JP4193672B2 - Norbornene resin and process for producing the same - Google Patents
Norbornene resin and process for producing the same Download PDFInfo
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- JP4193672B2 JP4193672B2 JP2003364331A JP2003364331A JP4193672B2 JP 4193672 B2 JP4193672 B2 JP 4193672B2 JP 2003364331 A JP2003364331 A JP 2003364331A JP 2003364331 A JP2003364331 A JP 2003364331A JP 4193672 B2 JP4193672 B2 JP 4193672B2
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- general formula
- norbornene
- atom
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- Prior art date
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- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 title claims description 89
- 229920005989 resin Polymers 0.000 title claims description 57
- 239000011347 resin Substances 0.000 title claims description 57
- 238000000034 method Methods 0.000 title claims description 5
- 239000000178 monomer Substances 0.000 claims description 72
- 238000007142 ring opening reaction Methods 0.000 claims description 32
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 28
- 125000000623 heterocyclic group Chemical group 0.000 claims description 27
- 150000002430 hydrocarbons Chemical group 0.000 claims description 27
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 125000005843 halogen group Chemical group 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 16
- 125000001424 substituent group Chemical group 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 125000004434 sulfur atom Chemical group 0.000 claims description 16
- 125000005647 linker group Chemical group 0.000 claims description 15
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 125000002950 monocyclic group Chemical group 0.000 claims description 13
- 125000003367 polycyclic group Chemical group 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000002837 carbocyclic group Chemical group 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 27
- -1 cyclic olefin Chemical class 0.000 description 23
- 239000010408 film Substances 0.000 description 22
- 230000003287 optical effect Effects 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 18
- 238000005984 hydrogenation reaction Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 229920005672 polyolefin resin Polymers 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000012788 optical film Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 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 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 4
- 238000005649 metathesis reaction Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- CEZOPAJMZDAYBD-UHFFFAOYSA-N tetradec-12-ene-5,7-dione Chemical compound CCCCC(CC(CCCCC=CC)=O)=O CEZOPAJMZDAYBD-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- VODGIHGZLYFMOJ-UHFFFAOYSA-N tridec-12-ene-5,7-dione Chemical compound CCCCC(=O)CC(=O)CCCCC=C VODGIHGZLYFMOJ-UHFFFAOYSA-N 0.000 description 3
- DNZZPKYSGRTNGK-PQZOIKATSA-N (1z,4z)-cycloocta-1,4-diene Chemical compound C1C\C=C/C\C=C/C1 DNZZPKYSGRTNGK-PQZOIKATSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-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
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 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
- 125000004429 atom Chemical group 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 2
- ZOLLIQAKMYWTBR-RYMQXAEESA-N cyclododecatriene Chemical compound C/1C\C=C\CC\C=C/CC\C=C\1 ZOLLIQAKMYWTBR-RYMQXAEESA-N 0.000 description 2
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 2
- 239000004913 cyclooctene Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 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
- 239000013307 optical fiber Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- VIHDTGHDWPVSMM-UHFFFAOYSA-N ruthenium;triphenylphosphane Chemical compound [Ru].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VIHDTGHDWPVSMM-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 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
- GEQNZVKIDIPGCO-UHFFFAOYSA-N 2,4-dimethoxyaniline Chemical compound COC1=CC=C(N)C(OC)=C1 GEQNZVKIDIPGCO-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 0 CC(CC1)*=*1C(*)* Chemical compound CC(CC1)*=*1C(*)* 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LDVUZGMQSSGKJC-UHFFFAOYSA-N O=C(C(C1)C2CC3C1C1C=CC3C1)OC2=O Chemical compound O=C(C(C1)C2CC3C1C1C=CC3C1)OC2=O LDVUZGMQSSGKJC-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- NBICYCZLCAMSBG-UHFFFAOYSA-L [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O Chemical compound [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O NBICYCZLCAMSBG-UHFFFAOYSA-L 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- WIWBLJMBLGWSIN-UHFFFAOYSA-L dichlorotris(triphenylphosphine)ruthenium(ii) Chemical compound [Cl-].[Cl-].[Ru+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 WIWBLJMBLGWSIN-UHFFFAOYSA-L 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- GNGHYFMQCBTLSA-UHFFFAOYSA-N ethyl 5-methylbicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OCC)(C)CC1C=C2 GNGHYFMQCBTLSA-UHFFFAOYSA-N 0.000 description 1
- FCCGTJAGEHZPBF-UHFFFAOYSA-N ethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OCC)CC1C=C2 FCCGTJAGEHZPBF-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- AEBDJCUTXUYLDC-UHFFFAOYSA-N methyl 5-methylbicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC)(C)CC1C=C2 AEBDJCUTXUYLDC-UHFFFAOYSA-N 0.000 description 1
- RMAZRAQKPTXZNL-UHFFFAOYSA-N methyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC)CC1C=C2 RMAZRAQKPTXZNL-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- CHWKGJOTGCSFNF-UHFFFAOYSA-N norbornene anhydride Chemical compound C1CC2C3C(=O)OC(=O)C3=C1C2 CHWKGJOTGCSFNF-UHFFFAOYSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 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 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000007704 transition Effects 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
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical class Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 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
Images
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
本発明は、透明性、高耐熱性、および有機溶媒への高い溶解性を兼ね備え、複屈折の大きさや波長依存性を特定の置換基によりコントロールすることができる、ノルボルネン系樹脂とその製造方法に関する。 The present invention relates to a norbornene-based resin having both transparency, high heat resistance, and high solubility in an organic solvent, and capable of controlling the size and wavelength dependency of birefringence with a specific substituent, and a method for producing the same. .
従来、透明樹脂は自動車部品、照明機器、電気部品など通常の透明性が要求される材料として用いられ、特に最近では、光学的性質が重視される光学材料としての応用が進みつつある。このような用途に好適に用いられる透明樹脂としては、ポリカーボネート系樹脂やアクリル系樹脂が知られている。しかし、アクリル系樹脂は透明性に優れているが、耐熱性や耐水性等の点で問題がある。一方、ポリカーボネート系樹脂は、耐熱性や耐水性においてはアクリル系樹脂より優れているが、複屈折が高いなどの問題がある。このため、最近では、透明性、耐水性（低吸水性）、低複屈折性、耐熱性などを兼ね備えている環状オレフィン系樹脂が光学材料用の透明樹脂として用いられ注目されている。このような技術としてはたとえば特許文献１〜６などが挙げられる。 Conventionally, transparent resins have been used as materials that require normal transparency, such as automobile parts, lighting equipment, and electrical parts, and in particular, recently, applications as optical materials where optical properties are important are being advanced. As transparent resins suitably used for such applications, polycarbonate resins and acrylic resins are known. However, acrylic resins are excellent in transparency, but have problems in terms of heat resistance and water resistance. On the other hand, polycarbonate resins are superior to acrylic resins in heat resistance and water resistance, but have problems such as high birefringence. For this reason, recently, a cyclic olefin-based resin having transparency, water resistance (low water absorption), low birefringence, heat resistance and the like has been used as a transparent resin for optical materials. Examples of such a technique include Patent Documents 1-6.
しかしながら、光学機器の機能や用途の高度化に伴い、これらの従来公知の環状オレフィン系樹脂でも、光学材料に求められる特性を十分に満たせない場合が生じてきている。特に、高度化した機能を有する光学機器においては、十分な低複屈折性が非常に重要な物性であり、より優れた低複屈折性を有する透明樹脂の開発が望まれている。 However, with the advancement of functions and applications of optical devices, there are cases where even these conventionally known cyclic olefin resins cannot sufficiently satisfy the characteristics required for optical materials. In particular, in an optical apparatus having an advanced function, sufficient low birefringence is a very important physical property, and development of a transparent resin having a better low birefringence is desired.
一方、特に最近注目されている光学用フィルム用の樹脂としてみても、上記特性は前記従来の樹脂の問題点を改善できるものであり、このため、環状オレフィン系樹脂からなるフィルムが光学用の各種フィルムとして提案されている。例えば、特許文献７〜１０には、環状オレフィン系樹脂のフィルムからなる位相差板が記載されている。また、特許文献１１〜１３には、環状オレフィン系樹脂のフィルムを偏光板の保護フィルムに使用することが記載されている。さらに、特許文献１４には、環状オレフィン系樹脂のフィルムからなる液晶表示素子用基板が記載されている。しかしながら、従来の環状オレフィン系樹脂からなる光学用フィルムは、延伸配向させて得られる透過光に位相差（複屈折）を与える機能が、透過光の波長が長波長になるにつれて透過光の位相差(複屈折)の絶対値が小さくなるという特性を有するため、可視光領域（４００〜８００ｎｍ）全てにおいて、例えば１／４波長等の特定の位相差を透過光に与えることが非常に困難であった。こうした事情は、従来の環状オレフィン系樹脂のみならず、他の樹脂からなる光学用フィルムでも同様であった。 On the other hand, the above-mentioned characteristics can improve the problems of the conventional resins, even when viewed as a resin for optical films that has attracted particular attention recently. For this reason, films made of cyclic olefin resins can be used in various optical applications. Proposed as a film. For example, Patent Documents 7 to 10 describe a retardation plate made of a cyclic olefin resin film. Patent Documents 11 to 13 describe that a film of a cyclic olefin resin is used as a protective film for a polarizing plate. Furthermore, Patent Document 14 describes a substrate for a liquid crystal display element made of a film of a cyclic olefin resin. However, the conventional optical film made of a cyclic olefin resin has a function of giving a phase difference (birefringence) to transmitted light obtained by stretching and orientation, and the phase difference of transmitted light becomes longer as the wavelength of transmitted light becomes longer. Since the absolute value of (birefringence) is small, it is very difficult to give the transmitted light a specific phase difference such as a quarter wavelength in all the visible light region (400 to 800 nm). It was. This situation was the same not only for conventional cyclic olefin resins but also for optical films made of other resins.
上記に示す高度な光学用途に用いる樹脂は、一般的な光学特性のほかに複屈折の波長依存性、大きさをいかにコントロールするかが大きな課題である。 Resins used for the above-mentioned advanced optical applications have a major problem of how to control the wavelength dependence and size of birefringence in addition to general optical characteristics.
本発明は、上記課題を達成すべく成されたものであり、鋭意検討した結果、特定のノルボルネン系開環重合体及びその水素添加物は、重合組成比および置換基を選定することにより複屈折の大きさおよび波長依存性をコントロールすることができ、複屈折の特異な波長依存性(長波長になるに従い複屈折が大きくなる)、低複屈折性かつ透明性、非常に高い耐熱性を有することを見出し、本発明を完成するに至った。
本発明は、所望の複屈折特性および波長依存性を有するとともに、透明性および耐熱性に優れた光学材料を製造し得る、新規なノルボルネン系樹脂およびその製造方法を提供することを課題としている。 An object of the present invention is to provide a novel norbornene-based resin and a method for producing the same that can produce an optical material having desired birefringence characteristics and wavelength dependency, and having excellent transparency and heat resistance.
本発明のノルボルネン系樹脂は、下記一般式（１）で表される構造単位（１）を有し、かつ、該構造単位（１）が、下記式（Ａ）で表される化合物から導かれる構造単位であることを特徴としている。
The norbornene-based resin of the present invention has a structural unit (1) represented by the following general formula (1) , and the structural unit (1) is derived from a compound represented by the following formula (A). It is a structural unit .
（一般式（１）中、ｃおよびｄは０であり、ｅおよびｆは１である。Ｘは、式：−ＣＨ＝ＣＨ−で表される基または式：−ＣＨ2ＣＨ2−で表される基である。Ｒ 1 、Ｒ 7 〜Ｒ 14 は水素原子を表す。Ｒ15は、下記一般式（１−１）で表される基を示す。）
(In general formula (1), c and d are 0, and e and f are 1. X is a group represented by the formula: —CH═CH— or a formula: —CH 2 CH 2 —. R 1 and R 7 to R 14 represent a hydrogen atom, and R 15 represents a group represented by the following general formula (1-1) .
（一般式（１−１）中、Ｒ16〜Ｒ24はそれぞれ独立に、水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子、またはケイ素原子を含む連結基を有しても良い置換または非置換の炭素数１〜３０の炭化水素基；または極性基を表す。一般式（１−１）においてｇおよびｈは０または正の整数である。ただし、ｇ＝ｈ＝０のときは、Ｒ20、Ｒ16、Ｒ17、Ｒ23、およびＲ24の少なくともいずれか１つに水素以外の置換基を有するか、または、Ｒ17とＲ20またはＲ24とＲ20は相互に結合して炭素環または複素環（これらの炭素環または複素環は単環構造でも良いし、他の環が縮合して多環構造を形成しても良い。）を形成する。）
(In General Formula (1-1), each of R 16 to R 24 is independently a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom, or a substituent that may have a linking group containing a silicon atom; An unsubstituted hydrocarbon group having 1 to 30 carbon atoms; or a polar group, in the general formula (1-1), g and h are 0 or a positive integer, provided that when g = h = 0, At least one of R 20 , R 16 , R 17 , R 23 , and R 24 has a substituent other than hydrogen, or R 17 and R 20 or R 24 and R 20 are bonded to each other A carbocycle or a heterocycle (these carbocycles or heterocycles may be monocyclic structures or other rings may be condensed to form a polycyclic structure ) .
このような本発明のノルボルネン系樹脂は、下記一般式（２）で表される構造単位（２）をさらに有することが好ましく、構造単位（２）の割合が、全構造単位中９８モル％以下であることも好ましい。 Such a norbornene-based resin of the present invention preferably further has a structural unit (2) represented by the following general formula (2), and the proportion of the structural unit (2) is 98 mol% or less in the total structural units. It is also preferable.
（一般式（２）中、ｌおよびｍはそれぞれ独立に０〜２の整数であり、ｊおよびｋはそれぞれ独立に０〜３の整数である。Ｙは式：−ＣＨ＝ＣＨ−で表される基または式：−ＣＨ(In General Formula (2), l and m are each independently an integer of 0 to 2, and j and k are each independently an integer of 0 to 3. Y is represented by the formula: —CH═CH—. Group or formula: -CH
22
ＣＨCH
22
−で表される基である。ＲIt is group represented by-. R
3333
〜Ｒ~ R
4242
は、それぞれ独立に水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子、またはケイ素原子を含む連結基を有しても良い置換または非置換の炭素数１〜３０の炭化水素基；または極性基を表す。ＲAre each independently a hydrogen atom; a halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom; or polar Represents a group. R
3939
とＲAnd R
4040
、またはＲOr R
4141
とＲAnd R
4242
は一体化して２価の炭化水素基を形成しても良く、ＲMay be integrated to form a divalent hydrocarbon group, R
3939
またはＲOr R
4040
とＲAnd R
4141
またはＲOr R
4242
とは相互に結合して炭素環または複素環（これらの炭素環または複素環は単環構造でも良いし、他の環が縮合して多環構造を形成しても良い。）を形成しても良い。）Are bonded to each other to form a carbocycle or a heterocycle (these carbocycles or heterocycles may be monocyclic structures or other rings may be condensed to form a polycyclic structure). Also good. )
本発明のノルボルネン系樹脂では、前記一般式（１）におけるＸおよび前記一般式（２）におけるＹの合計の９０モル％以上が、−ＣＨIn the norbornene resin of the present invention, 90 mol% or more of the total of X in the general formula (1) and Y in the general formula (2) is —CH
22
ＣＨCH
22
−で表される基であることが好ましい。-Is preferably a group represented by-.
本発明のノルボルネン系樹脂の製造方法は、下記一般式（３）で表され、下記式（Ａ）で表される単量体を含むノルボルネン系単量体（３）を、必要に応じて下記一般式（４）で表されるノルボルネン系単量体（４）とともに開環（共）重合することを特徴としている。
The norbornene-based resin production method of the present invention is represented by the following general formula (3), and the norbornene-based monomer (3) containing the monomer represented by the following formula (A) It is characterized by ring-opening (co) polymerization with the norbornene monomer (4) represented by the general formula (4).
（一般式（３）中、ｃおよびｄは０であり、ｅおよびｆは１である。Ｒ 1 、Ｒ 7 〜Ｒ 14 は水素原子を表す。Ｒ15は、下記一般式（３−１）で表される基を示す。）
(In the general formula (3), c and d are 0, .R 1, R 7 ~R 14 is .R 15 represents a hydrogen atom e and f is 1, the following general formula (3-1) in showing a group represented by.)
（一般式（３−１）中、Ｒ16〜Ｒ 24 はそれぞれ独立に、水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子、またはケイ素原子を含む連結基を有しても良い置換または非置換の炭素数１〜３０の炭化水素基；または極性基を表す。一般式（３−１）においてｇおよびｈは０または正の整数である。ただし、ｇ＝ｈ＝０のときは、Ｒ20、Ｒ16、Ｒ17、Ｒ23、およびＲ24の少なくともいずれか１つに水素以外の置換基を有するか、または、Ｒ17とＲ20またはＲ24とＲ20は相互に結合して炭素環または複素環（これらの炭素環または複素環は単環構造でも良いし、他の環が縮合して多環構造を形成しても良い。）を形成する。）
(In General Formula (3-1) , R 16 to R 24 each independently represent a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom, or a substituent that may have a linking group containing a silicon atom; An unsubstituted hydrocarbon group having 1 to 30 carbon atoms; or a polar group, in the general formula (3-1), g and h are 0 or a positive integer, provided that when g = h = 0, R 20, R 16, R 17 , R 23, and either have a substituent other than hydrogen in at least one of R 24, or, R 17 and R 20 or R 24 and R 20 are bonded to each other A carbocycle or a heterocycle (these carbocycles or heterocycles may be monocyclic structures or other rings may be condensed to form a polycyclic structure ).
（一般式（４）中、ｌおよびｍはそれぞれ独立に０〜２の整数であり、ｊおよびｋはそれぞれ独立に０〜３の整数である。Ｒ33〜Ｒ42は、それぞれ独立に水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子、またはケイ素原子を含む連結基を有しても良い置換または非置換の炭素数１〜３０の炭化水素基；または極性基を表す。Ｒ39とＲ40、またはＲ41とＲ42は一体化して２価の炭化水素基を形成しても良く、Ｒ39またはＲ40とＲ41またはＲ42とは相互に結合して炭素環または複素環（これらの炭素環または複素環は単環構造でも良いし、他の環が縮合して多環構造を形成しても良い。）を形成しても良い。）
このような本発明のノルボルネン系樹脂の製造方法では、前記一般式（３）で表されるノルボルネン系単量体（３）を、必要に応じて前記一般式（４）で表されるノルボルネン系単量体（４）とともに開環（共）重合し、次いで水素添加することが好ましい。
(In the general formula (4), l and m are each independently an integer of 0 to 2, and j and k are each independently an integer of 0 to 3. R 33 to R 42 are each independently a hydrogen atom. a halogen atom; and represents a or polar groups .R 39; an oxygen atom, a sulfur atom, a nitrogen atom or a linking group containing a silicon atom hydrocarbon group which may substituted or unsubstituted 1 to 30 carbon atoms, R 40 , or R 41 and R 42 may be combined to form a divalent hydrocarbon group, and R 39 or R 40 and R 41 or R 42 are bonded to each other to form a carbocyclic or heterocyclic ring ( These carbocycles or heterocycles may have a monocyclic structure, or other rings may be condensed to form a polycyclic structure.
In such a method for producing a norbornene-based resin of the present invention, the norbornene-based monomer (3) represented by the general formula (3) is replaced with the norbornene-based resin represented by the general formula (4) as necessary. It is preferable to perform ring-opening (co) polymerization with the monomer (4) and then hydrogenate.
本発明のノルボルネン系樹脂、すなわち開環（共）重合体およびその水素添加物（水添体）は、使用する単量体の種類を選定することにより、複屈折の大きさならびに波長依存性を制御することができる。また、本発明のノルボルネン系樹脂、特に水添体は、複屈折の制御が容易に行えるのみでなく、高耐熱性および高透明性を兼ね備えており、光ディスク、光磁気ディスク、光学レンズ（ｆθレンズ、ピックアップレンズ、レーザープリンター用レンズ、カメラ用レンズ等）眼鏡レンズ、光学フィルム（ディスプレイ用フィルム、位相差フィルム、偏光フィルム、透明導電フィルム等）、光学シート、光ファイバー、導光板、光拡散板、光カード、光ミラー、IC・LSI・LED封止材などに好適に使用できる。 The norbornene-based resin of the present invention, that is, the ring-opening (co) polymer and its hydrogenated product (hydrogenated product) have a birefringence magnitude and wavelength dependency by selecting the type of monomer used. Can be controlled. The norbornene-based resin of the present invention, particularly a hydrogenated body, not only can easily control birefringence, but also has high heat resistance and high transparency, and is an optical disk, magneto-optical disk, optical lens (fθ lens). , Pickup lens, laser printer lens, camera lens, etc.) spectacle lens, optical film (display film, retardation film, polarizing film, transparent conductive film, etc.), optical sheet, optical fiber, light guide plate, light diffusion plate, light It can be suitably used for cards, optical mirrors, IC / LSI / LED sealing materials, and the like.
以下、本発明について具体的に説明する。
＜ノルボルネン系樹脂＞
本発明のノルボルネン系樹脂は、下記一般式（１）で表される構造単位（１）を必須の成分として含み、さらに必要に応じて下記一般式（２）で表される構造単位（２）を含ん
でもよい。このような本発明のノルボルネン樹脂は、通常、後述する特定のノルボルネン系単量体の、開環（共）重合体またはその水素添加物である。なお、本発明において、（共）重合とは、重合または共重合を表す。
Hereinafter, the present invention will be specifically described.
<Norbornene resin>
The norbornene-based resin of the present invention contains a structural unit (1) represented by the following general formula (1) as an essential component and, if necessary, a structural unit (2) represented by the following general formula (2). May be included. Such a norbornene resin of the present invention is usually a ring-opening (co) polymer or a hydrogenated product of a specific norbornene-based monomer described later. In the present invention, (co) polymerization represents polymerization or copolymerization.
（一般式（１）中、ａ、ｂ、ｅ、およびｆはそれぞれ独立に０〜３の整数であり、ｃおよびｄはそれぞれ独立に０〜２の整数である。Ｘは、式：−ＣＨ＝ＣＨ−で表される基または式：−ＣＨ2ＣＨ2−で表される基である。Ｒ1〜Ｒ14は、それぞれ独立に、水素原子；
ハロゲン原子；酸素原子、窒素原子、硫黄原子もしくはケイ素原子を含む連結基を有しても良い置換もしくは非置換の炭素数１〜３０の炭化水素基；よりなる群から選ばれる原子もしくは基を表す。Ｒ15は、下記一般式（１−１）または一般式（１−２）で表される基を示す。）
(In General Formula (1), a, b, e, and f are each independently an integer of 0 to 3, and c and d are each independently an integer of 0 to 2. X is a formula: —CH A group represented by ═CH— or a group represented by the formula: —CH 2 CH 2 —, wherein R 1 to R 14 each independently represents a hydrogen atom;
A halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing an oxygen atom, nitrogen atom, sulfur atom or silicon atom; represents an atom or group selected from the group consisting of . R 15 represents a group represented by the following general formula (1-1) or general formula (1-2). )
（一般式（１−１）および（１−２）において、Ｒ16〜Ｒ32はそれぞれ独立に、水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子、またはケイ素原子を含む連結基を有しても良い置換または非置換の炭素数1〜３０の炭化水素基；または極性基を表す。一般式
（１−１）においてｇおよびｈは０または正の整数である。ただし、ｇ＝ｈ＝０のときは、Ｒ20、Ｒ16、Ｒ17、Ｒ23、およびＲ24の少なくともいずれか１つに水素以外の置換基を有するか、または、Ｒ17とＲ20またはＲ24とＲ20は相互に結合して炭素環または複素環（これらの炭素環または複素環は単環構造でも良いし、他の環が縮合して多環構造を形成しても良い。）を形成する。一般式（１−２）においてｉは０または１以上の整数である。）
(In General Formulas (1-1) and (1-2), R 16 to R 32 each independently have a linking group containing a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom. A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or a polar group, wherein g and h are 0 or a positive integer in the general formula (1-1), where g = h When = 0, at least one of R 20 , R 16 , R 17 , R 23 , and R 24 has a substituent other than hydrogen, or R 17 and R 20 or R 24 and R 20 Are bonded to each other to form a carbocycle or a heterocycle (these carbocycles or heterocycles may be monocyclic structures or other rings may be condensed to form a polycyclic structure). In formula (1-2), i is 0 or an integer of 1 or more.)
（一般式（２）中、ｌおよびｍはそれぞれ独立に０〜２の整数であり、ｊおよびｋはそれぞれ独立に０〜３の整数である。Ｙは式：−ＣＨ＝ＣＨ−で表される基または式：−ＣＨ2ＣＨ2−で表される基である。Ｒ33〜Ｒ42は、それぞれ独立に水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子、またはケイ素原子を含む連結基を有しても良い置換または非置換の炭素数1〜３０の炭化水素基；または極性基を表す。Ｒ39とＲ40、またはＲ41
とＲ42は一体化して２価の炭化水素基を形成しても良く、Ｒ39またはＲ40とＲ41またはＲ42とは相互に結合して炭素環または複素環（これらの炭素環または複素環は単環構造でも良いし、他の環が縮合して多環構造を形成しても良い。）を形成しても良い。）
ここで、上記一般式（１）、一般式（１−１）、一般式（１−２）、一般式（２）において、Ｒ1〜Ｒ14、Ｒ33〜Ｒ42、およびＲ16〜Ｒ32により表される、水素原子；ハロゲン
原子；酸素原子、硫黄原子、窒素原子、またはケイ素原子を含む連結基を有しても良い置換または非置換の炭素数1〜３０の炭化水素基；ならびに極性基について説明する。
(In General Formula (2), l and m are each independently an integer of 0 to 2, and j and k are each independently an integer of 0 to 3. Y is represented by the formula: —CH═CH—. Or a group represented by the formula: —CH 2 CH 2 — wherein R 33 to R 42 each independently represent a hydrogen atom, a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom-containing linkage. hydrocarbon group which may substituted or unsubstituted 1 to 30 carbon atoms which may have a group; .R 39 and R 40 represents a or polar groups, or R 41,
And R 42 may be combined to form a divalent hydrocarbon group, and R 39 or R 40 and R 41 or R 42 are bonded to each other to form a carbocyclic or heterocyclic ring (these carbocyclic or heterocyclic rings). The ring may be a monocyclic structure, or other rings may be condensed to form a polycyclic structure. )
Here, in the general formula (1), the general formula (1-1), the general formula (1-2), and the general formula (2), R 1 to R 14 , R 33 to R 42 , and R 16 to R are used. A hydrogen atom represented by 32 ; a halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom; and The polar group will be described.
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。 Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
炭素原子数１〜３０の炭化水素基としては、例えば、メチル基、エチル基、プロピル基等のアルキル基；シクロペンチル基、シクロヘキシル基等のシクロアルキル基；ビニル基、アリル基等のアルケニル基；エチリデン基、プロピリデン基等のアルキリデン基；フェニル基、ナフチル基、アントラセニル基等の芳香族基などが挙げられる。これらの炭化水素基は置換されていてもよく、置換基としては例えばフッ素、塩素、臭素等のハロゲン原子、フェニルスルホニル基、シアノ基等が挙げられる。 Examples of the hydrocarbon group having 1 to 30 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 and allyl group; Groups, alkylidene groups such as propylidene groups; aromatic groups such as phenyl groups, naphthyl groups, and anthracenyl groups. These hydrocarbon groups may be substituted, and examples of the substituent include halogen atoms such as fluorine, chlorine and bromine, phenylsulfonyl group and cyano group.
このような置換または非置換の炭化水素基は、直接環構造に結合していてもよいし、あるいは連結基(linkage)を介して結合していてもよい。連結基としては、例えば炭素原子
数１〜１０の２価の炭化水素基（例えば、-(CH2)ｌ-、ｌは１〜10の整数、で表されるア
ルキレン基）；酸素原子、窒素原子、イオウ原子またはケイ素原子を含む連結基（例えば、カルボニル基(-CO-)、カルボニルオキシ基(-COO-)、スルホニル基(-SO2-)、スルホニルエステル基（-SO2-O-）、エーテル結合(-O-)、チオエーテル結合(-S-)、イミノ基(-NH-)
、アミド結合(-NHCO-)、シロキサン結合(-Si(R)2O-、Rはメチル、エチル等のアルキル基)；あるいはこれらの２種以上が組合さって連なったものが挙げられる。
Such a substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure, or may be bonded via a linkage. Examples of the linking group include a divalent hydrocarbon group having 1 to 10 carbon atoms (for example,-(CH 2 ) 1-, l is an alkylene group represented by an integer of 1 to 10); oxygen atom, nitrogen A linking group containing an atom, sulfur atom or silicon atom (for example, a carbonyl group (—CO—), a carbonyloxy group (—COO—), a sulfonyl group (—SO 2 —), a sulfonyl ester group (—SO 2 —O—) ), Ether bond (-O-), thioether bond (-S-), imino group (-NH-)
Amide bond (-NHCO-), siloxane bond (-Si (R) 2 O-, R is an alkyl group such as methyl or ethyl); or a combination of two or more of these in combination.
極性基としては、例えば水酸基、炭素原子数１〜１０のアルコキシ基、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、エトキシ基等が挙げられ；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等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等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等が挙げられ；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等が挙げられ；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等が挙げられ；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等が挙げられ；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等が挙げられる。
Examples of the polar group include a hydroxyl group, an alkoxy 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, a triorganosilyl group, Examples thereof include an amino group, an acyl group, an alkoxysilyl group, a sulfonyl group, and a carboxyl group. 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 and triethylsilyl group. Le group and the like; examples of the amino group include primary amino groups, alkoxysilyl The group for example a trimethoxysilyl group, triethoxysilyl group, and the like.
上述のように、一般式（１−１）中の、Ｒ17とＲ20およびＲ20とＲ24、一般式（２）中の、Ｒ39とＲ40、Ｒ41とＲ42、およびＲ42とＲ43、とは各々対になって相互に結合して、炭素環または複素環（これらの炭素環または複素環は単環構造でもよいし、他の環が縮合して多環構造を形成してもよい。）を形成してもよい。このとき形成される炭素環または複素環は芳香環でもよいし非芳香環でもよい。ただし、一般式（１）で表される環構造は除く。 As described above, R 17 and R 20 and R 20 and R 24 in the general formula (1-1), R 39 and R 40 , R 41 and R 42 , and R 42 in the general formula (2). And R 43 are bonded to each other in pairs to form a carbocyclic or heterocyclic ring (these carbocyclic or heterocyclic rings may be monocyclic structures or other rings may be condensed to form a polycyclic structure). May be formed). The carbocyclic or heterocyclic ring formed at this time may be an aromatic ring or a non-aromatic ring. However, the ring structure represented by the general formula (1) is excluded.
このような構造単位（１）としては、具体的には、後述するノルボルネン系単量体（３）に由来する構造単位、すなわちノルボルネン系単量体（３）を開環（共）重合した際に生じる構造単位またはこれに水素添加して生じる構造単位が挙げられ、構造単位（２）としては、具体的には、後述するノルボルネン系単量体（４）に由来する構造単位、すなわちノルボルネン系単量体（４）を開環（共）重合した際に生じる構造単位またはこれに水素添加して生じる構造単位が挙げられる。 As such a structural unit (1), specifically, a structural unit derived from a norbornene monomer (3) described later, that is, when the norbornene monomer (3) is subjected to ring-opening (co) polymerization. Or a structural unit generated by hydrogenation thereto. Specifically, the structural unit (2) is a structural unit derived from a norbornene monomer (4) described later, that is, a norbornene system. Examples thereof include a structural unit produced when ring-opening (co) polymerizing the monomer (4) or a structural unit produced by hydrogenation thereof.
本発明のノルボルネン系樹脂において、構造単位（１）は、一種単独であってもよく、２種以上であってもよい。また、本発明のノルボルネン系樹脂が構造単位（２）有する場合、構造単位（２）は、一種単独であってもよく、２種以上であってもよい。 In the norbornene-based resin of the present invention, the structural unit (1) may be a single type or two or more types. In addition, when the norbornene-based resin of the present invention has the structural unit (2), the structural unit (2) may be one kind or two or more kinds.
本発明のノルボルネン系樹脂は、前記一般式（１）中、ｃ＝０かつｄ＝０である構造単位（１）を有することが好ましく、ｅ＝１かつｆ＝１である構造単位（１）を有することが好ましく、ｃ＝０、ｄ＝０、ｅ＝１、ｆ＝１である構造単位（１）を有することがより好ましい。 The norbornene-based resin of the present invention preferably has the structural unit (1) in which c = 0 and d = 0 in the general formula (1), and the structural unit (1) in which e = 1 and f = 1. The structural unit (1) is preferably c = 0, d = 0, e = 1, and f = 1.
また、本発明のノルボルネン系樹脂は、前記一般式（１）において、Ｒ15が前記一般式（１−１）で表される基であり、一般式（１−１）中、ｇ＝０、ｈ＝０であり、かつＲ16またはＲ23の少なくとも一方が水素以外の置換基である構造単位（１）を有することが好ましく、Ｒ15が前記一般式（１−１）で表される基であり、一般式（１−１）中、ｇ＝０、ｈ＝０であり、Ｒ16またはＲ23の少なくとも一方が水素以外の置換基であり、かつＲ17、Ｒ20、またはＲ24の少なくともいずれか一つに水素以外の置換基を有する構造単位（１）を有することがより好ましい。 Moreover, norbornene-based resin of the present invention, in the general formula (1) is a group R 15 is represented by the general formula (1-1), in the general formula (1-1), g = 0, It is preferable that h = 0 and at least one of R 16 or R 23 has the structural unit (1) which is a substituent other than hydrogen, and R 15 is a group represented by the general formula (1-1) In general formula (1-1), g = 0, h = 0, at least one of R 16 or R 23 is a substituent other than hydrogen, and R 17 , R 20 , or R 24 It is more preferable to have the structural unit (1) having a substituent other than hydrogen in at least one of them.
本発明のノルボルネン系樹脂は、構造単位（２）を、全構造単位中９８モル％以下、好ましくは９５モル％以下、より好ましくは９０モル％以下の割合で有するのが望ましい。また、本発明のノルボルネン系樹脂は、構造単位（１）を、全構造単位中２モル％以上、好ましくは５モル％以上の割合で有するのが望ましい。 The norbornene-based resin of the present invention desirably has the structural unit (2) in a proportion of 98 mol% or less, preferably 95 mol% or less, more preferably 90 mol% or less in all the structural units. In addition, the norbornene-based resin of the present invention desirably has the structural unit (1) in a proportion of 2 mol% or more, preferably 5 mol% or more in all the structural units.
また、本発明のノルボルネン系樹脂は、前記一般式（１）におけるＸおよび前記一般式（２）におけるＹの合計の８０モル％以上、好ましくは９０モル％以上、より好ましくは９５％以上が、−ＣＨ2ＣＨ2−で表される基であるのが望ましい。このように、ＸもしくはＹとして、−ＣＨ＝ＣＨ−で表される基が少なく、−ＣＨ2ＣＨ2−で表される基が多い場合には、ノルボルネン系樹脂の反応性の低いため、本発明のノルボルネン系樹脂あるい
はそれからなる成形体が耐熱安定に優れ、熱による着色、変質などが生じにくいので好ましい。
Further, the norbornene resin of the present invention is 80 mol% or more, preferably 90 mol% or more, more preferably 95% or more of the total of X in the general formula (1) and Y in the general formula (2). -CH 2 CH 2 - is preferably a group represented by. Thus, when X or Y has a small number of groups represented by —CH═CH— and a large number of groups represented by —CH 2 CH 2 —, the reactivity of the norbornene resin is low. The norbornene-based resin of the invention or a molded body comprising the same is preferred because it is excellent in heat resistance stability and hardly undergoes coloration or alteration due to heat.
本発明のノルボルネン系樹脂は、本発明の効果を損なわない範囲において、上述の構造単位（１）および構造単位（２）以外の構造単位を有していてもよい。このような構造単位としては、たとえば、シクロブテン、シクロペンテン、シクロオクテン、シクロドデセン等の環状オレフィンや１，４−シクロオクタジエン、ジシクロペンタジエン、シクロドデカトリエン等の非共役環状ポリエンに由来する構造単位などが挙げられる。 The norbornene-based resin of the present invention may have a structural unit other than the structural unit (1) and the structural unit (2) as long as the effects of the present invention are not impaired. Examples of such structural units include structural units derived from cyclic olefins such as cyclobutene, cyclopentene, cyclooctene, and cyclododecene, and non-conjugated cyclic polyenes such as 1,4-cyclooctadiene, dicyclopentadiene, and cyclododecatriene. Is mentioned.
このような本発明のノルボルネン系樹脂の分子量などの性状は、特に限定されるものではなく、用途や使用方法等により適宜選択されるが、たとえば光学部品や電気電子材料の分野に用いる場合には、ウッベローデ型粘度計で測定される対数粘度（ηinh）が、通常
０．２〜５．０、好ましくは０．３〜４．０、さらに好ましくは０．３５〜２．０程度；ゲルパーミエーションクロマトグラフィー（ＧＰＣ、テトラヒドロフラン溶媒、ポリスチレン換算）による分子量測定での数平均分子量（Ｍｎ）が、通常１０００〜５０万、好ましくは２０００〜３０万、さらに好ましくは５０００〜３０万程度、重量平均分子量（Ｍｗ）が、通常５０００〜２００万、好ましくは１万〜１００万、さらに好ましくは３万〜５０万程度；ηinhが０．２未満程度であるのが望ましい。
＜ノルボルネン系樹脂の製造方法＞
本発明のノルボルネン系樹脂の製造方法では、下記一般式（３）で表されるノルボルネン系単量体（３）を、必要に応じて下記一般式（４）で示されるノルボルネン系単量体（４）とともに、開環（共）重合する。また、本発明のノルボルネン系樹脂の製造方法では、下記一般式（３）で表されるノルボルネン系単量体（３）を、必要に応じて下記一般式（４）で示されるノルボルネン系単量体（４）とともに開環（共）重合し、次いで水素添加するのが好ましい。上述した本発明のノルボルネン系樹脂は、このような本発明のノルボルネン系樹脂の製造方法により製造することができる。
Such properties as the molecular weight of the norbornene-based resin of the present invention are not particularly limited, and are appropriately selected depending on the application and usage method. For example, when used in the field of optical components and electrical and electronic materials. The logarithmic viscosity (ηinh) measured with a Ubbelohde viscometer is usually 0.2 to 5.0, preferably 0.3 to 4.0, more preferably about 0.35 to 2.0; gel permeation The number average molecular weight (Mn) in molecular weight measurement by chromatography (GPC, tetrahydrofuran solvent, polystyrene conversion) is usually 1000 to 500,000, preferably 2000 to 300,000, more preferably about 5000 to 300,000, and weight average molecular weight ( Mw) is usually 5,000 to 2,000,000, preferably 10,000 to 1,000,000, more preferably about 30,000 to 500,000; ηinh is less than about 0.2 It is desirable that
<Method for producing norbornene resin>
In the method for producing a norbornene resin of the present invention, a norbornene monomer (3) represented by the following general formula (3) is replaced with a norbornene monomer (3) represented by the following general formula (4) as necessary. 4) and ring-opening (co) polymerization. Moreover, in the manufacturing method of the norbornene-type resin of this invention, the norbornene-type monomer represented by the following general formula (4) is made into the norbornene-type monomer (3) represented by the following general formula (3) as needed. It is preferred to ring-open (co) polymerize with the body (4) and then hydrogenate. The norbornene-based resin of the present invention described above can be produced by such a method for producing a norbornene-based resin of the present invention.
（一般式（３）中、ａ、ｂ、ｅ、およびｆはそれぞれ独立に０〜３の整数であり、ｃおよびｄは独立に０〜２の整数である。Ｒ1〜Ｒ14は、それぞれ独立に、水素原子；ハロゲン
原子；酸素原子、窒素原子、硫黄原子もしくはケイ素原子を含む連結基を有しても良い置換もしくは非置換の炭素数１〜３０の炭化水素基；よりなる群から選ばれる原子もしくは基を表す。Ｒ15は、下記一般式（３−１）または一般式（３−２）で表される基を示す。）
(In General Formula (3), a, b, e, and f are each independently an integer of 0 to 3, and c and d are independently an integer of 0 to 2. R 1 to R 14 are respectively Independently selected from the group consisting of a hydrogen atom; a halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom; R 15 represents a group represented by the following general formula (3-1) or general formula (3-2).
（一般式（３−１）および（３−２）において、Ｒ16〜Ｒ32はそれぞれ独立に、水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子、またはケイ素原子を含む連結基を有しても良い置換または非置換の炭素数１〜３０の炭化水素基；または極性基を表す。一般式（３−１）においてｇおよびｈは０または正の整数である。ただし、ｇ＝ｈ＝０のときは、Ｒ20、Ｒ16、Ｒ17、Ｒ23、およびＲ24の少なくともいずれか１つに水素以外の置換基を有するか、または、Ｒ17とＲ20またはＲ24とＲ20は相互に結合して炭素環または複素環（これらの炭素環または複素環は単環構造でも良いし、他の環が縮合して多環構造を形成しても良い。）を形成する。一般式（３−２）においてｉは０または１以上の整数である。） (In the general formulas (3-1) and (3-2), R 16 to R 32 each independently have a linking group containing a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom. A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or a polar group, wherein g and h are 0 or a positive integer in the general formula (3-1), where g = h When = 0, at least one of R 20 , R 16 , R 17 , R 23 , and R 24 has a substituent other than hydrogen, or R 17 and R 20 or R 24 and R 20 Are bonded to each other to form a carbocycle or a heterocycle (these carbocycles or heterocycles may be monocyclic structures or other rings may be condensed to form a polycyclic structure). In formula (3-2), i is 0 or an integer of 1 or more.)
（一般式（４）中、ｌおよびｍはそれぞれ独立に０〜２の整数であり、ｊおよびｋはそれぞれ独立に０〜３の整数である。Ｒ33〜Ｒ42は、それぞれ独立に水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子、またはケイ素原子を含む連結基を有しても良い置換または非置換の炭素数１〜３０の炭化水素基；または極性基を表す。Ｒ39とＲ40、またはＲ41とＲ42は一体化して２価の炭化水素基を形成しても良く、Ｒ39またはＲ40とＲ41またはＲ42とは相互に結合して炭素環または複素環（これらの炭素環または複素環は単環構造でも良いし、他の環が縮合して多環構造を形成しても良い。）を形成しても良い。）。 (In the general formula (4), l and m are each independently an integer of 0 to 2, and j and k are each independently an integer of 0 to 3. R 33 to R 42 are each independently a hydrogen atom. a halogen atom; and represents a or polar groups .R 39; an oxygen atom, a sulfur atom, a nitrogen atom or a linking group containing a silicon atom hydrocarbon group which may substituted or unsubstituted 1 to 30 carbon atoms, R 40 , or R 41 and R 42 may be combined to form a divalent hydrocarbon group, and R 39 or R 40 and R 41 or R 42 are bonded to each other to form a carbocyclic or heterocyclic ring ( These carbocycles or heterocycles may have a monocyclic structure, or other rings may be condensed to form a polycyclic structure.
以下、ノルボルネン系単量体（３）および（４）についてさらに具体的に説明するが、これらに限定されるものではない。 Hereinafter, although norbornene-type monomer (3) and (4) are demonstrated more concretely, it is not limited to these.
ノルボルネン系単量体（３）
本発明で使用されるノルボルネン系単量体（３）は、上記一般式（３）で表される単量体であって、例えば、テトラヒドロフタル酸無水物とシクロペンタジエンまたはジシクロ
ペンタジエンとの反応から得られる６-オキサ-テトラシクロ[９．２．１．０2,10．０4,8]トリデカ-１２-エン-５，７-ジオンのようなノルボルネン酸無水物と芳香族アミンとの
反応で得られるイミド化合物が挙げられ、より具体的には次の化合物を例示できる。
Norbornene monomer (3)
The norbornene monomer (3) used in the present invention is a monomer represented by the above general formula (3), for example, reaction of tetrahydrophthalic anhydride with cyclopentadiene or dicyclopentadiene. obtained from 6-oxa - tetracyclo [9.2.1.0 2,10. 0 4,8] trideca-12-imide compound obtained by reaction of a norbornene anhydride and an aromatic amine such as ene-5,7-dione and the like, more specifically may be exemplified the following compounds .
などが挙げられる。これらのノルボルネン系単量体（３）は単独で使用することもできるし、２種以上を併用して用いることもできる。 Etc. These norbornene monomers (3) can be used alone or in combination of two or more.
本発明では、これらのうち、一般式（３）のｃ=０、ｄ＝０、ｅ＝１、ｆ＝１であり、
かつＲ1〜Ｒ14の何れもが水素原子または何れか一つがメチル基であり、さらに、Ｒ15が
一般式（３−１）もしくは一般式（３−２）で示される基であるノルボルネン系単量体（３）が、得られるノルボルネン系開環重合体もしくはその水素添加物の耐熱性が高く、ま
た、吸水性を低くする上で好ましい。さらに、一般式（３）のｃ=０、ｄ＝０、ｅ＝１、
ｆ＝１であり、かつＲ1〜Ｒ14の何れもが水素原子または何れか一つがメチル基であり、
さらに、Ｒ15が一般式（３−１）もしくは一般式（３−２）で示される基であり、一般式（３−１）のｇ＝ｈ＝０、または、一般式（３−２）のｉ＝０である単量体（１）を用いることが有効である。
In the present invention, among these, c = 0, d = 0, e = 1, f = 1 in the general formula (3),
And any one of R 1 to R 14 is a hydrogen atom or any one is a methyl group, and R 15 is a group represented by the general formula (3-1) or the general formula (3-2). Monomer (3) is preferred in that the norbornene-based ring-opening polymer or hydrogenated product obtained has high heat resistance and low water absorption. Furthermore, c = 0, d = 0, e = 1 in the general formula (3),
f = 1, and any one of R 1 to R 14 is a hydrogen atom or any one is a methyl group,
Further, R 15 is a group represented by the general formula (3-1) or the general formula (3-2), and g = h = 0 in the general formula (3-1), or the general formula (3-2) It is effective to use the monomer (1) in which i = 0.
ノルボルネン系単量体（４）
本発明で必要に応じて使用されるノルボルネン系単量体（４）は、上記一般式（４）で表される単量体であって、具体例としては、次の化合物を例示できる。
Norbornene monomer (4)
The norbornene-based monomer (4) used as necessary in the present invention is a monomer represented by the above general formula (4), and specific examples thereof include the following compounds.
これらのノルボルネン系単量体（４）は、上述のノルボルネン系単量体（３）と組み合わせて使用することができ、1種単独で使用してもよく、２種以上を併用してもよい。 These norbornene monomers (4) can be used in combination with the norbornene monomer (3) described above, and may be used alone or in combination of two or more. .
これらのうち、得られる共重合体の耐熱性、溶解性および他素材との密着性・接着性等のバランスから、一般式（４）のＲ39〜Ｒ42のうち少なくとも１つが−（ＣＨ2）nＣＯＯＲ43で表されるカルボン酸エステル基（ここで、Ｒ43は炭素数１〜２０の炭化水素基、ｎは０〜１０の整数である。）であるノルボルネン系単量体（４）が好ましく、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−エトキシカルボニルビシクロ［２．２．１］ヘプト−２−エン、５−エトキシカルボニルビシクロ［２．２．１］ヘプト−２−エン、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−ドデセンが、その製造方法が容易な点で特に好ましい。
Of these, at least one of R 39 to R 42 in the general formula (4) is — (CH 2 ) from the balance of the heat resistance, solubility, adhesion to other materials, adhesion, and the like of the obtained copolymer. ) expressed a carboxylic acid ester group (wherein the at n COOR 43, R 43 is a hydrocarbon group having 1 to 20 carbon atoms, n represents an integer of 0.) in a norbornene-based monomer (4) 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-ethoxy Carbonylbicyclo [2.2.1] hept-2-ene, 5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.
1 2,5 . 1 7,10 ] -3-dodecene is particularly preferred because of its ease of production.
なお、上記のＲ43で表される炭素原子数１〜２０の炭化水素基としては、例えばメチル基、エチル基、プロピル基等のアルキル基、フェニル基等のアリール基、ベンジル基等のアラルキル基があげられる。好ましくは、メチル基、エチル基、フェニル基であり、特に
好ましくは、メチル基またはエチル基である。
Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 43 include alkyl groups such as methyl group, ethyl group and propyl group, aryl groups such as phenyl group, and aralkyl groups such as benzyl group. Can be given. A methyl group, an ethyl group, and a phenyl group are preferable, and a methyl group or an ethyl group is particularly preferable.
本発明において、ノルボルネン系単量体（３）とノルボルネン系単量体（４）との使用割合は、モル比で、通常１００／０〜２／９８、好ましくは１００／０〜５／９５、さらに好ましくは、１００／０〜１０／９０である。 In the present invention, the use ratio of the norbornene monomer (3) to the norbornene monomer (4) is usually 100/0 to 2/98, preferably 100/0 to 5/95, as a molar ratio. More preferably, it is 100/0 to 10/90.
ノルボルネン系単量体（３）の使用割合が２／９８よりも小さい場合、本発明の効果である、複屈折の特異な波長依存性(長波長になるに従い複屈折が大きくなる)や低複屈折性が得られない場合がある。なお、ノルボルネン系単量体（３）およびノルボルネン系単量体（４）以外の共重合可能な単量体も使用する場合には、ノルボルネン系単量体（３）の使用量は、上記本発明の効果を得るために、全単量体に対して２モル％以上使用することが好ましい。 When the use ratio of the norbornene monomer (3) is smaller than 2/98, the birefringence has a unique wavelength dependency (birefringence increases as the wavelength becomes longer) and low birefringence, which are effects of the present invention. In some cases, refractive properties cannot be obtained. When a copolymerizable monomer other than the norbornene monomer (3) and the norbornene monomer (4) is also used, the amount of the norbornene monomer (3) used is as described above. In order to acquire the effect of invention, it is preferable to use 2 mol% or more with respect to all the monomers.
本発明においては、本発明の効果を損なわない範囲において、ノルボルネン系単量体（３）および（４）以外の共重合可能な単量体、例えばシクロブテン、シクロペンテン、シクロオクテン、シクロドデセン等の環状オレフィンや１，４−シクロオクタジエン、ジシクロペンタジエン、シクロドデカトリエン等の非共役環状ポリエンを使用することもできる。 In the present invention, copolymerizable monomers other than norbornene monomers (3) and (4), for example, cyclic olefins such as cyclobutene, cyclopentene, cyclooctene, and cyclododecene, within the range not impairing the effects of the present invention. Alternatively, non-conjugated cyclic polyenes such as 1,4-cyclooctadiene, dicyclopentadiene, and cyclododecatriene can also be used.
また、本発明においては、上記ノルボルネン系単量体（３）等の開環重合を、ポリブタジエン、ポリイソプレン、スチレン−ブタジエン、エチレン−非共役ジエン重合体、ノルボルネン系単量体の開環（共）重合の未水添物などの存在下で行ってもよい。 In the present invention, the ring-opening polymerization of the norbornene monomer (3) or the like is carried out by ring opening (co-polymerization) of polybutadiene, polyisoprene, styrene-butadiene, ethylene-nonconjugated diene polymer, norbornene monomer. ) The polymerization may be performed in the presence of an unhydrogenated product.
重合
以下、本発明における（共）重合の条件をさらに説明する。
開環（共）重合触媒：
本発明の製造方法において、開環（共）重合に用いる触媒は、上述のノルボルネン系単量体（３）および必要に応じて（４）を開環（共）重合できる触媒であればよく、特に限定されるものではないが、たとえば、文献「Ｏｌｅｆｉｎ， Ａｃａｄｅｍｉｃ Ｐｒｅｓｓ １９９７」に記載されている触媒が好ましく用いられる。
Polymerization will be further described the (co) polymerization conditions in the present invention.
Ring-opening (co) polymerization catalyst:
In the production method of the present invention, the catalyst used for the ring-opening (co) polymerization may be any catalyst that can ring-open (co) polymerize the norbornene monomer (3) and, if necessary, (4), Although not particularly limited, for example, a catalyst described in the document “Olefin, Academic Press 1997” is preferably used.
このような触媒としては、たとえば（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）Ｌｉ、Ｎａ、Ｋ、Ｍｇ、Ｃａ、Ｚｎ、Ｃｄ、Ｈｇ、Ｂ、Ａｌ、Ｓｉ、Ｓｎ、Ｐｄなどの化合物であって、少なくとも１つの当該元素−炭素結合あるいは当該元素−水素結合を有するものから選ばれた少なくとも１種との組合せからなるメタセシス重合触媒があげられる。またこの場合に触媒の活性を高めるために、後述の添加剤（ｃ）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（ｄ）助触媒を用いない周期表第４族〜８族遷移金属−カルベン錯体やメタラシクロブタン錯体などからなるメタセシス触媒が挙げられる。
Examples of such a catalyst include (a) at least one selected from compounds of W, Mo, Re, V, and Ti, and (b) Li, Na, K, Mg, Ca, Zn, Cd, and Hg. A metathesis polymerization catalyst comprising a combination of at least one selected from the group consisting of at least one element-carbon bond or the element-hydrogen bond, such as B, Al, Si, Sn, Pd, etc. can give. In this case, in order to increase the activity of the catalyst, an additive (c) described later may be added. Examples of the other catalyst include (d) a metathesis catalyst composed of a
上記（ａ）成分として適当なＷ、Ｍｏ、Ｒｅ、Ｖ、およびＴｉの化合物の代表例としては、ＷＣｌ6、ＭｏＣｌ5、ＲｅＯＣｌ3、ＶＯＣｌ3、ＴｉＣｌ4など特開平１−２４０５
１７号公報に記載の化合物を挙げることができる。
Representative examples of W, Mo, Re, V, and Ti compounds suitable as the component (a) include WCl 6 , MoCl 5 , ReOCl 3 , VOCl 3 , TiCl 4 and the like.
The compounds described in No. 17 can be mentioned.
上記（ｂ）成分の具体例としては、ｎ−Ｃ4Ｈ9Ｌｉ、（Ｃ2Ｈ5）3Ａl、（Ｃ2Ｈ5）2Ａ
ｌＣｌ、（Ｃ2Ｈ5）1.5ＡｌＣｌ1.5、（Ｃ2Ｈ5）ＡｌＣｌ2、メチルアルモキサン、Ｌｉ
Ｈなど特開平１−２４０５１７号公報に記載の化合物を挙げることができる。
Specific examples of the component (b) include n-C 4 H 9 Li, (C 2 H 5 ) 3 Al, and (C 2 H 5 ) 2 A.
lCl, (C 2 H 5 ) 1.5 AlCl 1.5 , (C 2 H 5 ) AlCl 2 , methylalumoxane, Li
Examples thereof include compounds described in JP-A-1-240517 such as H.
添加剤である（ｃ）成分の代表例としては、アルコール類、アルデヒド類、ケトン類、アミン類などが好適に用いることができるが、更に特開平１−２４０５１７号公報に示さ
れる化合物を使用することができる。
As typical examples of the component (c) which is an additive, alcohols, aldehydes, ketones, amines and the like can be suitably used, but further compounds described in JP-A-1-240517 are used. be able to.
上記（ｄ）成分の代表例としてはＷ（＝Ｎ−２，６−Ｃ6Ｈ3 iＰｒ2）（＝ＣＨtＢｕ）
（ＯtＢｕ）2、Ｍｏ（＝Ｎ−２，６−Ｃ6Ｈ3 iＰｒ2）（＝ＣＨtＢｕ）（ＯtＢｕ）2、Ｒ
ｕ（＝ＣＨＣＨ＝ＣＰｈ2）（ＰＰｈ3）2Ｃｌ2、Ｒｕ（＝ＣＨＰｈ2）［Ｐ（Ｃ6Ｈ11）3
］2Ｃｌ2などがあげられる。
As a typical example of the component (d), W (= N-2,6-C 6 H 3 i Pr 2 ) (= CH t Bu)
(O t Bu) 2 , Mo (= N-2,6-C 6 H 3 i Pr 2 ) (= CH t Bu) (O t Bu) 2 , R
u (= CHCH = CPh 2 ) (PPh 3 ) 2 Cl 2 , Ru (= CHPh 2 ) [P (C 6 H 11 ) 3
], Etc. 2 Cl 2, and the like.
メタセシス触媒の使用量としては、上記（ａ）成分とノルボルネン系単量体（単量体（３）と単量体（４）との合計）とのモル比で「（ａ）成分：ノルボルネン系単量体」が、通常１：５００〜１：５０００００となる範囲、好ましくは１：１０００〜１：１０００００となる範囲であるのが望ましい。（ａ）成分と（ｂ）成分との割合は、金属原子比で「（ａ）：（ｂ）」が１：１〜１：５０、好ましくは１：２〜１：３０の範囲であるのが望ましい。（ａ）成分と（ｃ）成分との割合は、モル比で「（ｃ）：（ａ）」が０．００５：１〜１５：１、好ましくは０．０５：１〜７：１の範囲であるのが望ましい。また、触媒（ｄ）の使用量は、（ｄ）成分とノルボルネン系単量体（単量体（３）と単量体（４）との合計）とのモル比で「（ｄ）成分：特定単量体」が、通常１：５００〜１：５００００となる範囲、好ましくは１：１００〜１：１００００となる範囲であるのが望ましい。
分子量調節剤：
開環（共）重合で得られる開環（共）重合体の分子量の調節は、重合温度、触媒の種類、溶媒の種類によっても行うことができるが、本発明においては、分子量調節剤を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。ここで、好適な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−デセンなどのα−オレフィン類およびスチレンを挙げることができ、これらのうち、１−ブテン、１−ヘキセンが特に好ましい。これらの分子量調節剤は、単独であるいは２種以上を混合して用いることができる。分子量調節剤の使用量は、開環（共）重合反応に供されるノルボルネン系単量体（単量体（３）と単量体（４）との合計）１モルに対して０．００５〜０．６モル、好ましくは０．０２〜０．５モルの範囲であるのが望ましい。
開環（共）重合反応用溶媒：
開環（共）重合反応において用いられる溶媒（単量体、メタセシス触媒および分子量調節剤を溶解または分散する溶媒）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、デカンなどのアルカン類；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、ノルボルナンなど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、クメンなどの芳香族炭化水素；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などのハロゲン化アルカン、ハロゲン化アリールなどの化合物；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など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、ジメトキシエタンなどのエーテル類を挙げることができ、これらは単独であるいは混合して用いることができる。これらのうちでは、芳香族炭化水素が好ましい。溶媒の使用量としては、「溶媒：ノルボルネン系単量体（重量比）」が、通常１：１〜１０：１となる量、好ましくは１：１〜５：１となる量であるのが望ましい。
The amount of the metathesis catalyst used is the molar ratio of the above component (a) and the norbornene monomer (total of monomer (3) and monomer (4)) "(a) component: norbornene The “monomer” is usually in the range of 1: 500 to 1: 500,000, preferably 1: 1000 to 1: 100,000. The ratio of the component (a) to the component (b) is such that the metal atomic ratio of “(a) :( b)” is in the range of 1: 1 to 1:50, preferably 1: 2 to 1:30. Is desirable. The ratio of the component (a) to the component (c) is such that the molar ratio “(c) :( a)” is 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1. It is desirable that The amount of the catalyst (d) used is the molar ratio of the component (d) and the norbornene monomer (the total of the monomer (3) and the monomer (4)) “(d) component: The “specific monomer” is usually in the range of 1: 500 to 1: 50000, preferably in the range of 1: 100 to 1: 10000.
Molecular weight regulator:
The molecular weight of the ring-opening (co) polymer obtained by ring-opening (co) polymerization can be adjusted by the polymerization temperature, the type of catalyst, and the type of solvent. In the present invention, the molecular weight regulator is reacted. It is preferable to adjust by making it coexist in a system. Here, examples of suitable molecular weight regulators include α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. Styrene can be mentioned, and among these, 1-butene and 1-hexene are particularly preferable. These molecular weight regulators can be used alone or in admixture of two or more. The amount of the molecular weight regulator used is 0.005 with respect to 1 mole of norbornene-based monomer (total of monomer (3) and monomer (4)) subjected to the ring-opening (co) polymerization reaction. It is desirable to be in the range of -0.6 mol, preferably 0.02-0.5 mol.
Solvent for ring-opening (co) polymerization reaction:
Examples of the solvent used in the ring-opening (co) polymerization reaction (solvent that dissolves or disperses the monomer, the metathesis catalyst, and the molecular weight regulator) include alkanes such as pentane, hexane, heptane, octane, nonane, and decane; cyclohexane , Cycloalkanes such as cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform , Compounds such as halogenated alkanes such as tetrachloroethylene, aryl halides; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate; Ether, tetrahydrofuran, there may be mentioned ethers such as dimethoxyethane, it can be used singly or in combination. Of these, aromatic hydrocarbons are preferred. The amount of the solvent used is that the amount of “solvent: norbornene monomer (weight ratio)” is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1. desirable.
水素添加
上記の開環（共）重合により得られるノルボルネン系樹脂では、構造単位（１）中のＸと構造単位（２）中のＹはいずれも-CH=CH-で表されるオレフィン性不飽和基の状態であ
る。係る開環（共）重合体は、そのまま本発明のノルボルネン系樹脂として使用することもできるが、耐熱安定性の観点からさらに水素添加を行うことが望ましく、上記のオレフィン性不飽和基が水素添加されて前記ＸとＹとが-CH2-CH2-で表される基に転換された水
素添加物を本発明のノルボルネン系樹脂として使用することが好ましい。このため本発明のノルボルネン系樹脂の製造方法では、上述の開環（共）重合に続いて、水素添加を行うことが好ましい。
Hydrogenation In the norbornene-based resin obtained by the above ring-opening (co) polymerization, X in the structural unit (1) and Y in the structural unit (2) are both represented by —CH═CH—. It is in a saturated group state. Such a ring-opening (co) polymer can be used as it is as the norbornene resin of the present invention, but it is desirable to perform hydrogenation from the viewpoint of heat stability, and the above olefinically unsaturated group is hydrogenated. The hydrogenated product in which X and Y are converted to a group represented by —CH 2 —CH 2 — is preferably used as the norbornene resin of the present invention. Therefore, in the method for producing a norbornene-based resin of the present invention, it is preferable to perform hydrogenation following the above-described ring-opening (co) polymerization.
本発明でいう水素添加物とは、上記のオレフィン性不飽和基が水素添加されたものであり、ノルボルネン系単量体（３）もしくは単量体（４）に基づく側鎖の芳香環は実質的に水素添加されていないものである。 The hydrogenated product in the present invention is a product obtained by hydrogenating the above olefinically unsaturated group, and the side chain aromatic ring based on the norbornene monomer (3) or monomer (4) is substantially It is not hydrogenated.
なお、水素添加する割合としては、上記ＸおよびＹの少なくとも８０％以上、好ましくは９０％以上、さらに好ましくは９５％以上である。水素添加する割合が高いほど、得られるノルボルネン系樹脂の熱による着色や劣化が抑制されるため好ましい。 The ratio of hydrogenation is at least 80% or more of X and Y, preferably 90% or more, and more preferably 95% or more. The higher the ratio of hydrogenation, the better the coloration and deterioration of the resulting norbornene resin due to heat.
水素添加反応は、ノルボルネン系単量体（３）もしくは他の単量体に基づく側鎖の芳香環が実質的に水素添加されない条件で行われる必要がある。通常は、開環（共）重合体の溶液に水素添加触媒を添加し、これに常圧〜３００気圧、好ましくは３〜２００気圧の水素ガスを０〜２００℃、さらに好ましくは２０〜１８０℃で作用させることによって行われる。 The hydrogenation reaction needs to be performed under conditions where the side chain aromatic ring based on the norbornene monomer (3) or other monomer is not substantially hydrogenated. Usually, a hydrogenation catalyst is added to a ring-opening (co) polymer solution, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, is added to 0 to 200 ° C., more preferably 20 to 180 ° C. Is done by acting on.
水素添加触媒としては、通常のオレフィン性化合物の水素添加反応に用いられるものを使用することができる。この水素添加触媒としては、不均一系触媒および均一系触媒が公知である。不均一系触媒としては、パラジウム、白金、ニッケル、ロジウム、ルテニウムなどの貴金属触媒物質を、カーボン、シリカ、アルミナ、チタニアなどの担体に担持させた固体触媒を挙げることができる。また、均一系触媒としては、ナフテン酸ニッケル／トリエチルアルミニウム、ニッケルアセチルアセトナート／トリエチルアルミニウム、オクテン酸コバルト／ｎ−ブチルリチウム、チタノセンジクロリド／ジエチルアルミニウムモノクロリド、酢酸ロジウム、クロロトリス（トリフェニルホスフィン）ロジウム、ジクロロトリス（トリフェニルホスフィン）ルテニウム、クロロヒドロカルボニルトリス（トリフェニルホスフィン）ルテニウム、ジクロロカルボニルトリス（トリフェニルホスフィン）ルテニウムなどを挙げることができる。触媒の形態は粉末でも粒状でもよい。 As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. As this hydrogenation catalyst, a heterogeneous catalyst and a homogeneous catalyst are known. Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania. In addition, homogeneous catalysts include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium. Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, and the like. The form of the catalyst may be powder or granular.
これらの水素添加触媒は、ノルボルネン系単量体（３）もしくは他の単量体に基づく側鎖の芳香環が実質的に水素添加されないようにするために、その添加量を調整する必要があるが、通常は、「開環（共）重合体：水素添加触媒（重量比）」が、１：１×１０-6〜１：２となる割合で使用される。 These hydrogenation catalysts need to be adjusted in amount so that the side chain aromatic ring based on the norbornene monomer (3) or other monomer is not substantially hydrogenated. However, “ring-opening (co) polymer: hydrogenation catalyst (weight ratio)” is usually used at a ratio of 1: 1 × 10 −6 to 1: 2.
本発明においては、得られるノルボルネン系樹脂である開環（共）重合体またはその水素添加物の、ウッベローデ型粘度計で測定される対数粘度（ηinh）が、通常０．２〜５
．０、好ましくは０．３〜４．０、さらに好ましくは０．３５〜２．０であるのが望ましい。また、ノルボルネン系樹脂のゲルパーミエーションクロマトグラフィー（ＧＰＣ、テトラヒドロフラン溶媒、ポリスチレン換算）による分子量の測定では数平均分子量（Ｍｎ）は、通常１０００〜５０万、好ましくは２０００〜３０万、さらに好ましくは５０００〜３０万であり、重量平均分子量（Ｍｗ）は、通常５０００〜２００万、好ましくは１万〜１００万、さらに好ましくは３万〜５０万であるのが望ましい。ηinhが０．２未満、
Ｍｎが１０００未満あるいはＭｗが５０００未満であると、成形物の強度が著しく低下する。一方、ηinhが５．０以上、Ｍｎが５０万以上あるいはＭｗが２００万以上であると
、開環重合体またはその水素添加物の溶融粘度あるいは溶液粘度が高くなりすぎて、所望の成形品を得ることが困難になる場合がある。
In the present invention, the logarithmic viscosity (ηinh) measured by a Ubbelohde viscometer of the ring-opening (co) polymer which is a norbornene-based resin or a hydrogenated product thereof is usually 0.2-5.
. 0, preferably 0.3 to 4.0, more preferably 0.35 to 2.0. Further, in the measurement of molecular weight by gel permeation chromatography (GPC, tetrahydrofuran solvent, polystyrene conversion) of norbornene-based resin, the number average molecular weight (Mn) is usually 1000 to 500,000, preferably 2000 to 300,000, more preferably 5000. It is desirable that the weight average molecular weight (Mw) is usually 5,000 to 2,000,000, preferably 10,000 to 1,000,000, and more preferably 30,000 to 500,000. ηinh is less than 0.2,
If the Mn is less than 1000 or the Mw is less than 5000, the strength of the molded product is significantly reduced. On the other hand, if ηinh is 5.0 or more, Mn is 500,000 or more, or Mw is 2 million or more, the melt viscosity or solution viscosity of the ring-opening polymer or its hydrogenated product becomes too high, and a desired molded product is obtained. It may be difficult to obtain.
本発明に係るノルボルネン系樹脂には、公知の各種添加剤を添加することができる。例えば２，６−ジーt−ブチル−４−メチルフェノール、２，２−メチレンビス（４−エチ
ル−６−ｔ−ブチルフェノール）、２，５−ジ−ｔ−ブチルヒドロキノン、ペンタエリスリトール テトラキス[３−（３，５−ジ−ｔ−ブチル−４−ヒドキシフェニル）プロピ
オネート]、４，４−チオビス−（６−ｔ−ブチル−３−メチルフェノール）、１，１−
ビス（４−ヒドロキシフェニル）シクロヘキサン、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、３，３’，３”、５，５’，５”−ヘキサ−ｔ−ブチル−ａ、ａ’、ａ”−（メシチレン−２，４，６−トリイル）トリ−ｐ−クレゾールなどのフェノール系、ヒドロキノン系酸化防止剤、または例えばトリス（４−メトキシ−３，５−ジフェニル）フォスファイト、トリス（ノニルフェニル）フォスファイト、トリス（２，４−ジ−t−ブチルフェニル）フォスファイトなどのりん系酸化
防止剤をあげることができ、これらの酸化防止剤の１種または２種以上を添加することにより、開環（共）重合体またはその水素添加物の酸化安定性を向上することができる。また、紫外線吸収剤、例えば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、２，２’−メチレンビス［４−（１，１，３，３−テトラメチルブチル）−６−[（２Ｈ−ベンゾトリアゾール−２−イル）フェノール]］などを添加することによって耐光性を向上することができる。また、本発明に係るノルボルネン系樹脂には、加工性を向上させる目的で、滑剤などの添加剤を添加することもできる。
Various known additives can be added to the norbornene resin according to the present invention. For example, 2,6-di-t-butyl-4-methylphenol, 2,2-methylenebis (4-ethyl-6-t-butylphenol), 2,5-di-t-butylhydroquinone, pentaerythritol tetrakis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4-thiobis- (6-tert-butyl-3-methylphenol), 1,1-
Bis (4-hydroxyphenyl) cyclohexane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-t Phenolic, hydroquinone antioxidants such as butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, or for example tris (4-methoxy-3,5- Phosphorous antioxidants such as diphenyl) phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite can be mentioned, and one of these antioxidants or By adding two or more kinds, the oxidation stability of the ring-opening (co) polymer or its hydrogenated product can be improved, and an ultraviolet absorber such as 2,4- Dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol] In addition, an additive such as a lubricant can be added to the norbornene resin according to the present invention for the purpose of improving processability.
本発明に係るノルボルネン系樹脂は、特異な複屈折の波長依存性、低複屈折および高耐熱性、高度な透明性を有している。このことから本発明に係るノルボルネン系樹脂は、光学部品や電気電子材料などの分野の用途において特に有用であり、例えば、光ディスク、光磁気ディスク、光学レンズ（ｆθレンズ、ピックアップレンズ、レーザープリンター用レンズ、カメラ用レンズ等）、眼鏡レンズ、光学フィルム（ディスプレイ用フィルム、位相差フィルム、偏光フィルム、透明導電フィルム、波長板、光ピックアップフィルム等）、液晶配向膜、光学シート、光ファイバー、導光板、光拡散板、光カード、光ミラー、IC・LSI・LED封止材などの用途が挙げられる。 The norbornene resin according to the present invention has unique birefringence wavelength dependency, low birefringence, high heat resistance, and high transparency. Therefore, the norbornene-based resin according to the present invention is particularly useful in the field of applications such as optical parts and electrical and electronic materials. For example, optical discs, magneto-optical discs, optical lenses (fθ lenses, pickup lenses, laser printer lenses) , Camera lenses, etc.), eyeglass lenses, optical films (display films, retardation films, polarizing films, transparent conductive films, wave plates, optical pickup films, etc.), liquid crystal alignment films, optical sheets, optical fibers, light guide plates, light Applications include diffusion plates, optical cards, optical mirrors, IC / LSI / LED encapsulants, etc.
実施例
以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。
EXAMPLES Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited to the following examples.
実施例、比較例中の各種測定および評価は以下のとおりに行った。
（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℃、窒素気流下で測定を行った。
（重量平均分子量および分子量分布）
東ソー株式会社製HLC-8020ゲルパーミエーションクロマトグラフィー（GPC）を用い、
テトラヒドロフラン（THF）溶媒を用い、ポリスチレン換算の重量平均分子量（Mw）、分
子量分布（Mw/Mn）を測定した。Mnは数平均分子量を表す。
（構造確認）
核磁気共鳴分光計（ＮＭＲ）はＢｒｕｋｅｒ社製ＡＶＡＮＣＥ５００を用い、重水素化クロロホルム中で1Ｈ−ＮＭＲおよび13Ｃ−ＮＭＲを測定した。
Various measurements and evaluations in Examples and Comparative Examples were performed as follows.
(Glass transition temperature: Tg)
Using a DSC6200 manufactured by Seiko Instruments Inc., the temperature increase rate was measured at 20 ° C. per minute under a nitrogen stream.
(Weight average molecular weight and molecular weight distribution)
Using HLC-8020 gel permeation chromatography (GPC) manufactured by Tosoh Corporation
Using a tetrahydrofuran (THF) solvent, the polystyrene-reduced weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured. Mn represents a number average molecular weight.
(Structure confirmation)
As a nuclear magnetic resonance spectrometer (NMR), 1 H-NMR and 13 C-NMR were measured in deuterated chloroform using an AVANCE 500 manufactured by Bruker.
赤外分光計（ＩＲ）は日本分光社製ＦＴ／ＩＲ−４２０を用いて測定した。
（位相差、複屈折評価）
ガラス板上に樹脂のトルエンないし塩化メチレン溶液をキャストし、乾燥後、厚さ５０〜２００μｍ、残留溶媒０．５〜０．８％の無色透明なフィルムを得た。フィルムのＴｇ＋１０℃の温度にて１．３〜２．０倍に１軸延伸した。この延伸フィルムをレターデーション測定器（KOBRA21DH:王子計測社製）を用いてレターデーション（Re）を測定した。
The infrared spectrometer (IR) was measured using FT / IR-420 manufactured by JASCO Corporation.
(Evaluation of phase difference and birefringence)
A toluene or methylene chloride solution of the resin was cast on a glass plate, and after drying, a colorless and transparent film having a thickness of 50 to 200 μm and a residual solvent of 0.5 to 0.8% was obtained. The film was uniaxially stretched 1.3 to 2.0 times at a temperature of Tg + 10 ° C. Retardation (Re) of this stretched film was measured using a retardation measuring device (KOBRA21DH: manufactured by Oji Scientific Instruments).
合成例
＜６-（２、４-ジメトキシフェニル）-６-アザ-テトラシクロ[９．２．１．０2,10．０4,8] テトラデカ-１２-エン-５，７-ジオン（下記構造式（Ａ））の合成＞
ステンレス製の密閉容器にテトラヒドロフタル酸無水物（５０ｇ、０．３３ｍｏｌ）およびジシクロペンタジエン（２１．７ｇ、０．１６ｍｏｌ）を仕込み、１８０℃で６時間反応させた。その後、反応系を３ｍｍＨｇに減圧し、１３０℃に加熱することにより原料を留去して下記構造式（Ｂ）で表される６-オキサ-テトラシクロ[９．２．１．０2,10．
０4,8]トリデカ-１２-エン-５，７-ジオンを主成分とする粗生成物２４．３ｇを得た。得られた６-オキサ-テトラシクロ[９．２．１．０2,10．０4,8]トリデカ-１２-エン-５，７-ジオン粗体のＧＰＣで測定した純度は８０％であった。
Synthesis Example <6- (2,4-dimethoxyphenyl) -6-aza - tetracyclo [9.2.1.0 2,10. 0 4,8 ] Synthesis of tetradec-12-ene-5,7-dione (the following structural formula (A))>
Tetrahydrophthalic anhydride (50 g, 0.33 mol) and dicyclopentadiene (21.7 g, 0.16 mol) were charged into a stainless steel sealed container and reacted at 180 ° C. for 6 hours. Thereafter, the reaction system was reduced to 3 mmHg, represented by the following structural formula by removing the material by heating to 130 ℃ (B) 6- oxa - tetracyclo [9.2.1.0 2,10.
0 4,8] trideca-12-ene-5,7-dione The crude product 24.3g mainly. The resulting 6-oxa - tetracyclo [9.2.1.0 2,10. The purity of the [0 4,8 ] tridec-12-ene-5,7-dione crude product as measured by GPC was 80%.
還流管を取り付けた５００ｍL ３口フラスコに構造式（Ｂ）で表される６-オキサ-テトラシクロ[９．２．１．０2,10．０4,8]トリデカ-１２-エン-５，７-ジオンを主成分とす
る前述の粗体（２４．３ｇ）、２,４‐ジメトキシアニリン（１３．５ｇ、 ０．０８８ｍｏｌ）を仕込み、更に溶媒として酢酸２００ｍｌを添加した。昇温すると反応系は均一となり、その後３時間還流を行った。反応系を放冷後、酢酸を減圧留去し、得られた個体をメタノールで洗浄して赤褐色固体２８．０ｇ（粗収率：９０％） を得た。得られた固体
をシリカゲルカラムクロマトグラフィー（展開溶媒：ジクロロメタン）で精製後、さらにメタノールで再結晶し、白色固体１１．０ｇ（収率：３５％）を得た。得られた６-（２
、４-ジメトキシフェニル）-６-アザ-テトラシクロ[９．２．１．０2,10．０4,8] テトラデカ-１２-エン-５，７-ジオンのＩＲ、1Ｈ−ＮＭＲ、13Ｃ−ＮＭＲスペクトルを図１、
図２、図３にそれぞれ示す。
Represented by the structural formula (B) in 500 mL 3-neck flask equipped with a reflux condenser 6-oxa - tetracyclo [9.2.1.0 2,10. 0 4,8 ] tridec-12-ene-5,7-dione as a main component, the aforementioned crude product (24.3 g) and 2,4-dimethoxyaniline (13.5 g, 0.088 mol) were charged. 200 ml of acetic acid was added as a solvent. When the temperature was raised, the reaction system became uniform and then refluxed for 3 hours. After allowing the reaction system to cool, acetic acid was distilled off under reduced pressure, and the resulting solid was washed with methanol to obtain 28.0 g of a reddish brown solid (crude yield: 90%). The obtained solid was purified by silica gel column chromatography (developing solvent: dichloromethane) and then recrystallized from methanol to obtain 11.0 g (yield: 35%) of a white solid. Obtained 6- (2
, 4-dimethoxyphenyl) -6-aza - tetracyclo [9.2.1.0 2,10. [0 4,8 ] IR, 1 H-NMR and 13 C-NMR spectra of tetradeca-12-ene-5,7-dione are shown in FIG.
It shows in FIG. 2, FIG. 3, respectively.
＜開環重合体とその水素添加物の製造＞
ノルボルネン系単量体として、前記構造式Ａで表される６-（２、４-ジメトキシフェニル）-６-アザ-テトラシクロ[９．２．１．０2,10．０4,8] テトラデカ-１２-エン-５，７-ジオン ３．８ｇ、および、８−メトキシカルボニル−８−メチルテトラシクロ［４．
４．０．１2,5．１7,10］−３−ドデセン ２．５ｇ、分子量調節剤として１−へキセン
０．０７ｇおよびトルエン ２５．０ｇを、窒素置換した反応容器に仕込み、８０℃に加
熱した。これにトリエチルアルミニウム（０．６モル/L）のトルエン溶液 ０．２３ml、
メタノール変性WCl6トルエン溶液（０．０２５モル/L） ０．６９mlを加え、８０℃で３
時間反応させることにより、重量平均分子量（Mw）が１５．９x１０4,分子量分布（Mw/Mn）=３．２１の重合体が得られた。
<Production of ring-opening polymer and hydrogenated product thereof>
As norbornene monomer are represented by the structural formula A 6- (2,4-dimethoxyphenyl) -6-aza - tetracyclo [9.2.1.0 2,10. 0 4,8 ] tetradec-12-ene-5,7-dione 3.8 g and 8-methoxycarbonyl-8-methyltetracyclo [4.
4.0.1 2,5 . 1 7,10 ] -3-dodecene 2.5 g, 1-hexene as molecular weight regulator
0.07 g and 25.0 g of toluene were charged into a nitrogen-substituted reaction vessel and heated to 80 ° C. To this, 0.23 ml of a toluene solution of triethylaluminum (0.6 mol / L),
Add 0.69 ml of methanol-modified WCl 6 toluene solution (0.025 mol / L) and add 3 at 80 ° C.
By carrying out the reaction for a time, a polymer having a weight average molecular weight (Mw) of 15.9 × 10 4 and a molecular weight distribution (Mw / Mn) = 3.21 was obtained.
ここで得られた重合体溶液をオートクレーブに入れ、さらにトルエンを３００ｇ加えた。水素添加反応触媒であるRuHCl(CO)[P(C6H5)3]3をモノマー仕込み量に対して２５００ppm添加し、水素ガス圧を９−１０MPa、温度を１６０−１６５℃とし、３時間の反応を行った。反応終了後、多量のメタノール溶液に沈殿させることにより水素添加物を得た。得られた水素添加物は、重量平均分子量（Mw）＝１６．２x１０4、分子量分布（Mw/Mn）＝２
．７２、固有粘度（ηinh）＝０．８８、ガラス転移温度（Tg）＝１９０．３℃であった
。また、ＮＭＲ測定により求めたこの水素添加物の水素添加率は９９．０％以上であり、芳香環残存率は１００％であった。６-（２、４-ジメトキシフェニル）-６-アザ-テトラ
シクロ[９．２．１．０2,10．０4,8] テトラデカ-１２-エン-５，７-ジオンに由来する構造単位の割合は３４．６ｍｏｌ％であった。得られた開環重合水添添加物のＩＲ、1Ｈ−
ＮＭＲ、13Ｃ−ＮＭＲスペクトルを図４、図５、図６にそれぞれ示す。
The polymer solution obtained here was put into an autoclave, and 300 g of toluene was further added. Add 2,500 ppm of RuHCl (CO) [P (C 6 H 5 ) 3 ] 3 as a hydrogenation reaction catalyst to the charged amount of monomer, set the hydrogen gas pressure to 9-10 MPa and the temperature to 160-165 ° C. for 3 hours. The reaction was performed. After completion of the reaction, a hydrogenated product was obtained by precipitation in a large amount of methanol solution. The resulting hydrogenated product has a weight average molecular weight (Mw) = 16.2x10 4, a molecular weight distribution (Mw / Mn) = 2
. 72, intrinsic viscosity (ηinh) = 0.88, glass transition temperature (Tg) = 190.3 ° C. Further, the hydrogenation rate of this hydrogenated product determined by NMR measurement was 99.0% or more, and the aromatic ring residual rate was 100%. 6- (2,4-dimethoxyphenyl) -6-aza - tetracyclo [9.2.1.0 2,10. 0 4,8] tetradec-12-proportion of the structural unit derived from ene-5,7-dione was 34.6mol%. IR of the obtained ring-opening polymerization hydrogenated additive, 1 H-
The NMR and 13 C-NMR spectra are shown in FIGS. 4, 5, and 6, respectively.
得られた開環重合水添体の溶媒キャスト法で成形したフィルムを延伸した後にレターデーション（Re、位相差）を測定し、フィルムの厚さ（ｄ）から複屈折の評価を行った。測定波長550nmでの複屈折（Re550/d＝Δn550）の結果を表１に示す。また、実施例に示す開環共重合水添体のレターデーション（Re）の波長依存性について評価した。各波長のレターデーション（Re）と550nmでのレターデーション（Re550）比の測定結果を表１に示す。 After stretching the film formed by the solvent casting method of the obtained ring-opening polymerization hydrogenated product, retardation (Re, retardation) was measured, and birefringence was evaluated from the thickness (d) of the film. Table 1 shows the results of birefringence (Re550 / d = Δn550) at a measurement wavelength of 550 nm. In addition, the wavelength dependency of retardation (Re) of the ring-opening copolymer hydrogenated product shown in Examples was evaluated. Table 1 shows the measurement results of the retardation (Re) at each wavelength and the retardation (Re550) ratio at 550 nm.
比較例１
ノルボルネン系単量体として下記構造式Ｃで表される８−メトキシカルボニル−８−メチルテトラシクロ［４．４．０．１2,5．１7,10］−３−ドデセンを５０ｇと、１−へキ
セン ３．６ｇおよびトルエン １００ｇを窒素置換した反応容器に仕込み、８０℃に加熱した。これにトリエチルアルミニウム（０．６モル/L）のトルエン溶液 ０．０９ml、メ
タノール変性WCl6トルエン溶液（０．０２５モル/L） ０．２９mlを加え、８０℃で３時
間反応させることにより重合体を得た。次いで、実施例１と同様にして水素添加反応を行い、重合体の水素添加物を得た。得られた水素添加物は、ガラス転移温度（Tg）＝１６７℃、重量平均分子量（Mw）＝５６０００、分子量分布（Mw/Mn）＝３．２であった。また
、ＮＭＲ測定によるこの水素添加物の水素添加率は９９．０%以上であった。
Comparative Example 1
As norbornene monomer represented by the following structural formula C 8- methoxycarbonyl-8-methyl-tetracyclo [4.4.0.1 2, 5. 1 7,10 ] -3-dodecene (50 g), 1-hexene (3.6 g) and toluene (100 g) were charged into a nitrogen-substituted reaction vessel and heated to 80 ° C. To this was added 0.09 ml of a toluene solution of triethylaluminum (0.6 mol / L) and 0.29 ml of a methanol-modified WCl6 toluene solution (0.025 mol / L) and reacted at 80 ° C. for 3 hours to obtain a polymer. Obtained. Next, a hydrogenation reaction was performed in the same manner as in Example 1 to obtain a polymer hydrogenated product. The obtained hydrogenated product had a glass transition temperature (Tg) = 167 ° C., a weight average molecular weight (Mw) = 56000, and a molecular weight distribution (Mw / Mn) = 3.2. Further, the hydrogenation rate of this hydrogenated product by NMR measurement was 99.0% or more.
得られた水素添加物について、実施例１と同様にしてレターデーション（Re、位相差）を測定し、フィルムの厚さ（ｄ）から複屈折の評価を行った。測定波長550nmでの複屈折
（Re550/d＝Δn550）の結果を表１に示す。また、実施例と同様にしてレターデーション
（Re）の波長依存性について評価した。各波長のレターデーション（Re）と550nmでのレ
ターデーション（Re550）比の測定結果を表１に示す。
With respect to the obtained hydrogenated product, retardation (Re, retardation) was measured in the same manner as in Example 1, and birefringence was evaluated from the thickness (d) of the film. Table 1 shows the results of birefringence (Re550 / d = Δn550) at a measurement wavelength of 550 nm. Further, the wavelength dependency of retardation (Re) was evaluated in the same manner as in the Examples. Table 1 shows the measurement results of the retardation (Re) at each wavelength and the retardation (Re550) ratio at 550 nm.
この結果より、比較例１に比べ実施例１では複屈折が低いことがわかった。また、比較例１で得られた水素添加物では、測定波長に対して依存性が小さく、短波長側で若干大きくなるが、実施例１で得られた水素添加物では、長波長側になるに従いレターデーション比が大きくなることがわかった。 From this result, it was found that the birefringence was lower in Example 1 than in Comparative Example 1. The hydrogenated product obtained in Comparative Example 1 is less dependent on the measurement wavelength and slightly increases on the short wavelength side, whereas the hydrogenated product obtained in Example 1 is on the long wavelength side. It was found that the retardation ratio increased according to the results.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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