2012108510A1 (en) | 2011-02-11 | 2012-08-16 | 三菱瓦斯化学株式会社 | Process for manufacturing branched aromatic polycarbonate resin with desired degree of branching |
| US8871865B2 (en) | 2006-08-01 | 2014-10-28 | Sabic Global Technologies B.V. | Flame retardant thermoplastic polycarbonate compositions |
-
1998
- 1998-04-27 JP JP11686698A patent/JPH11302370A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001342248A (en) * | 2000-06-01 | 2001-12-11 | Teijin Ltd | Method for producing aromatic polycarbonate |
| JP2002226571A (en) * | 2001-02-06 | 2002-08-14 | Teijin Ltd | Copolymerized polycarbonate, method for producing the same and resin composition |
| JP4713750B2 (en) * | 2001-02-06 | 2011-06-29 | 帝人株式会社 | Copolycarbonate, process for producing the same, and resin composition |
| JP2010132929A (en) * | 2002-04-22 | 2010-06-17 | Mitsubishi Chemicals Corp | Method of producing aromatic polycarbonate composition |
| JP2005336332A (en) * | 2004-05-27 | 2005-12-08 | Teijin Chem Ltd | Method for producing branched polycarbonate resin |
| US8030400B2 (en) | 2006-08-01 | 2011-10-04 | Sabic Innovative Plastics Ip B.V. | Thermoplastic polycarbonate compositions with improved chemical and scratch resistance |
| US8871865B2 (en) | 2006-08-01 | 2014-10-28 | Sabic Global Technologies B.V. | Flame retardant thermoplastic polycarbonate compositions |
| JP2012006998A (en) * | 2010-06-22 | 2012-01-12 | Teijin Chem Ltd | Polycarbonate resin-made hollow container having carbon film coating thereon |
| WO2012108510A1 (en) | 2011-02-11 | 2012-08-16 | 三菱瓦斯化学株式会社 | Process for manufacturing branched aromatic polycarbonate resin with desired degree of branching |
| US8969505B2 (en) | 2011-02-11 | 2015-03-03 | Mitsubishi Gas Chemical Company, Inc. | Process for manufacturing branched aromatic polycarbonate resin with desired degree of branching |
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