JP5601056B2 - Resin composition and optical component comprising the same - Google Patents
Resin composition and optical component comprising the same Download PDFInfo
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- JP5601056B2 JP5601056B2 JP2010153878A JP2010153878A JP5601056B2 JP 5601056 B2 JP5601056 B2 JP 5601056B2 JP 2010153878 A JP2010153878 A JP 2010153878A JP 2010153878 A JP2010153878 A JP 2010153878A JP 5601056 B2 JP5601056 B2 JP 5601056B2
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- 239000011342 resin composition Substances 0.000 title claims description 67
- 230000003287 optical effect Effects 0.000 title claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 84
- -1 phenol compound Chemical class 0.000 claims description 46
- 125000004432 carbon atom Chemical group C* 0.000 claims description 34
- 238000007142 ring opening reaction Methods 0.000 claims description 33
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 31
- 229910052698 phosphorus Inorganic materials 0.000 claims description 31
- 239000011574 phosphorus Substances 0.000 claims description 31
- 125000004122 cyclic group Chemical group 0.000 claims description 28
- 229920005672 polyolefin resin Polymers 0.000 claims description 28
- 229920001577 copolymer Polymers 0.000 claims description 27
- 150000002989 phenols Chemical class 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- 238000005227 gel permeation chromatography Methods 0.000 claims description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 230000009477 glass transition Effects 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000013585 weight reducing agent Substances 0.000 claims description 7
- 150000001721 carbon Chemical group 0.000 claims description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 230000004580 weight loss Effects 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 125000002950 monocyclic group Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 75
- 150000002430 hydrocarbons Chemical group 0.000 description 29
- 239000000243 solution Substances 0.000 description 27
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- 239000000499 gel Substances 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 14
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 13
- 239000003963 antioxidant agent Substances 0.000 description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 11
- 238000012545 processing Methods 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000000779 smoke Substances 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical class Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000001145 hydrido group Chemical group *[H] 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].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.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- OWTNUJIQXMQJKA-UHFFFAOYSA-N ruthenium;triphenylphosphane Chemical compound [Ru].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 OWTNUJIQXMQJKA-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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 3
- XUFPYLQWLKKGDQ-UHFFFAOYSA-N 4,4a,9,9a-tetrahydro-1,4-methano-1h-fluorene Chemical compound C12CC3=CC=CC=C3C1C1C=CC2C1 XUFPYLQWLKKGDQ-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 239000013307 optical fiber Substances 0.000 description 3
- 239000012788 optical film Substances 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-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
- 229920003023 plastic Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 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 3
- 239000003566 sealing material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 2
- PGNNHYNYFLXKDZ-UHFFFAOYSA-N 5-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2C1=CC=CC=C1 PGNNHYNYFLXKDZ-UHFFFAOYSA-N 0.000 description 2
- CSRQAJIMYJHHHQ-UHFFFAOYSA-N 9-ethylidenetetracyclo[6.2.1.13,6.02,7]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1=CC CSRQAJIMYJHHHQ-UHFFFAOYSA-N 0.000 description 2
- 0 CC(CC(c1c(C)cc(*C(CCc(cc2C(C)(C)C)cc(C(C)(C)C)c2O)=O)c(C(C)(C)C)c1)c(cc1C(C)(C)C)c(C)cc1OC(CCc(cc1C(C)(C)C)cc(C(C)(C)C)c1O)=O)c(cc1C(C)(C)C)c(C)cc1OC(CCc(cc1C(C)(C)C)cc(C(C)(C)C)c1O)=O Chemical compound CC(CC(c1c(C)cc(*C(CCc(cc2C(C)(C)C)cc(C(C)(C)C)c2O)=O)c(C(C)(C)C)c1)c(cc1C(C)(C)C)c(C)cc1OC(CCc(cc1C(C)(C)C)cc(C(C)(C)C)c1O)=O)c(cc1C(C)(C)C)c(C)cc1OC(CCc(cc1C(C)(C)C)cc(C(C)(C)C)c1O)=O 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-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
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000003545 alkoxy 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
- 238000004458 analytical method Methods 0.000 description 2
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 2
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 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 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- RRTJOAHJZQVSSE-UHFFFAOYSA-N 1,3,2-dioxaphosphepine Chemical compound C=1C=COPOC=1 RRTJOAHJZQVSSE-UHFFFAOYSA-N 0.000 description 1
- RWNNRGBCWXOVAC-UHFFFAOYSA-N 1,4-bis[bis(aziridin-1-yl)phosphoryl]piperazine Chemical compound C1CN1P(N1CCN(CC1)P(=O)(N1CC1)N1CC1)(=O)N1CC1 RWNNRGBCWXOVAC-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- UOYKBJNWNACIRX-UHFFFAOYSA-N 2,3,3-trifluorobicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(F)C2(F)F UOYKBJNWNACIRX-UHFFFAOYSA-N 0.000 description 1
- ZGNJHKOQQSEQRR-UHFFFAOYSA-N 2,3-bis(trifluoromethyl)bicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(C(F)(F)F)C2C(F)(F)F ZGNJHKOQQSEQRR-UHFFFAOYSA-N 0.000 description 1
- DKFVTFNJIYIYNV-UHFFFAOYSA-N 2,3-difluorobicyclo[2.2.1]hept-5-ene Chemical compound C1C2C(F)C(F)C1C=C2 DKFVTFNJIYIYNV-UHFFFAOYSA-N 0.000 description 1
- ZCAIOHDMWSETCE-UHFFFAOYSA-N 2-(5-methyl-5-bicyclo[2.2.1]hept-2-enyl)naphthalene Chemical compound C1=CC=CC2=CC(C3(C4CC(C=C4)C3)C)=CC=C21 ZCAIOHDMWSETCE-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- WBWXVCMXGYSMQA-UHFFFAOYSA-N 3,9-bis[2,4-bis(2-phenylpropan-2-yl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C=1C=C(OP2OCC3(CO2)COP(OC=2C(=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C(C)(C)C=2C=CC=CC=2)OC3)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 WBWXVCMXGYSMQA-UHFFFAOYSA-N 0.000 description 1
- AESQDCMZHBUWPN-UHFFFAOYSA-N 4h-1,3,2-dioxaphosphinine Chemical compound C1OPOC=C1 AESQDCMZHBUWPN-UHFFFAOYSA-N 0.000 description 1
- SJQUAKKVMGAVKS-UHFFFAOYSA-N 5,5-bis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C(F)(F)F)(C(F)(F)F)CC1C=C2 SJQUAKKVMGAVKS-UHFFFAOYSA-N 0.000 description 1
- UWQSIGZFGLPCHM-UHFFFAOYSA-N 5,5-difluorobicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(F)(F)CC1C=C2 UWQSIGZFGLPCHM-UHFFFAOYSA-N 0.000 description 1
- UVFFMASFIIKUOD-UHFFFAOYSA-N 5-(chloromethyl)bicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCl)CC1C=C2 UVFFMASFIIKUOD-UHFFFAOYSA-N 0.000 description 1
- FEYUUIYEFBYGPR-UHFFFAOYSA-N 5-(fluoromethyl)bicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CF)CC1C=C2 FEYUUIYEFBYGPR-UHFFFAOYSA-N 0.000 description 1
- PBNBTJLQHASCPE-UHFFFAOYSA-N 5-(trifluoromethyl)bicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C(F)(F)F)CC1C=C2 PBNBTJLQHASCPE-UHFFFAOYSA-N 0.000 description 1
- UHSJKAJNNDVGHT-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enyl(tributoxy)silane Chemical compound C1C2C([Si](OCCCC)(OCCCC)OCCCC)CC1C=C2 UHSJKAJNNDVGHT-UHFFFAOYSA-N 0.000 description 1
- HHKDWDAAEFGBAC-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enyl(triethoxy)silane Chemical compound C1C2C([Si](OCC)(OCC)OCC)CC1C=C2 HHKDWDAAEFGBAC-UHFFFAOYSA-N 0.000 description 1
- LUMNWCHHXDUKFI-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enylmethanol Chemical compound C1C2C(CO)CC1C=C2 LUMNWCHHXDUKFI-UHFFFAOYSA-N 0.000 description 1
- QHJIJNGGGLNBNJ-UHFFFAOYSA-N 5-ethylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CC)CC1C=C2 QHJIJNGGGLNBNJ-UHFFFAOYSA-N 0.000 description 1
- LFBHYIUTPVORTR-UHFFFAOYSA-N 5-fluorobicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(F)CC1C=C2 LFBHYIUTPVORTR-UHFFFAOYSA-N 0.000 description 1
- OXGPYKJRQDQTQU-UHFFFAOYSA-N 5-methyl-5-(trifluoromethyl)bicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)(C(F)(F)F)CC1C=C2 OXGPYKJRQDQTQU-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- PBIDTCFSVFIAOT-UHFFFAOYSA-N 9,9-difluorotetracyclo[6.2.1.13,6.02,7]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1(F)F PBIDTCFSVFIAOT-UHFFFAOYSA-N 0.000 description 1
- LYNAXHUAVQITQG-UHFFFAOYSA-N 9-(trifluoromethyl)tetracyclo[6.2.1.13,6.02,7]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1C(F)(F)F LYNAXHUAVQITQG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FEHMOVWELOPMEE-UHFFFAOYSA-N C(=O)=C1C2C3C4C=CC(C3C(C1)C2)C4 Chemical compound C(=O)=C1C2C3C4C=CC(C3C(C1)C2)C4 FEHMOVWELOPMEE-UHFFFAOYSA-N 0.000 description 1
- NMIVHSDHQOAROH-UHFFFAOYSA-N C12C3C=CC(CCC4C5C2CC(C4C1)C5)C3 Chemical compound C12C3C=CC(CCC4C5C2CC(C4C1)C5)C3 NMIVHSDHQOAROH-UHFFFAOYSA-N 0.000 description 1
- PEMJSEWVUKBDMC-UHFFFAOYSA-N C1C(C23)C=CC1C3C1CC2CC1CF Chemical compound C1C(C23)C=CC1C3C1CC2CC1CF PEMJSEWVUKBDMC-UHFFFAOYSA-N 0.000 description 1
- CGHIGJHJDBOSPE-UHFFFAOYSA-N C1CC23CC1C1C2CCC2CC(C=C2)C31 Chemical compound C1CC23CC1C1C2CCC2CC(C=C2)C31 CGHIGJHJDBOSPE-UHFFFAOYSA-N 0.000 description 1
- YHMKWBHTXYMVCG-UHFFFAOYSA-N CO[Si](C1C2C=CC(C1)C2)(OC)OC.NCC2C1C=CC(C2)C1 Chemical compound CO[Si](C1C2C=CC(C1)C2)(OC)OC.NCC2C1C=CC(C2)C1 YHMKWBHTXYMVCG-UHFFFAOYSA-N 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
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- QXKHYNVANLEOEG-UHFFFAOYSA-N Methoxsalen Chemical group C1=CC(=O)OC2=C1C=C1C=COC1=C2OC QXKHYNVANLEOEG-UHFFFAOYSA-N 0.000 description 1
- KAKGPYGBZOWPEF-UHFFFAOYSA-N N[Mn]C1=CCC2C(C3)(CCC4)C34C12 Chemical compound N[Mn]C1=CCC2C(C3)(CCC4)C34C12 KAKGPYGBZOWPEF-UHFFFAOYSA-N 0.000 description 1
- FDBMBOYIVUGUSL-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C FDBMBOYIVUGUSL-UHFFFAOYSA-N 0.000 description 1
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- JOTGQABKKXBQQR-UHFFFAOYSA-N [4-[4,4-bis[5-tert-butyl-4-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2-methylphenyl]butan-2-yl]-2-tert-butyl-5-methylphenyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound C=1C(C(C)(C)C)=C(OC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C=C(C)C=1C(C)CC(C=1C(=CC(OC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C(C=1)C(C)(C)C)C)C(C(=C1)C)=CC(C(C)(C)C)=C1OC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 JOTGQABKKXBQQR-UHFFFAOYSA-N 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
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000005199 aryl carbonyloxy group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- UELGRCOBOPRCQU-UHFFFAOYSA-N biphenylene;hydroxyphosphanyloxyphosphinous acid Chemical compound OPOPO.C1=CC=C2C3=CC=CC=C3C2=C1 UELGRCOBOPRCQU-UHFFFAOYSA-N 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- JVOCWUZGKVURAV-UHFFFAOYSA-N butyl 4-methyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4-carboxylate Chemical compound C1C(C23)C=CC1C3C1CC2CC1(C)C(=O)OCCCC JVOCWUZGKVURAV-UHFFFAOYSA-N 0.000 description 1
- AJVSSYFQWYBQMV-UHFFFAOYSA-N butyl tetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4-carboxylate Chemical compound C1C(C23)C=CC1C3C1CC2CC1C(=O)OCCCC AJVSSYFQWYBQMV-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 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
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 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
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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
- HSYKJCVXJHCKEB-UHFFFAOYSA-N ethyl 4-methyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4-carboxylate Chemical compound C1C(C23)C=CC1C3C1CC2CC1(C)C(=O)OCC HSYKJCVXJHCKEB-UHFFFAOYSA-N 0.000 description 1
- CGXYLLNYPIBZSE-UHFFFAOYSA-N ethyl tetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4-carboxylate Chemical compound C1C(C23)C=CC1C3C1CC2CC1C(=O)OCC CGXYLLNYPIBZSE-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction 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
- 238000002347 injection Methods 0.000 description 1
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- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 239000006078 metal deactivator 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
- ZDFOSSPNFAQIOM-UHFFFAOYSA-N methyl 8-tetracyclo-[4.4.0.12,5.17,10]dodecene-3-carboxylate Chemical compound C1C(C23)C=CC1C3C1CC2CC1C(=O)OC ZDFOSSPNFAQIOM-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
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- VINIKTJHJMNSIR-UHFFFAOYSA-N naphthalen-1-yl 4-methyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4-carboxylate Chemical compound C1=CC=C2C(OC(=O)C3(C4CC(C5C6CC(C=C6)C54)C3)C)=CC=CC2=C1 VINIKTJHJMNSIR-UHFFFAOYSA-N 0.000 description 1
- ITAIJOKDSGPPHZ-UHFFFAOYSA-N naphthalen-1-yl tetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4-carboxylate Chemical compound C1=CC=C2C(OC(=O)C3C4CC(C5C6CC(C=C6)C54)C3)=CC=CC2=C1 ITAIJOKDSGPPHZ-UHFFFAOYSA-N 0.000 description 1
- LUNFPODXCUSVFX-UHFFFAOYSA-N naphthalen-2-yl 4-methyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4-carboxylate Chemical compound C1=CC=CC2=CC(OC(=O)C3(C4CC(C5C6CC(C=C6)C54)C3)C)=CC=C21 LUNFPODXCUSVFX-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
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- 239000012766 organic filler Substances 0.000 description 1
- GJXAPHONGGLIOM-UHFFFAOYSA-N oxaphosphepine Chemical compound O1C=CC=CC=P1 GJXAPHONGGLIOM-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- VGXOXHRUFVBLBN-UHFFFAOYSA-N pentacyclo[6.5.1.13,6.02,7.09,13]pentadec-4-ene Chemical compound C1C2C3C(C=C4)CC4C3C1C1C2CCC1 VGXOXHRUFVBLBN-UHFFFAOYSA-N 0.000 description 1
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 1
- JRRWDDUBHFRERA-UHFFFAOYSA-N phenyl tetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4-carboxylate Chemical compound C1C(C2C3CC(C=C3)C22)CC2C1C(=O)OC1=CC=CC=C1 JRRWDDUBHFRERA-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- MDRSNFPBVFZYPI-UHFFFAOYSA-N propan-2-yl 4-methyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4-carboxylate Chemical compound C1C(C23)C=CC1C3C1CC2CC1(C)C(=O)OC(C)C MDRSNFPBVFZYPI-UHFFFAOYSA-N 0.000 description 1
- RPUOIWGUZZSFBB-UHFFFAOYSA-N propan-2-yl tetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4-carboxylate Chemical compound C1C(C23)C=CC1C3C1CC2CC1C(=O)OC(C)C RPUOIWGUZZSFBB-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- XPWCPKAPHLQSKF-UHFFFAOYSA-N propyl 4-methyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4-carboxylate Chemical compound C1C(C23)C=CC1C3C1CC2CC1(C)C(=O)OCCC XPWCPKAPHLQSKF-UHFFFAOYSA-N 0.000 description 1
- IYJVDXMMWSPICZ-UHFFFAOYSA-N propyl tetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4-carboxylate Chemical compound C1C(C23)C=CC1C3C1CC2CC1C(=O)OCCC IYJVDXMMWSPICZ-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
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- 239000012488 sample solution Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002834 transmittance Methods 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
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、環状オレフィン系樹脂と特定の酸化防止剤とからなる樹脂組成物に関する。
より詳しくは、過酷な加工条件においてもガス発生および発塵が少なく、また成型品が着色したり成型物中にゲルを生じたりせずに光学部品を成型し得る樹脂組成物に関する。
The present invention relates to a resin composition comprising a cyclic olefin resin and a specific antioxidant.
More specifically, the present invention relates to a resin composition capable of molding an optical component without causing gas generation and dust generation even under severe processing conditions, and without causing the molded product to be colored or gel in the molded product.
環状オレフィン系樹脂は、ガラス転移温度および光線透過率が高く、屈折率の異方性が小さいため、従来の光学フィルムと比べて複屈折性が低いなどの特長を有しており、耐熱性、透明性および光学特性に優れた熱可塑性樹脂として注目されている。 Cyclic olefin-based resins have high glass transition temperature and high light transmittance, and low refractive index anisotropy, so they have features such as low birefringence compared to conventional optical films, heat resistance, It attracts attention as a thermoplastic resin excellent in transparency and optical properties.
そこで上記の特長を利用して、例えば、光ディスク、光学レンズ、光ファイバー、透明プラスチック基盤および低誘電材料などの電子・光学材料ならびに光半導体封止などの封止材料の分野などにおいて環状オレフィン系樹脂を応用することが検討されている。 Therefore, by utilizing the above features, for example, in the fields of optical and optical materials such as optical disks, optical lenses, optical fibers, transparent plastic substrates and low dielectric materials, and sealing materials such as optical semiconductor sealing, cyclic olefin-based resins are used. Application is under consideration.
一方で、近年の各種部材の軽量化、小型化および薄型化といった要求に応えるために、高温・高せん断下での加工が必要となってきている。しかしながら、環状オレフィン系樹脂はその優れた耐熱性のために、加工するには過酷な条件にすることが必要であり、酸化劣化を抑えるために酸化防止剤の添加が必須である。特許文献1および2には環状オレフィン系樹脂と各種酸化防止剤とを含有する樹脂組成物が開示されているが、用いられる酸化防止剤が射出成型や押出し成型の加工温度に耐えられず、1)分解・揮発して金型またはロールを汚染する、2)分解物が副反応を起こし微小なゲルを生成し、これが光学部品の欠陥となる、あるいは3)樹脂加工品が黄色に変色し外観を損ねるなどの問題があった。 On the other hand, in order to meet the recent demands for reducing the weight, size and thickness of various members, processing under high temperature and high shear is required. However, the cyclic olefin-based resin needs to be subjected to severe conditions for processing because of its excellent heat resistance, and addition of an antioxidant is essential to suppress oxidative degradation. Patent Documents 1 and 2 disclose resin compositions containing cyclic olefin-based resins and various antioxidants, but the antioxidants used cannot withstand the processing temperatures of injection molding and extrusion molding, and 1 2) Decomposition and volatilization contaminates the mold or roll 2) Decomposition product causes side reaction to produce fine gel, which becomes a defect of optical component 3) Resin processed product turns yellow and appearance There was a problem such as damage.
そのため、上記問題を解決し、高温で射出成型や押出し成型を行っても環状オレフィン系樹脂が本来有する高透明性、低着色および高耐熱性を損なわない樹脂組成物の開発が強く望まれていた。 Therefore, development of a resin composition that solves the above problems and does not impair the high transparency, low coloring, and high heat resistance inherent to the cyclic olefin resin even when injection molding or extrusion molding is performed at a high temperature has been strongly desired. .
本発明は、高温・高せん断下で加工してもガス発生や発塵が少なく、環状オレフィン系樹脂が本来有する高透明性、低着色および高耐熱性を損なわない樹脂組成物を提供することを課題とする。 The present invention provides a resin composition that generates little gas and generates dust even when processed under high temperature and high shear, and does not impair the high transparency, low coloration, and high heat resistance inherent in cyclic olefin resins. Let it be an issue.
本発明者らは、環状オレフィン系樹脂に特定のヒンダードフェノール系化合物を含有させることにより、上記問題を解決する樹脂組成物が得られることを見出し、本発明を完成させた。 The present inventors have found that a resin composition that solves the above problems can be obtained by containing a specific hindered phenol compound in a cyclic olefin resin, and completed the present invention.
すなわち、本発明には以下の事項が含まれる。
〔1〕下記式(1)で表される化合物に由来する構造単位を有する環状オレフィン系樹脂(A)と、下記式(2)で表される基を1分子内に2個以上有するフェノール系化合物(B)とを含有することを特徴とする樹脂組成物。
That is, the present invention includes the following matters.
[1] A cyclic olefin resin (A) having a structural unit derived from a compound represented by the following formula (1), and a phenol type having two or more groups represented by the following formula (2) in one molecule A resin composition comprising a compound (B).
〔2〕前記フェノール系化合物(B)が下記要件(B−i)および(B−ii)を満たす〔1〕に記載の樹脂組成物。
(B−i):分子量が800以上
(B−ii):窒素下において300℃で1時間加熱したときの重量減少率が15%以下
[2] The resin composition according to [1], wherein the phenolic compound (B) satisfies the following requirements (Bi) and (B-ii).
(B-i): molecular weight is 800 or more (B-ii): weight loss rate when heated at 300 ° C. for 1 hour under nitrogen is 15% or less
〔3〕前記フェノール系化合物(B)が、下記式(2−1)で表される化合物であることを特徴とする〔1〕または〔2〕に記載の樹脂組成物。 [3] The resin composition as described in [1] or [2], wherein the phenol compound (B) is a compound represented by the following formula (2-1).
〔4〕前記フェノール系化合物(B)が下記式(2−a)に示す化合物であることを特徴とする〔1〕〜〔3〕のいずれかに記載の樹脂組成物。 [4] The resin composition according to any one of [1] to [3], wherein the phenol compound (B) is a compound represented by the following formula (2-a).
〔6〕さらに下記要件(C−i)および(C−ii)を満たす含リン化合物(C)を含有し、該含リン化合物(C)が、環状オレフィン系樹脂(A)100重量部に対して0.005〜5重量部含まれることを特徴とする〔1〕〜〔5〕のいずれかに記載の樹脂組成物。
(C−i):単一化合物においてはその相対分子質量が400以上、多分散性混合物においてはゲルパーミエーションクロマトグラフィー(GPC)による重量平均分子量(Mw)が400以上、
(C−ii):窒素下において250℃で1時間加熱したときの重量減少率が50%以下
[6] A phosphorus-containing compound (C) that further satisfies the following requirements (Ci) and (C-ii) is further contained, and the phosphorus-containing compound (C) is based on 100 parts by weight of the cyclic olefin-based resin (A). 0.005 to 5 parts by weight of the resin composition according to any one of [1] to [5].
(Ci): In a single compound, the relative molecular mass is 400 or more, and in a polydisperse mixture, the weight average molecular weight (Mw) by gel permeation chromatography (GPC) is 400 or more,
(C-ii): Weight reduction rate when heated at 250 ° C. for 1 hour under nitrogen is 50% or less
〔7〕前記含リン化合物(C)が下記式(3)で表される構造を含むことを特徴とする〔6〕に記載の樹脂組成物。 [7] The resin composition as described in [6], wherein the phosphorus-containing compound (C) includes a structure represented by the following formula (3).
〔8〕前記含リン化合物(C)が下記式(3−a)〜(3−c)で表される化合物から選ばれる少なくとも1種を主成分とすることを特徴とする〔6〕または〔7〕に記載の樹脂組成物。 [8] The phosphorus-containing compound (C) contains at least one selected from compounds represented by the following formulas (3-a) to (3-c) as a main component [6] or [6] 7].
〔10〕前記開環(共)重合水添体(A−2)のガラス転移温度(Tg)が100〜250℃であることを特徴とする〔5〕または〔9〕に記載の樹脂組成物。
〔11〕前記開環(共)重合水添体(A−2)の芳香環の不飽和結合を除く炭素−炭素二重結合部の水素添加率が90%以上であることを特徴とする〔5〕、〔9〕または〔10〕に記載の樹脂組成物。
[10] The resin composition as described in [5] or [9], wherein the ring-opening (co) polymerized hydrogenated product (A-2) has a glass transition temperature (Tg) of 100 to 250 ° C. .
[11] The hydrogenation rate of the carbon-carbon double bond portion excluding the unsaturated bond of the aromatic ring of the ring-opening (co) polymerized hydrogenated product (A-2) is 90% or more [ [5], [9] or [10].
〔12〕〔1〕〜〔11〕のいずれかに記載の樹脂組成物からなる光学部品。 [12] An optical component comprising the resin composition according to any one of [1] to [11].
本発明によれば、環状オレフィン系樹脂に特定のフェノール系化合物を含有させることにより、高温や高せん断下で加工しても分解または揮発によるガス発生および発塵が少なく、環状オレフィン系樹脂が本来有している高透明性、耐熱性および低着色性を損なうこのない樹脂組成物が得られる。 According to the present invention, by including a specific phenol compound in the cyclic olefin resin, there is little gas generation and dust generation due to decomposition or volatilization even if processed under high temperature or high shear, and the cyclic olefin resin is inherently A resin composition which does not impair the high transparency, heat resistance and low colorability possessed is obtained.
また上記フェノール系化合物に加え、特定の含リン化合物を併用すると、フェノール系化合物の含有量を低減しても色相改良効果が認められるため、要求される特性によって品質バランスをコントロールすることができる。 Further, when a specific phosphorus-containing compound is used in combination with the phenolic compound, a hue improving effect is recognized even if the content of the phenolic compound is reduced, so that the quality balance can be controlled by required characteristics.
したがって、本発明の樹脂組成物は光学フィルム、光ディスク、光学レンズ、光ファイバー、透明プラスチック基盤および低誘電材料などの電子・光学材料ならびに光半導体の封止材料などに好適である。 Therefore, the resin composition of the present invention is suitable for an optical film, an optical disk, an optical lens, an optical fiber, a transparent plastic substrate, a low dielectric material and other electronic / optical materials, and an optical semiconductor sealing material.
以下、本発明の樹脂組成物および該樹脂組成物からなる光学部品について説明する。
本発明の樹脂組成物は、下記式(1)で表される化合物に由来する構造単位を有する環状オレフィン系樹脂(A)、下記式(2)で表される基を1分子内に2個以上有するフェノール系化合物(B)を含有することを特徴とする。
Hereinafter, the resin composition of the present invention and the optical component comprising the resin composition will be described.
The resin composition of the present invention comprises a cyclic olefin resin (A) having a structural unit derived from a compound represented by the following formula (1), and two groups represented by the following formula (2) in one molecule. It contains the phenol compound (B) having the above.
[環状オレフィン系樹脂(A)]
本発明で用いられる環状オレフィン系樹脂(A)は、下記式(1)で表される化合物から誘導される下記A−1〜A−6のいずれかの重合体のうち少なくとも1種である。
A−1;式(1)で表される化合物の開環(共)重合体
A−2;開環(共)重合体(A−1)を水素添加して得られる開環(共)重合水添体
A−3;開環(共)重合体(A−1)をフリーデルクラフト反応により環化した後、水素添加した開環(共)重合水添体
A−4;式(1)で表される化合物の付加(共)重合体
A−5;式(1)で表される化合物と、エチレンまたは一置換エチレンとの付加共重合体A−6;式(1)で表される化合物と、ビニル環状炭化水素および環式ジエンから選ばれる少なくとも1種の単量体との付加共重合体およびその付加共重合水添体
下記式(1)で表される化合物について説明する。
[Cyclic olefin resin (A)]
The cyclic olefin resin (A) used in the present invention is at least one of the following polymers A-1 to A-6 derived from a compound represented by the following formula (1).
A-1: Ring-opening (co) polymer A-2 of the compound represented by the formula (1); Ring-opening (co) polymerization obtained by hydrogenating the ring-opening (co) polymer (A-1) Hydrogenated A-3; ring-opened (co) polymer (A-1) cyclized by Friedel-Craft reaction and then hydrogenated ring-opened (co) polymerized hydrogenated A-4; formula (1) Addition (co) polymer A-5 of a compound represented by formula: Addition copolymer A-6 of a compound represented by formula (1) and ethylene or monosubstituted ethylene; represented by formula (1) Addition copolymer of compound and at least one monomer selected from vinyl cyclic hydrocarbon and cyclic diene, and addition copolymer hydrogenated compound The compound represented by the following formula (1) 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。
炭素原子数1〜30の炭化水素基としては、例えば、メチル基、エチル基およびプロピル基などのアルキル基;シクロペンチル基およびシクロヘキシル基などのシクロアルキル基;ビニル基、アリル基およびプロペニル基などのアルケニル基などが挙げられる。
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
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, allyl group and propenyl group. Group and the like.
上記炭素原子数1〜30の炭化水素基は直接環構造に結合してもよいし、連結基を介して環に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、アルキレン基);酸素原子、窒素原子、硫黄原子もしくはケイ素原子を有する基(例えば、カルボニル基(−CO−)、オキシカルボニル基(−O(CO)−)、カルボニルオキシ基(−COO−)、スルホン基(−SO2−)、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−、−CONH−)およびシロキサン結合(−OSi(R)−)(Rはメチル基およびエチル基などのアルキル基)などが挙げられ、これらを複数含む連結基であってもよい。 The hydrocarbon group having 1 to 30 carbon atoms may be directly bonded to the ring structure, or may be bonded to the ring through a linking group. Examples of the linking group include a divalent hydrocarbon group having 1 to 10 carbon atoms (for example, an alkylene group); a group having an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom (for example, a carbonyl group (—CO— ), Oxycarbonyl group (—O (CO) —), carbonyloxy group (—COO—), sulfone group (—SO 2 —), ether bond (—O—), thioether bond (—S—), imino group (-NH-), amide bond (-NHCO-, -CONH-) and siloxane bond (-OSi (R)-) (wherein R is an alkyl group such as a methyl group and an ethyl group) and the like are included. It may be a linking group.
その他の極性基とは、上記連結基を介して結合した炭化水素基以外の極性基のことであり、例えば、水酸基、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が挙げられる。さらに具体的には、上記アルコキシ基としては、メトキシ基およびエトキシ基など;カルボニルオキシ基としては、アセトキシ基およびプロピオニルオキシ基などのアルキルカルボニルオキシ基、ならびにベンゾイルオキシ基などのアリールカルボニルオキシ基;アルコキシカルボニル基としては、メトキシカルボニル基およびエトキシカルボニル基など;アリーロキシカルボニル基としては、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およびビフェニリルオキシカルボニル基など;トリオルガノシロキシ基としては、トリメチルシロキシ基およびトリエチルシロキシ基など;トリオルガノシリル基としては、トリメチルシリル基およびトリエチルシリル基など;アミノ基としては、第一級アミノ基;アルコキシシリル基としては、トリメトキシシリル基およびトリエトキシシリル基などが挙げられる。 The other polar group is a polar group other than the hydrocarbon group bonded through the above linking group. For example, a hydroxyl group, an alkoxy group, a carbonyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, Examples thereof include an amide group, an imide group, a triorganosiloxy group, a triorganosilyl group, 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 arylcarbonyloxy group such as a benzoyloxy group; Examples of the carbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group; examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a naphthyloxycarbonyl group, a fluorenyloxycarbonyl group, and a biphenylyloxycarbonyl group; Trimethylsiloxy group, triethylsiloxy group, etc .; triorganosilyl group, trimethylsilyl group, triethylsilyl group, etc .; amino group, primary amine Amino group; the alkoxysilyl group, such as trimethoxysilyl group and triethoxysilyl group.
上記式(1)で表される化合物において、aおよびbはそれぞれ独立に0または1であり、好ましくはa=b=0である。cおよびdはそれぞれ独立に0〜2の整数であり、好ましくは0〜1の整数、より好ましくはc=0でかつd=0または1である。a〜dがこの範囲だと、式(1)で表される化合物を製造するための原料の入手性および経済性ならびに式(1)で表される化合物の生産性の面で好ましい。 In the compound represented by the above formula (1), a and b are each independently 0 or 1, and preferably a = b = 0. c and d are each independently an integer of 0 to 2, preferably an integer of 0 to 1, more preferably c = 0 and d = 0 or 1. When a to d are within this range, it is preferable in terms of the availability and economics of raw materials for producing the compound represented by formula (1) and the productivity of the compound represented by formula (1).
式(1)で表される化合物の具体例としては、
ビシクロ[2.2.1]ヘプト−2−エン、
Specific examples of the compound represented by the formula (1) include
Bicyclo [2.2.1] hept-2-ene,
ペンタシクロ[8.4.0.12,5.19,12.08,13]−3−ヘキサデセン
Pentacyclo [8.4.0.1 2,5 .1 9,12 .0 8,13] -3- hexadecene
上記式(1)で表される化合物は、単独でまたは2種以上組み合わせて用いられる。
The compounds represented by the above formula (1) are used alone or in combination of two or more.
(共重合性単量体)
上記(A−1)〜(A−6)を合成するのに用いられる共重合性単量体としては、例えば、シクロブテン、シクロペンテン、シクロヘプテンおよびシクロオクテンなどの公知のシクロオレフィンが挙げられる。
(Copolymerizable monomer)
Examples of the copolymerizable monomer used to synthesize the above (A-1) to (A-6) include known cycloolefins such as cyclobutene, cyclopentene, cycloheptene, and cyclooctene.
本発明において、上記環状オレフィン系樹脂は、公知の方法により得ることができ、例えば、特開平1−132626号公報、特開2006−77257号公報および特開2008−955号公報に記載の方法により得られるものを用いることができる。 In the present invention, the cyclic olefin-based resin can be obtained by a known method, for example, by the methods described in JP-A Nos. 1-132626, 2006-77257, and 2008-955. What is obtained can be used.
これらの環状オレフィン系樹脂(A−1)〜(A−6)のうち、好ましくは(A−2)〜(A−5)、特に好ましくは(A−2)である。開環(共)重合水添体(A−2)は、耐熱性、機械的強度、加工性、透明性および生産性などに優れるため好ましい。 Of these cyclic olefin-based resins (A-1) to (A-6), (A-2) to (A-5) are preferable, and (A-2) is particularly preferable. The ring-opening (co) polymerized hydrogenated product (A-2) is preferable because it is excellent in heat resistance, mechanical strength, processability, transparency and productivity.
上記環状オレフィン系樹脂(A)の固有粘度[η]inhは好ましくは0.2〜5dL/g、より好ましくは0.3〜3dL/g、特に好ましくは0.3〜1.0dL/gである。 The intrinsic viscosity [η] inh of the cyclic olefin resin (A) is preferably 0.2 to 5 dL / g, more preferably 0.3 to 3 dL / g, and particularly preferably 0.3 to 1.0 dL / g. is there.
上記環状オレフィン系樹脂(A)のテトラヒドロフランを溶媒とし、標準ポリスチレン換算のゲルパーミエーションクロマトグラフィー(GPC)による重量平均分子量(Mw)は好ましくは30,000〜200,000、より好ましくは32,000〜180,000、特に好ましくは35,000〜160,000の範囲であり、分子量分布(Mw/Mn)は、好ましくは1.5〜4.0、より好ましくは1.7〜3.7であり、特に好ましくは2.0〜3.5である。なお、環状オレフィン系樹脂(A)の好ましい態様である開環(共)重合水添体(A−2)のゲルパーミエーションクロマトグラフィー(GPC)による標準ポリスチレン換算の重量平均分子量(Mw)は好ましくは30,000〜200,000、より好ましくは31,000〜150,000、特に好ましくは32,000〜120,000である。開環(共)重合水添体(A−2)の重量平均分子量(Mw)が上記の範囲にあると、加工性および強度が両立できるため好ましい。 The weight average molecular weight (Mw) by gel permeation chromatography (GPC) in terms of standard polystyrene is preferably 30,000 to 200,000, more preferably 32,000 using tetrahydrofuran of the cyclic olefin resin (A) as a solvent. ˜180,000, particularly preferably 35,000 to 160,000, and the molecular weight distribution (Mw / Mn) is preferably 1.5 to 4.0, more preferably 1.7 to 3.7. Yes, particularly preferably 2.0 to 3.5. In addition, the weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography (GPC) of the ring-opening (co) polymerized hydrogenated product (A-2) which is a preferred embodiment of the cyclic olefin resin (A) is preferable. Is 30,000 to 200,000, more preferably 31,000 to 150,000, and particularly preferably 32,000 to 120,000. It is preferable that the weight average molecular weight (Mw) of the ring-opening (co) polymerized hydrogenated product (A-2) is in the above range since both workability and strength can be achieved.
固有粘度[η]inh、重量平均分子量(Mw)および分子量分布(Mw/Mn)が上記範囲にあるとき、環状オレフィン系樹脂(A)の耐熱性、耐水性、耐薬品性および機械的特性が良好である。 When the intrinsic viscosity [η] inh, weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) are in the above ranges, the cyclic olefin resin (A) has heat resistance, water resistance, chemical resistance and mechanical properties. It is good.
上記環状オレフィン系樹脂(A)のガラス転移温度(Tg)としては、通常110〜350℃、好ましくは110〜250℃、より好ましくは110〜220℃、特に好ましくは110〜200℃である。Tgが110℃未満の場合、高温条件下での使用時に変形する場合がある。一方、Tgが350℃を超えると成形加工が困難になる場合がある。つまり、Tgが350℃を超えると、成形加工時の加熱温度を高くしなければならず、熱によって樹脂が劣化する可能性が高くなる場合がある。また、環状オレフィン系樹脂(A)の好ましい態様である開環(共)重合水添体(A−2)のガラス転移温度(Tg)は好ましくは100〜250℃、より好ましくは105〜220℃、特に好ましくは110〜210℃である。開環(共)重合水添体(A−2)のガラス転移温度(Tg)が上記の範囲にあると、溶融加工が容易で且つ実用的な耐熱性を有するため好ましい。 As glass transition temperature (Tg) of the said cyclic olefin resin (A), it is 110-350 degreeC normally, Preferably it is 110-250 degreeC, More preferably, it is 110-220 degreeC, Most preferably, it is 110-200 degreeC. When Tg is less than 110 ° C., it may be deformed during use under high temperature conditions. On the other hand, when Tg exceeds 350 ° C., molding may be difficult. That is, when Tg exceeds 350 ° C., the heating temperature during the molding process must be increased, and the possibility that the resin is deteriorated by heat may increase. The glass transition temperature (Tg) of the ring-opening (co) polymerized hydrogenated product (A-2) which is a preferred embodiment of the cyclic olefin resin (A) is preferably 100 to 250 ° C, more preferably 105 to 220 ° C. Especially preferably, it is 110-210 degreeC. It is preferable that the glass transition temperature (Tg) of the ring-opening (co) polymerized hydrogenated product (A-2) is in the above range because melt processing is easy and there is practical heat resistance.
上記環状オレフィン系樹脂(A)を水素添加する場合、芳香環の不飽和結合を除く炭素-炭素二重結合の水素添加率が90%以上であることが好ましく、95%以上であることがより好ましい。水素添加率が上記範囲にあるとき、耐熱性および着色性がより良好となる。なお、必要に応じて芳香環の不飽和結合も水素添加してもよい。 When hydrogenating the said cyclic olefin resin (A), it is preferable that the hydrogenation rate of the carbon-carbon double bond except the unsaturated bond of an aromatic ring is 90% or more, and it is more preferable that it is 95% or more. preferable. When the hydrogenation rate is in the above range, heat resistance and colorability become better. If necessary, the unsaturated bond of the aromatic ring may be hydrogenated.
上記環状オレフィン系樹脂(A)には、必要に応じて、例えば、特開平9−221577号公報および特開平10−287732号公報に記載の特定の炭化水素系樹脂、特定の公知の熱可塑性樹脂および熱可塑性エラストマー、ゴム質重合体、有機微粒子、および無機微粒子などを0〜60重量%の量で配合してもよい。 Examples of the cyclic olefin resin (A) include specific hydrocarbon resins and specific known thermoplastic resins described in JP-A-9-221577 and JP-A-10-287732 as necessary. Further, thermoplastic elastomers, rubbery polymers, organic fine particles, inorganic fine particles and the like may be blended in an amount of 0 to 60% by weight.
[フェノール系化合物(B)]
本発明で用いられるフェノール系化合物(B)は、下記式(2)で表される基を1分子内に2個以上有することを特徴とする。
[Phenolic compound (B)]
The phenolic compound (B) used in the present invention has two or more groups represented by the following formula (2) in one molecule.
Xはメチレン基または炭素原子数2〜10のアルキレン基を表す。上記炭素原子数2〜10のアルキレン基としては、例えば、エチレン基、プロピレン基、イソプロピレン基、n−ブチレン基、イソブチレン基、s−ブチレン基およびt−ブチレン基などのアルキレン基が挙げられ、好ましくはエチレン基が挙げられる。 X represents a methylene group or an alkylene group having 2 to 10 carbon atoms. Examples of the alkylene group having 2 to 10 carbon atoms include alkylene groups such as ethylene group, propylene group, isopropylene group, n-butylene group, isobutylene group, s-butylene group and t-butylene group, Preferably an ethylene group is mentioned.
なお、フェノール性化合物(B)は脂肪族エステル構造を有さないのが望ましい。脂肪族エステル構造は熱安定性が不十分であるため、高温加工時に分解し、生じたアルコールやカルボン酸が樹脂組成物と反応することによって微小ゲルを生じる場合があるためである。なお、脂肪族エステル構造とは−CO−O−Rで表され、Rが直鎖または分岐のアルキル基であるものをいう。 The phenolic compound (B) preferably does not have an aliphatic ester structure. This is because the aliphatic ester structure has insufficient thermal stability, and therefore decomposes during high-temperature processing, and the resulting alcohol or carboxylic acid may react with the resin composition to form a microgel. The aliphatic ester structure is represented by —CO—O—R, where R is a linear or branched alkyl group.
前記フェノール系化合物(B)は、下記式(2−1)で表される化合物であることが好ましい。 The phenolic compound (B) is preferably a compound represented by the following formula (2-1).
前記炭素原子数3〜12の鎖状炭化水素基としては、プロパン、ブタン、ペンタン、ヘキサン、ヘプタンおよびオクタンなどが挙げられ、これらの基のn個の水素が式(2)で表される基で置換されている。また上記鎖状炭化水素基としては、式(2)で表される基以外にも置換基を有していてもよい。 Examples of the chain hydrocarbon group having 3 to 12 carbon atoms include propane, butane, pentane, hexane, heptane, and octane, and n hydrogens of these groups are represented by the formula (2). Has been replaced by Moreover, as said chain | strand-shaped hydrocarbon group, you may have a substituent other than group represented by Formula (2).
前記炭素原子数4〜8の環状炭化水素基としては、シクロブタン、シクロペンタン、シクロヘキサン、シクロヘプタンおよびシクロオクタンなどが挙げられ、これらの基のn個の水素が式(2)で表される基で置換されている。また上記鎖状炭化水素基としては、式(2)で表される基以外にも置換基を有していてもよい。 Examples of the cyclic hydrocarbon group having 4 to 8 carbon atoms include cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and n hydrogens of these groups are represented by the formula (2). Has been replaced by Moreover, as said chain | strand-shaped hydrocarbon group, you may have a substituent other than group represented by Formula (2).
上記フェノール系化合物(B)として具体的には、下記式(2−a)に示す1,1,3-トリス[2-メチル-4-〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオニルオキシ〕-5-t-ブチルフェニル]ブタンが挙げられる。 Specific examples of the phenol compound (B) include 1,1,3-tris [2-methyl-4- [3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionyloxy] -5-t-butylphenyl] butane.
本発明で用いられるフェノール系化合物(B)は、式(2)で表される基のようなフェノール構造部分を1分子内に2個以上有することに加えて、ヒンダード構造を有するため、酸化防止剤の副反応が抑制される。
上記フェノール系化合物(B)の要件(B−i)および(B−ii)を満たすことが好ましい。
The phenolic compound (B) used in the present invention has a hindered structure in addition to having two or more phenolic structural parts such as the group represented by the formula (2) in one molecule, so that it is antioxidant. The side reaction of the agent is suppressed.
It is preferable to satisfy the requirements (B-i) and (B-ii) of the phenol compound (B).
(B−i):分子量が800以上である。フェノール系化合物(B)は、単一化合物である場合のほか、いろいろな分子量をもつ化合物の混合物(以下「多分散性混合物」という。)である場合がある。単一化合物である場合においては、その相対分子質量が好ましくは800以上であり、より好ましくは800〜3000、特に好ましくは850〜2800、特に好ましくは900〜2500である。一方、多分散性混合物においては、ゲルパーミエーションクロマトグラフィー(GPC)による標準ポリスチレン換算の重量平均分子量(Mw)が好ましくは800以上、より好ましくは800〜4000、特に好ましくは850〜3500、特に好ましくは900〜3000であり、分子量分布(Mw/Mn)が1.01〜3.0、好ましくは1.02〜2.7、より好ましくは1.03〜2.5である。フェノール系化合物(B)の分子量および分子量分布が上記の範囲にあると、樹脂組成物の加工時のフェノール系化合物(B)の揮発が十分に抑制され、かつ、樹脂成型品中でも酸化防止剤が十分な移行性を有するため長期に渡って酸化劣化が抑制される。本発明では、フェノール系化合物(B)として、単一化合物のみを用いてもよいし、多分散性混合物を用いてもよい。なお、相対分子質量とは炭素の質量を12とした際の分子の質量をいう。 (Bi): The molecular weight is 800 or more. The phenolic compound (B) may be a single compound or a mixture of compounds having various molecular weights (hereinafter referred to as “polydispersed mixture”). In the case of a single compound, the relative molecular mass is preferably 800 or more, more preferably 800 to 3000, particularly preferably 850 to 2800, and particularly preferably 900 to 2500. On the other hand, in the polydisperse mixture, the weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography (GPC) is preferably 800 or more, more preferably 800 to 4000, particularly preferably 850 to 3500, particularly preferably. Is 900 to 3000, and the molecular weight distribution (Mw / Mn) is 1.01 to 3.0, preferably 1.02 to 2.7, more preferably 1.03 to 2.5. When the molecular weight and molecular weight distribution of the phenolic compound (B) are in the above ranges, volatilization of the phenolic compound (B) during the processing of the resin composition is sufficiently suppressed, and an antioxidant is also present in the resin molded product. Oxidation degradation is suppressed over a long period because it has sufficient migration. In the present invention, only a single compound may be used as the phenol compound (B), or a polydisperse mixture may be used. The relative molecular mass refers to the mass of a molecule when the mass of carbon is 12.
(B−ii):窒素下において300℃で1時間加熱したときの重量減少率が15%以下、より好ましくは13%以下、特に好ましくは10%以下である。重量減少率が上記の範囲にあると、熱分解物による金型汚染およびロール汚染を抑制することができる。なお、重量減少率の求め方を説明すると、TG/DTAを用いて試料を窒素雰囲気下で昇温速度40℃/minで室温から300±5℃まで昇温し、1時間ホールドした後、重量を測定する。初期重量および加熱後の重量から重量減少率(%)を求める。 (B-ii): The weight loss rate when heated at 300 ° C. for 1 hour under nitrogen is 15% or less, more preferably 13% or less, and particularly preferably 10% or less. When the weight reduction rate is in the above range, mold contamination and roll contamination due to pyrolyzate can be suppressed. The method of obtaining the weight reduction rate will be described. Using TG / DTA, the sample was heated from room temperature to 300 ± 5 ° C. at a temperature rising rate of 40 ° C./min in a nitrogen atmosphere, held for 1 hour, Measure. The weight reduction rate (%) is determined from the initial weight and the weight after heating.
上記フェノール性化合物(B)の添加量は、環状オレフィン系樹脂(A)100重量部に対して、通常0.01〜3重量部、好ましくは0.02〜2.5重量部、より好ましくは0.03〜2重量部である。フェノール性化合物(B)の添加量が上記範囲にあると、本発明の樹脂組成物の酸化劣化を十分に防止することができる。また、上記フェノール性化合物(B)は比較的揮発性が低いが、上記範囲を超えて添加すれば揮発成分の量が増加する傾向にある。また、酸化防止剤は高温下において樹脂の酸化を防止する一方で自身が劣化して着色する場合があり、樹脂の酸化を防止し得る必要量を超えた添加は悪影響を及ぼすことがある。このため、フェノール性化合物(B)の添加量は上記範囲にするのが望ましい。 The amount of the phenolic compound (B) added is usually 0.01 to 3 parts by weight, preferably 0.02 to 2.5 parts by weight, more preferably 100 parts by weight of the cyclic olefin resin (A). 0.03 to 2 parts by weight. When the addition amount of the phenolic compound (B) is in the above range, the oxidative deterioration of the resin composition of the present invention can be sufficiently prevented. Moreover, although the said phenolic compound (B) is comparatively low volatility, if it adds exceeding the said range, it exists in the tendency for the quantity of a volatile component to increase. In addition, the antioxidant may prevent the resin from being oxidized at a high temperature, but may deteriorate and color itself, and addition exceeding the necessary amount capable of preventing the oxidation of the resin may have an adverse effect. For this reason, it is desirable that the addition amount of the phenolic compound (B) is in the above range.
[含リン化合物(C)]
本発明の樹脂組成物は環状オレフィン系樹脂(A)およびフェノール性化合物(B)以外に含リン化合物(C)を含有してもよい。本発明で用いられる含リン化合物(C)は、それ自体の熱安定性はそれほど高くないが、樹脂組成物の色相および加工安定性を改良することができる。ここで、加工安定性とは、例えば、樹脂組成物を加工するときのゲル発生、発煙および発塵などを最低限に抑えることをいう。なお、含リン化合物は、上記含リン化合物(C)を含めて、通常、酸化防止剤として知られる。
含リン化合物(C)としては、下記(C−i)および(C−ii)を満たすものであれば特に構造は限定されない。
[Phosphorus-containing compound (C)]
The resin composition of the present invention may contain a phosphorus-containing compound (C) in addition to the cyclic olefin resin (A) and the phenolic compound (B). The phosphorus-containing compound (C) used in the present invention is not so high in its own thermal stability, but can improve the hue and processing stability of the resin composition. Here, the processing stability refers to, for example, minimizing gel generation, smoke generation, dust generation and the like when processing a resin composition. In addition, a phosphorus containing compound is normally known as antioxidant including the said phosphorus containing compound (C).
The structure of the phosphorus-containing compound (C) is not particularly limited as long as it satisfies the following (Ci) and (C-ii).
(C−i):含リン化合物(C)の分子量は、単一化合物である場合においては、その相対分子質量が好ましくは400以上、より好ましくは400〜3000、さらに好ましくは500〜2700、特に好ましくは600〜2500である。多分散性混合物である場合は、ゲルパーミエーションクロマトグラフィー(GPC)による標準ポリスチレン換算の重量平均分子量(Mw)が好ましくは400以上、より好ましくは400〜5000、特に好ましくは450〜4500であり、分子量分布(Mw/Mn)が1.01〜3.0、好ましくは1.02〜2.5、より好ましくは1.03〜2.3である。本発明では、含リン化合物(C)として、単一化合物のみを用いてもよいし、多分散性混合物を用いてもよい。含リン化合物(C)の分子量および分子量分布が上記範囲にあると、樹脂組成物の色相を良好に保ち、ゲル発生を防止し、かつ、発煙および発塵を最低限に抑えることができる。 (Ci): When the molecular weight of the phosphorus-containing compound (C) is a single compound, the relative molecular mass thereof is preferably 400 or more, more preferably 400 to 3000, still more preferably 500 to 2700, particularly Preferably it is 600-2500. In the case of a polydisperse mixture, the weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography (GPC) is preferably 400 or more, more preferably 400 to 5000, particularly preferably 450 to 4500, The molecular weight distribution (Mw / Mn) is 1.01 to 3.0, preferably 1.02 to 2.5, and more preferably 1.03 to 2.3. In the present invention, as the phosphorus-containing compound (C), only a single compound may be used, or a polydisperse mixture may be used. When the molecular weight and molecular weight distribution of the phosphorus-containing compound (C) are in the above ranges, the hue of the resin composition can be kept good, gel formation can be prevented, and smoke and dust can be minimized.
(C−ii):含リン化合物(C)を窒素下において250℃で1時間加熱したときの重量減少率は、好ましくは50%以下、より好ましくは40%以下、特に好ましくは30%以下である。なお、重量減少率の求め方を説明すると、TG/DTAを用いて試料を窒素雰囲気下、昇温速度40℃/minで室温から250±3℃まで昇温し、1時間ホールドした後、重量を測定する。初期重量および加熱後の重量から重量減少率を求める。 (C-ii): The weight loss rate when the phosphorus-containing compound (C) is heated at 250 ° C. for 1 hour under nitrogen is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less. is there. The method for obtaining the weight reduction rate will be described. Using TG / DTA, the sample was heated from room temperature to 250 ± 3 ° C. at a temperature rising rate of 40 ° C./min in a nitrogen atmosphere, held for 1 hour, Measure. The weight reduction rate is determined from the initial weight and the weight after heating.
上記含リン化合物は下記式(3)で表される構造を含むことが好ましい。 The phosphorus-containing compound preferably includes a structure represented by the following formula (3).
炭化水素基としてはアルキル基およびアリール基が挙げられる。アルキル基としては、例えば、メチル基、エチル基、プロピル基、n−ブチル基、イソブチル基およびt−ブチル基などが挙げられる。また、これらのアルキル基の水素原子は他の置換基で置換されていてもよく、特にヒンダードフェノール基で置換されていると着色を十分に抑制することができるため好ましい。アリール基としてはフェニル基、ビフェニル基およびナフチル基などが挙げられる。また、これらのアリール基の水素原子は他の置換基で置換されていてもよく、例えば、下記式(4)で表される化合物のようにビフェニレン基を介して上記式(3)と対象構造を形成してもよい。このような構造はリン系酸化防止剤の効果を維持しながらも分子量増大による自身の揮発性低減が可能なため好ましい。 Examples of the hydrocarbon group include an alkyl group and an aryl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, and a t-butyl group. In addition, the hydrogen atom of these alkyl groups may be substituted with other substituents, and in particular, substitution with a hindered phenol group is preferable because coloring can be sufficiently suppressed. Examples of the aryl group include a phenyl group, a biphenyl group, and a naphthyl group. Moreover, the hydrogen atom of these aryl groups may be substituted with other substituents. For example, the compound represented by the above formula (3) and the target structure via a biphenylene group like the compound represented by the following formula (4) May be formed. Such a structure is preferable because the volatility can be reduced by increasing the molecular weight while maintaining the effect of the phosphorus antioxidant.
上記含リン化合物(C)として具体例には、トリス(2,4-ジ-t-ブチルフェニル)ホスファイト、テトラキス(2,4-ジ-t-ブチルフェニル)-4,4'-ビフェニレンジホスホナイトを主成分とする混合物(例えばクラリアントジャパン(株)製;ホスタノックスP-EPQ)、テトラキス(2,4-ジ-t-ブチルフェニル-5-メチル)-4,4'-ビフェニレンジホスホナイトを主成分とする混合物(例えば大崎工業(株)製;GSY-P101)、6-[3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロポキシ]-2,4,8,10-テトラ-t-ブチルジベンズ[d,f][1,3,2]ジオキサホスフェピン、ビス(2,6-ジ-t-ブチル-4-メチルフェニル)ペンタエリスリトールジホスファイトおよびビス(2,4-ジクミルフェニル)ペンタエリスリトールジホスファイトなどが挙げられる。これらのうち、特に好ましくは低揮発性および低着色性の点で、式(3−a)に示すトリス(2,4-ジ-t-ブチルフェニル)ホスファイト、式(3−b)に示す6-[3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロポキシ]-2,4,8,10-テトラ-t-ブチルジベンズ[d,f][1,3,2]ジオキサホスフェピンおよび式(3−c)に示すテトラキス(2,4-ジ-t-ブチルフェニル-5-メチル)-4,4'-ビフェニレンジホスホナイトが挙げられる。 Specific examples of the phosphorus-containing compound (C) include tris (2,4-di-t-butylphenyl) phosphite and tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenedi. Mixtures mainly composed of phosphonite (for example, Clariant Japan Co., Ltd .; Hostanox P-EPQ), tetrakis (2,4-di-t-butylphenyl-5-methyl) -4,4'-biphenylenediphospho A mixture containing knight as a main component (eg, Osaki Kogyo Co., Ltd .; GSY-P101), 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8 , 10-Tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphine, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,4-Dicumylphenyl) pentaerythritol diphosphite. Of these, tris (2,4-di-t-butylphenyl) phosphite represented by the formula (3-a) and formula (3-b) are particularly preferable in terms of low volatility and low colorability. 6- [3- (3-t-Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] di And oxaphosphepine and tetrakis (2,4-di-t-butylphenyl-5-methyl) -4,4′-biphenylenediphosphonite represented by the formula (3-c).
これらの含リン化合物(C)は1種単独でも、2種以上組み合わせて用いることもできる。2種以上組み合わせて用いる場合、特に式(3−a)、(3−b)または(3−c)に示す化合物を主成分として用いるのが好ましい。 These phosphorus-containing compounds (C) can be used alone or in combination of two or more. When two or more types are used in combination, it is particularly preferable to use a compound represented by the formula (3-a), (3-b) or (3-c) as a main component.
なお、含リン化合物(C)を併用すると、上記フェノール系化合物(B)の含有量を低減しても色相改良効果が認められるため、要求される特性によって品質バランスをコントロールすることができる。 When the phosphorus-containing compound (C) is used in combination, the hue improving effect is recognized even when the content of the phenolic compound (B) is reduced. Therefore, the quality balance can be controlled by the required characteristics.
[樹脂組成物]
本発明の樹脂組成物は、環状オレフィン系樹脂(A)、フェノール系化合物(B)および必要に応じて含リン化合物(C)を溶融混練して製造することができる。
[Resin composition]
The resin composition of the present invention can be produced by melt-kneading the cyclic olefin resin (A), the phenol compound (B) and, if necessary, the phosphorus-containing compound (C).
上記樹脂組成物には、本発明の効果が損なわれない範囲で、光安定剤、紫外線吸収剤、赤外線吸収剤、帯電防止剤、分散剤、加工性向上剤、塩素捕捉剤、難燃剤、結晶化核剤、ブロッキング防止剤、防曇剤、離型剤、染料、顔料、蛍光増白剤、有機充填材、無機充填材、中和剤、滑剤、分解剤、金属不活性化剤、汚染防止材および抗菌剤などの公知の添加剤ならびに熱可塑性エラストマーなどの樹脂を添加することができる。
また、溶融混練には、ロール混練機、ミキサー、ホモミキサーまたはサンドミルなどの混練および分散機などの混練装置が用いられる。
In the resin composition, the light stabilizer, the ultraviolet absorber, the infrared absorber, the antistatic agent, the dispersant, the processability improver, the chlorine scavenger, the flame retardant, and the crystal are provided as long as the effects of the present invention are not impaired. Nucleating agent, antiblocking agent, antifogging agent, mold release agent, dye, pigment, fluorescent whitening agent, organic filler, inorganic filler, neutralizer, lubricant, decomposition agent, metal deactivator, antifouling Known additives such as materials and antibacterial agents and resins such as thermoplastic elastomers can be added.
For melt kneading, a kneading apparatus such as a kneading and dispersing machine such as a roll kneader, a mixer, a homomixer, or a sand mill is used.
[光学部品]
本発明の樹脂組成物は、高透明性、低着色性および高耐熱性を有するので、光学フィルム、光ディスク、光学レンズ、光ファイバー、透明プラスチック基盤および低誘電材料などの電子・光学材料ならびに光半導体の封止材料などに好適である。
[Optical parts]
Since the resin composition of the present invention has high transparency, low colorability, and high heat resistance, it can be used in electronic and optical materials such as optical films, optical disks, optical lenses, optical fibers, transparent plastic substrates and low dielectric materials, and optical semiconductors. Suitable for sealing materials and the like.
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、本発明はこれらの実施例に限定されるものではない。
実施例および比較例で用いた分析方法を以下に示す。
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
The analysis methods used in Examples and Comparative Examples are shown below.
<分析方法>
(1)GPC:ゲルパーミエーションクロマトグラフ装置(東ソー(株)製HLC-8220GPC、カラム;東ソー(株)製ガードカラムHXL-H、TSK gel G7000HXL、TSK gel GMHXL2本、TSK gel G2000HXLを順次連結、溶離液;テトラヒドロフラン、流速;1mL/min、サンプル濃度;0.7〜0.8wt%、サンプル注入量;70μL、測定温度;40℃、検出器;RI(40℃)、標準物質;東ソー(株)製TSKスタンダードポリスチレン)を用い、標準ポリスチレン換算の重量平均分子量(Mw)および分子量分布(Mw/Mn)を測定した。なお、Mnは標準ポリスチレン換算の数平均分子量である。
(2)NMR:超伝導核磁気共鳴吸収装置(NMR、Bruker社製、商品名:AVANCE500)を用い、重水素化クロロホルム中で1H−NMRを測定し、共重合組成比および水素添加率を求めた。
(3)対数粘度:ウッベローデ型粘度計を用いて、クロロホルム中、試料濃度0.5g/dL、温度30℃で測定した。
(4)ガラス転移温度(Tg):示差走査熱量計(SIIナノテクノロジー社製、商品名:DSC6220)を用いて、日本工業規格K7121に従って補外ガラス転移温度を求めた。
(5)走査型電子顕微鏡:日本電子(株)製JSM6360LA型を用いた。
<Analysis method>
(1) GPC: Gel permeation chromatograph apparatus (HLC-8220GPC manufactured by Tosoh Corporation, column; guard column HXL-H, TSK gel G7000HXL, two TSK gel GMHXL, TSK gel G2000HXL manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran, flow rate: 1 mL / min, sample concentration: 0.7 to 0.8 wt%, sample injection volume: 70 μL, measurement temperature: 40 ° C., detector: RI (40 ° C.), standard substance: TSK manufactured by Tosoh Corporation Standard polystyrene) was used to measure the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) in terms of standard polystyrene. In addition, Mn is the number average molecular weight of standard polystyrene conversion.
(2) NMR: 1 H-NMR was measured in deuterated chloroform using a superconducting nuclear magnetic resonance absorber (NMR, manufactured by Bruker, trade name: AVANCE500), and the copolymer composition ratio and hydrogenation rate were determined. Asked.
(3) Logarithmic viscosity: Measured using a Ubbelohde viscometer in chloroform at a sample concentration of 0.5 g / dL and a temperature of 30 ° C.
(4) Glass transition temperature (Tg): Extrapolated glass transition temperature was determined according to Japanese Industrial Standard K7121 using a differential scanning calorimeter (trade name: DSC6220, manufactured by SII Nano Technology).
(5) Scanning electron microscope: JSM6360LA type manufactured by JEOL Ltd. was used.
[合成例1]
単量体として下記式(1−a)に示す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100g、分子量調節剤として1−へキセン7.2g、およびトルエン200gを窒素置換した反応容器に仕込み、80℃に加熱した。
[Synthesis Example 1]
As a monomer, 8-methoxycarbonyl-8-methyltetracyclo represented by the following formula (1-a) [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene (100 g), 1-hexene (7.2 g) as a molecular weight regulator, and toluene (200 g) were charged into a nitrogen-substituted reaction vessel and heated to 80 ° C.
これにトリエチルアルミニウムのトルエン溶液(0.6mol/L)0.21mLおよびメタノール変性六塩化タングステン(WCl6)のトルエン溶液(0.025mol/L)0.86mLを加え、80℃で1時間反応させることにより開環重合体を得た。 To this, 0.21 mL of a toluene solution of triethylaluminum (0.6 mol / L) and 0.86 mL of a toluene solution of methanol-modified tungsten hexachloride (WCl 6 ) (0.025 mol / L) are added and reacted at 80 ° C. for 1 hour. As a result, a ring-opened polymer was obtained.
得られた開環重合体溶液に水素添加触媒であるクロロヒドリドカルボニルトリス(トリフェニルホスフィン)ルテニウム(RuHCl(CO)[P(C6H5)3]3)を0.04g添加し、水素ガス圧を9〜10MPaとし160〜165℃で3時間反応させた。 0.04 g of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (RuHCl (CO) [P (C 6 H 5 ) 3 ] 3 ) as a hydrogenation catalyst was added to the resulting ring-opening polymer solution, and hydrogen gas The pressure was 9 to 10 MPa and the reaction was carried out at 160 to 165 ° C. for 3 hours.
反応終了後、得られた反応混合物を多量のメタノール中に沈殿させることにより水素添加体を得た。この水素添加体を1Aという。
得られた水素添加体(1A)の収量は90g(収率90%)、ガラス転移温度(Tg)は163℃、重量平均分子量(Mw)は6.7×104、分子量分布(Mw/Mn)は5.0、対数粘度は0.45dL/g、水素添加率は99.0%以上であった。
After completion of the reaction, the resulting reaction mixture was precipitated in a large amount of methanol to obtain a hydrogenated product. This hydrogenated product is referred to as 1A.
The yield of the obtained hydrogenated product (1A) was 90 g (yield 90%), the glass transition temperature (Tg) was 163 ° C., the weight average molecular weight (Mw) was 6.7 × 10 4 , and the molecular weight distribution (Mw / Mn ) Was 5.0, the logarithmic viscosity was 0.45 dL / g, and the hydrogenation rate was 99.0% or more.
式(1−a)に示す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144g、式(1−b)に示す2−ノルボルネン6g、分子量調節剤として1−へキセン14.4gおよびトルエン225gを窒素置換した反応容器に仕込み、80℃に加熱した。
8-methoxycarbonyl-8-methyltetracyclo represented by the formula (1-a) [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene (144 g), 2-norbornene (6 g) represented by formula (1-b), 1-hexene (14.4 g) and molecular weight regulator (14.4 g) and toluene (225 g) were charged into a reaction vessel purged with nitrogen and heated to 80 ° C. Heated.
これにトリエチルアルミニウムのトルエン溶液(0.6mol/L)0.34mLおよびメタノール変性六塩化タングステン(WCl6)のトルエン溶液(0.025mol/L)1.37mLを加え、80℃で1時間反応させることにより開環共重合体を得た。 To this, 0.34 mL of a toluene solution of triethylaluminum (0.6 mol / L) and 1.37 mL of a toluene solution of methanol-modified tungsten hexachloride (WCl 6 ) (0.025 mol / L) are added and reacted at 80 ° C. for 1 hour. As a result, a ring-opening copolymer was obtained.
得られた開環共重合体溶液に水素添加触媒であるクロロヒドリドカルボニルトリス(トリフェニルホスフィン)ルテニウム(RuHCl(CO)[P(C6H5)3]3)を0.06g添加し、水素ガス圧を9〜10MPaとし160〜165℃で3時間反応させた。 To the obtained ring-opening copolymer solution, 0.06 g of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (RuHCl (CO) [P (C 6 H 5 ) 3 ] 3 ) as a hydrogenation catalyst was added, and hydrogen was added. The gas pressure was 9 to 10 MPa and the reaction was carried out at 160 to 165 ° C. for 3 hours.
反応終了後、得られた生成物を多量のメタノール中に沈殿させることにより水素添加物を得た。この水素添加体を2Aという。
得られた水素添加体(2A)の収量は90g(収率90%)、ガラス転移温度(Tg)は154℃、重量平均分子量(Mw)は7.4×104、分子量分布(Mw/Mn)は4.2、対数粘度は0.55dL/g、水素添加率は99.0%以上、共重合組成比[(1−a)由来の構造]/[(1−b)由来の構造]は95.8/4.2(重量比)であった。
After completion of the reaction, the resulting product was precipitated in a large amount of methanol to obtain a hydrogenated product. This hydrogenated product is referred to as 2A.
The yield of the obtained hydrogenated product (2A) was 90 g (yield 90%), the glass transition temperature (Tg) was 154 ° C., the weight average molecular weight (Mw) was 7.4 × 10 4 , and the molecular weight distribution (Mw / Mn ) Is 4.2, logarithmic viscosity is 0.55 dL / g, hydrogenation rate is 99.0% or more, copolymer composition ratio [structure derived from (1-a)] / [structure derived from (1-b)] Was 95.8 / 4.2 (weight ratio).
式(1−a)に示す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113.2g、式(1−b)に示す2−ノルボルネン1.5g、下記式(1−c)に示すジシクロペンタジエン35.3g、分子量調節剤として1−へキセン20.5gおよびトルエン225gを窒素置換した反応容器に仕込み、80℃に加熱した。
8-methoxycarbonyl-8-methyltetracyclo represented by the formula (1-a) [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene 113.2 g, 1.5 g of 2-norbornene represented by the formula (1-b), 35.3 g of dicyclopentadiene represented by the following formula (1-c), 1- A reaction vessel purged with nitrogen of 20.5 g of hexene and 225 g of toluene was charged and heated to 80 ° C.
これにトリエチルアルミニウムのトルエン溶液(0.6mol/L)0.34mLおよびメタノール変性六塩化タングステン(WCl6)のトルエン溶液(0.025mol/L)1.39mLを加え、80℃で1時間反応させることにより開環共重合体を得た。 To this, 0.34 mL of a toluene solution of triethylaluminum (0.6 mol / L) and 1.39 mL of a toluene solution of methanol-modified tungsten hexachloride (WCl 6 ) (0.025 mol / L) are added and reacted at 80 ° C. for 1 hour. As a result, a ring-opening copolymer was obtained.
得られた開環共重合体溶液に水素添加触媒である(4−ペンチルベンゾイロキシ)カルボニル(ヒドリド)ビス(トリフェニルホスフィン)ルテニウム(RuH(OCO-Ar-CH2CH2CH2CH2CH3)(CO)[P(C6H5)3]2)(Arはパラフェニレン基を表す)を0.06g添加し、90℃に昇温した後、水素ガス圧を9〜10MPaとし、さらに160〜165℃まで昇温して3時間反応させた。この水素添加体を3Aという。 (4-Pentylbenzoyloxy) carbonyl (hydrido) bis (triphenylphosphine) ruthenium (RuH (OCO—Ar—CH 2 CH 2 CH 2 CH 2 CH) as a hydrogenation catalyst was added to the obtained ring-opening copolymer solution. 3 ) 0.06 g of (CO) [P (C 6 H 5 ) 3 ] 2 ) (Ar represents a paraphenylene group) was added, the temperature was raised to 90 ° C., and the hydrogen gas pressure was adjusted to 9 to 10 MPa. Furthermore, the temperature was raised to 160 to 165 ° C. and the reaction was carried out for 3 hours. This hydrogenated product is referred to as 3A.
得られた水素添加体(3A)の収量は90g(収率90%)、ガラス転移温度(Tg)は141℃、重量平均分子量(Mw)は4.4×104、分子量分布(Mw/Mn)は5.1、対数粘度は0.41dL/g、水素添加率は99.0%以上、共重合組成比[(1−a)由来の構造]/[(1−b)由来の構造]/[(1−c)由来の構造]は75.3/1.1/23.6(重量比)であった。 The obtained hydrogenated product (3A) had a yield of 90 g (yield 90%), a glass transition temperature (Tg) of 141 ° C., a weight average molecular weight (Mw) of 4.4 × 10 4 , and a molecular weight distribution (Mw / Mn). ) Is 5.1, logarithmic viscosity is 0.41 dL / g, hydrogenation rate is 99.0% or more, copolymer composition ratio [structure derived from (1-a)] / [structure derived from (1-b)] / [Structure derived from (1-c)] was 75.3 / 1.1 / 23.6 (weight ratio).
前記式(1−a)に示す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133.5g、前記式(1−b)に示す2−ノルボルネン16.5g、分子量調節剤として1−へキセン15.4g、およびトルエン225gを窒素置換した反応容器に仕込み、80℃に加熱した。
8-methoxycarbonyl-8-methyltetracyclo represented by the above formula (1-a) [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene (133.5 g), 2-norbornene (16.5 g) represented by the formula (1-b), 15.4 g of 1-hexene as a molecular weight regulator, and 225 g of toluene were substituted with nitrogen. And heated to 80 ° C.
これにトリエチルアルミニウム(0.6mol/L)のトルエン溶液0.34mL、およびメタノール変性WCl6トルエン溶液(0.025モル/L)1.37mLを加え、80℃で1時間反応させることにより開環共重合体を得た。 To this was added 0.34 mL of a toluene solution of triethylaluminum (0.6 mol / L) and 1.37 mL of a methanol-modified WCl 6 toluene solution (0.025 mol / L), and the mixture was reacted at 80 ° C. for 1 hour to open the ring. A copolymer was obtained.
次いで、得られた開環共重合体溶液に水素添加触媒であるクロロヒドリドカルボニルトリス(トリフェニルホスフィン)ルテニウム(RuHCl(CO)[P(C6H5)3]3)を0.06g添加し、水素ガス圧を9〜10MPaとし、160〜165℃の温度で、3時間反応させた。 Next, 0.06 g of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (RuHCl (CO) [P (C 6 H 5 ) 3 ] 3 ) as a hydrogenation catalyst was added to the obtained ring-opening copolymer solution. The hydrogen gas pressure was 9 to 10 MPa, and the reaction was performed at a temperature of 160 to 165 ° C. for 3 hours.
反応終了後、得られた生成物を多量のメタノール中で沈殿させることにより水素添加物を得た[ガラス転移温度(Tg)=126℃、重量平均分子量(Mw)=5.0×104、分子量分布(Mw/Mn)=4.2、対数粘度0.43dL/g、収量90g(収率90%)]。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、共重合組成比は[(1−a)由来の構造]/[(1−b)由来の構造]=89/11(重量比)であった。以後、得られた開環共重合水添体を環状オレフィン系樹脂4Aとする。 After completion of the reaction, the product obtained was precipitated in a large amount of methanol to obtain a hydrogenated product [glass transition temperature (Tg) = 126 ° C., weight average molecular weight (Mw) = 5.0 × 10 4 , Molecular weight distribution (Mw / Mn) = 4.2, logarithmic viscosity 0.43 dL / g, yield 90 g (90% yield)]. The hydrogenation rate of the hydrogenated product determined by NMR measurement is 99.0% or more, and the copolymer composition ratio is [structure derived from (1-a)] / [structure derived from (1-b)] = 89. / 11 (weight ratio). Hereinafter, the obtained ring-opening copolymerized hydrogenated product is referred to as a cyclic olefin-based resin 4A.
[合成例5]
式(1−a)に示す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42.0g、下記式(1−d)に示す1,4,4a,9a−テトラヒドロ−1,4−メタノフルオレン28.0g、分子量調節剤として1−へキセン11.2gおよびトルエン105gを窒素置換した反応容器に仕込み、80℃に加熱した。
[Synthesis Example 5]
8-methoxycarbonyl-8-methyltetracyclo represented by the formula (1-a) [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene 42.0 g, 1,4,4a, 9a-tetrahydro-1,4-methanofluorene 28.0 g represented by the following formula (1-d), 1-hexene as a molecular weight regulator 11.2 g and 105 g of toluene were charged into a nitrogen-substituted reaction vessel and heated to 80 ° C.
これにトリエチルアルミニウム(0.2mol/L)のトルエン溶液1.15mLおよびメタノール変性六塩化タングステン(WCl6)のトルエン溶液(0.050mol/L)0.67mLを加え、80℃で1時間反応させることにより開環共重合体を得た。 To this, 1.15 mL of a toluene solution of triethylaluminum (0.2 mol / L) and 0.67 mL of a toluene solution of methanol-modified tungsten hexachloride (WCl 6 ) (0.050 mol / L) are added and reacted at 80 ° C. for 1 hour. As a result, a ring-opening copolymer was obtained.
得られた開環共重合体溶液にトルエン251g加えて希釈し、水素添加触媒である(4−ペンチルベンゾイロキシ)カルボニル(ヒドリド)ビス(トリフェニルホスフィン)ルテニウム(RuH(OCO-Ar-CH2CH2CH2CH2CH3)(CO)[P(C6H5)3]2)(Arはパラフェニレン基を表す)を0.02g添加し、水素ガス圧を9〜10MPaとし、さらに160〜165℃まで昇温して3時間反応させた。この水素添加体を5Aという。 The resulting ring-opening copolymer solution was diluted by adding 251 g of toluene, and (4-pentylbenzoyloxy) carbonyl (hydrido) bis (triphenylphosphine) ruthenium (RuH (OCO-Ar-CH 2 ) as a hydrogenation catalyst. 0.02 g of CH 2 CH 2 CH 2 CH 3 ) (CO) [P (C 6 H 5 ) 3 ] 2 ) (Ar represents a paraphenylene group) is added, the hydrogen gas pressure is adjusted to 9 to 10 MPa, The temperature was raised to 160 to 165 ° C. and reacted for 3 hours. This hydrogenated product is referred to as 5A.
反応終了後、得られた生成物を多量のメタノール中で沈殿させることにより水素添加物を得た[ガラス転移温度(Tg)=161℃、重量平均分子量(Mw)=8.3×104、分子量分布(Mw/Mn)=3.8、対数粘度0.51dL/g、収量63g(収率90%)]。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、共重合組成比は[(1−a)由来の構造]/[(1−d)由来の構造]=59/41(重量比)であった。以後、得られた開環共重合水添体を環状オレフィン系樹脂5Aとする。 After completion of the reaction, the resulting product was precipitated in a large amount of methanol to obtain a hydrogenated product [glass transition temperature (Tg) = 161 ° C., weight average molecular weight (Mw) = 8.3 × 10 4 , Molecular weight distribution (Mw / Mn) = 3.8, logarithmic viscosity 0.51 dL / g, yield 63 g (yield 90%)]. The hydrogenation rate of this hydrogenated product determined by NMR measurement is 99.0% or more, and the copolymer composition ratio is [structure derived from (1-a)] / [structure derived from (1-d)] = 59. / 41 (weight ratio). Hereinafter, the obtained ring-opening copolymerized hydrogenated product is referred to as a cyclic olefin-based resin 5A.
上記式(1−c)に示すジシクロペンタジエン45.0g、分子量調節剤として1−へキセン0.3gおよびシクロヘキサン103gを窒素置換した反応容器に仕込み、70℃に加熱した。
A reaction vessel purged with nitrogen of 45.0 g of dicyclopentadiene represented by the above formula (1-c), 0.3 g of 1-hexene and 103 g of cyclohexane as a molecular weight regulator was charged and heated to 70 ° C.
これにトリイソブチルアルミニウムのトルエン溶液(1.0mol/L)0.51mL、2−ブタノールのシクロヘキサン溶液(1.0mol/L)0.51mL、アセトンのトルエン溶液(0.1mol/L)1.70mlおよび六塩化タングステン(WCl6)のトルエン溶液(0.025mol/L)6.81mLを加え、70℃で1時間反応させることにより開環共重合体を得た。 To this, 0.51 mL of a toluene solution of triisobutylaluminum (1.0 mol / L), 0.51 mL of a cyclohexane solution of 2-butanol (1.0 mol / L), 1.70 ml of a toluene solution of acetone (0.1 mol / L) Then, 6.81 mL of a toluene solution (0.025 mol / L) of tungsten hexachloride (WCl 6 ) was added and reacted at 70 ° C. for 1 hour to obtain a ring-opening copolymer.
得られた開環共重合体溶液にシクロヘキサン456.4g加えて希釈し、水素添加触媒である(4−ペンチルベンゾイロキシ)カルボニル(ヒドリド)ビス(トリフェニルホスフィン)ルテニウム(RuH(OCO-Ar-CH2CH2CH2CH2CH3)(CO)[P(C6H5)3]2)(Arはパラフェニレン基を表す)を0.05g添加し、水素ガス圧を9〜10MPaとし、さらに160〜165℃まで昇温して3時間反応させた。この水素添加体を6Aという。 The obtained ring-opening copolymer solution was diluted by adding 456.4 g of cyclohexane and (4-pentylbenzoyloxy) carbonyl (hydrido) bis (triphenylphosphine) ruthenium (RuH (OCO-Ar-) as a hydrogenation catalyst. 0.05 g of CH 2 CH 2 CH 2 CH 2 CH 3 ) (CO) [P (C 6 H 5 ) 3 ] 2 ) (Ar represents a paraphenylene group) is added, and the hydrogen gas pressure is adjusted to 9 to 10 MPa. Further, the temperature was raised to 160 to 165 ° C. and reacted for 3 hours. This hydrogenated product is referred to as 6A.
反応終了後、得られた生成物を多量のメタノール中で沈殿させることにより水素添加物
を得た。得られた水素添加体(6A)の収量は40g(収率89%)、ガラス転移温度(Tg)は100℃であった。o−ジクロロベンゼンを用いてGPCを測定することで分子量を測定した。重量平均分子量(Mw)は6.8×104、分子量分布(Mw/Mn)は1.8、水素添加率は99.0%以上であった。以後、得られた開環共重合水添体を環状オレフィン系樹脂6Aとする。
After completion of the reaction, the resulting product was precipitated in a large amount of methanol to obtain a hydrogenated product. The yield of the obtained hydrogenated product (6A) was 40 g (yield 89%), and the glass transition temperature (Tg) was 100 ° C. The molecular weight was measured by measuring GPC using o-dichlorobenzene. The weight average molecular weight (Mw) was 6.8 × 10 4 , the molecular weight distribution (Mw / Mn) was 1.8, and the hydrogenation rate was 99.0% or more. Hereinafter, the obtained ring-opening copolymerized hydrogenated product is referred to as a cyclic olefin-based resin 6A.
[合成例7]
上記式(1−c)に示すジシクロペンタジエン31.5g、下記式(1−e)に示すテトラシクロ[4.4.0.12,5.17,10]−3−ドデセン38.5g、分子量調節剤として1−へキセン0.4gおよびシクロヘキサン165gを窒素置換した反応容器に仕込み、70℃に加熱した。
[Synthesis Example 7]
31.5 g of dicyclopentadiene represented by the above formula (1-c), and tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene 38.5 g, 0.4 g of 1-hexene as a molecular weight regulator and 165 g of cyclohexane were charged into a nitrogen-substituted reaction vessel and heated to 70 ° C.
これにトリイソブチルアルミニウムのトルエン溶液(1.0mol/L)0.96mL、2−ブタノールのシクロヘキサン溶液(1.0mol/L)0.72mL、アセトンのトルエン溶液(0.1mol/L)2.39mlおよび六塩化タングステン(WCl6)のトルエン溶液(0.025mol/L)9.57mLを加え、70℃で1時間反応させることにより開環共重合体を得た。 To this, 0.96 mL of a toluene solution of triisobutylaluminum (1.0 mol / L), 0.72 mL of a cyclohexane solution of 2-butanol (1.0 mol / L), 2.39 ml of a toluene solution of acetone (0.1 mol / L) Then, 9.57 mL of a toluene solution (0.025 mol / L) of tungsten hexachloride (WCl 6 ) was added and reacted at 70 ° C. for 1 hour to obtain a ring-opening copolymer.
得られた開環共重合体溶液にシクロヘキサン633g加えて希釈し、水素添加触媒である(4−ペンチルベンゾイロキシ)カルボニル(ヒドリド)ビス(トリフェニルホスフィン)ルテニウム(RuH(OCO-Ar-CH2CH2CH2CH2CH3)(CO)[P(C6H5)3]2)(Arはパラフェニレン基を表す)を0.04g添加し、水素ガス圧を9〜10MPaとし、さらに160〜165℃まで昇温して3時間反応させた。この水素添加体を7Aという。 The resulting ring-opening copolymer solution was diluted by adding 633 g of cyclohexane and (4-pentylbenzoyloxy) carbonyl (hydrido) bis (triphenylphosphine) ruthenium (RuH (OCO-Ar-CH 2 ) as a hydrogenation catalyst. 0.04 g of CH 2 CH 2 CH 2 CH 3 ) (CO) [P (C 6 H 5 ) 3 ] 2 ) (Ar represents a paraphenylene group) is added, the hydrogen gas pressure is adjusted to 9-10 MPa, The temperature was raised to 160 to 165 ° C. and reacted for 3 hours. This hydrogenated product is referred to as 7A.
反応終了後、得られた生成物を多量のメタノール中で沈殿させることにより水素添加物
を得た。得られた水素添加体(7A)の収量は65g(収率93%)、ガラス転移温度(Tg)は130℃であった。o−ジクロロベンゼンを用いてGPCを測定することで分子量を測定した。重量平均分子量(Mw)は4.5×104、分子量分布(Mw/Mn)は2.7、水素添加率は99.0%以上であった。共重合組成比は[(1−c)由来の構造]/[(1−d e)由来の構造]=46/54(重量比)であった。以後、得られた開環共重合水添体を環状オレフィン系樹脂7Aとする。
After completion of the reaction, the resulting product was precipitated in a large amount of methanol to obtain a hydrogenated product. The yield of the obtained hydrogenated product (7A) was 65 g (yield 93%), and the glass transition temperature (Tg) was 130 ° C. The molecular weight was measured by measuring GPC using o-dichlorobenzene. The weight average molecular weight (Mw) was 4.5 × 10 4 , the molecular weight distribution (Mw / Mn) was 2.7, and the hydrogenation rate was 99.0% or more. The copolymer composition ratio was [structure derived from (1-c)] / [structure derived from (1-de)] = 46/54 (weight ratio). Hereinafter, the obtained hydrogenated ring-opening copolymer is referred to as a cyclic olefin resin 7A.
合成例1で得られた水素添加体(1A)100gに対して、フェノール系化合物(B)として式(2−a)に示す1,1,3-トリス[2-メチル-4-[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオニルオキシ]-5-t-ブチルフェニル]ブタンを0.3g添加してラボプラストミルにて空気下、280℃で30分間混練し、樹脂組成物を得た。
For 1,100 g of the hydrogenated product (1A) obtained in Synthesis Example 1, 1,1,3-tris [2-methyl-4- [3-] represented by the formula (2-a) as the phenol compound (B) 0.3 g of (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -5-t-butylphenyl] butane was added and kneaded for 30 minutes at 280 ° C. under air in a lab plast mill. A resin composition was obtained.
なお、使用したフェノール系化合物(B)の性状を表1に示し、樹脂組成物の調製条件を表2に示す。 In addition, the property of the used phenol type compound (B) is shown in Table 1, and the preparation conditions of a resin composition are shown in Table 2.
実施例1において、水素添加体(1A)の代わりに、合成例2で得られた水素添加体(2A)を用いたこと以外は実施例1と同様にして樹脂組成物を得た。
In Example 1, a resin composition was obtained in the same manner as in Example 1 except that the hydrogenated product (2A) obtained in Synthesis Example 2 was used instead of the hydrogenated product (1A).
[実施例3]
実施例1において、水素添加体(1A)の代わりに、合成例3で得られた水素添加体(3A)を用いたこと以外は実施例1と同様にして樹脂組成物を得た。
[Example 3]
In Example 1, a resin composition was obtained in the same manner as in Example 1 except that the hydrogenated product (3A) obtained in Synthesis Example 3 was used instead of the hydrogenated product (1A).
[実施例4]
実施例3において、式(2−a)に示す化合物の量を0.3gから1.0gに変更したこと以外は実施例3と同様にして樹脂組成物を得た。
[Example 4]
In Example 3, a resin composition was obtained in the same manner as in Example 3 except that the amount of the compound represented by the formula (2-a) was changed from 0.3 g to 1.0 g.
[実施例5]
実施例3において、水素添加体(3A)および式(2−a)に示す化合物に加えて、さらに含リン化合物(C)として下記式(3−a)に示すトリス(2,4-ジ-t-ブチルフェニル)ホスファイトを0.3g添加したこと以外は実施例3と同様にして樹脂組成物を得た。
なお、使用した含リン化合物(C)の性状を表1に示す。
[Example 5]
In Example 3, in addition to the hydrogenated compound (3A) and the compound represented by the formula (2-a), tris (2,4-di- A resin composition was obtained in the same manner as in Example 3 except that 0.3 g of t-butylphenyl) phosphite was added.
The properties of the phosphorus-containing compound (C) used are shown in Table 1.
実施例5において、式(3−a)に示す化合物の代わりに、下記式(3−b)に示す6-[3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロポキシ]-2,4,8,10-テトラ-t-ブチルジベンズ[d,f][1,3,2]ジオキサホスフェピンを用いたこと以外は実施例5と同様にして樹脂組成物を得た。
In Example 5, instead of the compound represented by the formula (3-a), 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy represented by the following formula (3-b) A resin composition was obtained in the same manner as in Example 5 except that -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphepine was used. .
なお、使用した含リン化合物(C)の性状を表1に示す。 The properties of the phosphorus-containing compound (C) used are shown in Table 1.
実施例5において、式(3−a)に示す化合物の代わりに、下記式(3−c)に示すテトラキス(2,4-ジ-t-ブチル-5-メチルフェニル)-4,4'-ビフェニレンジホスホナイトを主成分とするリン系酸化防止剤(商品名;大崎工業(株)製GSY−P101)を用いたこと以外は実施例5と同様にして樹脂組成物を得た。
In Example 5, instead of the compound represented by the formula (3-a), tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4′- represented by the following formula (3-c) A resin composition was obtained in the same manner as in Example 5 except that a phosphorus-based antioxidant (trade name; GSY-P101 manufactured by Osaki Kogyo Co., Ltd.) mainly containing biphenylene diphosphonite was used.
なお、使用した含リン化合物(C)の性状を表1に示す。 The properties of the phosphorus-containing compound (C) used are shown in Table 1.
合成例4で得られた水素添加体(4A)100gに対して、フェノール系化合物(B)として前記式(2−a)に示す1,1,3-トリス[2-メチル-4-[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオニルオキシ]-5-t-ブチルフェニル]ブタンを3g添加してラボプラストミルにて空気下、260℃で30分間混練し、樹脂組成物を得た。
With respect to 100 g of the hydrogenated product (4A) obtained in Synthesis Example 4, 1,1,3-tris [2-methyl-4- [3] represented by the above formula (2-a) as a phenol compound (B) 3 g of-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -5-t-butylphenyl] butane was added and kneaded at 260 ° C. for 30 minutes in the air with a lab plast mill. A resin composition was obtained.
[実施例9]
実施例1において、水素添加体(1A)の代わりに、合成例5で得られた水素添加体(5A)を用いたこと以外は実施例1と同様にして樹脂組成物を得た。
なお、樹脂組成物の調製について表3に示す。
[Example 9]
In Example 1, a resin composition was obtained in the same manner as in Example 1 except that the hydrogenated product (5A) obtained in Synthesis Example 5 was used instead of the hydrogenated product (1A).
In addition, it shows in Table 3 about preparation of a resin composition.
[実施例10]
実施例1において、水素添加体(1A)の代わりに、合成例6で得られた水素添加体(6A)を用いたこと以外は実施例1と同様にして樹脂組成物を得た。
なお、樹脂組成物の調製について表3に示す。
[Example 10]
In Example 1, a resin composition was obtained in the same manner as in Example 1 except that the hydrogenated product (6A) obtained in Synthesis Example 6 was used instead of the hydrogenated product (1A).
In addition, it shows in Table 3 about preparation of a resin composition.
[実施例11]
実施例1において、水素添加体(1A)の代わりに、合成例7で得られた水素添加体(7A)を用いたこと以外は実施例1と同様にして樹脂組成物を得た。
なお、樹脂組成物の調製について表3に示す。
[Example 11]
In Example 1, a resin composition was obtained in the same manner as in Example 1 except that the hydrogenated product (7A) obtained in Synthesis Example 7 was used instead of the hydrogenated product (1A).
In addition, it shows in Table 3 about preparation of a resin composition.
[比較例1]
実施例3において、式(2−a)に示す化合物の代わりに、下記式(2'−a)に示す化合物を用いたこと以外は実施例3と同様にして樹脂組成物を得た。
[Comparative Example 1]
In Example 3, a resin composition was obtained in the same manner as in Example 3 except that the compound represented by the following formula (2′-a) was used instead of the compound represented by the formula (2-a).
なお、式(2'−a)に示す化合物の性状を表1に示し、樹脂組成物の調製について表2に示す。 The properties of the compound represented by the formula (2′-a) are shown in Table 1, and the preparation of the resin composition is shown in Table 2.
実施例4において、式(2−a)に示す化合物1.0gの代わりに、式(2'−a)に示す化合物1.5gを用いたこと以外は実施例4と同様にして樹脂組成物を得た。
In Example 4, a resin composition was obtained in the same manner as in Example 4 except that 1.5 g of the compound represented by the formula (2′-a) was used instead of 1.0 g of the compound represented by the formula (2-a). Got.
[比較例3]
実施例3において、式(2−a)に示す化合物の代わりに、下記式(2'−b)に示す化合物を用いたこと以外は実施例3と同様にして樹脂組成物を得た。
[Comparative Example 3]
In Example 3, a resin composition was obtained in the same manner as in Example 3 except that the compound represented by the following formula (2′-b) was used instead of the compound represented by the formula (2-a).
なお、式(2'−b)に示す化合物の性状を表1に示す。 In addition, Table 1 shows properties of the compound represented by the formula (2′-b).
実施例3において、式(2−a)に示す化合物の代わりに、下記式(2'−c)に示す化合物を用いたこと以外は実施例3と同様にして樹脂組成物を得た。
In Example 3, a resin composition was obtained in the same manner as in Example 3 except that the compound represented by the following formula (2′-c) was used instead of the compound represented by the formula (2-a).
なお、式(2'−c)に示す化合物の性状を表1に示す。 In addition, Table 1 shows properties of the compound represented by the formula (2′-c).
実施例および比較例で得られた樹脂組成物について以下の評価を行った。結果を表2および3に示す。
(1)発煙性評価:プラストミル混練時の発煙性を下記の基準で目視観察した。
○ 発煙しなかった
△ ほとんど発煙しなかった
× 発煙した
The following evaluation was performed about the resin composition obtained by the Example and the comparative example. The results are shown in Tables 2 and 3.
(1) Evaluation of smoke generation: The smoke generation during plastmill kneading was visually observed according to the following criteria.
○ No smoke △ Almost no smoke × No smoke
(2)色相評価:樹脂組成物をトルエンに溶解し濃度10重量%の溶液とした後、黄色度(YI)を測定して評価した。測定はスガ試験機(株)製SMカラーコンピューターSM−7−CHを用い、C光2゜視野透過測定を3回行いその平均値を求めた(測定試料:サンプル溶液20g使用、測定用セル:内径60mm、高さ30mmの円筒型ガラスセル)。 (2) Hue evaluation: The resin composition was dissolved in toluene to obtain a solution having a concentration of 10% by weight, and the yellowness (YI) was measured and evaluated. The measurement was performed using a SM color computer SM-7-CH manufactured by Suga Test Instruments Co., Ltd., and C-light 2 ° visual field transmission measurement was performed three times to obtain an average value (measurement sample: using 20 g of sample solution, measurement cell: A cylindrical glass cell having an inner diameter of 60 mm and a height of 30 mm).
(3)ゲル評価:樹脂組成物をトルエンに溶解し濃度10重量%の溶液とした後、1.0μm孔径のPTFE製フィルターでろ過した。ろ過後にフィルターを空気下、260℃で30分間焼成することでフィルター上に残留していたトルエン不溶成分(ゲル)を酸化発色(茶変)させ、実体顕微鏡にてその数を数えてろ過面積とろ過量から樹脂組成物1g中のゲル数を計算し、100個/g未満を○、500個/g以上を×とした。なお、ゲルとはフィルター上に平面的に存在し、かつ、焼成により茶変した有機物をいい、繊維形状のもの、および立体的な形状のものは環境由来の異物としてゲル数として数えなかった。 (3) Gel evaluation: The resin composition was dissolved in toluene to obtain a solution having a concentration of 10% by weight, and then filtered through a PTFE filter having a pore size of 1.0 μm. After filtration, the filter is baked at 260 ° C. for 30 minutes in the air to cause toluene insoluble component (gel) remaining on the filter to oxidize and develop color (brown). The number of gels in 1 g of the resin composition was calculated from the filtration amount, and less than 100 pieces / g was evaluated as ○ and 500 pieces / g or more as x. The gel is an organic substance that exists in a plane on the filter and has been browned by firing, and those having a fiber shape and three-dimensional shape were not counted as the number of gels as foreign substances derived from the environment.
(4)透明性評価:プラストミル混練で得られた樹脂組成物の透明性を下記の基準で目視観察した。
○ 透明であった
△ 僅かに白濁した
× 白濁した
表2の結果から、環状オレフィン系樹脂(A)に特定のフェノール系化合物(B)を添加した樹脂組成物は、従来から問題とされてきた加工時の着色、ゲル生成および発煙といった問題をすべて改善できることがわかる。さらに、例えば、実施例4および7の比較結果から、含リン化合物(C)を併用すると、フェノール系化合物(B)の添加量を低減しても色相改良効果が認められるため、要求される特性によって品質バランスをコントロールすることができる。
(4) Transparency evaluation: The transparency of the resin composition obtained by plastmill kneading was visually observed according to the following criteria.
○ It was transparent △ Slightly cloudy × Cloudy From the results in Table 2, a resin composition obtained by adding a specific phenol compound (B) to a cyclic olefin resin (A) has been conventionally regarded as a problem. It can be seen that all the problems such as coloring during processing, gel formation and fuming can be improved. Further, for example, from the comparison results of Examples 4 and 7, when the phosphorus-containing compound (C) is used in combination, the hue improving effect is recognized even when the amount of the phenolic compound (B) is reduced, so that the required characteristics are obtained. Can control the quality balance.
Claims (8)
(B−i):分子量が800以上
(B−ii):窒素下において300℃で1時間加熱したときの重量減少率が15%以下 The resin composition according to claim 1, wherein the compound represented by the formula (2-1) satisfies the following requirements (B-i) and (B-ii).
(B-i): molecular weight is 800 or more (B-ii): weight loss rate when heated at 300 ° C. for 1 hour under nitrogen is 15% or less
該含リン化合物(C)が下記式(3−a)〜(3−c)で表される化合物から選ばれる少なくとも1種であり、かつ、該含リン化合物(C)が、環状オレフィン系樹脂(A)100重量部に対して0.005〜5重量部含まれることを特徴とする請求項1〜3のいずれかに記載の樹脂組成物。
(C−i):単一化合物においてはその相対分子質量が400以上、多分散性混合物においてはゲルパーミエーションクロマトグラフィー(GPC)による重量平均分子量(Mw
)が400以上、
(C−ii):窒素下において250℃で1時間加熱したときの重量減少率が50%以下
The phosphorus-containing compound (C) is at least one selected from compounds represented by the following formulas (3-a) to (3-c) , and the phosphorus-containing compound (C) is a cyclic olefin resin. (A) 0.005-5 weight part is contained with respect to 100 weight part, The resin composition in any one of Claims 1-3 characterized by the above-mentioned.
(Ci): The relative molecular mass of a single compound is 400 or more, and the weight average molecular weight (Mw) by gel permeation chromatography (GPC) in a polydisperse mixture.
) Is 400 or more,
(C-ii): Weight reduction rate when heated at 250 ° C. for 1 hour under nitrogen is 50% or less
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