CN116507650A - Cyclic olefin resin composition and molded article - Google Patents
Cyclic olefin resin composition and molded article Download PDFInfo
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- CN116507650A CN116507650A CN202280007708.2A CN202280007708A CN116507650A CN 116507650 A CN116507650 A CN 116507650A CN 202280007708 A CN202280007708 A CN 202280007708A CN 116507650 A CN116507650 A CN 116507650A
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- carbon atoms
- cyclic olefin
- single ring
- rings
- general formula
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- 239000011342 resin composition Substances 0.000 title claims abstract description 48
- 229920005672 polyolefin resin Polymers 0.000 title description 7
- 125000004122 cyclic group Chemical group 0.000 title description 6
- -1 ester compound Chemical class 0.000 claims abstract description 48
- 150000001925 cycloalkenes Chemical class 0.000 claims abstract description 34
- 229920001577 copolymer Polymers 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 15
- 239000000194 fatty acid Substances 0.000 claims abstract description 15
- 229930195729 fatty acid Natural products 0.000 claims abstract description 15
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 67
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 61
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims description 59
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 35
- 229920000223 polyglycerol Polymers 0.000 claims description 35
- 125000005843 halogen group Chemical group 0.000 claims description 27
- 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 21
- 125000001153 fluoro group Chemical group F* 0.000 claims description 19
- 229910052731 fluorine Inorganic materials 0.000 claims description 18
- 230000003287 optical effect Effects 0.000 claims description 17
- 150000001336 alkenes Chemical class 0.000 claims description 11
- 125000000217 alkyl group Chemical group 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
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 125000002950 monocyclic group Chemical group 0.000 claims description 4
- 125000003367 polycyclic group Chemical group 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- 238000000465 moulding Methods 0.000 description 21
- 238000011109 contamination Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- 239000000178 monomer Substances 0.000 description 16
- 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 description 15
- 150000002430 hydrocarbons Chemical group 0.000 description 14
- 229940049964 oleate Drugs 0.000 description 12
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 229920005604 random copolymer Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- JYKSTGLAIMQDRA-UHFFFAOYSA-N tetraglycerol Chemical compound OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO JYKSTGLAIMQDRA-UHFFFAOYSA-N 0.000 description 6
- WLTSXAIICPDFKI-FNORWQNLSA-N (E)-3-dodecene Chemical compound CCCCCCCC\C=C\CC WLTSXAIICPDFKI-FNORWQNLSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 238000001746 injection moulding Methods 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
- 239000000203 mixture Substances 0.000 description 4
- 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
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 150000004671 saturated fatty acids Chemical class 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 3
- 235000021122 unsaturated fatty acids Nutrition 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 125000002723 alicyclic group Chemical group 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
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-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
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 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
- 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
- OTTZHAVKAVGASB-UHFFFAOYSA-N 2-heptene Natural products CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-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
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 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
- 239000000539 dimer Substances 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
- 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
- 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003384 imaging method 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 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
- 239000003002 pH adjusting agent Substances 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
- 239000000843 powder Substances 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
- 235000003441 saturated fatty acids Nutrition 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
- 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 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing Methods 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
- 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
-
- 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
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- 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
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a cycloolefin resin composition comprising a cycloolefin copolymer (A), an ester compound (B) of a polyglycerin and a fatty acid, and a polyglycerin (C), wherein the amount of the compound (B) is 0.05 to 3 parts by mass based on 100 parts by mass of the cycloolefin copolymer (A), and the amount of the polyglycerin (C) is 0.001 to 0.04 parts by mass based on 100 parts by mass of the cycloolefin copolymer (A).
Description
Technical Field
The present invention relates to a cycloolefin resin composition and a molded article.
Background
The cyclic olefin copolymer is used for optical lenses such as an imaging lens, an fθ lens, and a pickup lens. The cyclic olefin copolymer 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 a resin composition containing such a cyclic olefin copolymer, for example, the invention described in patent document 1 is provided. Patent document 1 discloses a cycloolefin resin composition containing a cycloolefin polymer (a) and a triglycerol fatty acid ester.
Patent document 2 discloses a resin composition comprising a polymer having an alicyclic structure and a polyglycerin fatty acid ester-based additive, wherein the polyglycerin fatty acid ester-based additive is formed of 1 or 2 or more polyglycerin fatty acid ester compounds, the polyglycerin fatty acid ester-based additive has a hydroxyl value of 320 to 700mgKOH/g, and the polyglycerin fatty acid ester-based additive is contained in an amount of 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. 2018-172665
Patent document 2: international publication No. 2017/033968
Disclosure of Invention
Problems to be solved by the invention
In recent years, for example, a cyclic olefin copolymer is required to have durability under a severe wet heat resistance test such as 80 ℃ 90% rh as disclosed in patent document 1. If the cycloolefin copolymer does not contain a hydrophilizing agent such as the additive disclosed in patent document 2, there is a problem that fine cracks are generated in the cycloolefin resin at high temperature and high humidity, and the internal haze increases. On the other hand, there is a problem that compatibility with the cycloolefin resin is sometimes poor depending on the kind of the hydrophilic agent.
Further, there is a problem that the inside of the mold is contaminated when the cycloolefin resin composition is used to mold a molded body such as a lens. In particular, if the lens surface of the mold is contaminated, there is a problem in that the optical characteristics of the lens as a molded body may be degraded.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a cycloolefin resin composition that has low internal haze and can suppress contamination of the inside of a mold due to continuous molding.
Means for solving the problems
The present inventors have made intensive studies to solve the above problems. As a result, it was found that the mold was contaminated by vaporization of the hydrophilic agent, and unreacted alcohol contained as impurities in the hydrophilic agent contaminated the mold. Based on the above findings, the present inventors have further studied, and as a result, have found for the first time that a cyclic olefin copolymer resin composition having a low internal haze, capable of suppressing an increase in internal haze even under high temperature and high humidity, and capable of suppressing contamination inside a mold even when continuously molded, is obtained by containing a specific amount of polyglycerol, and have completed the present invention.
That is, according to the present invention, there are provided a cycloolefin resin composition and a molded article shown below.
[1] A cycloolefin resin composition comprising:
a cyclic olefin copolymer (A),
Ester compound (B) of polyglycerol and fatty acid
Polyglycerol (C),
the amount of the compound (B) is 0.05 to 3 parts by mass based on 100 parts by mass of the cyclic olefin copolymer (A),
the amount of the polyglycerol (C) is 0.001 parts by mass to 0.04 parts by mass based on 100 parts by mass of the cyclic olefin copolymer (a).
[2]
The cycloolefin resin composition according to [1] above,
the cyclic olefin copolymer (A) has a structural unit (a) and a structural unit (b),
structural unit (a): at least 1 structural unit derived from an olefin represented by the following general formula (I).
Structural unit (b): at least 1 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 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 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 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. In addition, when y=z=0, R 92 And R is R 99 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.
[3]
The cycloolefin resin composition according to [2] above,
the cyclic olefin polymer (A) has:
a repeating unit (AA) represented by the above 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 following formula (D-1), a compound represented by the following formula (D-2), and a compound represented by the following formula (D-3).
[ chemical 5]
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. Further, 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, 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 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 combined with each other to form a single ring or multiple rings, and further the single ring or the multiple rings may have a double bond, and the single ring or the multiple rings may be aromatic rings.
[ chemical 6]
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 is 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. Further, when q=1, R 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 combined with 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 formula (D-3), q is 1, 2 or 3, R 32 ～R 39 Each independently is 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. Further, when q=1, R 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, when q=2 or 3, R 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 multiple rings may have a double bond, and the single ring or multiple rings may be aromatic rings.
[4]
The cycloolefin resin composition according to any one of the above [1] to [3], wherein the cycloolefin copolymer (A) has a glass transition temperature of 130℃to 170℃as measured by a differential scanning calorimeter.
[5]
A molded article comprising the cycloolefin resin composition according to any one of the above [1] to [4 ].
[6]
The molded article according to [5] above, which is an optical member.
ADVANTAGEOUS EFFECTS OF INVENTION
The cycloolefin resin composition of the present invention can form a molded article having a higher wet heat resistance than conventional cycloolefin copolymers. In the case of such a molded article, the internal haze is low, and the increase in internal haze before and after the wet heat resistance test can be suppressed. Further, contamination of the inside of the mold due to continuous molding can be suppressed, and particularly contamination of the lens surface of the mold can be suppressed. Therefore, the present invention can be mainly used for optical applications and lenses.
Detailed Description
Hereinafter, embodiments according to the present invention will be described. In the embodiment, "a to B" representing the numerical range indicates a or more and B or less unless otherwise specified.
As described above, according to the knowledge of the present inventors, there is a problem that the conventional cyclic olefin copolymer and resin may have poor compatibility with the cyclic olefin resin depending on the type of the hydrophilic agent, while the internal haze and the like may occur when the resin is exposed to a high temperature and high humidity environment for a long period of time. Further, there is a problem that the inside of the mold is contaminated when the cycloolefin resin composition is used for molding into a molded article such as a lens.
The present inventors have intensively studied to solve the above problems. As a result, it has been found that a molded article obtained from a cycloolefin resin composition containing a specific amount of polyglycerol has higher wet heat resistance than a molded article obtained from a conventional cycloolefin resin composition, and contamination of the inside of a mold due to continuous molding can be suppressed, and the present invention has been completed.
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 copolymer (A),
Ester compound (B) of polyglycerol and fatty acid
Polyglycerol (C),
the amount of the compound (B) is 0.05 to 3 parts by mass based on 100 parts by mass of the cyclic olefin copolymer (A),
the amount of the polyglycerol (C) is 0.001 parts by mass to 0.04 parts by mass based on 100 parts by mass of the cyclic olefin copolymer (a).
According to the cycloolefin resin composition according to the present embodiment, contamination of the inside of the mold due to continuous molding can be suppressed, and particularly contamination of the lens surface of the mold can be suppressed. In addition, not only the inside of the mold but also contamination of the vent can be suppressed.
Further, 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, the molded article can maintain transparency before and after the heat and humidity resistance test, and thus can be suitably used for applications requiring transparency.
[ Cyclic olefin copolymer (A) ]
The cyclic olefin copolymer (a) according to the present embodiment is a copolymer having a structural unit derived from a cyclic olefin as an essential constituent unit.
Examples of the cyclic olefin copolymer (a) include a copolymer (A1) of ethylene or an α -olefin and a cyclic olefin.
The cyclic olefin compound constituting the copolymer (A1) according to the present embodiment is not particularly limited, and examples thereof include cyclic olefin monomers described in paragraphs 0037 to 0063 of international publication No. 2006/0110861.
The cyclic olefin copolymer (A1) according to the present embodiment preferably has a structural unit (a) and a structural unit (b) from the viewpoint of being able to improve heat resistance while maintaining a good balance of properties of transparency and refractive index of the obtained optical member, or being able to improve moldability.
Structural unit (a): at least 1 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 1 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. In addition, when y=z=0, R 92 And R is R 99 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 copolymer (A1) according to the present embodiment is an olefin monomer which is formed into a constituent unit represented by the above general formula (I) by addition polymerization. Specifically, an olefin monomer represented by the following general formula (Ia) corresponding to the above general formula (I) is 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 above 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 these, 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 an amount of 2 or more.
When the total of the constituent units constituting the cyclic olefin copolymer according to the present embodiment is 100 mol%, the proportion of the structural unit (a) derived from the 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.
In addition, the proportion of structural units (a) derived from olefins can be determined by 13 C-NMR.
The cyclic olefin monomer which is one of the copolymerization raw materials of the copolymer (A1) according to the present embodiment is a cyclic olefin monomer which is formed by addition polymerization of 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 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 carbon atoms to be bonded 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 99 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 above 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) in a solvent is further improved, and thus 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), those described in paragraphs 0037 to 0063 of International publication No. 2006/0110861 can be used.
Specifically, examples thereof include 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 (b) of the general formula (IIa), (IIIa) or (IVa), the cyclic olefin of the general formula (IIa) is preferred.
As the cyclic olefin monomer represented by the above 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 the advantage of easily maintaining the elastic modulus of the copolymer and the optical member.
When the total of the constituent units constituting the copolymer (A1) according to the present embodiment is 100 mol%, the proportion of the constituent unit (b) derived from the cyclic olefin monomer 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 copolymerization type of the copolymer (A1) according to the present embodiment is not particularly limited, and examples thereof include random copolymers and block copolymers. In this embodiment, since an optical member excellent in optical properties such as transparency, refractive index, and birefringence and having high accuracy can be obtained, a random copolymer is preferably used as the copolymer (A1) according to this embodiment.
As the copolymer (A1) according to the present embodiment, ethylene and tetracyclo [4.4.0.1 ] are preferable 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 (A1) according to the present embodiment may be used alone or in combination of 1 or 2 or more.
The copolymer (A1) according to the present embodiment can be produced by, for example, the methods described in Japanese patent application laid-open No. 60-168708, japanese patent application laid-open No. 61-120816, japanese patent application laid-open No. 61-115912, japanese patent application laid-open No. 61-115916, japanese patent application laid-open No. 61-271308, japanese patent application laid-open No. 61-272216, japanese patent application laid-open No. 62-252406, japanese patent application laid-open No. 62-252407, and the like, and by selecting appropriate conditions.
In this embodiment, the cyclic olefin copolymer (A) preferably 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, and the cyclic olefin having an aromatic ring 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. Further, 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, 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 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 combined with each other to form a single ring or multiple rings, and further the single ring or the multiple rings may have a double bond, and the single ring or the multiple rings 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 is 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. Further, when q=1, R 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 combined with 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 is 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. Further, when q=1, R 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, when q=2 or 3, R 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 multiple rings may have a double bond, and the single ring or multiple rings may be aromatic rings.
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, or an aromatic hydrocarbon group. More specifically, examples of the alkyl group include methyl, ethyl, propyl, isopropyl, pentyl, hexyl, octyl, decyl, dodecyl, and octadecyl. 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), the occurrence of haze before and after the wet heat resistance test can be further suppressed. Further, contamination of the inside of the mold due to continuous molding can be further suppressed.
The total 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 in the cyclic olefin copolymer (a) according to the present embodiment 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, and still more preferably 40 mol% or more and 78 mol% or less, based on 100 mol% of the total structural units.
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 was performed.
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 an in-vehicle 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 used, and the glass transition temperature is measured when the temperature is raised from normal temperature to 200℃at a temperature-raising rate of 10℃per minute in a nitrogen atmosphere, then kept for 5 minutes, then cooled to 30℃at a temperature-lowering rate of 10℃per minute, then kept for 5 minutes, and then raised to 200℃at a temperature-raising rate of 10℃per minute.
[ ester Compound (B) of polyglycerol and fatty acid ]
The ester compound (B) according to the present embodiment is an ester compound of a polyglycerin and a fatty acid, and is an ester of a polyglycerin having 8 to 24 carbon atoms and a saturated or unsaturated fatty acid having a dimer or more. The ester compound (B) is preferably an ester of triglycerin as a trimer with a saturated or unsaturated fatty acid having 8 to 24 carbon atoms.
The cyclic olefin resin composition according to the present embodiment contains the ester compound (B), so that the cyclic olefin resin can suppress the generation of fine cracks and can suppress the increase of internal haze even under high temperature and high humidity conditions.
Examples of esters of such polyglycerols with saturated or unsaturated fatty acids include triglycerol oleate, tetraglycerol oleate, and polyglycerol oleate.
The content of the ester compound (B) in the cycloolefin resin composition according to the present embodiment is generally 0.05 parts by mass or more and 3 parts by mass or less, preferably 0.5 parts by mass or more and 2 parts by mass or less, and more preferably 0.8 parts by mass or more and 1.5 parts by mass or less, based on 100 parts by mass of the cycloolefin copolymer (a).
If the content of the ester compound (B) is not less than the above lower limit, the amount of change in the internal haze before and after the wet heat resistance test can be suppressed. If the upper limit is less than or equal to the above, the internal haze before the wet heat resistance test can be suppressed.
[ polyglycerol (C) ]
The cycloolefin resin composition according to the present embodiment contains a specific amount of polyglycerol (C). This can suppress mold contamination during continuous molding caused by vaporization of alcohol contained as an impurity in the hydrophilic agent.
Examples of the polyglycerol (C) include diglycerol, triglycerol, tetraglycerol, and the like, but are not limited thereto. The polyglycerin may be used alone in an amount of 1 kind or in an amount of 2 or more kinds.
The content of the polyglycerol (C) is 0.001 to 0.04 parts by mass, preferably 0.001 to 0.03 parts by mass, and more preferably 0.01 to 0.015 parts by mass, based on 100 parts by mass of the cyclic olefin copolymer (a).
If the polyglycerin (C) is in the above range, the amount of change in the internal haze can be reduced even before and after a wet heat resistance test (for example, 95% rh1008 hours at 85 ℃) which is more severe than the conventional wet heat resistance test. Further, contamination inside the mold can be suppressed at the time of continuous molding of the molded body.
The adjustment of the content of the polyglycerol (C) may be performed by, for example, adding and adjusting the cycloolefin resin composition in the preparation of the cycloolefin resin composition. As another embodiment, a method of adjusting the content by adding polyglycerol in an amount that does not react with the ester compound (B) at the time of preparing the hydrophilic agent can be exemplified. The method of adjusting the content of the polyglycerol (C) according to the present embodiment is not particularly limited if the content is within the above-mentioned range.
(other Components)
The cycloolefin resin according to the present embodiment can be blended with a weather resistant stabilizer, a heat resistant stabilizer, an antioxidant, a metal deactivator, a hydrochloric acid absorber, an antistatic agent, a flame retardant, a sliding 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 as required within a 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 a molded article is not particularly limited, and a known method can be used. Although also depending on the use and shape thereof, for example, extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendaring molding, foaming molding, and the like can be applied. Among these, injection molding is preferable from the viewpoints of moldability and productivity. The molding conditions may be appropriately selected depending on the purpose of use or the molding method, and for example, the resin temperature in injection molding is generally 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 by, for example, the following method: a method of melt-kneading the cyclic olefin copolymer (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 copolymer (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 copolymer (A) and other components, if necessary, is added to a poor solvent to precipitate them.
Then, the obtained molded article is annealed, for example, in the range of (glass transition temperature (Tg) of the cyclic olefin copolymer (A) -40) DEG C to (glass transition temperature (Tg) of the cyclic olefin copolymer (A) -5) DEG C for 2 to 8 hours, whereby an optical member can be obtained. By performing the annealing treatment, molecules of the cyclic olefin copolymer (a) in the molded article are relaxed, and the free volume is reduced. 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 conditions are made severe, the molded article is deformed and cannot be reduced, so that it is preferable to perform the annealing under the above conditions within a range where the molded article is not deformed. That is, the annealing treatment is preferably performed at such a temperature and for such a time that the molded article is not deformed.
The optical member obtained in the above manner is 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. Further, 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, they are illustrative 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 in which the object of the present invention can be achieved 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)
(preparation of catalyst)
VO (OC) 2 H 5 )Cl 2 Dilution with cyclohexane produced a cyclohexane solution of the vanadium catalyst having a vanadium concentration of 6.7 mmol/L. Ethylaluminum sesquichloride (Al (C) 2 H 5 ) 1.5 Cl 1.5 ) Dilution with cyclohexane produced 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 the copolymerization reaction, the cyclohexane solution of the vanadium catalyst prepared by the above method was supplied to the polymerizer so that the concentration of the vanadium catalyst relative to cyclohexane in the polymerizer became 0.6 mmol/L.
Further, ethylaluminum 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 8℃and the polymerization pressure was 1.8kg/cm 2 G, continuously carrying out copolymerization reaction to obtain ethylene and tetracyclo [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 an ethylene-tetracyclic [4.4.0.1 ] extracted from a polymerizer 2,5 .1 7,10 ]To the 3-dodecene copolymer solution, water and a 25% by mass NaOH solution as a pH adjuster were added to stop the polymerization reaction. In addition, ethylene-tetracyclo [4.4.0.1 ] 2,5 .1 7,10 ]Removing catalyst residues present in the-3-dodecene copolymerDeashing) to obtain polymer solution a.
In the ethylene-tetracyclo [4.4.0.1 ] subjected to the above-mentioned deashing treatment 2,5 .1 7,10 ]Pentaerythritol-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate as stabilizer in cyclohexane solution of the 3-dodecene copolymer (Polymer solution A, polymer concentration 7.7% by mass)]After the addition of the copolymer in an amount of 0.4 parts by mass based on 100 parts by mass of the copolymer, an effective capacity of 1.0cm was temporarily used 3 Is mixed for 1 hour in the stirring tank.
(desolventizing)
20kg/cm was used as a heat source 2 In a double tube heater (outer tube diameter 2B, inner tube diameter 3/4B, length 21 m) of the water vapor of G, a cyclohexane solution of the copolymer having a concentration of 5 mass% was supplied in an amount of 150kg/H, and heated to 180 ℃.
Using 25kg/cm as a heat source 2 The double-tube flash dryer (outer tube diameter 2B, inner tube diameter 3/4B, length 27 m) and flash hopper (volume 200L) for steam of G removed most of the unreacted monomers together with cyclohexane as a polymerization solvent from the cyclohexane solution of the copolymer having undergone the above heating step, thereby obtaining a cyclic olefin random copolymer (cyclic olefin copolymer (a-1)) in a molten state after flash drying. The glass transition temperature (Tg) of the cyclic olefin copolymer (A-1) obtained by measurement with a differential scanning calorimeter was 161 ℃.
< ester Compound of polyglycerol and fatty acid (B) >)
As the ester compound (B) of polyglycerol and fatty acid, triglycerol oleate is used.
Polyglycerol (C) >, and
polyglycerol (C-1): mixtures of triglycerol and tetraglycerol.
Triglycerol tetraglycerol=6:1
Polyglycerol (C-2): diglycerol and mixtures of triglycerol and tetraglycerol.
Diglycerol triglycerol tetraglycerol=5:60:9
(extrusion)
After the above-mentioned cyclic olefin copolymer (A-1) in a molten state was charged into a resin charging section of an extruder by using a twin-screw kneading extruder having a vent, 0.90 parts by mass of triglycerol oleate per 100 parts by mass of the cyclic olefin copolymer (A-1) and 0.0072 parts by mass of polyglycerol (C-1) per 0.0072 parts by mass of the cyclic olefin copolymer (A-1) were added to a barrel section of the extruder downstream of the vent while sucking the copolymer from the vent section via a trap (trap) by a vacuum pump for the purpose of removing volatiles. 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.
Next, the kneaded product was pelletized by an underwater pelletizer installed at the outlet of the extruder, and the obtained pellets were dried with hot air at 100℃for 4 hours.
Further, a resin having a resin amount of about 3 to 5 times as large as the resin amount calculated from the average residence time in the polymerizer was allowed to flow for washing, and then a sample was collected, whereby a resin composition containing the cyclic olefin copolymer (A-1) was obtained. In order to suppress the mixing of iron atoms (Fe), a stainless steel piping and a polymerization apparatus are used in the polymer production facility.
Example 2
A resin composition was produced in the same manner as in example 1, except that the amount of triglycerol oleate added was 0.80 part by mass based on 100 parts by mass of the cyclic olefin copolymer (a-1), and the amount of polyglycerol (C-1) added was 0.0064 part by mass based on 100 parts by mass of the cyclic olefin copolymer (a-1).
Example 3
A resin composition was produced in the same manner as in example 1, except that the amount of triglycerol oleate added was 1.5 parts by mass based on 100 parts by mass of the cyclic olefin copolymer (a-1), and the amount of polyglycerol (C-1) added was 0.012 parts by mass based on 100 parts by mass of the cyclic olefin copolymer (a-1).
Example 4
TOPAS (registered trademark) COC 5013L-10 (manufactured by Polymer Co., ltd., an addition copolymer of norbornene and ethylene, hereinafter referred to as a cyclic olefin copolymer (A-2)) as the cyclic olefin copolymer (A) was fed into a twin screw extruder (manufactured by Nippon Steel Co., ltd.: TEX44SS-30 BW-3V). Further, 0.90 parts by mass of triglycerol oleate and 0.0072 parts by mass of polyglycerol (C-1) were added to 100 parts by mass of the cyclic olefin copolymer (A-2), and melt-kneaded to form pellets, thereby obtaining a pellet-shaped resin composition.
Example 5
A resin composition was produced in the same manner as in example 4, except that the amount of triglycerol oleate added was 1.5 parts by mass based on 100 parts by mass of the cyclic olefin copolymer (a-2), and the amount of polyglycerol (C-1) added was 0.012 parts by mass based on 100 parts by mass of the cyclic olefin copolymer (a-2).
Example 6
A resin composition was produced in the same manner as in example 1, except that the amount of triglycerol oleate to be added was 0.85 part by mass based on 100 parts by mass of the cyclic olefin copolymer (a-1), and the polyglycerin (C) was used as the polyglycerin (C) instead of the polyglycerin (C-1), and the amount of triglycerol oleate to be added was 0.063 part by mass based on 100 parts by mass of the cyclic olefin copolymer (a-1).
Example 7
A resin composition was produced in the same manner as in example 1, except that the amount of triglycerol oleate added was 4.0 parts by mass based on 100 parts by mass of the cyclic olefin copolymer (a-1), and the amount of polyglycerol (C-1) added was 0.032 parts by mass based on 100 parts by mass of the cyclic olefin copolymer (a-1).
< evaluation >
[ internal haze ]
The obtained resin composition was injection molded at a cylinder temperature of 275℃and a mold temperature of 120℃using an injection molding machine (ROBOSHOT S2000i-30α, manufactured by FANUC Co., ltd.) to obtain a test piece having an optical surface of 35mm X65 mm X3 mmt in thickness.
The internal haze of the test piece was measured by using benzyl alcohol in accordance with JIS K-7105.
[ damp-heat resistance test ]
The test piece produced at the time of measuring the internal haze was left for 1008 hours at a temperature of 85℃under an atmosphere having a relative humidity of 95%. 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 before the damp heat resistance test (hereinafter, Δinternal haze) was measured by subtracting the internal haze after the damp heat resistance test.
[ contamination of mold lens surface ]
The obtained resin composition was injection molded using a mold and an injection molding machine (ROBOSHOT S2000i-30α, manufactured by FANUC Co., ltd.) for forming a flat lens having a lens portion diameter of 6.0mm and a lens portion thickness of 0.5mm at a barrel temperature of 285℃and a mold temperature of 105℃and was subjected to total molding 4500 times. Every 900 times, contamination of the lens surface of the mold was observed by a digital microscope VHX-5000 (manufactured by KEYENCE Co.).
The molding times at which contamination of the lens surface was observed are shown in table 1. The case where no occurrence occurred even 4500 times was set as "none".
The results of examples 1 to 7 are shown in Table 1. "-" means that no evaluation was performed.
TABLE 1
In examples 1 to 5 containing the ester compound (B) of polyglycerol and fatty acid and the specific amount of polyglycerol (C), the internal haze was low, and the occurrence of internal haze before and after the wet heat resistance test was suppressed. Further, contamination of the inside of the mold due to continuous molding can be suppressed, and particularly contamination of the lens surface of the mold can be suppressed.
On the other hand, in example 6 containing polyglycerol in a specific amount or more, the mold lens surface contamination could not be suppressed, and the surface contamination occurred at the time of molding 900 times. With respect to example 7, the pellets produced cloudiness, and therefore no mold lens face contamination was evaluated.
The present application claims priority based on japanese application publication No. 2021-018162, filed 2/8/2021, the entire disclosure of which is incorporated herein.
Claims (6)
1. A cycloolefin resin composition comprising:
a cyclic olefin copolymer (A),
Ester compound (B) of polyglycerol and fatty acid
Polyglycerol (C),
the amount of the compound (B) is 0.05 to 3 parts by mass based on 100 parts by mass of the cyclic olefin copolymer (A),
the amount of the polyglycerol (C) is 0.001 to 0.04 parts by mass based on 100 parts by mass of the cyclic olefin copolymer (a).
2. The cycloolefin resin composition according to claim 1,
the cyclic olefin copolymer (A) has a structural unit (a) and a structural unit (b),
structural unit (a): at least 1 structural unit derived from an olefin represented by the following general formula (I),
structural unit (b): at least 1 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 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 positive integerNumber 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 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 carbon atoms to be bonded 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 99 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 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.
3. The cycloolefin resin composition according to claim 2,
the cyclic olefin copolymer (A) comprises:
the repeating unit (AA) represented by the general formula (II) and the 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 following formula (D-1), a compound represented by the following formula (D-2), and a compound represented by the following formula (D-3),
[ chemical 5]
In the 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 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 combined with each other to form a single ring or a plurality of rings, and furthermore 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 formula (D-2), n and m are eachIndependently 0,1 or 2, q is 1, 2 or 3, R 18 ～R 31 Each independently is 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 one another to form a single ring or multiple rings, and 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 combined with each other to form a single ring or a plurality of rings, the single ring or the plurality of rings may have a double bond, and furthermore the single ring or the plurality of rings may be aromatic rings,
[ chemical 7]
In the formula (D-3), q is 1, 2 or 3, R 32 ～R 39 Each independently is 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 36 And R is R 37 、R 37 And R is R 38 、R 38 And R is R 39 Can combine with each other to form a single ring or multiple rings, and in addition, when q=2 or 3, R 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 furthermore the single ring or the multiple rings may be aromatic rings.
4. The cycloolefin resin composition according to any one of claims 1 to 3, wherein the cycloolefin copolymer (A) has a glass transition temperature of 130℃to 170℃as measured by a differential scanning calorimeter.
5. A molded article comprising the cycloolefin resin composition according to any one of claims 1 to 4.
6. The molded article according to claim 5, which is an optical member.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021018162 | 2021-02-08 | ||
| JP2021-018162 | 2021-02-08 | ||
| PCT/JP2022/004197 WO2022168901A1 (en) | 2021-02-08 | 2022-02-03 | Cyclic olefin-based resin composition and molded article |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116507650A true CN116507650A (en) | 2023-07-28 |
Family
ID=82742336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280007708.2A Pending CN116507650A (en) | 2021-02-08 | 2022-02-03 | Cyclic olefin resin composition and molded article |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7509933B2 (en) |
| KR (1) | KR20230096027A (en) |
| CN (1) | CN116507650A (en) |
| TW (1) | TW202233754A (en) |
| WO (1) | WO2022168901A1 (en) |
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|---|---|---|---|---|
| CN1191804A (en) * | 1997-01-30 | 1998-09-02 | 三井化学株式会社 | Multilayer film for packaging |
| JP2001055480A (en) * | 1999-06-11 | 2001-02-27 | Mitsui Chemicals Inc | Cyclic olefin-based resin composition and its molded product |
| JP2002194230A (en) * | 2000-12-25 | 2002-07-10 | Asahi Denka Kogyo Kk | Resin composition |
| JP2006232714A (en) * | 2005-02-24 | 2006-09-07 | Riken Vitamin Co Ltd | Method for producing high purity triglycerol monofatty acid ester |
| CN103788603A (en) * | 2012-10-31 | 2014-05-14 | 中国石油化工股份有限公司 | Polylactic acid bidirectional stretching matte thin film and preparation method thereof |
| JP2015137362A (en) * | 2014-01-25 | 2015-07-30 | 三菱樹脂株式会社 | polyester resin composition |
| JP2015199939A (en) * | 2014-03-31 | 2015-11-12 | 三井化学株式会社 | Resin composition and use thereof |
| CN107849337A (en) * | 2015-08-27 | 2018-03-27 | 日本瑞翁株式会社 | Resin combination and resin-formed body |
| CN108369377A (en) * | 2015-12-08 | 2018-08-03 | 富士胶片株式会社 | Radiation sensitive resin composition, cured film, pattern forming method, solid-state imager and image display device |
| JP2018172665A (en) * | 2017-03-31 | 2018-11-08 | 三井化学株式会社 | Cyclic olefinic resin composition, molding and optical component |
-
2022
- 2022-02-03 KR KR1020237017560A patent/KR20230096027A/en unknown
- 2022-02-03 WO PCT/JP2022/004197 patent/WO2022168901A1/en active Application Filing
- 2022-02-03 JP JP2022579596A patent/JP7509933B2/en active Active
- 2022-02-03 CN CN202280007708.2A patent/CN116507650A/en active Pending
- 2022-02-07 TW TW111104308A patent/TW202233754A/en unknown
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1191804A (en) * | 1997-01-30 | 1998-09-02 | 三井化学株式会社 | Multilayer film for packaging |
| JP2001055480A (en) * | 1999-06-11 | 2001-02-27 | Mitsui Chemicals Inc | Cyclic olefin-based resin composition and its molded product |
| JP2002194230A (en) * | 2000-12-25 | 2002-07-10 | Asahi Denka Kogyo Kk | Resin composition |
| JP2006232714A (en) * | 2005-02-24 | 2006-09-07 | Riken Vitamin Co Ltd | Method for producing high purity triglycerol monofatty acid ester |
| CN103788603A (en) * | 2012-10-31 | 2014-05-14 | 中国石油化工股份有限公司 | Polylactic acid bidirectional stretching matte thin film and preparation method thereof |
| JP2015137362A (en) * | 2014-01-25 | 2015-07-30 | 三菱樹脂株式会社 | polyester resin composition |
| JP2015199939A (en) * | 2014-03-31 | 2015-11-12 | 三井化学株式会社 | Resin composition and use thereof |
| CN107849337A (en) * | 2015-08-27 | 2018-03-27 | 日本瑞翁株式会社 | Resin combination and resin-formed body |
| CN108369377A (en) * | 2015-12-08 | 2018-08-03 | 富士胶片株式会社 | Radiation sensitive resin composition, cured film, pattern forming method, solid-state imager and image display device |
| JP2018172665A (en) * | 2017-03-31 | 2018-11-08 | 三井化学株式会社 | Cyclic olefinic resin composition, molding and optical component |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7509933B2 (en) | 2024-07-02 |
| TW202233754A (en) | 2022-09-01 |
| KR20230096027A (en) | 2023-06-29 |
| WO2022168901A1 (en) | 2022-08-11 |
| JPWO2022168901A1 (en) | 2022-08-11 |
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