CN116981734A - Cyclic olefin resin composition and molded article - Google Patents
Cyclic olefin resin composition and molded article Download PDFInfo
- Publication number
- CN116981734A CN116981734A CN202280021066.1A CN202280021066A CN116981734A CN 116981734 A CN116981734 A CN 116981734A CN 202280021066 A CN202280021066 A CN 202280021066A CN 116981734 A CN116981734 A CN 116981734A
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- carbon atoms
- cyclic olefin
- compound
- general formula
- mass
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- 239000011342 resin composition Substances 0.000 title claims abstract description 48
- 125000004122 cyclic group Chemical group 0.000 title description 3
- 229920005672 polyolefin resin Polymers 0.000 title description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 78
- 239000000194 fatty acid Substances 0.000 claims abstract description 78
- 229930195729 fatty acid Natural products 0.000 claims abstract description 78
- 150000001875 compounds Chemical class 0.000 claims abstract description 70
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 60
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 50
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 40
- 150000001925 cycloalkenes Chemical class 0.000 claims abstract description 34
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 diester compound Chemical class 0.000 claims description 115
- 125000004432 carbon atom Chemical group C* 0.000 claims description 64
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 42
- 125000005843 halogen group Chemical group 0.000 claims description 27
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims description 26
- 230000003287 optical effect Effects 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 125000001153 fluoro group Chemical group F* 0.000 claims description 19
- 229910052731 fluorine Inorganic materials 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 10
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 9
- 125000003367 polycyclic group Chemical group 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000002950 monocyclic group Chemical group 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- AGNTUZCMJBTHOG-UHFFFAOYSA-N 3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]propane-1,2-diol Chemical compound OCC(O)COCC(O)COCC(O)CO AGNTUZCMJBTHOG-UHFFFAOYSA-N 0.000 abstract description 23
- 239000000178 monomer Substances 0.000 description 33
- 235000011187 glycerol Nutrition 0.000 description 20
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 150000002430 hydrocarbons Chemical group 0.000 description 14
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 14
- 239000003381 stabilizer Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000011109 contamination Methods 0.000 description 10
- WLTSXAIICPDFKI-FNORWQNLSA-N (E)-3-dodecene Chemical compound CCCCCCCC\C=C\CC WLTSXAIICPDFKI-FNORWQNLSA-N 0.000 description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 229920005604 random copolymer Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 3
- PHDVPEOLXYBNJY-KTKRTIGZSA-N 2-(2-hydroxyethoxy)ethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCOCCO PHDVPEOLXYBNJY-KTKRTIGZSA-N 0.000 description 3
- OTTZHAVKAVGASB-UHFFFAOYSA-N 2-heptene Natural products CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000007423 decrease Effects 0.000 description 2
- 229940105990 diglycerin Drugs 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- 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 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
- OTTZHAVKAVGASB-HYXAFXHYSA-N 2-Heptene Chemical compound CCCC\C=C/C OTTZHAVKAVGASB-HYXAFXHYSA-N 0.000 description 1
- OLGHJTHQWQKJQQ-UHFFFAOYSA-N 3-ethylhex-1-ene Chemical compound CCCC(CC)C=C OLGHJTHQWQKJQQ-UHFFFAOYSA-N 0.000 description 1
- YPVPQMCSLFDIKA-UHFFFAOYSA-N 3-ethylpent-1-ene Chemical compound CCC(CC)C=C YPVPQMCSLFDIKA-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- OPMUAJRVOWSBTP-UHFFFAOYSA-N 4-ethyl-1-hexene Chemical compound CCC(CC)CC=C OPMUAJRVOWSBTP-UHFFFAOYSA-N 0.000 description 1
- SUWJESCICIOQHO-UHFFFAOYSA-N 4-methylhex-1-ene Chemical compound CCC(C)CC=C SUWJESCICIOQHO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- BTCUMMXRRUIJHU-UHFFFAOYSA-N acenaphthylene cyclopenta-1,3-diene Chemical group C1C=CC=C1.C1=CC(C=C2)=C3C2=CC=CC3=C1 BTCUMMXRRUIJHU-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 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
- GVRWIAHBVAYKIZ-UHFFFAOYSA-N dec-3-ene Chemical compound CCCCCCC=CCC GVRWIAHBVAYKIZ-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 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 1
- 239000008188 pellet Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 108010040933 progressin Proteins 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
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Abstract
A cycloolefin resin composition comprising a cycloolefin polymer (A), a diglyceride compound (B) of triglycerol and a fatty acid, and a monoester compound (C) of diglycerol and a fatty acid or a monoester compound (C) of glycerol and a fatty acid, the molecular weight of which is 70% or less of that of the compound (B), wherein the total amount of the compound (B) and the compound (C) is 0.10 parts by mass or more and 3 parts by mass or less per 100 parts by mass of the polymer (A).
Description
Technical Field
The present invention relates to a cycloolefin resin composition and a molded article.
Background
The cyclic olefin polymer is used for optical lenses such as an imaging lens, an fθ lens, and a pickup lens. The cyclic olefin polymer used for such a molded article such as an optical lens is required to have characteristics such as high transparency, excellent dimensional stability, excellent heat resistance, and excellent moisture resistance.
As an invention of the cyclic olefin polymer, for example, a resin composition containing a diglycerol monooleate or the like in the cyclic olefin polymer described in patent document 1 is known. Patent document 1 describes a resin composition comprising a polymer having a repeating structural unit at least a part of which contains an alicyclic structure, and a fatty acid ester of a fatty acid and a polyol having one or more ether groups.
Patent document 2 describes a cycloolefin resin composition containing a cycloolefin polymer (a) and a triglycerin fatty acid ester.
Patent document 3 describes a resin composition containing a polymer having an alicyclic structure and a polyglycerin fatty acid ester-based additive, wherein the polyglycerin fatty acid ester-based additive is composed of one or more polyglycerin fatty acid ester compounds, and the content of the polyglycerin fatty acid ester-based additive is 0.2 to 2.0 parts by weight relative to 100 parts by weight of the polymer having an alicyclic structure.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2015-199939
Patent document 2: japanese patent application laid-open No. 2018-172665
Patent document 3: international publication No. 2017/033968
Disclosure of Invention
Problems to be solved by the invention
The cyclic olefin polymer is liable to generate microcracks after a high temperature and high humidity test, and the generated microcracks reduce the optical properties of the molded article. That is, the internal haze of the molded article increases due to microcracks, and the optical characteristics as lenses, for example, decrease.
As one of the methods for preventing the generation of microcracks, there is a method of adding a hydrophilic stabilizer to a cyclic olefin polymer. By adding the hydrophilic stabilizer, the generation of microcracks can be prevented.
However, according to the studies of the present inventors, it is known that: depending on the kind of the hydrophilic stabilizer, dirt derived from the hydrophilic stabilizer may adhere to a portion of the mold that contacts the molded article and a portion of the mold vent during molding. If dirt adheres to the portion of the mold that contacts the molded article, the dirt adheres to the surface of the molded article. For example, when a lens is molded, dirt adheres to the lens surface, and the optical characteristics are degraded.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a cycloolefin resin composition capable of suppressing the generation of microcracks and the generation of mold contamination.
Means for solving the problems
The present inventors have made intensive studies to solve the above problems. The result shows that: the present invention has been completed by solving both the generation of microcracks and the mold contamination by using a specific hydrophilic stabilizer and a monoester of glycerin or diglycerin with a fatty acid having a molecular weight lower than that of the above hydrophilic stabilizer.
That is, according to the present invention, there are provided a cycloolefin resin composition, a molded body, and an optical member shown below.
[1]
A cycloolefin resin composition comprising:
A cyclic olefin polymer (A),
A diester compound (B) of triglycerin and a fatty acid, and
a monoester compound (C) of a diglycerol and a fatty acid or a monoester compound (C) of a glycerol and a fatty acid, the molecular weight of which is 70% or less of that of the compound (B),
the total amount of the compound (B) and the compound (C) is 0.10 parts by mass or more and 3 parts by mass or less per 100 parts by mass of the cyclic olefin polymer (a).
[2]
The cycloolefin resin composition according to [1] above,
the cyclic olefin polymer (A) contains at least one selected from the group consisting of a cyclic olefin copolymer (A-1) and a cyclic olefin ring-opened polymer (A-2).
[3]
The cycloolefin resin composition according to [2], wherein the cycloolefin polymer (A) contains the copolymer (A-1),
the cyclic olefin copolymer (A-1) has a structural unit (a) and a structural unit (b).
Structural unit (a): at least one structural unit derived from an olefin represented by the following general formula (I).
Structural unit (b): one or more cyclic olefin-derived structural units selected from the group consisting of a repeating unit (AA) represented by the following general formula (II), a repeating unit (AB) represented by the following general formula (III), and a repeating unit (AC) represented by the following general formula (IV).
[ chemical 1]
In the general formula (I), R 300 Represents a hydrogen atom or a straight or branched hydrocarbon group having 1 to 29 carbon atoms.
[ chemical 2]
In the general formula (II), u is 0 or 1, v is 0 or a positive integer, and w is 0 or 1.R is R 61 ～R 78 R is as follows a1 And R is b1 Which may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an haloalkane having 1 to 20 carbon atomsA group, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. R is R 75 ～R 78 May combine with each other to form a single ring or multiple rings.
[ chemical 3]
In the above general formula (III), x and d are each independently an integer of 0 or 1 or more. y and z are each independently integers from 0 to 2. R is R 81 ～R 99 The two groups may be the same or different, and are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group. R is R 89 And R is 90 Bound carbon atoms to R 93 To carbon atoms or R 91 The carbon atoms to be bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. When y=z=0, R 92 And R is R 95 Or R is 95 And R is R 99 May combine with each other to form a monocyclic or polycyclic aromatic ring.
[ chemical 4]
In the above general formula (IV), R 100 、R 101 And each of them may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. f is 1-18.
[4]
The cycloolefin resin composition according to [3], wherein the cycloolefin copolymer (A-1) has a repeating unit (AA) represented by the general formula (II) and a structural unit (D) derived from a cycloolefin having an aromatic ring, the repeating unit (AA) contains no aromatic ring,
the cyclic olefin having an aromatic ring contains one or more selected from the group consisting of a compound represented by the general formula (D-1), a compound represented by the general formula (D-2), and a compound represented by the general formula (D-3).
[ chemical 5]
In the above general formula (D-1), n and q are each independently 0, 1 or 2.R is R 1 ～R 17 Each independently is a hydrogen atom, a halogen atom other than fluorine atom, or a hydrocarbon group of 1 to 20 carbon atoms which may be substituted with a halogen atom other than fluorine atom, R 10 ～R 17 One of which is a bond. When q=0, R 10 And R is R 11 、R 11 And R is R 12 、R 12 And R is R 13 、R 13 And R is R 14 、R 14 And R is R 15 、R 15 And R is R 10 May combine with each other to form a single ring or multiple rings. When q=1 or 2, R 10 And R is R 11 、R 11 And R is R 17 、R 17 And R is R 12 、R 12 And R is R 13 、R 13 And R is R 14 、R 14 And R is R 15 、R 15 And R is R 16 、R 16 And R is R 16 、R 17 And R is R 17 、R 16 And R is R 10 May be bonded to each other to form a single ring or multiple rings, and the single ring or multiple rings may have a double bond, and may be aromatic rings.
[ chemical 6]
In the above general formula (D-2), n and m are each independently 0, 1 or 2, and q is 1, 2 or 3.R is R 18 ～R 31 Each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom. In addition, R when q=1 28 And R is R 29 、R 29 And R is R 30 、R 30 And R is R 31 Can combine with each other to form a single ring or multiple rings. In addition, when q=2 or 3, R 28 And R is R 28 、R 28 And R is R 29 、R 29 And R is R 30 、R 30 And R is R 31 、R 31 And R is R 31 May be bonded to each other to form a single ring or multiple rings, the single ring or multiple rings may have a double bond, and the single ring or multiple rings may be aromatic rings.
[ chemical 7]
In the above general formula (D-3), q is 1, 2 or 3, R 32 ～R 39 Each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom. In addition, R when q=1 36 And R is R 37 、R 37 And R is R 38 、R 38 And R is R 39 May combine with each other to form a single ring or multiple rings. In addition, R when q=2 or 3 36 And R is R 36 、R 36 And R is R 37 、R 37 And R is R 38 、R 38 And R is R 39 、R 39 And R is R 39 May be bonded to each other to form a single ring or multiple rings, the single ring or multiple rings may have a double bond, and the single ring or multiple rings may be aromatic rings.
[5]
A cycloolefin resin composition according to any one of the above [1] to [4],
The molecular weight of the compound (B) is 300 to 2000.
[6]
A cycloolefin resin composition according to any one of the above [1] to [5],
the glass transition temperature of the cyclic olefin polymer (A) is 130 to 170 ℃ inclusive, as measured by a Differential Scanning Calorimeter (DSC).
[7]
A molded article comprising the cycloolefin resin composition according to any one of the above [1] to [6 ].
[8]
The molded article according to [7] above, which is an optical member.
Effects of the invention
According to the cycloolefin resin composition of the present invention, a molded article as an optical member that can suppress the generation of microcracks and the generation of mold contamination can be obtained. In the case of such a molded article, the internal haze is low, and an increase in the internal haze before and after the heat and humidity resistance test can be suppressed. Therefore, the present invention can be mainly used for optical applications and lenses.
Detailed Description
The present invention will be described below based on embodiments. In the present embodiment, "a to B" representing the numerical range represents a or more and B or less unless otherwise specified.
As described above, according to the findings of the present inventors, there is a problem that dirt derived from the hydrophilic stabilizer adheres to a portion of the mold that contacts the molded article and a mold vent portion at the time of molding, depending on the kind of the hydrophilic stabilizer.
The present inventors have made intensive studies to solve the above problems. As a result, it has been found that both the generation of microcracks and the mold contamination can be solved by using a specific hydrophilic stabilizer together with a monoester of glycerol or diglycerol having a molecular weight lower than that of the above hydrophilic stabilizer and a fatty acid.
That is, the cycloolefin resin composition according to the present embodiment is as follows.
Cyclic olefin resin composition
The cycloolefin resin composition according to the present embodiment includes:
a cyclic olefin polymer (A),
A diester compound (B) of triglycerin and a fatty acid,
A monoester compound (C) of a diglycerol and a fatty acid or a monoester compound (C) of a glycerol and a fatty acid, the molecular weight of which is 70% or less of that of the compound (B),
the total amount of the compound (B) and the compound (C) is 0.10 parts by mass or more and 3 parts by mass or less per 100 parts by mass of the polymer (a).
In the case of the cycloolefin resin composition according to the present embodiment, the generation of microcracks and the generation of mold contamination can be suppressed. In addition, in the case of the molded article of the cycloolefin resin composition according to the present embodiment, the internal haze is low, and the increase in the internal haze before and after the wet heat resistance test can be reduced. Further, since the molded article can maintain transparency before and after the wet heat resistance test, it can be suitably used for applications requiring transparency.
[ Cyclic olefin Polymer (A) ]
The cyclic olefin polymer (a) according to the present embodiment is a copolymer having a structural unit derived from a cyclic olefin as an essential structural unit.
The cyclic olefin polymer (A) preferably contains at least one selected from the group consisting of a cyclic olefin copolymer (A-1) and a ring-opened polymer (A-2) of a cyclic olefin. The heat resistance and moldability can be further improved while maintaining the balance between the transparency and refractive index of the obtained optical member well.
(Cyclic olefin copolymer (A-1))
Examples of the cyclic olefin copolymer (A-1) according to the present embodiment include copolymers of ethylene or an α -olefin and a cyclic olefin.
The cyclic olefin compound constituting the cyclic olefin copolymer (A-1) is not particularly limited, and examples thereof include cyclic olefin monomers described in paragraphs 0037 to 0063 of International publication No. 2006/0118161.
The cyclic olefin copolymer (a-1) preferably has a structural unit (a) and a structural unit (b) from the viewpoint of further improving the optical characteristics of the obtained optical member. The optical characteristics refer to characteristics such as transparency and refractive index of the optical member.
Structural unit (a): at least one structural unit derived from an olefin represented by the following general formula (I).
[ chemical 8]
In the general formula (I), R 300 Represents a hydrogen atom or a straight or branched hydrocarbon group having 1 to 29 carbon atoms.
Structural unit (b): at least one structural unit derived from a cyclic olefin selected from the group consisting of a repeating unit (AA) represented by the following general formula (II), a repeating unit (AB) represented by the following general formula (III), and a repeating unit (AC) represented by the following general formula (IV).
[ chemical 9]
In the general formula (II), u is 0 or 1, v is 0 or a positive integer, and w is 0 or 1.R is R 61 ～R 78 R is as follows a1 And R is b1 The two groups may be the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. R is R 75 ～R 78 May combine with each other to form a single ring or multiple rings.
[ chemical 10]
In the above general formula (III), x and d are each independently an integer of 0 or 1 or more. y and z are each independently integers from 0 to 2. R is R 81 ～R 99 The two groups may be the same or different, and are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group. R is R 89 And R is 90 Bound carbon atoms to R 93 To carbon atoms or R 91 The carbon atoms to be bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. When y=z=0, R 92 And R is R 95 Or R is 95 And R is R 99 May combine with each other to form a monocyclic or polycyclic aromatic ring.
[ chemical 11]
In the above general formula (IV), R 100 、R 101 And each of them may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. f is 1-18.
The olefin monomer which is one of the copolymerization raw materials of the cyclic olefin copolymer (a-1) according to the present embodiment is a monomer which is subjected to addition polymerization to form a structural unit represented by the above general formula (I). Specifically, an olefin monomer represented by the following general formula (Ia) corresponding to the above general formula (I) can be used.
[ chemical 12]
In the above general formula (Ia), R 300 Represents a hydrogen atom or a straight-chain or branched hydrocarbon group having 1 to 29 carbon atoms.
Examples of the olefin monomer represented by the general formula (Ia) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-hexene, 4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Among them, ethylene and propylene are preferable, and ethylene is particularly preferable, from the viewpoint of obtaining an optical member having more excellent heat resistance, mechanical characteristics and optical characteristics. The olefin monomer represented by the above general formula (Ia) may be used in two or more kinds.
When the total of the structural units constituting the cyclic olefin copolymer (a-1) according to the present embodiment is 100 mol%, the proportion of the structural unit (a) derived from an olefin is preferably 5 mol% or more and 95 mol% or less, more preferably 20 mol% or more and 90 mol% or less, still more preferably 40 mol% or more and 80 mol% or less, and particularly preferably 50 mol% or more and 70 mol% or less.
The proportion of the structural unit (a) derived from the olefin may be determined by 13 C-NMR was performed.
The cyclic olefin monomer which is one of the copolymerization raw materials of the cyclic olefin copolymer (a-1) according to the present embodiment is a monomer obtained by addition polymerization to form a cyclic olefin-derived structural unit (b) represented by the general formula (II), the general formula (III) or the general formula (IV). Specifically, cyclic olefin monomers represented by the general formulae (IIa), (IIIa) and (IVa) corresponding to the general formula (II), the general formula (III) and the general formula (IV) are used.
[ chemical 13]
In the above formula (IIa), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 to 2, more preferably 0 or 1, w is 0 or 1, R 61 ～R 78 R is as follows a1 And R is b1 May be the same or different from each other, and is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 75 ～R 78 May combine with each other to form a single ring or multiple rings.
[ chemical 14]
In the above general formula (IIIa), x and d are each independently an integer of 0 or 1 or more, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, y and z are each independently 0, 1 or 2, R 81 ～R 99 Which may be the same or different from each other, is a hydrogen atom,A halogen atom, an aliphatic hydrocarbon group having an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms or an alkoxy group, R 89 And R is 90 Bound carbon atoms to R 93 To carbon atoms or R 91 The bonded carbon atoms may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y=z=0, R 95 And R is R 92 Or R is 95 And R is R 99 May combine with each other to form a monocyclic or polycyclic aromatic ring.
[ 15]
In the above formula (IVa), R 100 、R 101 And each of them may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1.ltoreq.f.ltoreq.18.
By using the olefin monomer represented by the general formula (Ia) and the cyclic olefin monomer represented by the general formula (IIa), (IIIa) or (IVa) as the copolymerization component, the solubility of the cyclic olefin copolymer (a-1) in a solvent is further improved, the moldability is improved, and the yield of the product is improved.
As specific examples of the cyclic olefin monomer represented by the general formula (IIa), (IIIa) or (IVa), compounds described in paragraphs 0037 to 0063 of International publication No. 2006/0110861 can be used.
Specifically, there may be mentioned bicyclo-2-heptene derivatives (bicyclohept-2-ene derivatives), tricyclo-3-decene derivatives, tricyclo-3-undecene derivatives, tetracyclo-3-dodecene derivatives, pentacyclo-4-pentadecene derivatives, pentacyclopentadecene derivatives, pentacyclo-3-pentadecene derivatives, pentacyclo-4-hexadecene derivatives, pentacyclo-3-hexadecene derivatives, hexacyclo-4-heptadecene derivatives, heptacyclo-5-eicosene derivatives, heptacyclo-4-eicosene derivatives, heptacyclo-5-eicosene derivatives, octacyclo-5-docosene derivatives, nonacyclo-5-eicosopenem derivatives, nonacyclo-6-eicosene derivatives, cyclopentadiene-acenaphthylene adducts, 1, 4a,9 a-tetrahydrofluorene derivatives, 1, 4-methylene-1, 4a,5,10 a-hexahydroanthracene derivatives and cycloalkylene derivatives having 3 to 20 carbon atoms.
Among the cyclic olefin monomers represented by the general formula (IIa), (IIIa) or (IVa), the cyclic olefin represented by the general formula (IIa) is preferable.
As the cyclic olefin monomer represented by the above general formula (IIa), bicyclo [2.2.1 ] is preferably used]-2-heptene (also known as norbornene), tetracyclo [4.4.0.1 ] 2,5 .1 7,10 ]3-dodecene (also known as tetracyclododecene), more preferably tetracyclo [4.4.0.1 ] is used 2,5 .1 7,10 ]-3-dodecene. These cyclic olefins have a rigid ring structure, and thus have an advantage that the elastic modulus of the copolymer and the optical member is easily maintained.
When the total of the structural units constituting the cyclic olefin copolymer (a-1) according to the present embodiment is 100 mol%, the proportion of the structural unit (b) derived from the cyclic olefin is preferably 5 mol% or more and 95 mol% or less, more preferably 10 mol% or more and 80 mol% or less, still more preferably 20 mol% or more and 60 mol% or less, and particularly preferably 30 mol% or more and 50 mol% or less.
The type of copolymerization of the cyclic olefin copolymer (a-1) according to the present embodiment is not particularly limited, and examples thereof include random copolymers and block copolymers. In the present embodiment, random copolymers are preferably used as the cyclic olefin copolymer (a-1) in the present embodiment, since optical components excellent in optical properties such as transparency, refractive index, and birefringence and high accuracy can be obtained.
The cyclic olefin copolymer (A-1) according to the present embodiment is preferably ethylene and tetracyclo [4.4.0.1 ] 2, 5 .1 7,10 ]Random copolymers of 3-dodecene and ethylene with bicyclo [2.2.1]Random copolymers of 2-heptene, more preferably ethylene with tetracyclo [4.4.0.1 ] 2,5 .1 7,10 ]Random copolymers of 3-dodecene.
The copolymer (A-1) according to the present embodiment may be used alone or in combination of two or more.
The copolymer (A-1) according to the present embodiment can be produced by selecting appropriate conditions according to the methods of, for example, JP-A-60-168708, JP-A-61-120816, JP-A-61-115912, JP-A-61-115916, JP-A-61-271308, JP-A-61-272216, JP-A-62-252406, JP-A-62-252407 and the like.
The cyclic olefin copolymer (A-1) has a repeating unit (AA) represented by the general formula (II) and a structural unit (D) derived from a cyclic olefin having an aromatic ring, wherein the repeating unit (AA) does not contain an aromatic ring, and the cyclic olefin having an aromatic ring preferably contains one or more selected from the group consisting of a compound represented by the following formula (D-1), a compound represented by the following formula (D-2), and a compound represented by the following formula (D-3).
[ 16]
In the above (D-1), n and q are each independently 0, 1 or 2.R is R 1 ～R 17 Each independently is a hydrogen atom, a halogen atom other than fluorine atom, or a hydrocarbon group of 1 to 20 carbon atoms which may be substituted with a halogen atom other than fluorine atom, R 10 ～R 17 One of which is a bond. When q=0, R 10 And R is R 11 、R 11 And R is R 12 、R 12 And R is R 13 、R 13 And R is R 14 、R 14 And R is R 15 、R 15 And R is R 10 May combine with each other to form a single ring or multiple rings. In addition, R when q=1 or 2 10 And R is R 11 、R 11 And R is R 17 、R 17 And R is R 17 、R 17 And R is R 12 、R 12 And R is R 13 、R 13 And R is R 14 、R 14 And R is R 15 、R 15 And R is R 16 、R 16 And R is R 16 、R 16 And R is R 10 May be bonded to each other to form a single ring or multiple rings, and the single ring or multiple rings may have a double bond, and may be aromatic rings.
[ chemical 17]
In the above formula (D-2), n and m are each independently 0, 1 or 2, and q is 1, 2 or 3.R is R 18 ～R 31 Each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom. In addition, R when q=1 28 And R is R 29 、R 29 And R is R 30 、R 30 And R is R 31 May combine with each other to form a single ring or multiple rings. In addition, when q=2 or 3, R 28 And R is R 28 、R 28 And R is R 29 、R 29 And R is R 30 、R 30 And R is R 31 、R 31 And R is R 31 May be bonded to each other to form a single ring or multiple rings, the single ring or multiple rings may have a double bond, and the single ring or multiple rings may be aromatic rings.
[ chemical 18]
In the above formula (D-3), q is 1, 2 or 3, R 32 ～R 39 Each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom. In addition, R when q=1 36 And R is R 37 、R 37 And R is R 38 、R 38 And R is R 39 May combine with each other to form a single ring or multiple rings. In addition, R when q=2 or 3 36 And R is R 36 、R 36 And R is R 37 、R 37 And R is R 38 、R 38 And R is R 39 、R 39 And R is R 39 Can combine with each other to form a single ring or multiple rings, the single ringOr the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring may be an aromatic ring.
The hydrocarbon groups having 1 to 20 carbon atoms of (D-1) to (D-3) are, for example, independently of each other, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. More specifically, as the alkyl group, methyl, ethyl, propyl, isopropyl, pentyl, hexyl, octyl, decyl, dodecyl, octadecyl, and the like are exemplified. Examples of cycloalkyl groups include cyclohexyl groups and the like. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl, tolyl, naphthyl, benzyl and phenylethyl, and aralkyl groups. These hydrocarbon groups may be substituted with halogen atoms other than fluorine atoms.
In the case of the cyclic olefin copolymer (A-1), the occurrence of haze before and after the wet heat resistance test can be further suppressed. In addition, contamination of the inside of the mold due to continuous molding can be further suppressed.
When the total structural unit of the cyclic olefin copolymer (a-1) according to the present embodiment is 100 mol%, the content of the repeating unit (AA) represented by the general formula (II) and the structural unit (D) derived from the cyclic olefin having an aromatic ring is preferably 5 mol% or more and 95 mol% or less, more preferably 10 mol% or more and 90 mol% or less, still more preferably 20 mol% or more and 80 mol% or less, still more preferably 30 mol% or more and 80 mol% or less, still more preferably 40 mol% or more and 78 mol% or less.
In the present embodiment, the content of the repeating unit (AA) and the structural unit (D) can be determined, for example 1 H-NMR or 13 C-NMR.
(Ring-opened Polymer of cyclic olefin (A-2))
The cyclic olefin polymer (A) may be a ring-opened polymer (A-2) of a cyclic olefin.
Examples of the ring-opening polymer (A-2) of the cyclic olefin include ring-opening polymers of norbornene monomers, ring-opening polymers of norbornene monomers and other monomers capable of ring-opening copolymerization with the norbornene monomers, and hydrides thereof.
Examples of the norbornene monomer include bicyclo [2.2.1 ]]Hept-2-ene (conventional name: norbornene) and its derivatives (derivatives having substituents on the ring), tricyclo [4.3.0 1,6 .1 2,5 ]Decyl-3, 7-diene (dicyclopentadiene) and its derivatives, 7, 8-benzotricyclo [4.3.0.1 ] 2,5 ]Dec-3-ene (also known as 1, 4-methylene-1, 4a,9 a-tetrahydrofluorene and derivatives thereof, tetracyclo [ 4.4.0.1) 2,5 .1 7,10 ]3-dodecene (conventional name: tetracyclododecene), derivatives thereof, and the like.
Examples of the substituent substituted on the ring of these derivatives include an alkyl group, an alkylene group, a vinyl group, an alkoxycarbonyl group, and an alkylidene group. It should be noted that the substituent may have 1 or 2 or more substituents. Examples of the derivative having a substituent on the ring include 8-methoxycarbonyl-tetracyclo [4.4.0.1 ] 2,5 .1 7,10 ]Dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ] 2,5 .1 7,10 ]Dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ] 2,5 .1 7,10 ]Dodec-3-ene and the like.
These norbornene-based monomers may be used each alone or in combination of two or more.
The ring-opened polymer of the norbornene-based monomer, or the ring-opened polymer of the norbornene-based monomer and another monomer that can be ring-opened copolymerized with the norbornene-based monomer can be obtained by polymerizing a monomer component in the presence of a known ring-opening polymerization catalyst.
As the ring-opening polymerization catalyst, for example, a catalyst composed of a halide, nitrate, or acetylacetonate of a metal such as ruthenium or osmium, and a reducing agent can be used; catalysts comprising a halide of a metal such as titanium, zirconium, tungsten or molybdenum, an acetylacetone compound, or an organoaluminum compound.
Examples of the other monomer that can be ring-opened-copolymerized with the norbornene monomer include monocyclic cyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.
The hydrogenated product of the ring-opened polymer of the norbornene-based monomer, the hydrogenated product of the ring-opened polymer of the norbornene-based monomer and another monomer capable of ring-opening copolymerization with the norbornene-based monomer can be obtained by adding a known hydrogenation catalyst containing a transition metal such as nickel or palladium to a polymerization solution of the ring-opened polymer, and hydrogenating a carbon-carbon unsaturated bond.
The ring-opened polymer (A-2) of a cyclic olefin according to the present embodiment can be produced by selecting appropriate conditions according to the methods of JP-A-60-26024, JP-A-9-268250, JP-A-63-145324, JP-A-2001-72839, etc.
The ring-opening polymer (A-2) of the cyclic olefin according to the present embodiment may be used alone or in combination of two or more.
The content of the cyclic olefin copolymer (a) according to the present embodiment is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less, and still more preferably 95% by mass or more and 99% by mass or less in the resin composition.
The glass transition temperature (Tg) of the cyclic olefin copolymer (a) according to the present embodiment is preferably in the range of 130 ℃ to 170 ℃. When the glass transition temperature (Tg) of the cyclic olefin copolymer (a) is in the above range, a sufficient heat resistance can be obtained and good moldability can be obtained when the copolymer is used as an optical member requiring heat resistance such as a car-mounted camera lens or a camera lens for a portable device.
The glass transition temperature (Tg) of the cyclic olefin copolymer (a) according to the present embodiment can be measured using a Differential Scanning Calorimeter (DSC). For example, RDC220 manufactured by SII nanotechnology is heated from normal temperature to 200℃at a heating rate of 10℃per minute under a nitrogen atmosphere, then kept for 5 minutes, and then cooled to 30℃at a cooling rate of 10℃per minute, then kept for 5 minutes, and then heated to 200℃at a heating rate of 10℃per minute, and the glass transition temperature is measured.
[ Di-ester Compound of triglycerin and fatty acid (B) ]
The diester compound (B) according to the present embodiment is a diester compound of triglycerol and a fatty acid. The molecular weight of the diester compound (B) is preferably 300 to 2000, more preferably 400 to 1500, still more preferably 500 to 1000, still more preferably 700 to 900, as long as the diester compound is composed of triglycerol and a fatty acid.
Here, when the diester compound (B) includes two or more types of diester compounds, the molecular weight of the diester compound (B) refers to the molecular weight of the diester compound (B) having the largest content (hereinafter, "largest content" will also be referred to as "main component").
In this case, as long as the diester compound (B) of triglycerol and fatty acid is contained as the main component, a mixture of a monoester compound of triglycerol and fatty acid and a triester compound of triglycerol and fatty acid, that is, an ester compound of triglycerol and fatty acid may be used.
As an example of such a compound (B), at least one selected from the group consisting of triglycerol dioleate and triglycerol distearate is preferable, and triglycerol dioleate is more preferable.
[ monoester Compound of diglycerol with fatty acid or monoester Compound (C) of glycerol with fatty acid ]
The monoester compound (C) according to the present embodiment is a monoester compound of diglycerol and a fatty acid or a monoester compound of glycerol and a fatty acid. The molecular weight of the monoester compound (C) is lower than that of the diester compound (B), and is typically 70% or less, more preferably 65% or less, and still more preferably 60% or less of the diester compound (B).
The specific range of the molecular weight is preferably 100 to 500, more preferably 200 to 480, and even more preferably 300 to 450.
Here, in the case where the monoester compound (C) contains two or more monoester compounds, the molecular weight of the monoester compound (C) refers to the molecular weight of the monoester compound (C) of the main component.
The total amount of the diester compound (B) and the monoester compound (C) is 0.10 to 3 parts by mass, more preferably 0.15 to 2.5 parts by mass, still more preferably 0.18 to 2 parts by mass, still more preferably 0.20 to 1.5 parts by mass, still more preferably 0.25 to 1.2 parts by mass, still more preferably 0.30 to 1.0 part by mass, and still more preferably 0.35 to 0.80 parts by mass, based on 100 parts by mass of the cyclic olefin polymer (a). When the range is set to this range, both the generation of microcracks and the generation of mold contamination can be suppressed.
The mass ratio of the diester compound (B) to the monoester compound (C) is not particularly limited, but is preferably a diester compound (B): monoester compound (C) =1:4 to 4:1, more preferably a diester compound (B): monoester compound (C) =1:3 to 3:1, and still more preferably a diester compound (B): monoester compound (C) =1:2.5 to 2.5:1.
The content of the diester compound (B) in the cycloolefin resin composition according to the present embodiment is preferably 0.01 to 1.5 parts by mass, more preferably 0.05 to 1.0 part by mass, still more preferably 0.08 to 0.80 parts by mass, still more preferably 0.10 to 0.60 parts by mass, still more preferably 0.10 to 0.40 parts by mass, and still more preferably 0.10 to 0.30 parts by mass, based on 100 parts by mass of the cycloolefin polymer (a).
The content of the triglycerol and fatty acid ester compound (the mixture of the triglycerol and fatty acid diester compound (B), the triglycerol and fatty acid monoester compound, and the triglycerol and fatty acid triester compound) in the cycloolefin resin composition according to the present embodiment is preferably 0.05 to 2.5 parts by mass, more preferably 0.10 to 2.0 parts by mass, still more preferably 0.15 to 1.5 parts by mass, still more preferably 0.20 to 1.0 part by mass, and still more preferably 0.25 to 0.80 parts by mass, based on 100 parts by mass of the cycloolefin polymer (a).
The content of the monoester compound (C) in the cycloolefin resin composition according to the present embodiment is preferably 0.05 parts by mass or more and 2.0 parts by mass or less, more preferably 0.10 parts by mass or more and 1.5 parts by mass or less, still more preferably 0.15 parts by mass or more and 1.0 part by mass or less, still more preferably 0.20 parts by mass or more and 0.80 parts by mass or less, still more preferably 0.20 parts by mass or more and 0.60 parts by mass or less, still more preferably 0.25 parts by mass or more and 0.55 parts by mass or less, based on 100 parts by mass of the cycloolefin polymer (a).
By using the above-mentioned diester compound (B) and the glycerin or the monoglyceride compound (C) of diglycerin and a fatty acid having a molecular weight lower than that of the above-mentioned diester compound (B) in combination, both the generation of microcracks and the mold contamination can be suppressed at the same time.
This is because the monoester compound (C) has a lower molecular weight than the diester compound (B), and thus the monoester compound (C) has a higher volatility than the diester compound (B).
Specific examples of the monoester compound (C) include, but are not limited to, at least one selected from the group consisting of diglycerol monooleate and glycerol monostearate.
When the total amount of the cycloolefin resin composition is 100% by mass, the total amount of the cycloolefin polymer (a), the diester compound (B), and the monoester compound (C) in the cycloolefin resin composition is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more. By setting the lower limit value to be equal to or larger than the above, the optical performance can be further improved.
The upper limit of the total content is not particularly limited, but is preferably 100% by mass or less, and more preferably 98% by mass or less.
[ other Components ]
The cycloolefin resin composition according to the present embodiment may contain, if necessary, a weather-resistant stabilizer, a heat-resistant stabilizer, an antioxidant, a metal deactivator, a hydrochloric acid absorber, an antistatic agent, a flame retardant, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a natural oil, a synthetic oil, a wax, an organic or inorganic filler, and the like in a proper amount within the range that does not impair the object of the present embodiment.
The cycloolefin resin composition according to the present embodiment can be preferably formed into a molded body. The method for molding the cycloolefin resin composition to obtain the molded article is not particularly limited, and a known method can be used. Depending on the use and shape thereof, for example, extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, compression molding, vacuum molding, powder slush molding, calendaring molding, foaming molding, and the like can be applied. Among them, the injection molding method is preferable from the viewpoints of moldability and productivity. The molding conditions are appropriately selected depending on the purpose of use or the molding method, and the resin temperature at the time of injection molding is usually in the range of 150 to 400 ℃, preferably 200 to 350 ℃, more preferably 230 to 330 ℃.
The cycloolefin resin composition according to the present embodiment can be obtained, for example, by the following method: a method of melt-kneading the cyclic olefin polymer (a) and other components added as needed by using a known kneading apparatus such as an extruder or a banbury mixer; a method in which the cyclic olefin polymer (A) and other components added as needed are dissolved in a common solvent, and then the solvent is evaporated; and a method in which a solution of the cyclic olefin polymer (A) and other components added as needed is added to a poor solvent to precipitate the polymer. The diester compound (B) and the monoester compound (C) may be added before or during kneading when they are melt-kneaded in a kneading apparatus such as an extruder or a banbury mixer.
Next, the obtained molded article is annealed at a temperature ranging from (the glass transition temperature (Tg) of the cyclic olefin polymer (A) to 40) DEG C to (the glass transition temperature (Tg) of the cyclic olefin polymer (A) to 5) DEG C for 2 to 8 hours, for example, to obtain an optical member. By performing the annealing treatment, molecules of the cyclic olefin polymer (a) in the molded article relax, and the free volume decreases. Therefore, even when the heat treatment is performed, a change in specific gravity (change in volume) is less likely to occur.
Here, if the annealing treatment is performed under severe conditions, the molded article is deformed and cannot be recovered, and therefore, it is preferable to perform the annealing treatment under the above conditions within a range where the molded article is not deformed. That is, the annealing treatment is preferably performed at a temperature and for a time period such that deformation of the molded article is not caused.
The optical member obtained as described above was excellent in wet heat resistance. Therefore, the increase in internal haze before and after the wet heat resistance test can be suppressed, and the composition can be suitably used mainly for optical applications and lenses. In addition, since transparency can be maintained before and after the wet heat resistance test, the film can be suitably used for applications requiring transparency.
While the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.
The present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within a range that can achieve the object of the present invention are also included in the present invention.
Examples
Hereinafter, the present embodiment will be described in detail with reference to examples and the like. The present embodiment is not limited to the description of these examples.
Example 1
Polymerization of Cyclic olefin copolymer (A-1)
(preparation of catalyst)
VO (OC) was purified by cyclohexane 2 H 5 )Cl 2 Diluting to prepare a cyclohexane solution of the vanadium catalyst with the vanadium concentration of 6.7 mmol/L. Ethyl aluminum sesquichloride (Al (C) 2 H 5 ) 1.5 Cl 1.5 ) Diluted to prepare a cyclohexane solution of the organoaluminum compound catalyst having an aluminum concentration of 107 mmol/L.
(polymerization)
Ethylene and tetracyclo [4.4.0.1 ] were continuously conducted using a stirred polymerizer (inner diameter 500mm, reaction volume 100L) 2,5 .1 7,10 ]Copolymerization of 3-dodecene. Cyclohexane was used as the polymerization solvent. In progressIn this polymerization reaction, the cyclohexane solution of the vanadium catalyst prepared by the above method was fed into the polymerizer so that the vanadium catalyst concentration relative to the cyclohexane in the polymerizer became 0.6 mmol/L.
Further, ethyl aluminum sesquichloride as an organoaluminum compound was fed into the polymerizer so that the mass ratio of aluminum to vanadium (Al/V) became 18.0. The polymerization temperature was set at 8℃and the polymerization pressure was set at 1.8kg/cm 2 G continuously carrying out copolymerization reaction to obtain ethylene and tetracyclic [4.4.0.1 ] 2,5 .1 7,10 ]Copolymers of 3-dodecene (ethylene-tetracyclo [4.4.0.1 ] 2, 5 .1 7,10 ]-3-dodecene copolymer).
(deashing)
In the ethylene-tetracyclo [4.4.0.1 ] withdrawn from the polymerizer 2,5 .1 7,10 ]The polymerization was stopped by adding water and 25% by mass NaOH solution as a pH adjuster to the 3-dodecene copolymer solution. In addition, will be present in ethylene-tetracyclic [4.4.0.1 ] 2,5 .1 7,10 ]The catalyst residues in the 3-dodecene copolymer are removed (deashing) to give a polymer solution A.
Ethylene-tetracyclo [4.4.0.1 ] after the above-mentioned deashing treatment 2,5 .1 7,10 ]To a cyclohexane solution of a 3-dodecene copolymer (polymer solution A, polymer concentration: 7.7 mass%) was added pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer so that the amount of the stabilizer was 0.4 parts by mass based on 100 parts by mass of the copolymer]After that, the effective capacity of 1.0cm is used for the moment 3 Is mixed for 1 hour in the stirring tank.
(desolventizing)
At the time of using 20kg/cm 2 In a double tube humidifier (outer tube diameter 2B, inner tube diameter 3/4B, length 21 m) in which G steam was used as a heat source, a cyclohexane solution of the copolymer having a concentration of 5% by mass was supplied in an amount of 150kg/H and heated to 180 ℃.
By using 25kg/cm 2 G double tube flash dryer (outer tube diameter 2B, inner tube diameter 3/4B, length 27 m) and flash hopper (volume 200L)) Cyclohexane as a polymerization solvent is removed from the cyclohexane solution of the copolymer having undergone the above heating step together with most of the unreacted monomers, thereby obtaining a cyclic olefin random copolymer (resin a) in a molten state after flash drying. The glass transition temperature (Tg) of the resin a measured by a differential scanning calorimeter was 161 ℃.
< ester Compound of triglycerin and fatty acid >
(B-1): a triglycerol fatty acid ester compound comprising 40 mass% of triglycerol dioleate (molecular weight 769, triglycerol and fatty acid diester compound (B)), 20 mass% of a triglycerol and fatty acid monoester compound, 36 mass% of a triglycerol and fatty acid triester compound, and 4 mass% of triglycerol as a main component was used.
< ester Compound of diglycerol with fatty acid or ester Compound of glycerol with fatty acid >
(C-1): a glycerin fatty acid ester compound containing 99% by mass of glycerin monostearate (molecular weight 359, a monoester compound (C) of glycerin and fatty acid) as a main component, and 1% by mass of a diester compound of glycerin and fatty acid was used.
(C-2): a diglycerol fatty acid ester compound containing 87 mass% of diglycerol monooleate (molecular weight 430, a diglycerol and fatty acid monoester compound (C)), 8 mass% of a diglycerol and fatty acid diester compound, and 5 mass% of diglycerol as a main component was used.
Ester compound (D) of diglycerol and fatty acid having molecular weight of more than 70% of the above compound (B)
A diglycerol fatty acid ester compound containing 45 mass% of diglycerol dioleate (molecular weight 695, a diglycerol and fatty acid diester compound), 33 mass% of a diglycerol and fatty acid monoester compound, and 22 mass% of a diglycerol and fatty acid triester compound as main components was used.
(extrusion)
After the molten resin a was charged from the resin charging section of the extruder using a twin-screw kneading extruder with a vent, for the purpose of removing volatiles, the molten resin a was sucked from the vent section via a cold hydrazine (trap) by a vacuum pump, and 0.70 parts by mass of a triglycerin fatty acid ester compound (B-1) (wherein the amount of the triglycerin fatty acid diester compound (B) was 0.28 parts by mass) relative to 100 parts by mass of the resin a and 0.50 parts by mass of a glycerin fatty acid ester compound (C-1) (wherein the amount of the glycerin fatty acid monoester compound (C) was 0.495 parts by mass) were added to the barrel section on the downstream side of the vent section, and kneaded on the downstream side of the extruder. At this time, the conditions of the extruder were adjusted so that the difference between the maximum value and the minimum value of the resin temperature of the extruder splitter portion was 3℃or less.
Then, the kneaded product was pelletized by a water immersion pelletizer (underwater pelletizer) attached to the outlet of the extruder, and the obtained pellets were dried with hot air at 100℃for 4 hours.
Further, a resin of about 3 to 5 times the amount of the resin calculated from the average residence time in the polymerizer was flowed into the polymerizer to be washed, and then a sample was collected to obtain a resin composition containing a resin A. In order to suppress the mixing of iron atoms (Fe), stainless steel piping and polymerizers are used in polymer production equipment.
Example 2
A resin composition was produced in the same manner as in example 1, except that 0.32 parts by mass of the triglycerol fatty acid ester compound (B-1) (in which the amount of the triglycerol and fatty acid diester compound (B) was 0.13 parts by mass) and the glycerol fatty acid ester compound (C-1) per 100 parts by mass of the resin a were replaced with 0.32 parts by mass of the diglycerol fatty acid ester compound (C-2) (in which the amount of the diglycerol and fatty acid monoester compound (C) was 0.28 parts by mass) per 100 parts by mass of the resin a.
Comparative example 1
A resin composition was produced in the same manner as in example 1, except that the glycerin fatty acid ester compound (C-1) was not added.
Comparative example 2
A resin composition was produced in the same manner as in example 1, except that 0.32 parts by mass of the triglycerol fatty acid ester compound (B-1) in which the amount of the triglycerol and fatty acid diester compound (B) was 0.13 parts by mass, and the glycerol fatty acid ester compound (C-1) per 100 parts by mass of the resin a were replaced with 0.32 parts by mass of the diglycerol and fatty acid ester compound (D) in which the amount of the diglycerol and fatty acid diester compound was 0.14 parts by mass.
Comparative example 3
A resin composition was produced in the same manner as in example 1, except that 3.0 parts by mass of a triglycerol fatty acid ester compound (B-1) in which the amount of the triglycerol and fatty acid diester compound (B) was 1.2 parts by mass, and 3.5 parts by mass of a glycerol fatty acid ester compound (C-1) in which the amount of the glycerol and fatty acid monoester compound (C) was 3.47 parts by mass, relative to 100 parts by mass of the resin a, were added.
Comparative example 4
A resin composition was produced in the same manner as in example 1, except that 0.05 parts by mass of a triglycerol fatty acid ester compound (B-1) in which the amount of the triglycerol and fatty acid diester compound (B) was 0.02 parts by mass, and 0.03 parts by mass of a glycerol fatty acid ester compound (C-1) in which the amount of the glycerol and fatty acid monoester compound (C) was 0.297 parts by mass, relative to 100 parts by mass of the resin a, were added.
< evaluation >
(internal haze)
The obtained resin composition was injection molded at a cylinder temperature of 275℃and a mold temperature of 120℃by using an injection molding machine (ROBOSHOT S2000i-30α, manufactured by FANUC Co., ltd.) to form a 35mm X65 mm X3 mm thick test piece having an optical surface.
The internal haze of the test piece was measured by using benzyl alcohol according to JIS K-7136, and evaluated according to the following criteria.
0.5% or less: excellent (L.) Excellent
More than 0.5% and 1.0% below: (V)
Exceeding 1.0%: x-shaped glass tube
(moist heat resistance)
The test piece produced in the measurement of the internal haze was left to stand for 48 hours at a temperature of 85℃under an atmosphere having a relative humidity of 85%. Then, the mixture was taken out to an atmosphere having a temperature of 23℃and a relative humidity of 50%, and after 48 hours, the internal haze was measured.
The amount of change in the internal haze after the damp heat resistance test (hereinafter, Δ is the internal haze) was measured and evaluated based on the following criteria.
0.5% or less: excellent (L.) Excellent
More than 0.5% and 1.0% below: (V)
Exceeding 1.0%: x-shaped glass tube
(mold contamination)
The resin compositions obtained in examples 1 and 2 and comparative example 1 were continuously injection molded at a barrel temperature of 285℃and a mold temperature of 122℃using a mold and an injection molding machine (ROBOSHOT. Alpha. 30iA manufactured by FANUC Co.) for forming a flat lens having a lens portion diameter of 6.0mm and a lens portion thickness of 0.5mm, and evaluated for the number of molding times (Shot number) when fouling occurred on the lens surface, based on the following criteria.
Over 12000 times: excellent (L.) Excellent
More than 10000 times and 12000 times below: (V)
10000 times below: x-shaped glass tube
The evaluation was performed by microscopic observation.
TABLE 1
TABLE 2
Examples 1 and 2 have low internal haze, and can suppress the occurrence of internal haze before and after the heat and humidity resistance test, and can suppress the occurrence of microcracks. Further, in examples 1 and 2, mold contamination can be reduced as compared with comparative example 1.
In examples 1 and 2, the internal haze was lower than that of comparative examples 2 to 4, or the internal haze before and after the wet heat resistance test was suppressed, and the generation of microcracks was suppressed.
The present application claims priority based on japanese patent application No. 2021-048392 filed on 3/23 of 2021, the entire disclosure of which is incorporated herein by reference.
Claims (8)
1. A cycloolefin resin composition comprising:
a cyclic olefin polymer (A),
A diester compound (B) of triglycerin and a fatty acid, and
a compound (C) which is a monoester compound of diglycerol and a fatty acid or a monoester compound of glycerol and a fatty acid and has a molecular weight of 70% or less of the compound (B),
the total amount of the compound (B) and the compound (C) is 0.10 to 3 parts by mass based on 100 parts by mass of the cyclic olefin polymer (A).
2. The cycloolefin resin composition according to claim 1,
the cyclic olefin polymer (A) contains at least one selected from the group consisting of a cyclic olefin copolymer (A-1) and a ring-opened polymer (A-2) of a cyclic olefin.
3. The cycloolefin resin composition according to claim 2,
the cyclic olefin polymer (A) comprises the copolymer (A-1),
the cyclic olefin copolymer (A-1) has a structural unit (a) and a structural unit (b),
structural unit (a): at least one structural unit derived from an olefin represented by the following general formula (I),
structural unit (b): one or more cyclic olefin-derived structural units selected from the group consisting of a repeating unit (AA) represented by the following general formula (II), a repeating unit (AB) represented by the following general formula (III), and a repeating unit (AC) represented by the following general formula (IV),
[ chemical 1]
In the general formula (I), R 300 Represents a hydrogen atom or a straight or branched hydrocarbon group having 1 to 29 carbon atoms,
[ chemical 2]
In the general formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R 61 ～R 78 R is as follows a1 And R is b1 May be the same or different from each other, and is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 75 ～R 78 Can be combined with each other to form a single ring or multiple rings,
[ chemical 3]
In the general formula (III), x and d are each independently an integer of 0 or more than 1, y and z are each independently an integer of 0 to 2, R 81 ～R 99 May be the same or different from each other, and is a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms or an alkoxy group, R 89 And R is 90 Bound carbon atoms to R 93 To carbon atoms or R 91 The bonded carbon atoms may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y=z=0, R 92 And R is R 95 Or R is 95 And R is R 99 Can be combined with each other to formA monocyclic or polycyclic aromatic ring,
[ chemical 4]
In the general formula (IV), R 100 、R 101 And each of them may be the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1.ltoreq.f.ltoreq.18.
4. The cycloolefin resin composition according to claim 3,
the cyclic olefin copolymer (A-1) has a repeating unit (AA) represented by the general formula (II) and a structural unit (D) derived from a cyclic olefin having an aromatic ring, the repeating unit (AA) does not contain an aromatic ring,
the cyclic olefin having an aromatic ring contains one or more selected from the group consisting of a compound represented by the general formula (D-1), a compound represented by the general formula (D-2), and a compound represented by the general formula (D-3),
[ chemical 5]
In the general formula (D-1), n and q are each independently 0, 1 or 2, R 1 ～R 17 Each independently is a hydrogen atom, a halogen atom other than fluorine atom, or a hydrocarbon group of 1 to 20 carbon atoms which may be substituted with a halogen atom other than fluorine atom, R 10 ～R 17 One of them is a bond, and when q=0, R 10 And R is R 11 、R 11 And R is R 12 、R 12 And R is R 13 、R 13 And R is R 14 、R 14 And R is R 15 、R 15 And R is R 10 Can combine with each other to form a single ring or multiple rings, and in addition, when q=1 or 2, R 10 And R is R 11 、R 11 And R is R 17 、R 17 And R is R 12 、R 12 And R is R 13 、R 13 And R is R 14 、R 14 And R is R 15 、R 15 And R is R 16 、R 16 And R is R 16 、R 17 And R is R 17 、R 16 And R is R 10 May be combined with each other to form a single ring or a plurality of rings, and further the single ring or the plurality of rings may have a double bond, the single ring or the plurality of rings may be aromatic rings,
[ chemical 6]
In the general formula (D-2), n and m are each independently 0, 1 or 2, q is 1, 2 or 3, R 18 ～R 31 Each independently represents a hydrogen atom, a halogen atom other than fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than fluorine atom, and when q=1, R 28 And R is R 29 、R 29 And R is R 30 、R 30 And R is R 31 Can combine with each other to form a single ring or multiple rings, and R is additionally q=2 or 3 28 And R is R 28 、R 28 And R is R 29 、R 29 And R is R 30 、R 30 And R is R 31 、R 31 And R is R 31 Can combine with each other to form a single ring or a plurality of rings, the single ring or the plurality of rings can have a double bond, and further the single ring or the plurality of rings can be aromatic rings,
[ chemical 7]
In the general formula (D-3), q is 1, 2 or 3, R 32 ～R 39 Each independently represents a hydrogen atom, a halogen atom other than fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than fluorine atom, and R is represented by q=1 36 And R is R 37 、R 37 And R is R 38 、R 38 And R is R 39 Can be combined with each other to form a single ring or multiple ringsRing, in addition, R when q=2 or 3 36 And R is R 36 、R 36 And R is R 37 、R 37 And R is R 38 、R 38 And R is R 39 、R 39 And R is R 39 May be combined with each other to form a single ring or multiple rings, the single ring or the multiple rings may have a double bond, and further the single ring or the multiple rings may be aromatic rings.
5. The cycloolefin resin composition according to any one of claims 1 to 4,
the molecular weight of the compound (B) is 300-2000.
6. The cycloolefin resin composition according to any one of claims 1 to 5,
the glass transition temperature of the cyclic olefin polymer (A) is 130 ℃ to 170 ℃ as measured by a differential scanning calorimeter DSC.
7. A molded article comprising the cycloolefin resin composition according to any one of claims 1 to 6.
8. The molded article according to claim 7, which is an optical member.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021048392 | 2021-03-23 | ||
| JP2021-048392 | 2021-03-23 | ||
| PCT/JP2022/012445 WO2022202634A1 (en) | 2021-03-23 | 2022-03-17 | Cyclic olefin resin composition and molded body |
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| Publication Number | Publication Date |
|---|---|
| CN116981734A true CN116981734A (en) | 2023-10-31 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280021066.1A Pending CN116981734A (en) | 2021-03-23 | 2022-03-17 | Cyclic olefin resin composition and molded article |
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| Country | Link |
|---|---|
| JP (1) | JPWO2022202634A1 (en) |
| KR (1) | KR20230146079A (en) |
| CN (1) | CN116981734A (en) |
| TW (1) | TW202248249A (en) |
| WO (1) | WO2022202634A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6517066B2 (en) | 2014-03-31 | 2019-05-22 | 三井化学株式会社 | Resin composition and use thereof |
| WO2017033968A1 (en) | 2015-08-27 | 2017-03-02 | 日本ゼオン株式会社 | Resin composition and resin molded body |
| JP7195058B2 (en) | 2017-03-31 | 2022-12-23 | 三井化学株式会社 | Cyclic olefin resin composition, molded article and optical part |
| JP6812574B2 (en) * | 2017-11-29 | 2021-01-13 | 三井化学株式会社 | Cyclic olefin copolymer, cyclic olefin copolymer composition, molded article and medical container |
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- 2022-03-17 WO PCT/JP2022/012445 patent/WO2022202634A1/en active Application Filing
- 2022-03-17 CN CN202280021066.1A patent/CN116981734A/en active Pending
- 2022-03-17 JP JP2023509112A patent/JPWO2022202634A1/ja active Pending
- 2022-03-17 KR KR1020237031556A patent/KR20230146079A/en unknown
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| JPWO2022202634A1 (en) | 2022-09-29 |
| KR20230146079A (en) | 2023-10-18 |
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