JP5369672B2 - Manufacturing method of molded body and optical injection molded body - Google Patents
Manufacturing method of molded body and optical injection molded body Download PDFInfo
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- JP5369672B2 JP5369672B2 JP2008328636A JP2008328636A JP5369672B2 JP 5369672 B2 JP5369672 B2 JP 5369672B2 JP 2008328636 A JP2008328636 A JP 2008328636A JP 2008328636 A JP2008328636 A JP 2008328636A JP 5369672 B2 JP5369672 B2 JP 5369672B2
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- cyclic olefin
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- 238000002347 injection Methods 0.000 title claims description 16
- 239000007924 injection Substances 0.000 title claims description 16
- 230000003287 optical effect Effects 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 238000001746 injection moulding Methods 0.000 claims description 14
- 238000005227 gel permeation chromatography Methods 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 60
- 239000000178 monomer Substances 0.000 description 43
- -1 cyclic olefin Chemical group 0.000 description 29
- 229920000642 polymer Polymers 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 15
- 238000007142 ring opening reaction Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 230000009477 glass transition Effects 0.000 description 13
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 13
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000007809 chemical reaction catalyst Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- WLTSXAIICPDFKI-FNORWQNLSA-N (E)-3-dodecene Chemical compound CCCCCCCC\C=C\CC WLTSXAIICPDFKI-FNORWQNLSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000001118 alkylidene group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005649 metathesis reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LCSLWNXVIDKVGD-KQQUZDAGSA-N (3e,7e)-deca-3,7-diene Chemical compound CC\C=C\CC\C=C\CC LCSLWNXVIDKVGD-KQQUZDAGSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- CWIYBOJLSWJGKV-UHFFFAOYSA-N 5-methyl-1,3-dihydrobenzimidazole-2-thione Chemical compound CC1=CC=C2NC(S)=NC2=C1 CWIYBOJLSWJGKV-UHFFFAOYSA-N 0.000 description 2
- CSRQAJIMYJHHHQ-UHFFFAOYSA-N 9-ethylidenetetracyclo[6.2.1.13,6.02,7]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1=CC CSRQAJIMYJHHHQ-UHFFFAOYSA-N 0.000 description 2
- LUZRCAIWLRPMQK-UHFFFAOYSA-N 9-phenyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1C1=CC=CC=C1 LUZRCAIWLRPMQK-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 2
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- KHBCEJIYBVXXNN-UHFFFAOYSA-N (4-phenylphenyl) 4-methyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4-carboxylate Chemical compound C1C(C2C3CC(C=C3)C22)CC2C1(C)C(=O)OC(C=C1)=CC=C1C1=CC=CC=C1 KHBCEJIYBVXXNN-UHFFFAOYSA-N 0.000 description 1
- QZGLLAUSFHJNEK-UHFFFAOYSA-N (4-phenylphenyl) tetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4-carboxylate Chemical compound C1C(C2C3CC(C=C3)C22)CC2C1C(=O)OC(C=C1)=CC=C1C1=CC=CC=C1 QZGLLAUSFHJNEK-UHFFFAOYSA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 1
- FMZITCJWMYHQFG-UHFFFAOYSA-N 1,2,3,4,4a,5,8,8a-octahydro-2-methyl-1,4:5,8-dimethanonaphthalene Chemical compound C1C(C23)C=CC1C3C1CC2CC1C FMZITCJWMYHQFG-UHFFFAOYSA-N 0.000 description 1
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- ZZOCRFAYVJWKBF-UHFFFAOYSA-N 1,3,5-trichloro-2-[(2,4,6-trichlorophenyl)disulfanyl]benzene Chemical compound ClC1=CC(Cl)=CC(Cl)=C1SSC1=C(Cl)C=C(Cl)C=C1Cl ZZOCRFAYVJWKBF-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- OIRIHBWXSGNQBG-UHFFFAOYSA-N 1,3-dimethyl-2h-benzimidazole-2-thiol Chemical compound C1=CC=C2N(C)C(S)N(C)C2=C1 OIRIHBWXSGNQBG-UHFFFAOYSA-N 0.000 description 1
- QGKFQPPIXYPVIE-UHFFFAOYSA-N 1,4-dichloro-2-[(2,5-dichlorophenyl)disulfanyl]benzene Chemical compound ClC1=CC=C(Cl)C(SSC=2C(=CC=C(Cl)C=2)Cl)=C1 QGKFQPPIXYPVIE-UHFFFAOYSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- UPXNBKIXKLFISK-UHFFFAOYSA-N 1-(5-bicyclo[2.2.1]hept-2-enyl)naphthalene Chemical compound C1=CC=C2C(C3CC4CC3C=C4)=CC=CC2=C1 UPXNBKIXKLFISK-UHFFFAOYSA-N 0.000 description 1
- LZSSZWLFLJRXOW-UHFFFAOYSA-N 1-[2-[(1-acetylnaphthalen-2-yl)disulfanyl]naphthalen-1-yl]ethanone Chemical compound C1=CC2=CC=CC=C2C(C(=O)C)=C1SSC1=CC=C(C=CC=C2)C2=C1C(C)=O LZSSZWLFLJRXOW-UHFFFAOYSA-N 0.000 description 1
- KIRIOGATKMSJIW-UHFFFAOYSA-N 1-[4-[(4-acetylphenyl)disulfanyl]phenyl]ethanone Chemical compound C1=CC(C(=O)C)=CC=C1SSC1=CC=C(C(C)=O)C=C1 KIRIOGATKMSJIW-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- IQCDDWQDDMUOCQ-UHFFFAOYSA-N 1-chloro-2-[(2-chlorophenyl)disulfanyl]benzene Chemical compound ClC1=CC=CC=C1SSC1=CC=CC=C1Cl IQCDDWQDDMUOCQ-UHFFFAOYSA-N 0.000 description 1
- ZIXXRXGPBFMPFD-UHFFFAOYSA-N 1-chloro-4-[(4-chlorophenyl)disulfanyl]benzene Chemical compound C1=CC(Cl)=CC=C1SSC1=CC=C(Cl)C=C1 ZIXXRXGPBFMPFD-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- WXOHRQAMBKXWME-UHFFFAOYSA-N 1-methyl-2-methylsulfanylbenzimidazole Chemical compound C1=CC=C2N(C)C(SC)=NC2=C1 WXOHRQAMBKXWME-UHFFFAOYSA-N 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical group C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- NXCKJENHTITELM-UHFFFAOYSA-N 1-nitro-2-[(2-nitrophenyl)disulfanyl]benzene Chemical compound [O-][N+](=O)C1=CC=CC=C1SSC1=CC=CC=C1[N+]([O-])=O NXCKJENHTITELM-UHFFFAOYSA-N 0.000 description 1
- QXRJQSYBWURKHH-UHFFFAOYSA-N 2,2,3,3-tetrafluorobicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(F)(F)C2(F)F QXRJQSYBWURKHH-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- UOYKBJNWNACIRX-UHFFFAOYSA-N 2,3,3-trifluorobicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(F)C2(F)F UOYKBJNWNACIRX-UHFFFAOYSA-N 0.000 description 1
- ZGNJHKOQQSEQRR-UHFFFAOYSA-N 2,3-bis(trifluoromethyl)bicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(C(F)(F)F)C2C(F)(F)F ZGNJHKOQQSEQRR-UHFFFAOYSA-N 0.000 description 1
- DKFVTFNJIYIYNV-UHFFFAOYSA-N 2,3-difluorobicyclo[2.2.1]hept-5-ene Chemical compound C1C2C(F)C(F)C1C=C2 DKFVTFNJIYIYNV-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- HWHFWPFOFITIAE-UHFFFAOYSA-N 2-(5-bicyclo[2.2.1]hept-2-enyl)naphthalene Chemical compound C1=CC=CC2=CC(C3CC4CC3C=C4)=CC=C21 HWHFWPFOFITIAE-UHFFFAOYSA-N 0.000 description 1
- ZCAIOHDMWSETCE-UHFFFAOYSA-N 2-(5-methyl-5-bicyclo[2.2.1]hept-2-enyl)naphthalene Chemical compound C1=CC=CC2=CC(C3(C4CC(C=C4)C3)C)=CC=C21 ZCAIOHDMWSETCE-UHFFFAOYSA-N 0.000 description 1
- CMXJXFPEZDHKPW-UHFFFAOYSA-N 2-[(1-cyanonaphthalen-2-yl)disulfanyl]naphthalene-1-carbonitrile Chemical compound C1=CC2=CC=CC=C2C(C#N)=C1SSC1=CC=C(C=CC=C2)C2=C1C#N CMXJXFPEZDHKPW-UHFFFAOYSA-N 0.000 description 1
- FZFMOEQAUCLKLC-UHFFFAOYSA-N 2-[(2-ethoxycarbonylphenyl)disulfanyl]benzoic acid Chemical compound CCOC(=O)C1=CC=CC=C1SSC1=CC=CC=C1C(O)=O FZFMOEQAUCLKLC-UHFFFAOYSA-N 0.000 description 1
- GCXFFKSSLAVMIW-UHFFFAOYSA-N 2-chloro-1-[(2-chloronaphthalen-1-yl)disulfanyl]naphthalene Chemical compound C1=CC=C2C(SSC3=C4C=CC=CC4=CC=C3Cl)=C(Cl)C=CC2=C1 GCXFFKSSLAVMIW-UHFFFAOYSA-N 0.000 description 1
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- 229940017219 methyl propionate Drugs 0.000 description 1
- VBVLCVSJASSMCO-UHFFFAOYSA-N methyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-2-carboxylate Chemical compound COC(=O)C12C3C=CC(C2C2CCC1C2)C3 VBVLCVSJASSMCO-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical compound C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- ITAIJOKDSGPPHZ-UHFFFAOYSA-N naphthalen-1-yl tetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4-carboxylate Chemical compound C1=CC=C2C(OC(=O)C3C4CC(C5C6CC(C=C6)C54)C3)=CC=CC2=C1 ITAIJOKDSGPPHZ-UHFFFAOYSA-N 0.000 description 1
- LUNFPODXCUSVFX-UHFFFAOYSA-N naphthalen-2-yl 4-methyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4-carboxylate Chemical compound C1=CC=CC2=CC(OC(=O)C3(C4CC(C5C6CC(C=C6)C54)C3)C)=CC=C21 LUNFPODXCUSVFX-UHFFFAOYSA-N 0.000 description 1
- JWIZPFGSMSOXGM-UHFFFAOYSA-N naphthalen-2-yl tetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4-carboxylate Chemical compound C1=CC=CC2=CC(OC(=O)C3C4CC(C5C6CC(C=C6)C54)C3)=CC=C21 JWIZPFGSMSOXGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- LGOPTUPXVVNJFH-UHFFFAOYSA-N pentadecanethioic s-acid Chemical compound CCCCCCCCCCCCCCC(O)=S LGOPTUPXVVNJFH-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 1
- NUPNRRYKAIGHBL-UHFFFAOYSA-N phenyl 3-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate Chemical compound CC1C2C=CC(C1C(=O)OC1=CC=CC=C1)C2 NUPNRRYKAIGHBL-UHFFFAOYSA-N 0.000 description 1
- UAKXMUQGRAINJV-UHFFFAOYSA-N phenyl 5-methylbicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C(C=C2)CC2C1(C)C(=O)OC1=CC=CC=C1 UAKXMUQGRAINJV-UHFFFAOYSA-N 0.000 description 1
- AAMQMOVGLLMYEY-UHFFFAOYSA-N phenyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-2-carboxylate Chemical compound O(C1=CC=CC=C1)C(=O)C12C3C=CC(C2C2CCC1C2)C3 AAMQMOVGLLMYEY-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IYJVDXMMWSPICZ-UHFFFAOYSA-N propyl tetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4-carboxylate Chemical compound C1C(C23)C=CC1C3C1CC2CC1C(=O)OCCC IYJVDXMMWSPICZ-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920006352 transparent thermoplastic Polymers 0.000 description 1
- MZHULIWXRDLGRR-UHFFFAOYSA-N tridecyl 3-(3-oxo-3-tridecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCC MZHULIWXRDLGRR-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
本発明は、特定の環状オレフィン系重合体を用いた成形体の製造方法および光学射出成形体に関する。 The present invention relates to a method for producing a molded body using a specific cyclic olefin polymer and an optical injection molded body.
環状オレフィン系開環(共)重合体は、主鎖構造の剛直性に起因してガラス転移温度が高く、主鎖構造に嵩高い基が存在するために非晶性で光線透過率が高く、しかも屈折の異方性が小さいことにより低複屈折性を示すなどの特長を有しており、耐熱性、透明性、光学特性に優れた透明熱可塑性樹脂として注目されている。このような環状オレフィン系開環(共)重合体としては、例えば特許文献1〜6に記載のものなどが挙げられる。
上記の特徴を利用して、例えば光ディスク、光学レンズ、光ファイバーなどの光学材料、光半導体封止などの封止材料などの分野において、環状オレフィン系開環(共)重合体を応用することが検討されている。すなわち、従来から光学用フィルムとして使用されているポリカーボネート、ポリエステルあるいはトリアセチルアセテート等のフィルムは、光弾性係数が大きいために微小な応力変化により位相差が発現したり変化したりする問題や、耐熱性や吸水変形等の問題があるため、これらの問題を解決するものとして、環状オレフィン系開環(共)重合体からなる成形体が提案されている。
The cyclic olefin ring-opening (co) polymer has a high glass transition temperature due to the rigidity of the main chain structure, and is amorphous and has a high light transmittance due to the presence of bulky groups in the main chain structure. In addition, it has features such as low birefringence due to its low refraction anisotropy, and has attracted attention as a transparent thermoplastic resin excellent in heat resistance, transparency and optical properties. Examples of such cyclic olefin-based ring-opening (co) polymers include those described in Patent Documents 1 to 6.
Utilizing the above characteristics, it is considered to apply cyclic olefin-based ring-opening (co) polymers in fields such as optical materials such as optical disks, optical lenses, optical fibers, and sealing materials such as optical semiconductor sealing. Has been. In other words, films such as polycarbonate, polyester, and triacetyl acetate that have been used as optical films in the past have a large photoelastic coefficient. In order to solve these problems, a molded body made of a cyclic olefin-based ring-opening (co) polymer has been proposed.
しかしながら、耐熱性に優れた環状オレフィン系開環(共)重合体は、流動性が不足して成形が困難であり、流動性を向上させると重合体のガラス転移温度が下がって耐熱性が不足するという問題点があった。このため、耐熱性に優れ、かつ十分な流動性を有し成形性に優れる重合体が、強く望まれていた。
本発明は、成形性に優れた重合体を用いて耐熱性に優れた成形体を製造する方法と、耐熱性および成形性に優れた光学射出成形体を提供することを課題とする。 An object of the present invention is to provide a method for producing a molded article having excellent heat resistance using a polymer having excellent moldability, and an optical injection molded article having excellent heat resistance and moldability.
本発明の成形体の製造方法は、下記式(1)で表される繰り返し単位(1)、下記式(2)で表される繰り返し単位(2)および下記式(3)で表される繰り返し単位(3)を有し、かつ上記繰り返し単位(1)を全繰り返し単位100重量%に対して20〜50重量%有する環状オレフィン系重合体を、射出成形により成形することを特徴とする。 The method for producing a molded article of the present invention is a repeating unit (1) represented by the following formula (1), a repeating unit (2) represented by the following formula (2) and a repeating unit represented by the following formula (3). A cyclic olefin polymer having the unit (3) and having the repeating unit (1) in an amount of 20 to 50% by weight based on 100% by weight of all the repeating units is molded by injection molding.
(式(2)および式(3)中、R1〜R8は、それぞれ独立に、水素原子、ハロゲン原子、炭素数1〜30の炭化水素基、または極性基である。また、R1〜R4 およびR5〜R8のうち任意の2つが互いに結合して、アルキリデン基、単環または多環構造を形成しても良い。) (In the formula (2) and (3), R 1 to R 8 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group or a polar group, having 1 to 30 carbon atoms. Also, R 1 ~ Any two of R 4 and R 5 to R 8 may be bonded to each other to form an alkylidene group, monocyclic or polycyclic structure.)
環状オレフィン系重合体のゲルパーミエーションクロマトグラフィーによるポリスチレン換算重量平均分子量は、35,000〜55,000であることが好ましい。
環状オレフィン系重合体は、繰り返し単位(2)を全繰り返し単位100重量%に対して50〜80重量%有することが好ましい。
環状オレフィン系重合体は、繰り返し単位(3)を全繰り返し単位100重量%に対して0.1〜10重量%有することが好ましい。
It is preferable that the polystyrene conversion weight average molecular weight of the cyclic olefin polymer by gel permeation chromatography is 35,000 to 55,000.
The cyclic olefin polymer preferably has 50 to 80% by weight of the repeating unit (2) based on 100% by weight of all repeating units.
The cyclic olefin polymer preferably has 0.1 to 10% by weight of the repeating unit (3) based on 100% by weight of all repeating units.
本発明の光学射出成形体は、繰り返し単位(1)、繰り返し単位(2)および繰り返し単位(3)を有し、かつゲルパーミエーションクロマトグラフィーによるポリスチレン換算重量平均分子量が35,000〜55,000である環状オレフィン系重合体を含有することを特徴とする。 The optical injection molded article of the present invention has a repeating unit (1), a repeating unit (2) and a repeating unit (3), and has a polystyrene-reduced weight average molecular weight of 35,000 to 55,000 as determined by gel permeation chromatography. It is characterized by containing the cyclic olefin polymer which is.
本発明によれば、特定の3種の繰り返し単位を有する環状オレフィン系開環共重合体を用いることにより、成形性に優れ、耐熱性に優れた成形体の製造方法を提供することができる。また、本発明によれば、該樹脂組成物を用いた耐熱性および成形性に優れた光学射出成形体を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the molded object which was excellent in a moldability and excellent in heat resistance can be provided by using the cyclic olefin type ring-opening copolymer which has a specific 3 types of repeating unit. Moreover, according to this invention, the optical injection molded object excellent in the heat resistance and moldability using this resin composition can be provided.
以下、本発明について具体的に説明する。
環状オレフィン系重合体
本発明に用いられる環状オレフィン系重合体は、繰り返し単位(1)を全繰り返し単位100重量%に対して20〜50重量%有する開環共重合体水素化物である。
繰り返し単位(1)を与える単量体(以下、「単量体(1)」ともいう)としては、トリシクロ[4.3.0.12,5]デカ−3−エンおよびトリシクロ[4.3.0.12,5]デカ−3,7−ジエン(ジシクロペンタジエン)が挙げられる。トリシクロ[4.3.0.12,5]デカ−3,7−ジエンを用いる場合には、開環共重合の後、五員環の水素添加により繰り返し単位(1)が得られる。
Hereinafter, the present invention will be specifically described.
Cyclic Olefin Polymer The cyclic olefin polymer used in the present invention is a hydride of a ring-opening copolymer having 20 to 50% by weight of the repeating unit (1) based on 100% by weight of all repeating units.
Monomers that give the repeating unit (1) (hereinafter also referred to as “monomer (1)”) include tricyclo [4.3.0.1 2,5 ] dec-3-ene and tricyclo [4. 3.0.1 2,5 ] Deca-3,7-diene (dicyclopentadiene). When tricyclo [4.3.0.1 2,5 ] deca-3,7-diene is used, the repeating unit (1) is obtained by hydrogenation of a five-membered ring after ring-opening copolymerization.
繰り返し単位(2)を与える単量体(以下、「単量体(2)」ともいう)は、下記式(2m)で表される。 The monomer giving the repeating unit (2) (hereinafter also referred to as “monomer (2)”) is represented by the following formula (2m).
式(2m)中、R1〜R4は、式(2)と同様である。すなわち、R1〜R4は、それぞれ独立に、水素原子、ハロゲン原子、炭素数1〜30の炭化水素基、または極性基である。また、R1〜R4のうち任意の2つが互いに結合して、アルキリデン基、単環または多環構造を形成しても良い。 In formula (2m), R 1 to R 4 are the same as in formula (2). That is, R 1 to R 4 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a polar group. Further, any two of R 1 to R 4 may be bonded to each other to form an alkylidene group, a monocyclic structure or a polycyclic structure.
式(2)あるいは式(2m)において、ハロゲン原子としては、フッ素原子、塩素原子および臭素原子が挙げられる。炭素原子数1〜10の炭化水素基としては、例えば、メチル基、エチル基、プロピル基などのアルキル基;シクロペンチル基、シクロヘキシル基などのシクロアルキル基;ビニル基、アリル基、プロペニル基などのアルケニル基などが挙げられる。
極性基としては、たとえば、水酸基、炭素原子数1〜10のアルコキシル基、カルボニルオキシ基、アルコキシカルボニル基、アリーロキシカルボニル基、シアノ基、アミド基、イミド基、トリオルガノシロキシ基、トリオルガノシリル基、アミノ基、アシル基、アルコキシシリル基、スルホニル基、およびカルボキシル基などが挙げられる。さらに具体的には、上記アルコキシ基としては、例えばメトキシ基、エトキシ基などが挙げられ;カルボニルオキシ基としては、例えばアセトキシ基、プロピオニルオキシ基などのアルキルカルボニルオキシ基、およびベンゾイルオキシ基などのアリールカルボニルオキシ基が挙げられ;アルコキシカルボニル基としては、例えばメトキシカルボニル基、エトキシカルボニル基などが挙げられ;アリーロキシカルボニル基としては、例えばフェノキシカルボニル基、ナフチルオキシカルボニル基、フルオレニルオキシカルボニル基、ビフェニリルオキシカルボニル基などが挙げられ;トリオルガノシロキシ基としては例えばトリメチルシロキシ基、トリエチルシロキシ基などが挙げられ;トリオルガノシリル基としてはトリメチルシリル基、トリエチルシリル基などが挙げられ;アミノ基としては第1級アミノ基が挙げられ、アルコキシシリル基としては、例えばトリメトキシシリル基、トリエトキシシリル基などが挙げられる。
In the formula (2) or the formula (2m), examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the hydrocarbon group having 1 to 10 carbon atoms include alkyl groups such as methyl group, ethyl group, and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group, allyl group, and propenyl group. Group and the like.
Examples of the polar group include a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, a carbonyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an amide group, an imide group, a triorganosiloxy group, and a triorganosilyl group. Amino group, acyl group, alkoxysilyl group, sulfonyl group, carboxyl group, and the like. More specifically, examples of the alkoxy group include a methoxy group and an ethoxy group; examples of the carbonyloxy group include an alkylcarbonyloxy group such as an acetoxy group and a propionyloxy group, and an aryl such as a benzoyloxy group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group; examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a naphthyloxycarbonyl group, a fluorenyloxycarbonyl group, Biphenylyloxycarbonyl group and the like; examples of the triorganosiloxy group include trimethylsiloxy group and triethylsiloxy group; examples of the triorganosilyl group include trimethylsilyl group, Such Riechirushiriru group and the like; examples of the amino group include primary amino group, the alkoxysilyl group, for example trimethoxysilyl groups, such as triethoxysilyl group.
ここで、繰り返し単位(2)および単量体(2)は、少なくともひとつの極性基を有していることが好ましい。また、極性基が、下記式(4)で表される基であることが特に好ましい。すなわち、式(2)または式(2m)中、R1〜R4の少なくとも1つが、下記式(4)で表される基であることが特に好ましい。 Here, it is preferable that the repeating unit (2) and the monomer (2) have at least one polar group. The polar group is particularly preferably a group represented by the following formula (4). That is, it is particularly preferable that at least one of R 1 to R 4 in the formula (2) or the formula (2m) is a group represented by the following formula (4).
−(CH2)pCOOR’ ・・・(4)
(式(4)中、pは0または1〜5の整数であり、R’は炭素数1〜15の炭化水素基である。)
上記式(4)において、pの値が小さいものほど、また、R’が炭素数の小さいほど、得られる共重合体のガラス転移温度が高くなり耐熱性が向上するので好ましい。すなわち、pは通常0または1〜5の整数であるが、好ましくは0または1であり、また、R’は通常炭素数1〜15の炭化水素基であるが、好ましくは炭素数1〜3のアルキル基であるのが望ましい。
- (CH 2) p COOR ' ··· (4)
(In Formula (4), p is 0 or an integer of 1 to 5, and R ′ is a hydrocarbon group having 1 to 15 carbon atoms.)
In the above formula (4), the smaller the value of p and the smaller the R ′ carbon number, the higher the glass transition temperature of the resulting copolymer and the better the heat resistance. That is, p is usually 0 or an integer of 1 to 5, preferably 0 or 1, and R 'is usually a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 3 carbon atoms. It is desirable that it is an alkyl group.
極性基が上記式(4)で表される基である繰り返し単位(2)を有する場合には、共重合体の耐熱性と吸水(湿)性がバランスに優れるため好ましい。上記式(4)で表される極性基が結合した炭素原子にさらに結合しているアルキル基の炭素数は、1〜5であることが好ましく、さらに好ましくは1〜2、特に好ましくは1である。 When the polar group has a repeating unit (2) which is a group represented by the above formula (4), the copolymer is excellent in heat resistance and water absorption (wet) property, which is preferable. The number of carbon atoms of the alkyl group further bonded to the carbon atom to which the polar group represented by the above formula (4) is bonded is preferably 1 to 5, more preferably 1 to 2, particularly preferably 1. is there.
上記式(4)で表される基を有する単量体(2)としては、具体的には、
8−メトキシカルボニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−エトキシカルボニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−n−プロポキシカルボニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−イソプロポキシカルボニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−n−ブトキシカルボニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−フェノキシカルボニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−(1−ナフトキシ)カルボニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−(2−ナフトキシ)カルボニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−(4−フェニルフェノキシ)カルボニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−メチル−8−メトキシカルボニルテトラシクロ[4.4.0.12,5 .17,10]−3−ドデセン、
8−メチル−8−エトキシカルボニルテトラシクロ[4.4.0.12,5 .17,10]−3−ドデセン、
8−メチル−8−n−プロポキシカルボニル−テトラシクロ[4.4.0.12,5.17,10]ドデカ−3−エン、
8−メチル−8−イソプロポキシカルボニル−テトラシクロ[4.4.0.12,5.17,10]ドデカ−3−エン、
8−メチル−8−n−ブトキシカルボニル−テトラシクロ[4.4.0.12,5.17,10]ドデカ−3−エン、
8−メチル−8−フェノキシカルボニル−テトラシクロ[4.4.0.12,5.17,10]ドデカ−3−エン
8−メチル−8−(1−ナフトキシ)カルボニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−メチル−8−(2−ナフトキシ)カルボニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−メチル−8−(4−フェニルフェノキシ)カルボニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン
等を挙げることができる。
As the monomer (2) having a group represented by the above formula (4), specifically,
8 methoxycarbonyltetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8-ethoxycarbonyl tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8-n-propoxycarbonyl tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8 isopropoxycarbonyl tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8-n-butoxycarbonyl tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8 phenoxycarbonyl tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8- (1-naphthoxy) carbonyl tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8- (2-naphthoxy) carbonyl tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8- (4-phenylphenoxy) carbonyl tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene,
8-methyl-8-n-propoxycarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene,
8-methyl-8-isopropoxycarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene,
8-methyl-8-n-butoxycarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene,
8-methyl-8-phenoxycarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7,10] dodeca-3-ene 8-methyl-8- (1-naphthoxy) carbonyl tetracyclo [4.4.0.1 2, 5 .1 7,10] -3-dodecene,
8-methyl-8- (2-naphthoxy) carbonyl tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8-methyl-8- (4-phenylphenoxy) carbonyl tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene, and the like.
また、その他の単量体(2)としては、具体的には、
テトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−メチルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−エチルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−n−ブチルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−n−ヘキシルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−エチリデンテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−フェニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−フルオロテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−フルオロメチルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8−トリフルオロメチルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
8,8−ジフルオロテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン
等を挙げることができるが、これらの例示に限定されるものではない。
As other monomer (2), specifically,
Tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8-methyl tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8-ethyl tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8-n-butyl tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8-n-hexyl-tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8 ethylidene tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8-phenyl tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8-fluoro-tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8-fluoro-methyl tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8-trifluoromethyl-tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
8,8-difluoro-tetracyclo [4.4.0.1 2,5 .1 7,10] -3- Although dodecene and the like, but is not limited to these examples.
繰り返し単位(3)を与える単量体(以下、「単量体(3)」ともいう)は、下記式(3m)で表される。 The monomer giving the repeating unit (3) (hereinafter also referred to as “monomer (3)”) is represented by the following formula (3m).
式(3m)中、mおよびR5〜R8は、式(3)と同様である。すなわち、R5〜R8は、それぞれ独立に、水素原子、ハロゲン原子、炭素数1〜30の炭化水素基、または極性基である。また、R5〜R8のうち任意の2つが互いに結合して、アルキリデン基、単環または多環構造を形成しても良い。 In the formula (3m), m and R 5 to R 8 are the same as those in the formula (3). That is, R 5 to R 8 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a polar group. Further, any two of R 5 to R 8 may be bonded to each other to form an alkylidene group, a monocyclic structure or a polycyclic structure.
式(3)あるいは式(3m)におけるハロゲン原子、炭素数1〜30の炭化水素基および極性基は、前述した式(2)あるいは式(2m)における例示と同様である。
式(3)あるいは式(3m)におけるR5〜R8は、水素原子であることが最も好ましい。
The halogen atom, the hydrocarbon group having 1 to 30 carbon atoms and the polar group in formula (3) or formula (3m) are the same as those exemplified in formula (2) or formula (2m) described above.
R 5 to R 8 in Formula (3) or Formula (3m) are most preferably a hydrogen atom.
単量体(3)としては、具体的には、
ビシクロ[2.2.1]ヘプト−2−エン(2−ノルボルネン)、
5−メチルビシクロ[2.2.1]ヘプト−2−エン、
5−エチルビシクロ[2.2.1]ヘプト−2−エン、
5−シアノビシクロ[2.2.1]ヘプト−2−エン、
5−エチリデンビシクロ[2.2.1]ヘプト−2−エン、
8−エチリデンテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
5−フェニルビシクロ[2.2.1]ヘプト−2−エン、
5−フェニル−5―メチルビシクロ[2.2.1]ヘプト−2−エン、
8−フェニルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン、
5−n−ブチルビシクロ[2.2.1]ヘプト−2−エン、
5−n−ヘキシルビシクロ[2.2.1]ヘプト−2−エン、
5−シクロヘキシルビシクロ[2.2.1]ヘプト−2−エン、
5−(2−シクロヘキセニル)ビシクロ[2.2.1]ヘプト−2−エン、
5−n−オクチルビシクロ[2.2.1]ヘプト−2−エン、
5−n−デシルビシクロ[2.2.1]ヘプト−2−エン、
5−イソプロピルビシクロ[2.2.1]ヘプト−2−エン、
5−(1−ナフチル)ビシクロ[2.2.1]ヘプト−2−エン、
5−(2−ナフチル)ビシクロ[2.2.1]ヘプト−2−エン、
5−(2−ナフチル)−5−メチルビシクロ[2.2.1]ヘプト−2−エン、
5−(4−ビフェニル)ビシクロ[2.2.1]ヘプト−2−エン、
5−(4−ビフェニル)−5−メチルビシクロ[2.2.1]ヘプト−2−エン、
5−アミノメチルビシクロ[2.2.1]ヘプト−2−エン、
5−トリメトキシシリルビシクロ[2.2.1]ヘプト−2−エン、
5−トリエトキシシリルビシクロ[2.2.1]ヘプト−2−エン、
5−トリn−プロポキシシリルビシクロ[2.2.1]ヘプト−2−エン、
5−トリn−ブトキシシリルビシクロ[2.2.1]ヘプト−2−エン、
5−クロロメチルビシクロ[2.2.1]ヘプト−2−エン、
5−ヒドロキシメチルビシクロ[2.2.1]ヘプト−2−エン、
5−シクロヘセニルビシクロ[2.2.1]ヘプト−2−エン、
5−フルオロビシクロ[2.2.1]ヘプト−2−エン、
5−フルオロメチルビシクロ[2.2.1]ヘプト−2−エン、
5−トリフルオロメチルビシクロ[2.2.1]ヘプト−2−エン、
5,5−ジフルオロビシクロ[2.2.1]ヘプト−2−エン、
5,6−ジフルオロビシクロ[2.2.1]ヘプト−2−エン、
5,5−ビス(トリフルオロメチル)ビシクロ[2.2.1]ヘプト−2−エン、
5,6−ビス(トリフルオロメチル)ビシクロ[2.2.1]ヘプト−2−エン、
5−メチル−5−トリフルオロメチルビシクロ[2.2.1]ヘプト−2−エン、
5,5,6−トリフルオロビシクロ[2.2.1]ヘプト−2−エン、
5,5,6,6−テトラフルオロビシクロ[2.2.1]ヘプト−2−エン、
5−メチル−5−メトキシカルボニル−ビシクロ[2.2.1]ヘプト−2−エン、
5−メチル−5−フェノキシカルボニル−ビシクロ[2.2.1]ヘプト−2−エン、
5−メチル−6−メトキシカルボニル−ビシクロ[2.2.1]ヘプト−2−エン、
5−メチル−6−フェノキシカルボニル−ビシクロ[2.2.1]ヘプト−2−エン、
等を挙げることができるが、これらの例示に限定されるものではない。
As the monomer (3), specifically,
Bicyclo [2.2.1] hept-2-ene (2-norbornene),
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-cyanobicyclo [2.2.1] hept-2-ene,
5-ethylidenebicyclo [2.2.1] hept-2-ene,
8 ethylidene tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
5-phenylbicyclo [2.2.1] hept-2-ene,
5-phenyl-5-methylbicyclo [2.2.1] hept-2-ene,
8-phenyl tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene,
5-n-butylbicyclo [2.2.1] hept-2-ene,
5-n-hexylbicyclo [2.2.1] hept-2-ene,
5-cyclohexylbicyclo [2.2.1] hept-2-ene,
5- (2-cyclohexenyl) bicyclo [2.2.1] hept-2-ene,
5-n-octylbicyclo [2.2.1] hept-2-ene,
5-n-decylbicyclo [2.2.1] hept-2-ene,
5-isopropylbicyclo [2.2.1] hept-2-ene,
5- (1-naphthyl) bicyclo [2.2.1] hept-2-ene,
5- (2-naphthyl) bicyclo [2.2.1] hept-2-ene,
5- (2-naphthyl) -5-methylbicyclo [2.2.1] hept-2-ene,
5- (4-biphenyl) bicyclo [2.2.1] hept-2-ene,
5- (4-biphenyl) -5-methylbicyclo [2.2.1] hept-2-ene,
5-aminomethylbicyclo [2.2.1] hept-2-ene,
5-trimethoxysilylbicyclo [2.2.1] hept-2-ene,
5-triethoxysilylbicyclo [2.2.1] hept-2-ene,
5-tri-n-propoxysilylbicyclo [2.2.1] hept-2-ene,
5-tri-n-butoxysilylbicyclo [2.2.1] hept-2-ene,
5-chloromethylbicyclo [2.2.1] hept-2-ene,
5-hydroxymethylbicyclo [2.2.1] hept-2-ene,
5-cyclohexenylbicyclo [2.2.1] hept-2-ene,
5-fluorobicyclo [2.2.1] hept-2-ene,
5-fluoromethylbicyclo [2.2.1] hept-2-ene,
5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,5-difluorobicyclo [2.2.1] hept-2-ene,
5,6-difluorobicyclo [2.2.1] hept-2-ene,
5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,5,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-methyl-5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-methyl-6-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-methyl-6-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
However, it is not limited to these examples.
本発明に係る環状オレフィン系重合体は、繰り返し単位(1)を全繰り返し単位100重量%に対して20〜50重量%、好ましくは20〜40重量%、特に好ましくは20〜30重量%有する。繰り返し単位(1)の割合が20重量%未満であると、流動性が不足するという問題があり、50重量%を超えると、耐熱性が低下するという問題がある。
また、繰り返し単位(2)を、全繰り返し単位100重量%に対して好ましくは50〜80重量%、さらに好ましくは60〜80重量%、特に好ましくは70〜80重量%有する。繰り返し単位(2)を上記範囲で有することにより、耐熱性に優れた重合体を得ることができる。繰り返し単位(3)を、全繰り返し単位100重量%に対して好ましくは0.1〜10重量%、さらに好ましくは0.5〜8重量%、特に好ましくは0.5〜5重量%有する。繰り返し単位(3)を上記範囲で有することにより、成形性に優れた重合体をえることができる。
The cyclic olefin polymer according to the present invention has the repeating unit (1) in an amount of 20 to 50% by weight, preferably 20 to 40% by weight, particularly preferably 20 to 30% by weight based on 100% by weight of all the repeating units. When the proportion of the repeating unit (1) is less than 20% by weight, there is a problem that the fluidity is insufficient, and when it exceeds 50% by weight, there is a problem that the heat resistance is lowered.
Further, the repeating unit (2) is preferably 50 to 80% by weight, more preferably 60 to 80% by weight, particularly preferably 70 to 80% by weight based on 100% by weight of all repeating units. By having the repeating unit (2) in the above range, a polymer having excellent heat resistance can be obtained. The repeating unit (3) is preferably 0.1 to 10% by weight, more preferably 0.5 to 8% by weight, particularly preferably 0.5 to 5% by weight, based on 100% by weight of all repeating units. By having the repeating unit (3) in the above range, a polymer excellent in moldability can be obtained.
本発明に係る環状オレフィン系重合体は、繰り返し単位(1)、繰り返し単位(2)および繰り返し単位(3)のみからなる共重合体であってもよいが、必要に応じて、本発明の目的を損なわない範囲で、その他の共重合性単量体から導かれる繰り返し単位を有していてもよい。その他の共重合性単量体から導かれる繰り返し単位としては、繰り返し単位(1)〜(3)以外のノルボルネン骨格を有する環状オレフィン系単量体を開環共重合して導かれる繰り返し単位や、シクロブテン、シクロペンテン、シクロヘプテン、シクロオクテンなどのシクロオレフィン系単量体を開環共重合して導かれる繰り返し単位などが挙げられる。 The cyclic olefin polymer according to the present invention may be a copolymer composed of only the repeating unit (1), the repeating unit (2) and the repeating unit (3). As long as the above is not impaired, it may have a repeating unit derived from another copolymerizable monomer. As repeating units derived from other copolymerizable monomers, repeating units derived by ring-opening copolymerization of cyclic olefin monomers having a norbornene skeleton other than the repeating units (1) to (3), Examples thereof include repeating units derived by ring-opening copolymerization of cycloolefin monomers such as cyclobutene, cyclopentene, cycloheptene, and cyclooctene.
かかる環状オレフィン系重合体は、単量体(1)、単量体(2)、単量体(3)および必要に応じてその他の単量体を、開環共重合し、水素添加することにより製造することができる。 Such a cyclic olefin polymer is obtained by ring-opening copolymerization and hydrogenation of the monomer (1), the monomer (2), the monomer (3) and other monomers as required. Can be manufactured.
本発明で用いる環状オレフィン系重合体の分子量としては、ゲルパーミエーションクロマトグラフィー(以下、「GPC」ともいう)で測定されるポリスチレン換算の重量平均分子量(以下、「Mw」ともいう)が、好ましくは35,000〜55,000、さらに好ましくは40,000〜50,000である。Mwが35,000未満では、得られる成形体の強度が低いものとなる場合があり、55,000を超えると、流動性が不足して成形性が不十分になる場合がある。また、GPCで測定されるポリスチレン換算の数平均分子量(以下、「Mn」ともいう)は、好ましくは10,000〜25,000、さらに好ましくは10,000〜20,000である。また、本発明で用いる環状オレフィン系重合体の分子量分布(Mw/Mn)は、通常2.0〜3.5、好ましくは2.5〜3.5である。 The molecular weight of the cyclic olefin polymer used in the present invention is preferably a polystyrene-converted weight average molecular weight (hereinafter also referred to as “Mw”) measured by gel permeation chromatography (hereinafter also referred to as “GPC”). Is 35,000-55,000, more preferably 40,000-50,000. If Mw is less than 35,000, the strength of the resulting molded product may be low, and if it exceeds 55,000, fluidity may be insufficient and moldability may be insufficient. The number average molecular weight (hereinafter also referred to as “Mn”) in terms of polystyrene measured by GPC is preferably 10,000 to 25,000, and more preferably 10,000 to 20,000. The molecular weight distribution (Mw / Mn) of the cyclic olefin polymer used in the present invention is usually 2.0 to 3.5, preferably 2.5 to 3.5.
本発明で用いる環状オレフィン系重合体のガラス転移温度(Tg)は、110℃以上であることが好ましく、より好ましくは125〜250℃であり、さらに好ましくは125〜220℃、特に好ましくは130〜200℃である。Tgが110℃以上である場合には、優れた耐熱性を有するため好ましい。Tgが110℃未満である場合には、熱変形温度が低くなるため、耐熱性に問題が生じるおそれがあり、また、得られる成形体における温度による光学特性の変化が大きくなるという問題が生じることがある。一方、Tgが250℃を超える場合には、成形温度が高くなりすぎて本発明の共重合体が熱劣化する場合がある。 The glass transition temperature (Tg) of the cyclic olefin polymer used in the present invention is preferably 110 ° C. or higher, more preferably 125 to 250 ° C., further preferably 125 to 220 ° C., and particularly preferably 130 to 220 ° C. 200 ° C. A Tg of 110 ° C. or higher is preferable because of excellent heat resistance. When Tg is less than 110 ° C., the heat distortion temperature becomes low, which may cause a problem in heat resistance, and the problem that the change in optical properties due to temperature in the obtained molded article increases. There is. On the other hand, when Tg exceeds 250 ° C., the molding temperature becomes too high, and the copolymer of the present invention may be thermally deteriorated.
環状オレフィン系重合体の製造方法については、上述した各単量体の共重合に際しては、用いる各単量体の反応性に留意して重合条件を適宜選択して行うことができる。共重合に際しては、重合系中の単量体組成比が重合初期と後期とで大幅に変化しないことが好ましく、単量体濃度が経時的に変化する場合には、重合を早い段階でストップさせるか、重合系中に濃度の減少した単量体を連続的あるいは間欠的に重合系内に供給して、単量体組成比を一定に保つことが好ましい。このように単量体組成比を制御しながら共重合を行うと、透明性に優れた光学フィルムを形成可能な共重合体を得ることができる。 About the manufacturing method of a cyclic olefin type polymer, in the case of copolymerization of each monomer mentioned above, it can carry out by selecting the polymerization conditions suitably in consideration of the reactivity of each monomer to be used. During copolymerization, it is preferable that the monomer composition ratio in the polymerization system does not change significantly between the initial and late stages of polymerization, and when the monomer concentration changes over time, the polymerization is stopped at an early stage. Alternatively, it is preferable to keep the monomer composition ratio constant by supplying the monomer having a reduced concentration into the polymerization system continuously or intermittently into the polymerization system. When copolymerization is performed while controlling the monomer composition ratio in this way, a copolymer capable of forming an optical film excellent in transparency can be obtained.
本発明で用いる環状オレフィン系重合体を製造するのに好適に用いることのできる開環重合用の触媒としては、例えば、
(I)Olefin Metathesis and Metathesis Polymerization(K.J.IVIN, J.C.MOL, Academic Press 1997)に記載されている触媒が好ましく用いられる。このような触媒としては、例えば、(a)W、Mo、Re、VおよびTiの化合物から選ばれた少なくとも1種と、(b)アルカリ金属元素(例えば、Li、Na、K)、アルカリ土類金属元素(例えば、Mg、Ca)、第12族元素(例えば、Zn、Cd、Hg)、第13族元素(例えば、B、Al)、第14族元素(例えば、Si、Sn、Pd)等の化合物であって、少なくとも1つの当該元素−炭素結合または当該元素−水素結合を有するものから選ばれた少なくとも1種との組み合わせからなるメタセシス触媒が挙げられる。該触媒の活性を高めるために、後述の(c)添加剤が添加されたものであってもよい。
また、その他の触媒として、
(II)周期表第4族〜第8族の遷移金属−カルベン錯体やメタラシクロブタン錯体等からなるメタセシス触媒を用いることができる。
なお、上記触媒(I)と(II)とを組み合わせて用いても差し支えない。
Examples of the catalyst for ring-opening polymerization that can be suitably used for producing the cyclic olefin polymer used in the present invention include:
(I) A catalyst described in Olefin Metathesis and Metathesis Polymerization (KJIVIN, JCMOL, Academic Press 1997) is preferably used. Examples of such a catalyst include (a) at least one selected from compounds of W, Mo, Re, V and Ti, and (b) an alkali metal element (for example, Li, Na, K), alkaline earth. Group metal elements (eg, Mg, Ca), Group 12 elements (eg, Zn, Cd, Hg), Group 13 elements (eg, B, Al), Group 14 elements (eg, Si, Sn, Pd) And a metathesis catalyst comprising a combination with at least one selected from those having at least one of the element-carbon bond or the element-hydrogen bond. In order to enhance the activity of the catalyst, the additive (c) described later may be added.
As other catalysts,
(II) A metathesis catalyst composed of a transition metal-carbene complex or a metallacyclobutane complex of Groups 4 to 8 of the periodic table can be used.
The catalysts (I) and (II) may be used in combination.
本発明で用いる環状オレフィン系重合体の分子量の調節は、重合温度、触媒の種類、溶媒の種類等を調整することによっても行うことができるが、分子量調節剤を開環共重合の反応系に共存させることにより調節することが好ましい。分子量調節剤としては、例えば、エチレン、プロペン、1−ブテン、1−ペンテン、1−ヘキセン、1−ヘプテン、1−オクテン、1−ノネン、1−デセン等のα−オレフィン類およびスチレンが好ましく、これらのうち、1−ブテンおよび1−ヘキセンが特に好ましい。これらの分子量調節剤は、1種単独でも2種以上を組み合わせても使用することができる。この分子量調節剤の使用量は、全単量体1モル当り、通常、0.005〜0.6モル、好ましくは0.02〜0.5モルである。 The molecular weight of the cyclic olefin polymer used in the present invention can be adjusted by adjusting the polymerization temperature, the type of catalyst, the type of solvent, etc., but the molecular weight regulator is used as a reaction system for ring-opening copolymerization. It is preferable to adjust by coexisting. As the molecular weight regulator, for example, ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and other α-olefins and styrene are preferable. Of these, 1-butene and 1-hexene are particularly preferred. These molecular weight regulators can be used singly or in combination of two or more. The amount of the molecular weight regulator used is usually 0.005 to 0.6 mol, preferably 0.02 to 0.5 mol, per mol of all monomers.
開環共重合反応において用いられる溶媒(即ち、単量体、開環重合触媒、分子量調節剤等を溶解する溶媒)としては、例えば、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン等のアルカン類;シクロヘキサン、シクロヘプタン、シクロオクタン、デカリン、ノルボルナン等のシクロアルカン類;ベンゼン、トルエン、キシレン、エチルベンゼン、クメン等の芳香族炭化水素;クロロブタン、ブロムヘキサン、塩化メチレン、ジクロロエタン、ヘキサメチレンジブロミド、クロロベンゼン、クロロホルム、テトラクロロエチレン等のハロゲン化アルカン、ハロゲン化アリール等の化合物;酢酸エチル、酢酸n−ブチル、酢酸iso−ブチル、プロピオン酸メチル等の飽和カルボン酸エステル類;ジブチルエーテル、テトラヒドロフラン、ジメトキシエタン等のエーテル類が挙げられ、これらの中では芳香族炭化水素が好ましい。これらは1種単独でも2種以上を組み合わせても使用することができる。この開環重合反応用溶媒の使用量は、「溶媒:全単量体」の重量比が、通常、1:1〜10:1となる量であり、好ましくは1:1〜5:1となる量であるのが望ましい。 Examples of the solvent used in the ring-opening copolymerization reaction (that is, a solvent that dissolves a monomer, a ring-opening polymerization catalyst, a molecular weight regulator, etc.) include alkanes such as pentane, hexane, heptane, octane, nonane, and decane. Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene , Compounds such as halogenated alkanes such as chloroform and tetrachloroethylene, aryl halides; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate and methyl propionate; dibutyl ether, tetrahydro Emissions, include ethers such as dimethoxyethane, aromatic hydrocarbons are preferred among these. These can be used singly or in combination of two or more. The use amount of the solvent for the ring-opening polymerization reaction is such that the weight ratio of “solvent: total monomer” is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1. Is desirable.
触媒を添加する時のモノマー溶液の温度は、30〜200℃が好ましく、より好ましくは50℃〜180℃である。30℃未満の場合は重合体の収率が低下することがあり、200℃を超える場合は分子量コントロールが困難になることがある。 The temperature of the monomer solution when adding the catalyst is preferably 30 to 200 ° C, more preferably 50 to 180 ° C. When the temperature is lower than 30 ° C, the yield of the polymer may be lowered, and when it exceeds 200 ° C, it may be difficult to control the molecular weight.
開環共重合反応を行う際の反応時間は通常0.1〜10時間であるが、好ましくは0.1〜9時間、より好ましくは0.1〜8時間である。
各環状オレフィン系単量体を開環共重合しただけの開環共重合体は、その分子内にオレフィン性不飽和結合を有しており、耐熱着色などの問題を有しているため、係るオレフィン性不飽和結合は水素添加されることが好ましいが、係る水素添加反応も公知の方法を適用できる。例えば、特開昭63−218726号公報、特開平1−132626号公報、特開平1−240517号公報、特開平2−10221号公報などに記載された触媒や溶媒および温度条件などを適用することで、開環重合反応および水素添加反応を実施することができる。
The reaction time for carrying out the ring-opening copolymerization reaction is usually 0.1 to 10 hours, preferably 0.1 to 9 hours, more preferably 0.1 to 8 hours.
A ring-opening copolymer obtained by ring-opening copolymerization of each cyclic olefin-based monomer has an olefinic unsaturated bond in the molecule and has problems such as heat-resistant coloring. The olefinically unsaturated bond is preferably hydrogenated, but a known method can be applied to the hydrogenation reaction. For example, the catalysts, solvents, temperature conditions, and the like described in JP-A-63-218726, JP-A-1-132626, JP-A-1-240517, JP-A-2-10221, and the like are applied. The ring-opening polymerization reaction and the hydrogenation reaction can be carried out.
環状オレフィン系重合体のオレフィン性不飽和結合の水素添加率としては、通常80モル%以上、好ましくは90モル%以上、さらに好ましくは95モル%以上であることが望ましい。なお、本発明における水素添加反応とは、上記の通り、分子内のオレフィン性不飽和結合に対するものであり、本発明で用いる環状オレフィン系重合体が芳香族基を有する場合、係る芳香族基は屈折率など光学的な特性や耐熱性において有利に作用することもあるので、必ずしも水素添加される必要はない。 The hydrogenation rate of the olefinically unsaturated bond of the cyclic olefin polymer is usually 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more. In addition, as above-mentioned, the hydrogenation reaction in this invention is with respect to the olefinic unsaturated bond in a molecule | numerator, and when the cyclic olefin type polymer used by this invention has an aromatic group, the aromatic group concerned is Since it may act advantageously in optical characteristics such as refractive index and heat resistance, hydrogenation is not necessarily required.
本発明に係る環状オレフィン系重合体は、成形に用いる際、本発明の効果を損なわない範囲において、耐熱劣化性や耐光性の改良のために公知の酸化防止剤や紫外線吸収剤などの添加剤を添加して用いてもよい。例えば、下記フェノール系化合物、チオール系化合物、スルフィド系化合物、ジスルフィド系化合物、リン系化合物からなる群より選ばれる少なくとも1種の化合物を、本発明に係る重合体成分100重量部に対して0.01〜10重量部添加することで、耐熱劣化性を向上させることができる。 When the cyclic olefin polymer according to the present invention is used for molding, additives such as known antioxidants and ultraviolet absorbers are used for improving heat resistance and light resistance within a range not impairing the effects of the present invention. May be used. For example, at least one compound selected from the group consisting of the following phenol-based compounds, thiol-based compounds, sulfide-based compounds, disulfide-based compounds, and phosphorus-based compounds is added in an amount of 0.001 part by weight based on 100 parts by weight of the polymer component according to the present invention. By adding 01 to 10 parts by weight, the heat deterioration resistance can be improved.
フェノール系化合物としては、トリエチレングリコール−ビス[3−(3−t−ブチル−5−メチル−4−ヒドロキシフェニル)プロオネート]、1,6−ヘキサンジオール−ビス[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]、2,4−ビス−(n−オクチルチオ)−6−(4−ヒドロキシ−3,5−ジ−t−ブチルアニリノ)−3,5−トリアジン、ペンタエリスリチル−テトラキス[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]、2,2−チオ−ジエチレンビス[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]、オクタデシル−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]、N,N−ヘキサメチレンビス(3,5−ジ−t−ブチル−4−ヒドロキシ−ヒドロシンナマミド)、1,3,5−トリメチル−2,4,6−トリス(3,5−ジ−t−ブチル−4−ヒドロキシベンジル)ベンゼン、トリス−(3,5−ジ−t−ブチル−4−ヒドロキシベンジル)−イソシアヌレイト、3,9−ビス[2−〔3−(3−t−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオニルオキシ〕−1,1−ジメチルエチル]−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、などを挙げることができる。好ましくは、オクタデシル−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]、1,3,5−トリメチル−2,4,6−トリス(3,5−ジ−t−ブチル−4−ヒドロキシベンジル)ベンゼン、ペンタエリスリチル−テトラキス[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]が挙げられ、特に好ましくは、オクタデシル−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]などを挙げることができる。 Examples of phenolic compounds include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) proonate], 1,6-hexanediol-bis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -3,5-triazine, penta Erythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N-hexamethylenebis 3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) ) Benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5- Methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, and the like. Preferably, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Butyl-4-hydroxybenzyl) benzene, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], particularly preferably octadecyl-3- (3 5-di-t-butyl-4-hydroxyphenyl) propionate] and the like.
チオール系化合物としては、t−ドデシルメルカプタン、ヘキシルメルカプタンなどのアルキルメルカプタン、2−メルカプトベンズイミダゾール、2−メルカプト−6−メチルベンズイミダゾール、1−メチル−2−(メチルメルカプト)ベンズイミダゾール、2−メルカプト−1−メチルベンズイミダゾール、2−メルカプト−4−メチルベンズイミダゾール、2−メルカプト−5−メチルベンズイミダゾール、2−メルカプト−5,6−ジメチルベンズイミダゾール、2−(メチルメルカプト)ベンズイミダゾール、1−メチル−2−(メチルメルカプト)ベンズイミダゾール、2−メルカプト−1,3−ジメチルベンズイミダゾール、メルカプト酢酸などを挙げることができる。 Examples of thiol compounds include alkyl mercaptans such as t-dodecyl mercaptan and hexyl mercaptan, 2-mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1-methyl-2- (methylmercapto) benzimidazole, and 2-mercapto. -1-methylbenzimidazole, 2-mercapto-4-methylbenzimidazole, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5,6-dimethylbenzimidazole, 2- (methylmercapto) benzimidazole, 1- Examples include methyl-2- (methylmercapto) benzimidazole, 2-mercapto-1,3-dimethylbenzimidazole, mercaptoacetic acid, and the like.
スルフィド系化合物としては、2,2−チオ−ジエチレンビス〔3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート〕、2,2−チオビス(4−メチル−6−t−ブチルフェノール)、2,4−ビス(n−オクチルチオメチル)−6−メチルフェノール、ジラウリル3,3'−チオジプロピオネート、ジミリスチル3,3'−チオジプロピオネート、ジステアリル3,3'−チオジプロピオネート、ペンタエリスリチルテトラキス(3−ラウリルチオプロピオネート)、ジトリデシル3,3'−チオジプロピオネートなどを挙げることができる。 Examples of sulfide compounds include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thiobis (4-methyl-6-t- Butylphenol), 2,4-bis (n-octylthiomethyl) -6-methylphenol, dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'- Examples thereof include thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), and ditridecyl 3,3′-thiodipropionate.
ジスルフィド系化合物としては、ビス(4−クロロフェニル)ジスルフィド 、ビス(2−クロロフェニル)ジスルフィド、ビス(2,5−ジクロロフェニル)ジスルフィド 、ビス(2,4,6−トリクロロフェニル)ジスルフィド、ビス(2−ニトロフェニル)ジスルフィド 、2,2'−ジチオジ安息香酸エチル、ビス(4−アセチルフェニル)ジスルフィド 、ビス(4−カルバモイルフェニル)ジスルフィド、1,1'−ジナフチルジスルフィド 、2,2'−ジナフチルジスルフィド 、1,2'−ジナフチルジスルフィド 、2,2'−ビス(1 −クロロジナフチル)ジスルフィド 、1,1'−ビス(2 −クロロナフチル)ジスルフィド 、2,2'−ビス(1 −シアノナフチル)ジスルフィド、2,2'−ビス(1−アセチルナフチル)ジスルフィド、ジラウリル−3,3'−チオジプロピオン酸エステルなどを挙げることができる。 Disulfide compounds include bis (4-chlorophenyl) disulfide, bis (2-chlorophenyl) disulfide, bis (2,5-dichlorophenyl) disulfide, bis (2,4,6-trichlorophenyl) disulfide, bis (2-nitro Phenyl) disulfide, ethyl 2,2′-dithiodibenzoate, bis (4-acetylphenyl) disulfide, bis (4-carbamoylphenyl) disulfide, 1,1′-dinaphthyl disulfide, 2,2′-dinaphthyl disulfide, 1,2'-dinaphthyl disulfide, 2,2'-bis (1-chlorodinaphthyl) disulfide, 1,1'-bis (2-chloronaphthyl) disulfide, 2,2'-bis (1-cyanonaphthyl) Disulfide, 2,2'-bis (1-acetylnaphthyl) disulfide De, and the like dilauryl-3,3'-thiodipropionate.
リン系化合物としては、トリス(4−メトキシ−3,5−ジフェニル)ホスファイト、トリス(ノニルフェニル)ホスファイト、トリス(2,4−ジ−t−ブチルフェニル)ホスファイト、ビス(2,6−ジ−t−ブチル−4−メチルフェニル)ペンタエリストールジホスファイト、ビス(2,4−ジ−t−ブチルフェニル)ペンタエリスリトールジホスファイトなどを挙げることができる。 Examples of phosphorus compounds include tris (4-methoxy-3,5-diphenyl) phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, bis (2,6 -Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, and the like.
さらに、2,4−ジヒドロキシベンゾフェノン、2−ヒドロキシ−4−メトキシベンゾフェノンなどベンゾフェノン系化合物、N−(ベンジルオキシカルボニルオキシ)ベンゾトリアゾールなどのベンゾトリアゾール系化合物、あるいは2−エチルオキサニリド、2−エチル−2'−エトキシオキサニリドなどのオキサニリド系化合物を、共重合体100重量部に対して、0.01〜3重量部、好ましくは0.05〜2重量部添加することにより、耐光性を向上させることができる。 Further, benzophenone compounds such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, benzotriazole compounds such as N- (benzyloxycarbonyloxy) benzotriazole, 2-ethyloxanilide, 2-ethyl By adding 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight of an oxanilide-based compound such as -2'-ethoxyoxanilide to 100 parts by weight of the copolymer, light resistance is improved. Can be improved.
なお、添加剤であるこれらの化合物は、一種単独で用いてもよく、組み合わせて用いて
もよい。
また、本発明の環状オレフィン系重合体には、目的とする成形体の特性に応じて、その他の添加剤を添加してもよい。たとえば、着色された成形体を得ることを目的として、染料、顔料等の着色剤を添加してもよく、得られる成形体の平滑性を向上させることを特徴としてレベリング剤を添加してもよい。レベリング剤としては、たとえば、フッ素系ノニオン界面活性剤、特殊アクリル樹脂系レベリング剤、シリコーン系レベリング剤などが挙げられる。
In addition, these compounds which are additives may be used individually by 1 type, and may be used in combination.
Moreover, you may add another additive to the cyclic olefin polymer of this invention according to the characteristic of the target molded object. For example, for the purpose of obtaining a colored molded article, a colorant such as a dye or a pigment may be added, and a leveling agent may be added to improve the smoothness of the resulting molded article. . Examples of the leveling agent include a fluorine-based nonionic surfactant, a special acrylic resin leveling agent, and a silicone leveling agent.
成形体の製造方法および光学射出成形体
本発明の光学射出成形体は、上述した環状オレフィン系重合体を射出成形してなる。具体的には、上記環状オレフィン系重合体からなるペレットを射出成形して得られる。
本発明に用いる環状オレフィン系重合体は、射出成形の前に、予め、公知の方法で溶存する水分や酸素成分を除去することが好ましい。この際、熱風乾燥機、除湿乾燥機、窒素循環式乾燥機、除湿窒素循環式乾燥機、真空乾燥機など、公知の乾燥装置が用いられる。これらの乾燥装置のうち、色相均一性を有する成型品が得られやすい点で、減圧乾燥機、または窒素などの不活性ガスを循環させる乾燥機を使用することが好ましい。
乾燥温度および乾燥時間は特に限定されるものではないが、通常Tg−100℃〜Tg−20℃で、通常2〜6時間乾燥される。
Method for Producing Molded Body and Optical Injection Molded Body The optical injection molded body of the present invention is formed by injection molding the above-mentioned cyclic olefin polymer. Specifically, it is obtained by injection molding a pellet made of the above cyclic olefin polymer.
It is preferable that the cyclic olefin polymer used in the present invention removes water and oxygen components dissolved by a known method in advance before injection molding. At this time, a known drying device such as a hot air dryer, a dehumidifying dryer, a nitrogen circulating dryer, a dehumidifying nitrogen circulating dryer, or a vacuum dryer is used. Among these dryers, it is preferable to use a vacuum dryer or a dryer that circulates an inert gas such as nitrogen because a molded product having hue uniformity is easily obtained.
Although a drying temperature and drying time are not specifically limited, Usually, it is dried at Tg-100 degreeC-Tg-20 degreeC for 2 to 6 hours normally.
射出成形に使用される射出成形機は特に限定されないが、たとえば、シリンダーの方式としてはインライン方式、プリプラ方式;駆動方式としては油圧式、電動式、ハイブリッド式;型締め方式としては直圧式、トグル式;射出方向としては横型、縦型などが挙げられる。また、型締め方式は射出圧縮できるものでもよい。シリンダー径および型締め力は目的の成形体の形状により決まるが、一般に成形体の投影面積が大きい場合は型締め力を大きくすることが好ましく、成形体の容量が大きい場合はシリンダー径の大きくすることが好ましい。 The injection molding machine used for injection molding is not particularly limited. For example, the cylinder method is an in-line method, a pre-plastic method; the drive method is hydraulic, electric, hybrid; the mold clamping method is direct pressure, and toggle Formula: Examples of the injection direction include a horizontal type and a vertical type. Further, the mold clamping method may be one that can be injection-compressed. Cylinder diameter and clamping force are determined by the shape of the target molded body. Generally, it is preferable to increase the clamping force when the projected area of the molded body is large, and increase the cylinder diameter when the capacity of the molded body is large. It is preferable.
シリンダーがインライン式の場合、圧縮比、長さ/直径の比、サブフライトの有無などのスクリュー形状は適宜選択でき、スクリュー表面には、クロム系、チタン系、窒化物系、炭素系など、公知のコーティングを施してもよい。また、計量や射出動作の安定性を向上するためにスクリューの回転や圧力を制御する機構などを設けてもよい。また、シリンダー内や樹脂組成物を貯蔵するホッパー内を減圧にしたり、シリンダーおよびホッパーを窒素などの不活性ガスでシールしたりすることは、成形体が安定に得られるという観点から好ましい。 When the cylinder is an in-line type, the screw shape such as compression ratio, length / diameter ratio, subflight presence, etc. can be selected as appropriate, and the screw surface is known such as chromium, titanium, nitride, carbon, etc. The coating may be applied. Further, a mechanism for controlling the rotation and pressure of the screw may be provided in order to improve the stability of measurement and injection operation. Moreover, it is preferable from a viewpoint that a molded object can be obtained stably that pressure reduction is carried out in the cylinder and the hopper which stores a resin composition, or a cylinder and a hopper are sealed with inert gas, such as nitrogen.
本発明の成形体は、公知の材質や構造を有する金型を用いて製造される。このような金型は、成形体の形状に対応するキャビティーを有する。金型の好ましい材質としては、通常の炭素鋼、ステンレス鋼、またはこれらをベースにした公知の合金類が挙げられ、金型の表面に、焼き入れ処理、クロム、チタン、ダイヤモンドなどによる公知のコーティング処理、またはニッケル系金属、銅合金などによるパターン加工のための金属メッキを施してもよい。 The molded body of the present invention is manufactured using a mold having a known material or structure. Such a mold has a cavity corresponding to the shape of the molded body. Examples of preferable materials for the mold include ordinary carbon steel, stainless steel, and known alloys based on these, and the surface of the mold is subjected to quenching treatment, known coating with chromium, titanium, diamond, or the like. Metal plating for processing or pattern processing with nickel-based metal, copper alloy or the like may be applied.
また、集光や反射防止などを目的として成形体表面にパターンを形成する場合には、金型の金属コーティング面もしくは金属メッキ面、またはスタンパ表面に、放電加工機、切削加工機などの公知の加工機で直接パターンを形成してもよく、電鋳などの方法でパターンを形成してもよい。 In addition, when forming a pattern on the surface of the molded body for the purpose of collecting light or preventing reflection, a known method such as an electric discharge machine or a cutting machine is applied to the metal coating surface or metal plating surface of the mold or the stamper surface. The pattern may be formed directly by a processing machine, or the pattern may be formed by a method such as electroforming.
射出成形の際、成形体のソリの低減や安定した連続成形のために、金型のキャビティー内を減圧する方法または射出圧縮方法が好適に用いられる。
金型のキャビティー内を減圧して射出成形する場合、減圧度は、ゲージ圧で、好ましくは−0.08MPa以下、さらに好ましくは−0.09MPa以下、特に好ましくは−0.1MPa以下である。上記範囲を超えると、減圧度が不足し、光透過性および光拡散性に優れた成形体を得られないことがある。
上記範囲の減圧度は、公知の方法、たとえば真空ポンプを使用して達成される。キャビティー周囲やエジェクター機構部などに、Oリングなどの公知のシール材を使用することが好ましく、成形体に不純物が混入しないなどの範囲で真空用のグリスなどを使用してもよい。また、真空ポンプ等の減圧装置と接続するための吸引口は、金型内の任意の場所に設ければよいが、通常、エジェクター機構部、スプルーおよびランナーの端部、入れ子構造部などに設けられる。また、真空吸引シーケンスは、金型の開閉に併せて電磁バルブなどで制御してもよく、常時運転してもよく、溶融樹脂の充填時に金型のキャビティー内を所望の減圧度にできる方法であれば特に制限されない。
At the time of injection molding, a method of reducing the pressure in the cavity of the mold or an injection compression method is preferably used in order to reduce warping of the molded body and stable continuous molding.
When injection molding is performed by reducing the pressure inside the cavity of the mold, the degree of reduced pressure is a gauge pressure, preferably −0.08 MPa or less, more preferably −0.09 MPa or less, and particularly preferably −0.1 MPa or less. . When the above range is exceeded, the degree of reduced pressure is insufficient, and a molded article excellent in light transmittance and light diffusibility may not be obtained.
The degree of vacuum in the above range is achieved using a known method such as a vacuum pump. It is preferable to use a known sealing material such as an O-ring around the cavity or the ejector mechanism, and vacuum grease or the like may be used as long as no impurities are mixed into the molded body. In addition, the suction port for connecting to a decompression device such as a vacuum pump may be provided at any location in the mold, but is usually provided at the ejector mechanism, the end of the sprue and runner, the nested structure, etc. It is done. In addition, the vacuum suction sequence may be controlled by an electromagnetic valve or the like in conjunction with the opening and closing of the mold, may be operated at all times, and a method that allows the inside of the mold cavity to have a desired degree of decompression when filling with molten resin If it is, it will not be restrict | limited in particular.
金型のキャビティー内を減圧して射出成形する場合、キャビティーを閉じ減圧になった状態で溶融樹脂を射出するため、通常、射出遅延時間を設定する。射出遅延時間は、使用する真空ポンプの能力およびキャビティーサイズに依存するが、通常0.5〜3秒程度である。
一方、射出圧縮成形方法では、キャビティー間隔を成形体の厚みの1.5〜20倍に設定し、その隙間に溶融樹脂を射出し、シリンダー側で測定される樹脂の圧力を200〜2,000kgf/cm2の範囲に保持しながら、金型内の成形体面を圧縮し、キャビティーの間隔を狭くすればよい。
When injection molding is performed by reducing the pressure inside the mold cavity, the injection delay time is usually set in order to inject the molten resin with the cavity closed and reduced pressure. The injection delay time depends on the capacity of the vacuum pump used and the cavity size, but is usually about 0.5 to 3 seconds.
On the other hand, in the injection compression molding method, the cavity interval is set to 1.5 to 20 times the thickness of the molded body, molten resin is injected into the gap, and the resin pressure measured on the cylinder side is 200 to 2, What is necessary is just to compress the molded object surface in a metal mold | die, hold | maintaining in the range of 000 kgf / cm < 2 >, and narrow the space | interval of a cavity.
また、金型のコアを成形体の厚みの1.1倍〜10倍に設定して可動状態とし、そこに溶融樹脂を射出して、射出開始あるいは射出終了後から、可動側コアを平均速度0.01mm/sec〜1mm/secで圧縮してもよい。
これらの射出圧縮成形方法には、公知の成形機が用いられる。
Further, the mold core is set to a movable state by setting the mold core to 1.1 to 10 times the thickness of the molded body, and molten resin is injected into the mold core. You may compress at 0.01 mm / sec-1 mm / sec.
A known molding machine is used for these injection compression molding methods.
射出成形のその他の条件は、特に限定されるものではないが、通常、シリンダー温度が260〜350℃、金型温度は、環状オレフィン系重合体のガラス転移温度Tgに基づいて、通常Tg−1〜Tg−40℃、好ましくはTg−5〜Tg−25℃の範囲である。また、射出速度は、本発明の成形体の大きさや成形機のシリンダーサイズにより異なるが、たとえば、シリンダー径が28mmの場合、通常80mm/sec以上、好ましくは90〜250mm/secである。保圧では、成形体の形状が保持できる程度の最小圧・時間に適宜調整することが好ましい。 Other conditions for injection molding are not particularly limited, but the cylinder temperature is usually 260 to 350 ° C., and the mold temperature is usually Tg-1 based on the glass transition temperature Tg of the cyclic olefin polymer. It is -Tg-40 degreeC, Preferably it is the range of Tg-5-Tg-25 degreeC. The injection speed varies depending on the size of the molded product of the present invention and the cylinder size of the molding machine. For example, when the cylinder diameter is 28 mm, it is usually 80 mm / sec or more, preferably 90 to 250 mm / sec. In the holding pressure, it is preferable to appropriately adjust to the minimum pressure and time that can maintain the shape of the molded body.
さらに、金型内でのガス成分の圧縮による高温化に起因する樹脂の炭化や、金型内に滞留する揮発成分の凝縮防止を目的として、レンズのキャビティー周囲にガスベント機構を設けてもよい。通常ガスベントの厚みは、50〜150nmの深さで形成される。ガスベントはキャビティーの一部に設けてもよいが、ゲート部を除く全面に形成することも好ましい。また、このようなガスベントは、金型のゲート部、またはランナー部に形成してもよい。 Furthermore, a gas vent mechanism may be provided around the lens cavity for the purpose of preventing carbonization of the resin due to high temperature due to compression of the gas component in the mold and condensation of the volatile component staying in the mold. . Usually, the thickness of the gas vent is formed to a depth of 50 to 150 nm. The gas vent may be provided in a part of the cavity, but is preferably formed on the entire surface except the gate portion. Moreover, you may form such a gas vent in the gate part of a metal mold | die, or a runner part.
次に実施例によって本発明の方法を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。実施例および比較例で得られた共重合体および成形体の評価は下記の方法によって行った。 Next, the method of the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The copolymers and molded products obtained in Examples and Comparative Examples were evaluated by the following methods.
<ガラス転移温度(Tg)>
セイコーインスツルメンツ社製DSC6200を用いて、昇温速度を毎分20℃、窒素気流下で測定した。ガラス転移温度(Tg)は、微分示差走査熱量の最大ピーク温度(A点)および最大ピーク温度より−20℃の温度(B点)を示差走査熱量曲線上にプロットし、B点を起点とするベースライン上の接線とA点を起点とする接線との交点として求めた。
<Glass transition temperature (Tg)>
Using a DSC6200 manufactured by Seiko Instruments Inc., the rate of temperature increase was measured at 20 ° C. per minute under a nitrogen stream. For the glass transition temperature (Tg), the differential peak scanning calorie maximum peak temperature (point A) and the temperature of −20 ° C. from the maximum peak temperature (point B) are plotted on the differential scanning calorimetry curve, and the point B is the starting point. It was determined as the intersection of the tangent on the baseline and the tangent starting from point A.
<メルトフローレート(MFR)>
JIS K7210に準拠して、98N荷重、260℃でのMFRを測定した。
<Melt flow rate (MFR)>
Based on JIS K7210, MFR at a load of 98 N and 260 ° C. was measured.
<重量平均分子量および分子量分布>
ゲルパーミエーションクロマトグラフィー(GPC、東ソー株式会社製、商品名:HLC-8020)を用い、溶媒としてテトラヒドロフラン(THF)を用いて、ポリスチレン換算の重量平均分子量(Mw)および分子量分布(Mw/Mn)を測定した。
THFに溶解しないポリマーは、溶媒としてオルトジクロロベンゼンを用いて、GPC(Polymer Laboratories社製、商品名:PL−GPC220)を用い、ポリスチレン換算の重量平均分子量(Mw)および分子量分布(Mw/Mn)を測定した。
<Weight average molecular weight and molecular weight distribution>
Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) in terms of polystyrene using gel permeation chromatography (GPC, manufactured by Tosoh Corporation, trade name: HLC-8020) and using tetrahydrofuran (THF) as a solvent. Was measured.
Polymers that are not soluble in THF use orthodichlorobenzene as a solvent, GPC (manufactured by Polymer Laboratories, trade name: PL-GPC220), polystyrene-converted weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) Was measured.
<破断伸び>
射出成形で成形した試験片を用い、ASTM D638の方法により、樹脂の破断伸びを測定した。
<Elongation at break>
Using a test piece molded by injection molding, the elongation at break of the resin was measured by the method of ASTM D638.
<実施例1>
単量体(1)としてジシクロペンタジエン23.5重量部、単量体(2)として8−メチル−8−カルボキシメチルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン75.5重量部、単量体(3)として2−ノルボルネンを1重量部、分子量調節剤として1−ヘキセン14.7重量部、および溶媒としてトルエン150重量部を窒素置換した反応容器に加え、107℃に加熱した。これにトリエチルアルミニウムのトルエン溶液(0.6mol/l)0.40重量部、およびメタノール変性WCl6のトルエン溶液(0.025mol/l)1.8重量部を加え、107℃で1時間反応させることにより開環重合体を得た。
得られた開環重合体の溶液360重量部に水素添加反応触媒であるRu[4−CH3(CH2)4C6H4CO2]H(CO)[P(C6H5)3]を0.04重量部添加し、水素ガス圧を9〜10MPaとし、160〜165℃の温度で、3時間反応させた。反応終了後、得られた生成物を多量のメタノール中で沈殿させることにより水素添加物を得た[重量平均分子量(Mw)=45900、分子量分布(Mw/Mn)=2.8]。この水素添加物を、真空乾燥して環状オレフィン系重合体を得た。環状オレフィン系重合体のガラス転移温度(Tg)を測定したところ140℃であった。
<Example 1>
23.5 parts by weight of dicyclopentadiene as the monomer (1) and 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene 75.5 parts by weight, 1 part by weight of 2-norbornene as monomer (3), 14.7 parts by weight of 1-hexene as a molecular weight regulator, and 150 parts by weight of toluene as a solvent Was added to a reaction vessel purged with nitrogen and heated to 107 ° C. To this, 0.40 parts by weight of a toluene solution of triethylaluminum (0.6 mol / l) and 1.8 parts by weight of a toluene solution of methanol-modified WCl 6 (0.025 mol / l) are added and reacted at 107 ° C. for 1 hour. As a result, a ring-opened polymer was obtained.
Ru [4-CH 3 (CH 2 ) 4 C 6 H 4 CO 2 ] H (CO) [P (C 6 H 5 ) 3, which is a hydrogenation reaction catalyst, is added to 360 parts by weight of the obtained ring-opening polymer solution. 0.04 part by weight was added, the hydrogen gas pressure was adjusted to 9 to 10 MPa, and the reaction was performed at a temperature of 160 to 165 ° C. for 3 hours. After completion of the reaction, the resulting product was precipitated in a large amount of methanol to obtain a hydrogenated product [weight average molecular weight (Mw) = 45900, molecular weight distribution (Mw / Mn) = 2.8]. This hydrogenated product was vacuum-dried to obtain a cyclic olefin polymer. It was 140 degreeC when the glass transition temperature (Tg) of the cyclic olefin polymer was measured.
2軸押出機を用い、得られた環状オレフィン系重合体(1)を溶融混練りした後、ストランド上に押出し、水冷後フィーダールーダーを通してペレットを得た。得られたペレットを100℃の乾燥機にて2時間真空乾燥させた後、射出成形機(住友重機製 SG75M−S(シリンダー径28mm、型締め75ton))にて射出成形を行い、80mm×60mm×3.2mmの試験片を製造した。射出成形速度は、100mm/sec、シリンダー温度は、樹脂のTg+140〜160℃、金型温度は樹脂のTg−10〜−20℃の条件で行った。得られた試験片を用いて、破断伸びとMFRの評価を行った。結果を表1に示す。 The obtained cyclic olefin polymer (1) was melt-kneaded using a twin-screw extruder, then extruded onto a strand, cooled with water, and then pellets were obtained through a feeder ruler. The obtained pellets were vacuum-dried with a dryer at 100 ° C. for 2 hours, and then injection-molded with an injection molding machine (SG75M-S (cylinder diameter: 28 mm, mold clamping: 75 ton) manufactured by Sumitomo Heavy Industries), and 80 mm × 60 mm. A test piece of × 3.2 mm was produced. The injection molding speed was 100 mm / sec, the cylinder temperature was Tg + 140 to 160 ° C. of the resin, and the mold temperature was Tg−10 to −20 ° C. of the resin. Using the obtained test piece, elongation at break and MFR were evaluated. The results are shown in Table 1.
<実施例2>
単量体(1)としてジシクロペンタジエン23.5重量部、単量体(2)として8−メチル−8−カルボキシメチルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン75.5重量部、単量体(3)として2−ノルボルネンを1重量部、分子量調節剤として1−ヘキセン13.4重量部、および溶媒としてトルエン150重量部を窒素置換した反応容器に加え、107℃に加熱した。これにトリエチルアルミニウムのトルエン溶液(0.6mol/l)0.40重量部、およびメタノール変性WCl6のトルエン溶液(0.025mol/l)1.8重量部を加え、107℃で1時間反応させることにより開環重合体を得た。
<Example 2>
23.5 parts by weight of dicyclopentadiene as the monomer (1) and 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene 75.5 parts by weight, 1 part by weight of 2-norbornene as monomer (3), 13.4 parts by weight of 1-hexene as a molecular weight regulator, and 150 parts by weight of toluene as a solvent Was added to a reaction vessel purged with nitrogen and heated to 107 ° C. To this, 0.40 parts by weight of a toluene solution of triethylaluminum (0.6 mol / l) and 1.8 parts by weight of a toluene solution of methanol-modified WCl 6 (0.025 mol / l) are added and reacted at 107 ° C. for 1 hour. As a result, a ring-opened polymer was obtained.
得られた開環重合体の溶液360重量部に水素添加反応触媒であるRu[4−CH3(CH2)4C6H4CO2]H(CO)[P(C6H5)3]を0.04重量部添加し、水素ガス圧を9〜10MPaとし、160〜165℃の温度で、3時間反応させた。反応終了後、得られた生成物を多量のメタノール中で沈殿させることにより水素添加物を得た[重量平均分子量(Mw)=52100、分子量分布(Mw/Mn)=2.9]。この水素添加物を、真空乾燥して環状オレフィン系重合体を得た。環状オレフィン系重合体のガラス転移温度(Tg)を測定したところ140℃であった。
得られた環状オレフィン系重合体を用いた以外は実施例1と同様にして試験片を作製し、評価を行った。結果を表1に併せて示す。
Ru [4-CH 3 (CH 2 ) 4 C 6 H 4 CO 2 ] H (CO) [P (C 6 H 5 ) 3, which is a hydrogenation reaction catalyst, is added to 360 parts by weight of the obtained ring-opening polymer solution. 0.04 part by weight was added, the hydrogen gas pressure was adjusted to 9 to 10 MPa, and the reaction was performed at a temperature of 160 to 165 ° C. for 3 hours. After completion of the reaction, the resulting product was precipitated in a large amount of methanol to obtain a hydrogenated product [weight average molecular weight (Mw) = 52100, molecular weight distribution (Mw / Mn) = 2.9]. This hydrogenated product was vacuum-dried to obtain a cyclic olefin polymer. It was 140 degreeC when the glass transition temperature (Tg) of the cyclic olefin polymer was measured.
A test piece was prepared and evaluated in the same manner as in Example 1 except that the obtained cyclic olefin polymer was used. The results are also shown in Table 1.
<実施例3>
単量体(1)としてジシクロペンタジエン23.5重量部、単量体(2)として8−メチル−8−カルボキシメチルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン75.5重量部、単量体(3)として2−ノルボルネンを1重量部、分子量調節剤として1−ヘキセン16.8重量部、および溶媒としてトルエン150重量部を窒素置換した反応容器に加え、107℃に加熱した。これにトリエチルアルミニウムのトルエン溶液(0.6mol/l)0.40重量部、およびメタノール変性WCl6のトルエン溶液(0.025mol/l)1.8重量部を加え、107℃で1時間反応させることにより開環重合体を得た。
<Example 3>
23.5 parts by weight of dicyclopentadiene as the monomer (1) and 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene 75.5 parts by weight, 1 part by weight of 2-norbornene as monomer (3), 16.8 parts by weight of 1-hexene as a molecular weight regulator, and 150 parts by weight of toluene as a solvent Was added to a reaction vessel purged with nitrogen and heated to 107 ° C. To this, 0.40 parts by weight of a toluene solution of triethylaluminum (0.6 mol / l) and 1.8 parts by weight of a toluene solution of methanol-modified WCl 6 (0.025 mol / l) are added and reacted at 107 ° C. for 1 hour. As a result, a ring-opened polymer was obtained.
得られた開環重合体の溶液360重量部に水素添加反応触媒であるRu[4−CH3(CH2)4C6H4CO2]H(CO)[P(C6H5)3]を0.04重量部添加し、水素ガス圧を9〜10MPaとし、160〜165℃の温度で、3時間反応させた。反応終了後、得られた生成物を多量のメタノール中で沈殿させることにより水素添加物を得た[重量平均分子量(Mw)=40000、分子量分布(Mw/Mn)=2.9]。この水素添加物を、真空乾燥して環状オレフィン系重合体を得た。環状オレフィン系重合体のガラス転移温度(Tg)を測定したところ139℃であった。
得られた環状オレフィン系重合体を用いた以外は実施例1と同様にして試験片を作製し、評価を行った。結果を表1に併せて示す。
Ru [4-CH 3 (CH 2 ) 4 C 6 H 4 CO 2 ] H (CO) [P (C 6 H 5 ) 3, which is a hydrogenation reaction catalyst, is added to 360 parts by weight of the obtained ring-opening polymer solution. 0.04 part by weight was added, the hydrogen gas pressure was adjusted to 9 to 10 MPa, and the reaction was performed at a temperature of 160 to 165 ° C. for 3 hours. After completion of the reaction, the resulting product was precipitated in a large amount of methanol to obtain a hydrogenated product [weight average molecular weight (Mw) = 40000, molecular weight distribution (Mw / Mn) = 2.9]. This hydrogenated product was vacuum-dried to obtain a cyclic olefin polymer. It was 139 degreeC when the glass transition temperature (Tg) of the cyclic olefin polymer was measured.
A test piece was prepared and evaluated in the same manner as in Example 1 except that the obtained cyclic olefin polymer was used. The results are also shown in Table 1.
<実施例4>
単量体(1)としてジシクロペンタジエン44重量部、単量体(2)としてテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン55重量部、単量体(3)として2−ノルボルネンを1重量部、分子量調節剤として1−ヘキセン0.6重量部、および溶媒としてトルエン5重量部、シクロヘキサン235重量部を窒素置換した反応容器に加え、70℃に加熱した。これにトリイソブチルアルミニウムのトルエン溶液(1.0mol/l)1.3重量部、イソブチルアルコールのシクロヘキサン溶液(1.0mol/l)1.0重量部、アセトンのトルエン溶液(0.1mol/l)3.4重量部、およびWCl6のトルエン溶液(0.025mol/l)14重量部を加え、70℃で1時間反応させることにより開環重合体を得た。
<Example 4>
44 parts by weight of dicyclopentadiene as the monomer (1) and tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene 55 parts by weight, monomer (3) 2-norbornene 1 part by weight, molecular weight regulator 1-hexene 0.6 part by weight, solvent 5 parts by weight toluene, cyclohexane 235 parts by weight of the reaction vessel was purged with nitrogen and heated to 70 ° C. To this, 1.3 parts by weight of a toluene solution of triisobutylaluminum (1.0 mol / l), 1.0 part by weight of a cyclohexane solution of isobutyl alcohol (1.0 mol / l), a toluene solution of acetone (0.1 mol / l) A ring-opening polymer was obtained by adding 3.4 parts by weight and 14 parts by weight of a toluene solution of WCl 6 (0.025 mol / l) and reacting at 70 ° C. for 1 hour.
得られた開環重合体の溶液1500重量部に水素添加反応触媒であるRu[4−CH3(CH2)4C6H4CO2]H(CO)[P(C6H5)3]を0.1重量部添加し、水素ガス圧を9〜10MPaとし、160〜165℃の温度で、3時間反応させた。反応終了後、得られた生成物を多量のメタノール中で沈殿させることにより水素添加物を得た[重量平均分子量(Mw)=45300、分子量分布(Mw/Mn)=2.7]。この水素添加物を、真空乾燥して環状オレフィン系重合体を得た。環状オレフィン系重合体のガラス転移温度(Tg)を測定したところ130℃であった。
得られた環状オレフィン系重合体を用いた以外は実施例1と同様にして試験片を作製し、評価を行った。結果を表1に併せて示す。
Ru [4-CH 3 (CH 2 ) 4 C 6 H 4 CO 2 ] H (CO) [P (C 6 H 5 ) 3, which is a hydrogenation reaction catalyst, was added to 1500 parts by weight of the obtained ring-opened polymer solution. 0.1 part by weight was added, the hydrogen gas pressure was adjusted to 9 to 10 MPa, and the reaction was performed at a temperature of 160 to 165 ° C. for 3 hours. After completion of the reaction, the resulting product was precipitated in a large amount of methanol to obtain a hydrogenated product [weight average molecular weight (Mw) = 45300, molecular weight distribution (Mw / Mn) = 2.7]. This hydrogenated product was vacuum-dried to obtain a cyclic olefin polymer. The glass transition temperature (Tg) of the cyclic olefin polymer was measured and found to be 130 ° C.
A test piece was prepared and evaluated in the same manner as in Example 1 except that the obtained cyclic olefin polymer was used. The results are also shown in Table 1.
<比較例1>
単量体(3)を用いず、単量体(1)としてジシクロペンタジエン40重量部、単量体(2)として8−メチル−8−カルボキシメチルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン60重量部、分子量調節剤として1−ヘキセン14.1重量部、および溶媒としてトルエン150重量部を窒素置換した反応容器に加え、107℃に加熱した。これにトリエチルアルミニウムのトルエン溶液(0.6mol/l)0.40重量部、およびメタノール変性WCl6のトルエン溶液(0.025mol/l)1.8重量部を加え、107℃で1時間反応させることにより開環重合体を得た。
<Comparative Example 1>
Without using the monomer (3), 40 parts by weight of dicyclopentadiene as the monomer (1) and 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 2 as the monomer (2) , 5 . 1 7,10 ] -3-dodecene 60 parts by weight, 1-hexene 14.1 parts by weight as a molecular weight regulator and 150 parts by weight toluene as a solvent were added to a nitrogen-substituted reaction vessel and heated to 107 ° C. To this, 0.40 parts by weight of a toluene solution of triethylaluminum (0.6 mol / l) and 1.8 parts by weight of a toluene solution of methanol-modified WCl 6 (0.025 mol / l) are added and reacted at 107 ° C. for 1 hour. As a result, a ring-opened polymer was obtained.
得られた開環重合体の溶液360重量部に水素添加反応触媒であるRu[4−CH3(CH2)4C6H4CO2]H(CO)[P(C6H5)3]を0.04重量部添加し、水素ガス圧を9〜10MPaとし、160〜165℃の温度で、3時間反応させた。反応終了後、得られた生成物を多量のメタノール中で沈殿させることにより水素添加物を得た[重量平均分子量(Mw)=55000、分子量分布(Mw/Mn)=3.2]。この水素添加物を、真空乾燥して環状オレフィン系重合体を得た。環状オレフィン系重合体のガラス転移温度(Tg)を測定したところ135℃であった。
得られた環状オレフィン系重合体を用いた以外は実施例1と同様にして試験片を作製し、評価を行った。結果を表1に併せて示す。
Ru [4-CH 3 (CH 2 ) 4 C 6 H 4 CO 2 ] H (CO) [P (C 6 H 5 ) 3, which is a hydrogenation reaction catalyst, is added to 360 parts by weight of the obtained ring-opening polymer solution. 0.04 part by weight was added, the hydrogen gas pressure was adjusted to 9 to 10 MPa, and the reaction was performed at a temperature of 160 to 165 ° C. for 3 hours. After completion of the reaction, the resulting product was precipitated in a large amount of methanol to obtain a hydrogenated product [weight average molecular weight (Mw) = 55000, molecular weight distribution (Mw / Mn) = 3.2]. This hydrogenated product was vacuum-dried to obtain a cyclic olefin polymer. It was 135 degreeC when the glass transition temperature (Tg) of the cyclic olefin type polymer was measured.
A test piece was prepared and evaluated in the same manner as in Example 1 except that the obtained cyclic olefin polymer was used. The results are also shown in Table 1.
<比較例3>
単量体(1)を用いず、単量体(2)として8−メチル−8−カルボキシメチルテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン89重量部、その他の単量体として2−ノルボルネンを11重量部、分子量調節剤として1−ヘキセン16.8重量部、および溶媒としてトルエン150重量部を窒素置換した反応容器に加え、80℃に加熱した。これにトリエチルアルミニウムのトルエン溶液(0.6mol/l)0.20重量部、およびメタノール変性WCl6のトルエン溶液(0.025mol/l)0.89重量部を加え、80℃で1時間反応させることにより開環重合体を得た。
<Comparative Example 3>
Monomer (1) was not used, and 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene 89 parts by weight, 11 parts by weight of 2-norbornene as the other monomer, 16.8 parts by weight of 1-hexene as the molecular weight regulator, and 150 parts by weight of toluene as the solvent And heated to 80 ° C. To this, 0.20 parts by weight of a toluene solution of triethylaluminum (0.6 mol / l) and 0.89 parts by weight of a toluene solution of methanol-modified WCl 6 (0.025 mol / l) are added and reacted at 80 ° C. for 1 hour. As a result, a ring-opened polymer was obtained.
得られた開環重合体の溶液360重量部に水素添加反応触媒であるRuHCl(CO)[P(C6H5)3]3を0.04重量部添加し、水素ガス圧を9〜10MPaとし、160〜165℃の温度で、3時間反応させた。反応終了後、得られた生成物を多量のメタノール中で沈殿させることにより水素添加物を得た[重量平均分子量(Mw)=49700、分子量分布(Mw/Mn)=3.3]。この水素添加物を、真空乾燥して環状オレフィン系重合体を得た。環状オレフィン系重合体のガラス転移温度(Tg)を測定したところ130℃であった。
得られた環状オレフィン系重合体を用いた以外は実施例1と同様にして試験片を作製し、評価を行った。結果を表1に併せて示す。
To 360 parts by weight of the obtained ring-opening polymer solution, 0.04 part by weight of RuHCl (CO) [P (C 6 H 5 ) 3 ] 3 as a hydrogenation reaction catalyst was added, and the hydrogen gas pressure was 9 to 10 MPa. And reacted at a temperature of 160 to 165 ° C. for 3 hours. After completion of the reaction, the resulting product was precipitated in a large amount of methanol to obtain a hydrogenated product [weight average molecular weight (Mw) = 49700, molecular weight distribution (Mw / Mn) = 3.3]. This hydrogenated product was vacuum-dried to obtain a cyclic olefin polymer. The glass transition temperature (Tg) of the cyclic olefin polymer was measured and found to be 130 ° C.
A test piece was prepared and evaluated in the same manner as in Example 1 except that the obtained cyclic olefin polymer was used. The results are also shown in Table 1.
Claims (10)
−(CH2)pCOOR’ ・・・(4)
(式(4)中、pは、0又は1〜5の整数であり、R’は、炭素数1〜15の炭化水素基である。) The manufacturing method of the molded object of Claim 1 , Claim 2, or Claim 3 by which the polar group in said Formula (2) is represented by following formula (4).
- (CH 2) p COOR ' ··· (4)
(In Formula (4), p is 0 or an integer of 1 to 5, and R ′ is a hydrocarbon group having 1 to 15 carbon atoms.)
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CN101497700A (en) | 2009-08-05 |
TWI444426B (en) | 2014-07-11 |
JP2015120348A (en) | 2015-07-02 |
KR20090084729A (en) | 2009-08-05 |
KR101644186B1 (en) | 2016-07-29 |
TW200940640A (en) | 2009-10-01 |
KR20150085499A (en) | 2015-07-23 |
CN101497700B (en) | 2012-10-31 |
JP2013099950A (en) | 2013-05-23 |
JP2009203461A (en) | 2009-09-10 |
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