CN102076743B - 聚碳酸酯树脂片材 - Google Patents
聚碳酸酯树脂片材 Download PDFInfo
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- CN102076743B CN102076743B CN2009801253527A CN200980125352A CN102076743B CN 102076743 B CN102076743 B CN 102076743B CN 2009801253527 A CN2009801253527 A CN 2009801253527A CN 200980125352 A CN200980125352 A CN 200980125352A CN 102076743 B CN102076743 B CN 102076743B
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- polycarbonate resin
- sheet
- heat shrink
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- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 45
- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims description 72
- 238000001816 cooling Methods 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 35
- 238000003490 calendering Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 3
- -1 cyclic carbonate compound Chemical class 0.000 description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 20
- 238000003856 thermoforming Methods 0.000 description 20
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000012695 Interfacial polymerization Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 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 3
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical group CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 2
- ZBMWIKZBITYTCF-UHFFFAOYSA-N 4-[2,3-di(propan-2-yl)phenyl]phenol Chemical compound CC(C)C1=CC=CC(C=2C=CC(O)=CC=2)=C1C(C)C ZBMWIKZBITYTCF-UHFFFAOYSA-N 0.000 description 2
- PRRINTZNQPGZHB-UHFFFAOYSA-N 4-ethyl-2,6-dimethylphenol Chemical compound CCC1=CC(C)=C(O)C(C)=C1 PRRINTZNQPGZHB-UHFFFAOYSA-N 0.000 description 2
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- KVBVKLTZLPFPQN-UHFFFAOYSA-N ClC1=C(C=CC=C1)C1=CC=CC=C1.C(O)(O)=O Chemical compound ClC1=C(C=CC=C1)C1=CC=CC=C1.C(O)(O)=O KVBVKLTZLPFPQN-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010998 test method Methods 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
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 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
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ODNRTOSCFYDTKF-UHFFFAOYSA-N 1,3,5-Trimethyl-cyclohexan Natural products CC1CC(C)CC(C)C1 ODNRTOSCFYDTKF-UHFFFAOYSA-N 0.000 description 1
- LQWSBXWILISUST-UHFFFAOYSA-N 1,3,5-trimethylcyclohexane Chemical compound CC1[CH]C(C)CC(C)C1 LQWSBXWILISUST-UHFFFAOYSA-N 0.000 description 1
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical class CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 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
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-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
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 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
- 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
- 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
- GIXNHONPKYUROG-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)phenol Chemical class C1=CC(O)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C12 GIXNHONPKYUROG-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-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
- ZNPSUQQXTRRSBM-UHFFFAOYSA-N 4-n-Pentylphenol Chemical class CCCCCC1=CC=C(O)C=C1 ZNPSUQQXTRRSBM-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZAVAFBIZRXBKLD-UHFFFAOYSA-N C(O)(O)=O.BrC1=C(C=CC=C1)C1=CC=CC=C1 Chemical compound C(O)(O)=O.BrC1=C(C=CC=C1)C1=CC=CC=C1 ZAVAFBIZRXBKLD-UHFFFAOYSA-N 0.000 description 1
- ZGLGKQBRLGATKD-UHFFFAOYSA-N C(O)(O)=O.[N+](=O)([O-])C1=C(C=CC=C1)C1=CC=CC=C1 Chemical compound C(O)(O)=O.[N+](=O)([O-])C1=C(C=CC=C1)C1=CC=CC=C1 ZGLGKQBRLGATKD-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 125000004799 bromophenyl group Chemical group 0.000 description 1
- QYJXDIUNDMRLAO-UHFFFAOYSA-N butyl 4-methylbenzenesulfonate Chemical compound CCCCOS(=O)(=O)C1=CC=C(C)C=C1 QYJXDIUNDMRLAO-UHFFFAOYSA-N 0.000 description 1
- NIKBCKTWWPVAIC-UHFFFAOYSA-N butyl benzenesulfonate Chemical compound CCCCOS(=O)(=O)C1=CC=CC=C1 NIKBCKTWWPVAIC-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- ZQUZPFYNEARCQO-UHFFFAOYSA-N dinaphthalen-1-yl carbonate Chemical compound C1=CC=C2C(OC(OC=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 ZQUZPFYNEARCQO-UHFFFAOYSA-N 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- VRZVPALEJCLXPR-UHFFFAOYSA-N ethyl 4-methylbenzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=C(C)C=C1 VRZVPALEJCLXPR-UHFFFAOYSA-N 0.000 description 1
- XDRMBCMMABGNMM-UHFFFAOYSA-N ethyl benzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=CC=C1 XDRMBCMMABGNMM-UHFFFAOYSA-N 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
- 210000003195 fascia Anatomy 0.000 description 1
- HDVRLUFGYQYLFJ-UHFFFAOYSA-N flamenol Chemical compound COC1=CC(O)=CC(O)=C1 HDVRLUFGYQYLFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 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
- WPRKEVOIVHZQRM-UHFFFAOYSA-M hexyl sulfate;tetramethylazanium Chemical compound C[N+](C)(C)C.CCCCCCOS([O-])(=O)=O WPRKEVOIVHZQRM-UHFFFAOYSA-M 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- CZXGXYBOQYQXQD-UHFFFAOYSA-N methyl benzenesulfonate Chemical compound COS(=O)(=O)C1=CC=CC=C1 CZXGXYBOQYQXQD-UHFFFAOYSA-N 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
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Abstract
本发明的目的在于提供加热收缩率小且其波动小的可用于热成型用途的聚碳酸酯树脂片材及其制造方法。本发明涉及片材及其制造方法,该片材的特征在于,包含聚碳酸酯树脂、厚度为0.2~2.0mm,在180℃下将该片材加热处理10分钟时,挤出方向(MD)的加热收缩率为2~8%的范围,片材的宽度方向(TD)的加热收缩率的标准偏差为1.5以下。
Description
技术领域
本发明涉及热成型时尺寸稳定性和成型加工性优异的聚碳酸酯树脂片材。更具体地,涉及收缩时的尺寸稳定性、赋型性优异,抗冲击性、透明性优异的聚碳酸酯树脂片材。
背景技术
聚碳酸酯树脂由于价格低且轻质,透明性、成型性、光学特性、耐热性、尺寸稳定性、机械强度优异,因此已在各种领域中广泛利用。具体地,已在汽车的仪表板盘、仪表板、家电制品(洗衣机、微波炉等)的膜开关面板、移动电话等的壳体部件、空罐、空瓶等各种用途中使用。
但是,为了将聚碳酸酯树脂片材用于该用途,强烈要求表面外观良好,热成型时片材各部位的尺寸变化尽可能均匀、小且深拉深特性优异。
特别是对于汽车仪表板盘的热成型用片材,主要要求以下的特性。第1,可以列举热成型时片材的各部位的收缩特性均匀,即片材的各部位的加热收缩率的波动小。第2,可以列举在热成型用片材中,加热收缩率的波动小可连续再现。第3,可以列举片材的加热收缩率的值小。第4,可以列举片材的赋型性良好。
此外,作为表面外观良好的片材的制造方法,与将熔融挤出的片状物在原样的状态下不夹持加压而用一个冷却辊接收的单面接触方式相比,用2个冷却辊夹持加压的两面接触方式更优异。单面接触方式的模线(die line)容易明显,表面的凹凸变大。另外,对于单面接触方式而言,虽然加热收缩率小但热成型时没有片材的张力回复特性,因此存在热成型时对位困难,容易产生褶皱的问题。
专利文献1中提出了为了减小聚碳酸酯树脂片材的加热收缩率而规定冷却辊温度和冷却辊与冷却辊的速度比。该方法是单面接触方式的制法,存在片材表面外观略差,而且热成型时也无片材的张力回复因而对位困难、容易产生褶皱这样的问题。
此外,专利文献2中提出了规定聚碳酸酯树脂的粘均分子量和制造时的辊温度。该提案也是单面接触方式的制法,片材表面外观略差,另外热成型时也无片材的张力回复因而对位困难,容易产生褶皱。
此外,专利文献3中提出了分别设定多个冷却辊的温度和速度比,对片材不施加张力的制造方法。对于该方法,难以将片材稳定地挤出,是工业上不利的方法。
因此,两面接触方式的制法中,要求出现表面外观良好,片材各部位的加热收缩率小且均匀,成型加工性也优异的片材。
(专利文献1)日本特开2001-212868号公报
(专利文献2)日本特开2006-316124号公报
(专利文献3)日本特开昭60-214923号公报
发明内容
本发明的目的在于提供加热收缩率小且其波动小的可用于热成型用途的聚碳酸酯树脂片材及其制造方法。
本发明人对将聚碳酸酯树脂熔融,以夹持加压(两面接触)方式挤出成片状的方法进行了研究。发现在该方法中通过使夹持加压片状物时的压力值为特定的范围,能够得到片材宽度方向(TD)的厚度的波动小,片材外观良好,并且热成型时的片材各部位的加热收缩率及其波动小的片材,从而完成了本发明。
即,本发明包含以下的发明。
1.一种片材,其特征在于,是包含聚碳酸酯树脂、厚度为0.2~2.0mm的片材,在180℃下将该片材加热处理10分钟时,挤出方向(MD)的加热收缩率为2~8%的范围,片材的宽度方向(TD)的加热收缩率的标准偏差为1.5以下。
2.如上述1所述的片材,其中,片材的宽度方向(TD)的厚度的标准偏差为8以下。
3.一种成型品,是对上述1所述的片材进行热成型而得到。
4.一种制造上述1所述的片材的方法,其特征在于,包括以下各工序:
(i)将聚碳酸酯树脂从T型模熔融挤出为片状,
(ii)通过用冷却辊将片材夹持加压来进行冷却,
(iii)用转送辊将片材转移,
利用冷却辊夹持加压时的压延负荷为2~10吨的范围。
5.如上述4所述的方法,其中,冷却辊由沿挤出方向的第1~第3辊合计3个辊组成,在第1辊和第2辊之间将聚碳酸酯树脂熔融挤出,第1辊的温度为105~120℃,第2辊的温度为105~120℃,第3辊的温度为130~150℃。
附图说明
图1为用于制造本发明的片材的熔融挤出装置的概要图。
图2为用于制造比较例的片材的熔融挤出装置的概要图。
符号说明
A模
D橡胶辊
Q1:第1冷却辊
Q2:第2冷却辊
Q3:第3冷却辊
具体实施方式
以下对本发明的详细情况进行说明。
(聚碳酸酯树脂)
本发明中使用的聚碳酸酯树脂,除了采用界面聚合法、熔融酯交换法等使二元酚与碳酸酯前体反应而得到的产物以外,还包含采用固相酯交换法将碳酸酯预聚物聚合的产物、或采用环状碳酸酯化合物的开环聚合法聚合而得到的产物。
作为其中使用的二元酚的代表例,可以列举氢醌、间苯二酚、4,4’-二羟基联苯、双(4-羟基苯基)甲烷、双{(4-羟基-3,5-二甲基)苯基}甲烷、1,1-双(4-羟基苯基)乙烷、1,1-双(4-羟基苯基)-1-苯基乙烷、2,2-双(4-羟基苯基)丙烷(通称双酚A)、2,2-双{(4-羟基-3-甲基)苯基}丙烷、2,2-双{(4-羟基-3,5-二甲基)苯基}丙烷、2,2-双{(3-异丙基-4-羟基)苯基}丙烷、2,2-双{(4-羟基-3-苯基)苯基}丙烷、2,2-双(4-羟基苯基)丁烷、2,2-双(4-羟基苯基)-3-甲基丁烷、2,2-双(4-羟基苯基)-3,3-二甲基丁烷、2,4-双(4-羟基苯基)-2-甲基丁烷、2,2-双(4-羟基苯基)戊烷、2,2-双(4-羟基苯基)-4-甲基戊烷、1,1-双(4-羟基苯基)环己烷、1,1-双(4-羟基苯基)-4-异丙基环己烷、1,1-双(4-羟基苯基)-3,3,5-三甲基环己烷、9,9-双(4-羟基苯基)芴、9,9-双{(4-羟基-3-甲基)苯基}芴、α,α’-双(4-羟基苯基)-邻二异丙基苯、α,α’-双(4-羟基苯基)-间二异丙基苯、α,α’-双(4-羟基苯基)-对二异丙基苯、1,3-双(4-羟基苯基)-5,7-二甲基金刚烷、4,4’-二羟基二苯基砜、4,4’-二羟基二苯基亚砜、4,4’-二羟基二苯基硫醚、4,4’-二羟基二苯基酮、4,4’-二羟基二苯基醚和4,4’-二羟基二苯基酯等。它们可以单独使用或者将2种以上混合使用。
其中,优选由选自双酚A、2,2-双{(4-羟基-3-甲基)苯基}丙烷、2,2-双(4-羟基苯基)丁烷、2,2-双(4-羟基苯基)-3-甲基丁烷、2,2-双(4-羟基苯基)-3,3-二甲基丁烷、2,2-双(4-羟基苯基)-4-甲基戊烷、1,1-双(4-羟基苯基)-3,3,5-三甲基环己烷和α,α’-双(4-羟基苯基)-间二异丙基苯中的至少1种双酚得到的均聚物或共聚物。进一步优选使用双酚A的均聚物以及1,1-双(4-羟基苯基)-3,3,5-三甲基环己烷与选自双酚A、2,2-双{(4-羟基-3-甲基)苯基}丙烷和α,α’-双(4-羟基苯基)-间二异丙基苯中的一种以上单体的共聚物。特别优选双酚A的均聚物或1,1-双(4-羟基苯基)-3,3,5-三甲基环己烷和α,α’-双(4-羟基苯基)-间二异丙基苯的共聚物。
作为碳酸酯前体,使用酰卤、碳酸酯酯(カ一ボネ一トエステル)或卤代甲酸酯等,具体地可以列举光气、碳酸二苯酯或二元酚的二卤代甲酸酯等。
采用表面缩聚法或熔融酯交换法使上述二元酚和碳酸酯前体反应来制造聚碳酸酯树脂时,可以根据需要使用催化剂、末端终止剂、二元酚的抗氧化剂等。此外,聚碳酸酯树脂可以是将三官能以上的多官能性芳香族化合物共聚而得到的分支聚碳酸酯树脂,也可以是将芳香族或脂肪族的二官能性羧酸共聚而得到的聚酯碳酸酯树脂,还可以是将得到的聚碳酸酯树脂的2种以上混合而成的混合物。
作为三官能以上的多官能性芳香族化合物,可以列举均苯三酚、2,3’,4,5’,6-五羟基联苯(フロログルシド)、或4,6-二甲基-2,4,6-三(4-羟基苯基)庚烯-2、2,4,6-三甲基-2,4,6-三(4-羟基苯基)庚烷、1,3,5-三(4-羟基苯基)苯、1,1,1-三(4-羟基苯基)乙烷、1,1,1-三(3,5-二甲基-4-羟基苯基)乙烷、2,6-双(2-羟基-5-甲基苄基)-4-甲基苯酚、4-{4-[1,1-双(4-羟基苯基)乙基]苯}-α,α-二甲基苄基苯酚等三酚、四(4-羟基苯基)甲烷、双(2,4-二羟基苯基)酮、1,4-双(4,4-二羟基三苯基甲基)苯、或偏苯三酸、1,2,4,5-苯四酸、二苯甲酮四甲酸和它们的酰氯等。其中优选1,1,1-三(4-羟基苯基)乙烷、1,1,1-三(3,5-二甲基-4-羟基苯基)乙烷,特别优选1,1,1-三(4-羟基苯基)乙烷。
包含产生该分支聚碳酸酯树脂的多官能性化合物的情况下,在聚碳酸酯树脂中,其比例为0.001~1摩尔%,优选为0.005~0.5摩尔%,特别优选为0.01~0.3摩尔%。此外,特别是在熔融酯交换法的情况下,有时作为副反应产生分支结构,关于该分支结构量,在聚碳酸酯树脂总量中,为0.001~1摩尔%,优选为0.005~0.5摩尔%,特别优选为0.01~0.3摩尔%。应予说明,对于该比例,可以采用1H-NMR测定算出。
采用表面缩聚法的反应通常是二元酚和光气的反应,在酸结合剂和有机溶剂的存在下反应。作为酸结合剂,可以使用例如氢氧化钠、氢氧化钾等碱金属氢氧化物或吡啶等胺化合物。作为有机溶剂,可以使用例如二氯甲烷、氯苯等卤代烃。此外,为了促进反应,也可以使用例如三乙胺、四正丁基溴化铵、四正丁基溴化等叔胺、季铵化合物、季化合物等催化剂。此时,反应温度通常优选0~40℃,反应时间优选10分~5小时左右,反应中的pH优选保持在9以上。
此外,该聚合反应中,通常使用末端终止剂。作为该末端终止剂,可以使用单官能酚类。单官能酚类作为末端终止剂,一般用于分子量调节,而且得到的聚碳酸酯树脂的末端由基于单官能酚类的基团封端,因此与不是这样的树脂相比,热稳定性优异。作为该单官能酚类,一般为苯酚或低级烷基取代苯酚,作为具体例,可以列举例如苯酚、对叔丁基苯酚、对枯基苯酚和异辛基苯酚。
末端终止剂相对于得到的聚碳酸酯树脂的全部末端,较理想的是导入到至少5摩尔%、优选至少10摩尔%末端。更优选地,相对于全部末端,导入80摩尔%以上的末端终止剂,即来自二元酚的末端的羟基(OH基)为20摩尔%以下,特别优选地,相对于全部末端,导入90摩尔%以上的末端终止剂,即OH基为10摩尔%以下的情形。此外,末端终止剂可以单独使用或将2种以上混合使用。
采用熔融酯交换法的反应通常是二元酚和碳酸酯酯的酯交换反应,通过在惰性气体的存在下边加热二元酚和碳酸酯酯边混合,将生成的醇或酚馏出的方法进行。反应温度因生成的醇或酚的沸点等而异,通常为120~350℃的范围。反应后期将体系减压到1.33×103~13.3Pa左右,使生成的醇或酚的馏出容易。反应时间通常为1~4小时左右。
作为碳酸酯酯,可以列举可以被取代的碳原子数6~10的芳基、芳烷基或碳原子数1~4的烷基等的酯。具体地,可以列举碳酸二苯酯、碳酸双(氯苯基)酯、碳酸二萘酯、碳酸双(二苯基)酯、碳酸二甲酯、碳酸二乙酯、碳酸二丁酯等,其中优选碳酸二苯酯。
此外,为了加快聚合速度,可以使用聚合催化剂,作为该聚合催化剂,可以使用例如氢氧化钠、氢氧化钾、二元酚的钠盐、钾盐等碱金属化合物;氢氧化钙、氢氧化钡、氢氧化镁等碱土类金属化合物;氢氧化四甲铵、氢氧化四乙铵、三甲胺、三乙胺等含氮碱性化合物;碱金属、碱土类金属的醇盐类、碱金属、碱土类金属的有机酸盐类、锌化合物类、硼化合物类、铝化合物类、硅化合物类、锗化合物类、有机锡化合物类、铅化合物类、锇化合物类、锑化合物类、锰化合物类、钛化合物类、锆化合物类等通常用于酯化反应、酯交换反应的催化剂。催化剂可以单独使用,也可以将2种以上组合使用。这些聚合催化剂的使用量,相对于原料的二元酚1摩尔,优选在1×10-8~1×10-3当量、更优选在1×10-7~5×10-4当量的范围中选择。
此外,在该聚合反应中,为了减少酚性的端基,在缩聚反应的后期或结束后,优选加入例如碳酸双(氯苯基)酯、碳酸双(溴苯基)酯、碳酸双(硝基苯基)酯、碳酸双(苯基苯基)酯、氯苯基苯基碳酸酯、溴苯基苯基碳酸酯、硝基苯基苯基碳酸酯、苯基苯基碳酸酯、甲氧基羰基苯基苯基碳酸酯和乙氧基羰基苯基苯基碳酸酯等化合物。其中,优选2-氯苯基苯基碳酸酯、2-甲氧基羰基苯基苯基碳酸酯和2-乙氧基羰基苯基苯基碳酸酯,特别优选使用2-甲氧基羰基苯基苯基碳酸酯。
此外,在该聚合反应中,优选使用将催化剂的活性中和的失活剂。作为该失活剂的具体例,可以列举例如苯磺酸、对甲苯磺酸、苯磺酸甲酯、苯磺酸乙酯、苯磺酸丁酯、苯磺酸辛酯、苯磺酸苯酯、对甲苯磺酸甲酯、对甲苯磺酸乙酯、对甲苯磺酸丁酯、对甲苯磺酸辛酯、对甲苯磺酸苯酯等磺酸酯;还可以列举三氟甲磺酸、萘磺酸、磺化聚苯乙烯、丙烯酸甲酯-磺化苯乙烯共聚物、十二烷基苯磺酸-2-苯基-2-丙酯、十二烷基苯磺酸-2-苯基-2-丁酯、辛磺酸四丁基盐、癸磺酸四丁基盐、苯磺酸四丁基盐、十二烷基苯磺酸四乙基盐、十二烷基苯磺酸四丁基盐、十二烷基苯磺酸四己基盐、十二烷基苯磺酸四辛基盐、癸基铵丁基硫酸酯、癸基铵癸基硫酸酯、十二烷基铵甲基硫酸酯、十二烷基铵乙基硫酸酯、十二烷基甲基铵甲基硫酸酯、十二烷基二甲基铵十四烷基硫酸酯、十四烷基二甲基铵甲基硫酸酯、四甲基铵己基硫酸酯、癸基三甲基铵十六烷基硫酸酯、四丁基铵十二烷基苄基硫酸酯、四乙基铵十二烷基苄基硫酸酯、四甲基铵十二烷基苄基硫酸酯等化合物,但并不限于这些。也可以将这些化合物中的两种以上并用。失活剂中,优选盐或铵盐型。
作为该失活剂的量,相对于残存的催化剂1摩尔,优选以0.5~50摩尔的比例使用,此外,相对于聚合后的聚碳酸酯树脂,以0.01~500ppm的比例、更优选0.01~300ppm、特别优选0.01~100ppm的比例使用。
聚碳酸酯树脂的分子量并无特别限定。优选地,以粘均分子量(M)计,为1.5×104~4.0×104。更优选1.7×104~3.0×104,进一步优选1.8×104~2.8×104,特别优选2.0×104~2.5×104。粘均分子量(M)为1.5×104~4.0×104的聚碳酸酯树脂具有良好的强度和良好的成型加工性。此外,也可以将2种以上分子量不同的聚碳酸酯树脂混合使用。本发明中的粘均分子量是将由在20℃下将聚碳酸酯树脂0.7g溶解在二氯甲烷100ml中所得的溶液求得的比粘度(ηsp)代入下式而求出的。
ηsp/c=[η]+0.45×[η]2c(其中,[η]为特性粘度)
[η]=1.23×10-4M0.83
c=0.7
聚碳酸酯树脂中,在不损害本发明的目的的范围内,可以进一步添加显现其效果的量的各种添加剂、无机填充剂。作为各种添加剂,可以含有聚碳酸酯树脂以外的其他热塑性树脂。作为该热塑性树脂,可以列举聚酯树脂;聚砜树脂;聚醚醚酮树脂;聚苯硫醚树脂;聚苯醚树脂;聚乙烯树脂、聚丙烯树脂等聚烯烃系树脂;聚苯乙烯树脂、ABS树脂、AS树脂、MBS树脂等苯乙烯系树脂;聚酰胺树脂;丙烯酸树脂和各种热塑性弹性体(例如苯乙烯系、烯烃系、聚氨酯系、聚酯系、聚酰胺系、1,2-聚丁二烯系、氯乙烯系、氟系[氟橡胶]、离聚物树脂、氯化聚乙烯、有机硅系等)等。此外,可以列举阻燃剂(溴化双酚、溴化聚苯乙烯、溴化双酚A的碳酸酯低聚物、磷酸三苯酯、间苯二酚双(磷酸二(二甲苯)酯)、双酚A双(磷酸二苯酯)、红磷、有机磺酸碱金属盐类等)、阻燃助剂(锑酸钠、三氧化锑等)、防滴落剂(具有原纤形成能力的聚四氟乙烯等)、抗氧化剂(受阻酚系化合物等)、热稳定剂(磷系化合物)、紫外线吸收剂、抗静电剂、脱模剂、润滑剂、着色剂等。此外,作为无机填充剂,可以列举玻璃珠、滑石、云母等。
可通过转鼓、V型掺合机、纳塔混合机(ナウタ一ミキサ一)、班伯里混合机、混炼辊、挤出机等混合机将聚碳酸酯树脂与添加剂混合,接着进行熔融挤出,制造片材。
(挤出方向(MD)的加热收缩率)
本发明的聚碳酸酯树脂片材的加热收缩率小,而且其波动也小。即,在180℃下将该片材加热处理10分钟时,挤出方向(MD)的加热收缩率的范围为2~8%,优选为3~7%。如果是该范围内的加热收缩率,从热成型后的印刷的位置偏离小这点看优选。此外,挤出方向(MD)的加热收缩率的标准偏差优选为1.0以下,更优选为0.8以下,进一步优选为0.5以下。下限优选0,但在实用上可以为0.3以上。如果加热收缩率的标准偏差在上述范围内,从热成型后的收缩特性均匀这点看优选。
(宽度方向(TD)的加热收缩率)
另一方面,该片材的宽度方向(TD)的加热收缩率优选为2~10%,更优选为3~8%的范围。如果为该范围内的加热收缩率,从热成型后的印刷的位置偏离小这点看优选。此外,该片材的宽度方向(TD)的加热收缩率的标准偏差为1.5以下,优选为1.2以下,更优选为1.0以下。下限优选0,实用上可以为0.7以上。如果加热收缩率的标准偏差为上述范围内,从热成型后的收缩特性均匀这点看优选。
(厚度)
本发明的聚碳酸酯树脂片材的厚度为0.2~2.0mm,优选为0.2~1.5mm,更优选为0.3~1.0mm的范围。如果比0.2mm薄,挤出成型性降低,如果比2.0mm厚,热成型时的成型加工性降低。
此外,该片材的宽度方向(TD)的厚度的标准偏差优选为8以下,更优选为5以下。下限优选0,但实用上可以为3以上。如果厚度的标准偏差在上述范围内,从均匀赋型性优异这点看优选。
(片材的制造方法)
本发明的片材可通过如下方式制造:在从挤出机的T型模将熔融的聚碳酸酯树脂挤出成片状,使用存在旋转中心轴平行且在同一平面上的位置关系并且接近配置的3根冷却辊制造聚碳酸酯树脂片材的方法中,边向冷却辊的第1辊和中央的第2辊之间供给边用2根辊夹持加压(两面接触方式),然后通过另一端的第3辊的间隙进行牵引,此时,使向夹持加压片材的冷却辊施加的压力(压延负荷)为2~10吨的范围。
压延负荷优选为2~8吨的范围,更优选为2.5~6吨的范围。如果压延负荷比2吨低,难以均匀地形成树脂堆积(围堰(バンク)),容易产生外观不良。此外,如果压延负荷比10吨高,片材宽度方向(TD)的加热收缩率的波动变大,成型加工时的尺寸稳定性差。
压延负荷只在第1辊和第2辊之间赋予,第2辊和第3辊的间隔比片材厚度宽,不施加压力。
此外,上述3根冷却辊的温度优选第1辊为105~125℃,第2辊为105~125℃,第3辊为130~150℃。第1~第3冷却辊优选均对其表面进行了镜面精加工,热介质在其内部循环,能够控制温度。此外,作为此时使用的装置,不必是特别的装置,任意采用在片材、膜或制膜的制造中使用的装置。
此外,作为片材的加热收缩率的调整方法,采用冷却辊和牵引辊间的速度调整、夹持加压的第1冷却辊和第2冷却辊的速度调整、冷却辊的温度调整的调整方法也是有效的。
(热成型品)
根据本发明,也提供使用得到的聚碳酸酯树脂片材采用热成型等成型加工的汽车的仪表板盘、仪表板、家电制品(洗衣机、微波炉等)的膜开关面板、移动电话等的壳体部件、空罐、空瓶等各种成型品。
应予说明,聚碳酸酯树脂片材可以适时实施压花加工、UV照射、抗静电涂布、防粘连涂布等各种公知的表面处理。
实施例
以下通过实施例对本发明更详细地说明。应予说明,实施例中的特性采用下述的方法测定。
(1)加热收缩率
在实施例和比较例中得到的厚0.5mm或0.4mm的片材中,测定加热收缩率。
(i)宽度方向(TD)的加热收缩率的最大值、最小值、标准偏差
对于试验片,以片材宽度900mm的正中为中心,在宽度方向(TD)上取出150mm见方的试验片合计为6片,分别对其测定加热收缩率。加热收缩率按照JIS K6735的试验方法,在试验片上用圆规画出100mm的圆,放置到热风干燥机中的平坦的特氟隆(注册商标)制板上,在180℃处理10分钟后,测定变形的圆(椭圆形)的短径。
加热收缩率(RTD)采用以下的式算出。
RTD=(L0 TD-L1 TD)×100
L0 TD:处理前的宽度方向的长度=100mm
L1 TD:处理后的宽度方向的长度
将该测定重复4次,求出最大值和最小值。
此外,在合计24点的加热收缩率中,用标准偏差表示各测定值的波动,进行评价。
○:合计24点的加热收缩率的标准偏差为1.0以下,尺寸稳定性优异。
△:合计24点的加热收缩率的标准偏差超过1.0且为1.5以下,尺寸稳定性略差。
×:合计24点的加热收缩率的标准偏差超过1.5,因此尺寸稳定性差。
(ii)挤出方向(MD)的加热收缩率的最大值、最小值、标准偏差
对于试验片,在片材宽度900mm的中心部,在挤出方向(MD)上取出150mm见方的样品合计为10片,分别对其测定加热收缩率。加热收缩率按照JIS K6735的试验方法,在试验片上用圆规画出100mm的圆,放置到热风干燥机中的平坦的特氟隆(注册商标)制板上,在180℃处理10分钟后,测定变形的圆(椭圆形)的短径,求出最大值和最小值。
加热收缩率(RMD)采用以下的式算出。
RMD=(L0 MD-L1 MD)×100
L0 MD:处理前的挤出方向的长度=100mm
L1 MD:处理后的挤出方向的长度
此外,用标准偏差表示各测定值的波动,进行评价。
○:合计10点的加热收缩率的标准偏差为0.5以下,尺寸稳定性优异。
△:合计10点的加热收缩率的标准偏差超过0.5且为1.0以下,尺寸稳定性略差。
×:合计10点的加热收缩率的标准偏差超过1.0,因此尺寸稳定性差。
(2)厚度的最大值、最小值、标准偏差
在实施例和比较例中得到的厚0.5mm或0.4mm的片材中,用厚度计测定片材宽度方向(TD)的厚度,求出最大值、最小值、标准偏差。
(测定方法)
进行片材的宽度方向的各测定位置的厚度的测定。对于片材宽度900mm,在宽度方向每25mm间隔合计37点进行测定。
○:厚度的标准偏差为5以下,挤出稳定性优异。
△:厚度的标准偏差超过5且为8以下,挤出稳定性略差。
×:厚度的标准偏差超过8,因此挤出稳定性差。
(3)异物
在实施例和比较例中得到的厚0.5mm或0.4mm的片材中,使用片材宽度方向(TD)900mm、挤出方向(MD)500mm的尺寸的样品,对于采用投光机照射在白板上所形成的影子的大小,使用大藏省夹杂物测定图表,测定异物尺寸,由异物的投影尺寸换算为实际面积。水平白板与片材的距离为14cm。
实际面积是S(mm2)的情况下,如下所述进行评价。
○:S≥0.3为0个,并且0.1≤S<0.3为2个以下
△:S≥0.3为1个以下,并且0.1≤S<0.3为5个以下
×:S≥0.3为2个以上,或者0.1≤S<0.3为6个以上
(4)模线
在实施例和比较例中得到的厚0.5mm或0.4mm的片材中,使用片材宽度方向(TD)900mm、挤出方向(MD)500mm的尺寸的样品,对采用投光机映到白板的模线用目视进行评价。水平白板与片材的距离为14cm。
○:没有看到模线。
△:看到浅的模线。
×:看到深的模线。
实施例1~4和比较例1~2
利用设置了图1中所示装置的挤出机制造片材。T型模的宽度为1200mm,第1、第2、第3冷却辊均使用直径300mm的镜面辊,将由双酚A和光气采用界面聚合法制造的粘均分子量24000的聚碳酸酯树脂粉末从设定为280℃的T型模以排出量280kg/hr挤出。对于从T型模挤出的熔融树脂,以夹持加压(两面接触)方式用第1冷却辊和第2冷却辊以表1记载的压力对片材进行夹持加压,用第3冷却辊进一步冷却,接着对片材的两端部进行修整,将宽度900mm的片材挤出。
将第1冷却辊、第2冷却辊和第3冷却辊的各自的温度设定为115℃、115℃和145℃。
应予说明,对于将片材夹持加压时的压延负荷,测定第1冷却辊的左端部的测力传感器的值和第1冷却辊的右端部的测力传感器的值。将得到的片材的特性示于表1。
比较例3
利用设置了图2中所示装置的挤出机制造片材。T型模的宽度为1200mm,第1、第2、第3冷却辊均使用直径300mm的镜面辊,将由双酚A和光气采用界面聚合法制造的粘均分子量24000的聚碳酸酯树脂粉末从设定为280℃的T型模以排出量280kg/hr挤出。使从T型模挤出的熔融树脂落到第2辊上接触后,采用单面接触方式用第3冷却辊进一步冷却,接着对片材的两端部进行修整,将宽度900mm的片材挤出。将第2冷却辊、第3冷却辊的各自的温度设定为135℃、140℃。将得到的片材的特性示于表1。
本发明的片材,片材宽度方向(TD)的厚度的波动小,片材外观良好,并且热成型时的片材各部位的加热收缩率及其波动小。因此,本发明的片材的尺寸稳定性和赋型性优异。根据本发明的制造方法,能够制造片材宽度方向(TD)的厚度的波动小,片材外观良好,并且热成型时的片材各部位的加热收缩率及其波动小的片材。
Claims (3)
1.一种制造片材的方法,其特征在于,包括以下各工序:
(i)将聚碳酸酯树脂从T型模熔融挤出为片状,
(ii)通过用冷却辊将片材夹持加压来进行冷却,
(iii)用转送辊将片材转移,
利用冷却辊夹持加压时的压延负荷为2~10吨的范围,
所述片材包含聚碳酸酯树脂,厚度为0.2~2.0mm,在180℃将该片材加热处理10分钟时,
(a)片材的挤出方向MD的加热收缩率为2~8%的范围,其标准偏差为1.0以下,
(b)片材的宽度方向TD的加热收缩率为2~10%的范围,其标准偏差为1.5以下。
2.如权利要求1所述的方法,其中,片材的宽度方向TD的厚度的标准偏差为8以下。
3.如权利要求1所述的方法,其中,冷却辊由沿挤出方向的第1~第3辊合计3个辊组成,在第1辊和第2辊之间将聚碳酸酯树脂熔融挤出,第1辊的温度为105~120℃,第2辊的温度为105~120℃,第3辊的温度为130~150℃。
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