CN116897172A - 4-Methyl-1-pentene polymer - Google Patents
4-Methyl-1-pentene polymer Download PDFInfo
- Publication number
- CN116897172A CN116897172A CN202280018039.9A CN202280018039A CN116897172A CN 116897172 A CN116897172 A CN 116897172A CN 202280018039 A CN202280018039 A CN 202280018039A CN 116897172 A CN116897172 A CN 116897172A
- Authority
- CN
- China
- Prior art keywords
- polymer
- methyl
- pentene
- film
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 227
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 239000011248 coating agent Substances 0.000 claims abstract description 71
- 238000002844 melting Methods 0.000 claims abstract description 47
- 230000008018 melting Effects 0.000 claims abstract description 47
- 239000002904 solvent Substances 0.000 claims abstract description 42
- 239000004711 α-olefin Substances 0.000 claims abstract description 34
- 238000002425 crystallisation Methods 0.000 claims abstract description 18
- 230000008025 crystallization Effects 0.000 claims abstract description 18
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 238000005259 measurement Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 79
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 49
- 238000003860 storage Methods 0.000 abstract description 15
- 239000010408 film Substances 0.000 description 98
- 238000006116 polymerization reaction Methods 0.000 description 60
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 47
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- 239000000243 solution Substances 0.000 description 37
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 30
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 30
- 238000004519 manufacturing process Methods 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 19
- -1 cyclic olefin Chemical class 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 19
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 12
- 150000002431 hydrogen Chemical class 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000011068 loading method Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000010292 electrical insulation Methods 0.000 description 7
- 229910052726 zirconium Inorganic materials 0.000 description 7
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 238000006902 nitrogenation reaction Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 235000003441 saturated fatty acids Nutrition 0.000 description 3
- 150000004671 saturated fatty acids Chemical class 0.000 description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000113 methacrylic resin Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 235000021313 oleic acid Nutrition 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- RJUCIROUEDJQIB-GQCTYLIASA-N (6e)-octa-1,6-diene Chemical compound C\C=C\CCCC=C RJUCIROUEDJQIB-GQCTYLIASA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-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
- ISSYTHPTTMFJKL-UHFFFAOYSA-N 1-ethenylcyclopentene Chemical compound C=CC1=CCCC1 ISSYTHPTTMFJKL-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 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
- FEEIOCGOXYNQIM-UHFFFAOYSA-N 2,3-di(propan-2-ylidene)bicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(=C(C)C)C2=C(C)C FEEIOCGOXYNQIM-UHFFFAOYSA-N 0.000 description 1
- DOMHCBYZLIWUHE-UHFFFAOYSA-N 2-(chloromethyl)-3-prop-1-en-2-ylbicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(C(=C)C)C2CCl DOMHCBYZLIWUHE-UHFFFAOYSA-N 0.000 description 1
- IOHAVGDJBFVWGE-UHFFFAOYSA-N 2-ethylidene-3-propan-2-ylidenebicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(=CC)C2=C(C)C IOHAVGDJBFVWGE-UHFFFAOYSA-N 0.000 description 1
- SLQMKNPIYMOEGB-UHFFFAOYSA-N 2-methylhexa-1,5-diene Chemical compound CC(=C)CCC=C SLQMKNPIYMOEGB-UHFFFAOYSA-N 0.000 description 1
- UNUVUYPEOAILGM-UHFFFAOYSA-N 4-ethenylbicyclo[2.2.1]heptane Chemical compound C1CC2CCC1(C=C)C2 UNUVUYPEOAILGM-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 1
- UGJBFMMPNVKBPX-UHFFFAOYSA-N 5-propan-2-ylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C(C)C)CC1C=C2 UGJBFMMPNVKBPX-UHFFFAOYSA-N 0.000 description 1
- KUFDSEQTHICIIF-UHFFFAOYSA-N 6-methylhepta-1,5-diene Chemical compound CC(C)=CCCC=C KUFDSEQTHICIIF-UHFFFAOYSA-N 0.000 description 1
- UCKITPBQPGXDHV-UHFFFAOYSA-N 7-methylocta-1,6-diene Chemical compound CC(C)=CCCCC=C UCKITPBQPGXDHV-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- KFCXGMAACUSGIA-UHFFFAOYSA-L [Cl-].[Cl-].C1(=CC=CC=C1)C(C1=CC=CC=C1)=[Zr+2](C1=C(C=CC=2C3=CC=C(C=C3CC1=2)C(C)(C)C)C(C)(C)C)C1C=C(C=C1CC)C(C)(C)C Chemical compound [Cl-].[Cl-].C1(=CC=CC=C1)C(C1=CC=CC=C1)=[Zr+2](C1=C(C=CC=2C3=CC=C(C=C3CC1=2)C(C)(C)C)C(C)(C)C)C1C=C(C=C1CC)C(C)(C)C KFCXGMAACUSGIA-UHFFFAOYSA-L 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004573 interface analysis Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- AZSKHRTUXHLAHS-UHFFFAOYSA-N tris(2,4-di-tert-butylphenyl) phosphate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(=O)(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C AZSKHRTUXHLAHS-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
The present invention aims to provide a 4-methyl-1-pentene polymer which is excellent in storage stability and solubility when dissolved in a solvent, and is also excellent in at least one of heat resistance and appearance of a coating film when the coating film is stretched, for example, when the film is bent or used for flexible applications. The solution is that the 4-methyl-1-pentene polymer (A) is a copolymer of 4-methyl-1-pentene and at least 1 kind of linear alpha-olefin selected from the group consisting of C6-C20, and satisfies the following requirements (I) and (II). (I) The melting (endothermic) curve obtained by DSC has an endothermic end temperature (TmE) of 230 ℃ or lower. (II) the exothermic onset temperature (TcS) in the crystallization (exothermic) curve obtained by DSC measurement is 210 ℃ or lower.
Description
Technical Field
The present invention relates to 4-methyl-1-pentene polymers.
Background
Various coating agents for protection, insulation, planarization, heat resistance, light resistance, weather resistance, and the like can be used in display devices, semiconductor devices, optical members, printed circuit boards, and the like. Films produced using these coating agents often undergo a process exceeding 200 ℃ such as solder reflow and micromachining in the production of the above devices and the like, and therefore high heat resistance is required. Further, characteristics such as transparency and electrical insulation are required depending on the application. In particular, a film formed by using a coating agent on the electrode surface of a capacitor is required to have heat resistance and high electrical insulation properties in order to prevent electric leakage and voltage drop which are accumulated.
In the pressing process of circuit boards such as printed wiring boards, flexible printed wiring boards, and multilayer printed wiring boards, a release film is used to prevent the circuit boards from adhering to the pad. For example, in the case of a flexible printed wiring board, in order to protect a circuit portion having a base material (polyimide film or the like) of a predetermined circuit portion, the circuit portion is covered with a resin film with an adhesive, and a release film is further laminated and pressed (for example, patent document 1).
Against such a background, a coating agent capable of forming a film having high heat resistance and electrical insulation which can be used for a release film or the like is demanded. In response to such demands, coating agents containing acrylic resins, polycarbonate resins, fluorine resins, polyacetal resins, polyester resins, silicone resins, polyether sulfone resins, polyimide resins, polyarylate resins, cycloolefin resins, and the like have been proposed, but films having heat resistance and electrical insulation properties in good balance have not been successfully formed.
In recent years, as a transparent resin for coating having excellent heat resistance with a glass transition temperature of 200 ℃ or higher, a cyclic olefin addition polymer containing silyl groups has been proposed (for example, patent documents 2 and 3). However, although the cyclic olefin addition polymer has high heat resistance, it is rigid and lacks flexibility, and when it is formed into a film, it is liable to cause cracking or crazing. Therefore, when used as a mold release film or the like, the film may be broken, and electrical insulation may be lowered. Further, silyl groups are introduced in large amounts, and warpage due to shrinkage may occur during crosslinking, which causes problems such as high water absorption and high dielectric constant.
Further, as a composition containing a 4-methyl-1-pentene copolymer and a solvent, there is disclosed an example in which a composition obtained by dissolving a 4-methyl-1-pentene copolymer having a low molecular weight (or a melting point of 200 ℃ or less) which is soluble in a solvent is used for coating (for example, patent documents 4 and 5).
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2004-339491
Patent document 2: U.S. patent No. 5912313
Patent document 3: japanese patent application laid-open No. 2004-58339
Patent document 4: japanese patent laid-open No. 2013-227421
Patent document 5: japanese patent application laid-open No. 2015-34258
Disclosure of Invention
Problems to be solved by the invention
The 4-methyl-1-pentene copolymer described in patent document 4 is excellent in heat resistance, and the 4-methyl-1-pentene copolymer described in patent document 5 is excellent in storage stability.
However, it is known that: in applications requiring flexibility after coating, there is a concern that cracks or crazes may occur and the appearance may be deteriorated when stretching is performed because of lack of toughness in the related art. In particular, in the field of electric devices and in demolding applications, it is known that: in view of flexibility after coating, good appearance, environmental load, long life is required.
It is further known that 4-methyl-1-pentene copolymer is sometimes used in a high-temperature process and a use environment depending on the purpose, and thus the heat resistance is insufficient in the prior art. In addition, in particular in the field of electrical devices and in demolding applications, it is known that: in view of further heat resistance requirements and environmental load, long life is required.
In view of the problems in the prior art, an object of the present invention is to provide a 4-methyl-1-pentene polymer which is excellent in storage stability and solubility when dissolved in a solvent, and is also excellent in at least one of heat resistance and appearance of a coating film when the coating film is stretched such as when the film is bent or used for flexible applications.
Further, the object of the invention according to claim 2 is to provide a 4-methyl-1-pentene polymer which is excellent in storage stability when dissolved in a solvent, solubility, film appearance when a coated film is stretched such as when the film is bent or used for flexible applications.
Further, the object of the invention according to the 3 rd aspect is to provide a 4-methyl-1-pentene polymer which is excellent in storage stability, heat resistance and solubility when dissolved in a solvent.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by a specific 4-methyl-1-pentene polymer, thereby completing the present invention.
The invention of the 1 st aspect relates to the following [1].
[1]
A4-methyl-1-pentene polymer (A) which is a copolymer of 4-methyl-1-pentene and at least 1 selected from linear alpha-olefins having 6 to 20 carbon atoms and satisfies the following requirements (I) and (II).
(I) The melting (endothermic) curve obtained by DSC has an endothermic end temperature (TmE) of 230 ℃ or lower.
(II) the exothermic onset temperature (TcS) in the crystallization (exothermic) curve obtained by DSC measurement is 210 ℃ or lower.
The invention of the 2 nd aspect relates to the following [2] and [3].
[2]
The 4-methyl-1-pentene polymer (A) according to [1], wherein the melting point (Tm) as measured by DSC is 170 to 242 ℃.
[3]
The 4-methyl-1-pentene polymer (A) according to the above [1] or [2], which has an intrinsic viscosity [ eta ] of 1.7 to 5.5dl/g.
The 3 rd aspect of the present invention relates to the following [4].
[4]
The 4-methyl-1-pentene polymer (A) according to [1], wherein the melting point (Tm) as measured by DSC is 200 to 242 ℃.
The 1 st to 3 rd embodiments of the present invention further relate to, for example, the following [5] to [9].
[5]
The 4-methyl-1-pentene polymer (A) according to any one of the above [1] to [4], wherein the amount (U1) of the structural unit derived from 4-methyl-1-pentene is 84.0 to 100 mol% and the total amount (U2) of the structural unit derived from at least 1 selected from linear alpha-olefins having 6 to 20 carbon atoms is 16.0 to 0 mol% (wherein the total of the above U1 and the above U2 is 100 mol%).
[6]
The 4-methyl-1-pentene polymer (A) according to any one of the above [1] to [5], which is not modified.
[7]
A composition (X) comprising 0.1 to 50% by mass of the 4-methyl-1-pentene polymer (A) according to any one of the above [1] to [6] and 50 to 99.9% by mass of the solvent (B).
[8]
The composition (X) according to the above [7], wherein the solvent (B) is an organic solvent.
[9]
A coating agent comprising the composition (X) of the above-mentioned [7] or [8 ].
Effects of the invention
The 4-methyl-1-pentene polymer according to embodiment 1 of the present invention is excellent in storage stability and solubility in a solvent, and is also excellent in at least one of heat resistance and appearance of a coating film when the coating film is stretched, for example, when the film is bent or used for flexible applications.
The 4-methyl-1-pentene polymer according to the 2 nd aspect of the present invention is excellent in storage stability when dissolved in a solvent, solubility, film appearance when the film is stretched such as when the film is bent or used for flexible applications.
The 4-methyl-1-pentene polymer according to claim 3 is excellent in storage stability, heat resistance and solubility in a solvent.
Detailed Description
< 4-methyl-1-pentene Polymer >)
The 4-methyl-1-pentene polymer (A) (hereinafter also referred to as "polymer (A)") according to the embodiment 1 of the present invention is a copolymer of 4-methyl-1-pentene and at least 1 selected from linear alpha-olefins having 6 to 20 carbon atoms, and satisfies the following requirements (I) to (II).
The polymer (a) according to the invention 1 can be exemplified by the polymer (a) according to the invention 2 and the polymer (a) according to the invention 3. The polymer (a) according to the present invention refers to the polymer (a) according to the 1 st aspect of the present invention, which includes the polymer (a) according to the 2 nd aspect of the present invention and the polymer (a) according to the 3 rd aspect of the present invention, unless otherwise specified.
Examples of the linear alpha-olefin having 6 to 20 carbon atoms include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene.
Element (I): the melting (endothermic) curve obtained by DSC has an endothermic end temperature (TmE) of 230 ℃ or lower.
The endothermic end temperature means a temperature at which melting ends. The endothermic end temperature and the exothermic start temperature described later are different indices from what is generally called start (on set) and end (off set) of the intersection point of the base line and the steady-state line tangent.
The endothermic end temperature (TmE) is preferably less than 230 ℃, more preferably 228 ℃ or less, and even more preferably less than 228 ℃.
The polymer (a) according to the invention of the 2 nd aspect of the present invention having the value of the endothermic end temperature (TmE) within the above-mentioned range is preferable from the viewpoint of the appearance of the coating film.
Further, the polymer (a) according to the invention of the 3 rd aspect of the present invention having a value of the endothermic end temperature (TmE) within the above-mentioned range is preferable from the viewpoint of heat resistance. Therefore, a coating agent or the like obtained from a composition containing the polymer (a) is also excellent in heat resistance, and the properties of the coating agent or the like tend to be uniform.
The method for measuring the endothermic end temperature (TmE) is described in detail in examples.
Element (II):
the crystallization (exothermic) curve obtained by DSC measurement has an exothermic onset temperature (TcS) of 210 ℃ or lower. The exothermic onset temperature refers to a temperature at which crystallization begins.
The exothermic onset temperature (TcS) is preferably less than 210 ℃, more preferably 200 ℃ or less, and even more preferably less than 200 ℃.
The polymer (a) according to the invention of the 2 nd aspect of the present invention having a value of the heat release initiation temperature (TcS) within the above range is preferable from the viewpoint of the appearance of the coating film.
Further, the polymer (a) according to the invention of the 3 rd aspect of the present invention having a value of the heat release start temperature (TcS) within the above range is preferable from the viewpoint of heat resistance. Therefore, a coating agent or the like obtained from a composition containing the polymer (a) is also excellent in heat resistance, and the properties of the coating agent or the like tend to be uniform.
The method for measuring the exothermic initiation temperature (TcS) is described in detail in examples.
The polymer (A) according to the 2 nd aspect of the present invention has an intrinsic viscosity [ eta ] of usually 0.5 to 6.0dl/g, preferably 1.7 to 5.5dl/g, more preferably 1.8 to 5.3dl/g, still more preferably 2.0 to 5.3dl/g, still more preferably 2.2 to 5.3dl/g, and particularly preferably 2.2 to 5.2dl/g, as measured in decalin at 135 ℃.
The polymer (a) according to the invention of the 2 nd aspect of the present invention having the value of the intrinsic viscosity [ η ] within the above-mentioned range is preferable from the viewpoint of the appearance of the coating film. If the intrinsic viscosity [ eta ] is higher than 6.0dl/g, it is liable to become a lump or become uneven at the time of coating of the coating agent containing the polymer (A).
The polymer (A) according to the 3 rd embodiment of the present invention has an intrinsic viscosity [ eta ] of usually 0.5 to 6.0dl/g, preferably 1.7 to 5.3dl/g, more preferably 1.7 to 4.5dl/g, still more preferably 1.7 to 3.5dl/g, still more preferably 1.7 to 2.5dl/g, as measured in decalin at 135 ℃.
The polymer (A) according to the invention of the 3 rd aspect of which the value of the intrinsic viscosity [ eta ] is within the above-mentioned range is preferable from the viewpoint of heat resistance.
The value of the intrinsic viscosity [ eta ] can be adjusted by the amount of hydrogen added in the polymerization step in the production of the polymer (A).
The method for measuring the intrinsic viscosity [ eta ] is described in detail in examples.
The melting point (Tm) of the polymer (A) according to the embodiment 2 of the present invention is preferably 170 to 242 ℃, more preferably 170 to 232 ℃, still more preferably 170 to 220 ℃ as measured by DSC.
The polymer (a) according to the invention of the 2 nd aspect of which the melting point (Tm) falls within the above-mentioned range is preferable from the viewpoint of the appearance of the coating film.
The melting point (Tm) of the polymer (A) according to the 3 rd embodiment of the present invention is 200 to 242 ℃, preferably 200 to 232 ℃, more preferably 200 to 232 ℃ and 232 ℃ or lower, and even more preferably 200 to 220 ℃.
The polymer (A) according to the invention according to the 3 rd aspect of the present invention having a melting point (Tm) within the above range is preferable because the heat resistance of the coating film after solvent removal can be improved.
The value of the melting point (Tm) tends to depend on the stereoregularity of the polymer and the content of the α -olefin structural unit contained in the polymer. Therefore, the melting point (Tm) can be adjusted by further controlling the content of the α -olefin structural unit using a catalyst for olefin polymerization described later.
The method for measuring the melting point (Tm) is described in detail in examples.
Conventional 4-methyl-1-pentene polymers have problems in that they are difficult to dissolve in solvents and are used in coating agents and the like without using methods such as lowering the melting point, lowering the molecular weight, and modifying them. As disclosed in patent document 4, there is a method of using a 4-methyl-1-pentene polymer, which has a melting point reduced by limiting the kind of comonomer and setting the amount of comonomer to be high, as a coating agent. However, in this method, the intrinsic viscosity [ η ] is low, and the stretchability after coating and the appearance of the coating film are deteriorated. In this method, the melting point is limited to a region of 200 ℃ or lower, and heat resistance may be insufficient depending on the application.
In the polymer (a) according to the invention of the 2 nd aspect, as described above, it is preferable to maintain the melting point high, raise the intrinsic viscosity [ η ], and maintain the balance between the melting point and the intrinsic viscosity [ η ], so that the polymer (a) can have a composition made of a stretchable coating agent (also referred to as varnish) with little crystallization inhibition. That is, the amount of the comonomer can be adjusted so that the temperature at which crystallization starts and the temperature at which the crystals are completely dissolved are reduced to a minimum. Thus, the appearance and solubility of the coating film suitable for the purpose can be achieved. If the composition is within this range, the storage stability upon dissolution of the solvent is also ensured.
In the polymer (a) according to the 3 rd aspect of the present invention, as described above, the polymer (a) has a composition capable of being varnished by slightly suppressing crystallization while maintaining a high melting point of 200 ℃. That is, the amount of the comonomer is controlled so that the melting point Tm is 200 ℃ or higher and the temperature at which crystallization starts and the temperature at which the crystals are completely dissolved are reduced to a minimum. Thereby, heat resistance and solubility suitable for the purpose are achieved. If the composition is within this range, the storage stability upon dissolution of the solvent is also ensured.
The polymer (A) may or may not be modified. The polymer (A) can be dissolved in a solvent even if it is not modified, and the above object can be achieved. The polymer (a) may be a polymer which is not modified in its entirety or may be a polymer which is not modified in its part.
The polymer (A) contains a structural unit derived from 4-methyl-1-pentene and a structural unit derived from at least 1 selected from linear alpha-olefins having 6 to 20 carbon atoms.
The amount (U1) of the structural unit derived from 4-methyl-1-pentene is preferably 84.0 to 100 mol%, more preferably 90.0 to 99.0 mol%, still more preferably 94.0 to 98.5 mol%, particularly preferably 94.0 to 98.0 mol% in the present invention in the 2 nd embodiment, and particularly preferably 94.5 to 98.0 mol% in the present invention in the 3 rd embodiment. The total amount (U2) of the structural units derived from at least 1 selected from linear alpha-olefins having 6 to 20 carbon atoms is preferably 16.0 to 0 mol%, more preferably 10.0 to 1.0 mol%, still more preferably 6.0 to 1.5 mol%, in the embodiment of the present invention, 6.0 to 2.0 mol%, in the embodiment of the present invention, and in the embodiment of the present invention, 5.5 to 2.0 mol%. In the above, the total of U1 and U2 is set to 100 mol%.
The polymer (a) in which U1 and U2 are in the above-described range is preferable from the viewpoint of heat resistance.
In the present invention according to claim 2, a linear alpha-olefin having 6 to 20 carbon atoms is preferable from the viewpoint of appearance of a coating film, and in the present invention according to claim 3, a linear alpha-olefin having 6 to 18 carbon atoms is preferable from the viewpoint of heat resistance. Specifically, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, etc. are preferable, and among them, 1-decene, 1-hexadecene, 1-octadecene are preferable.
The linear alpha-olefin having 6 to 20 carbon atoms may be used in an amount of 1 or 2 or more.
The polymer (a) may contain structural units derived from other polymerizable compounds within a range not impairing the object of the present invention. Examples of such other polymerizable compounds include vinyl compounds having a cyclic structure such as styrene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids such as maleic anhydride and derivatives thereof; conjugated dienes such as butadiene, isoprene, pentadiene and 2, 3-dimethylbutadiene; non-conjugated polyenes such as 1, 4-hexadiene, 1, 6-octadiene, 2-methyl-1, 5-hexadiene, 6-methyl-1, 5-heptadiene, 7-methyl-1, 6-octadiene, dicyclopentadiene, cyclohexadiene, bicyclooctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2, 3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2, 2-norbornadiene, and the like.
The polymer (a) may contain units derived from such other polymerizable compounds in an amount of 10 mol% or less, preferably 5 mol% or less, more preferably 3 mol% or less, based on 100 mol% of the total of the structural units derived from all the polymerizable compounds contained in the polymer (a).
The method for measuring the content of a structural unit derived from 4-methyl-1-pentene and a structural unit derived from at least 1 selected from linear alpha-olefins having 6 to 20 carbon atoms in the polymer (A) is described in detail in examples.
The density of the polymer (A) is preferably 820 to 850 (kg/m) 3 ) More preferably 825 to 850kg/m 3 Further preferably 825 to 845kg/m 3 Particularly preferably 825 to 840kg/m 3 . The density value of the polymer (A) can be adjusted by selecting the type and content of the other olefin copolymerized with 4-methyl-1-pentene. Further, the density can be measured in accordance with JIS K6268. The polymer (a) having a density value within the above range is preferable from the viewpoint of appearance of the coating film.
The molecular weight distribution (Mw/Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer (A) as measured by Gel Permeation Chromatography (GPC), is preferably 1.0 to 3.5, more preferably 1.3 to 3.0, and even more preferably 1.5 to 2.5.
The value of the molecular weight distribution (Mw/Mn) can be adjusted by the kind of the catalyst for olefin polymerization, particularly the metallocene catalyst, which will be described later. The molecular weight distribution (Mw/Mn) can be measured by using an Alliance GPC-2000 type gel permeation chromatograph manufactured by Waters corporation.
The polymer (A) having a molecular weight distribution (Mw/Mn) within the above range is preferable from the viewpoints of transparency and mechanical properties. Further, if the molecular weight distribution of the polymer (a) is within the above range, affinity with a solvent to be described later is improved, and stability of the composition is improved.
The crystallization temperature (Tc) of the polymer (A) as measured by DSC is preferably 110 to 220 ℃, more preferably 120 to 205 ℃.
The value of the crystallization temperature (Tc) tends to depend on the stereoregularity of the polymer and the content of the linear alpha-olefin structural unit having 6 to 20 carbon atoms, and can be adjusted by using a catalyst for olefin polymerization described later and controlling the content of the linear alpha-olefin structural unit having 6 to 20 carbon atoms. The polymer (a) having a value of the crystallization temperature (Tc) within the above range is preferable from the viewpoint of moldability.
The polymer (A) can be obtained by polymerizing 4-methyl-1-pentene, the above specific olefin and, if necessary, the above other polymerizable compound in the presence of a catalyst for olefin polymerization by a known method.
Preferable examples of the catalyst for olefin polymerization include metallocene catalysts. As preferable metallocene catalysts, there may be mentioned those described in WO 01/53369, WO 01/27124, japanese patent application laid-open No. 3-193796, japanese patent application laid-open No. 02-41303 or WO 06/025540.
< composition >)
The composition (X) of the present invention comprises the above-mentioned 4-methyl-1-pentene polymer (A) and a solvent (B).
The content of the polymer (a) in the composition (X) is 0.1 to 50% by mass, preferably 0.5 to 30% by mass, more preferably 1.0 to 25% by mass, and even more preferably 5 to 20% by mass. The content of the solvent (B) in the composition (X) is 50 to 99.9 mass%, preferably 70 to 99.5 mass%, more preferably 75 to 99.0 mass%, and even more preferably 80 to 95 mass%.
By setting the content of the polymer (a) and the solvent (B) in the composition (X) within the above-described range, the composition (X) is excellent in balance between the operability and the ease of solvent removal in the production of a film from a coating agent when used as a coating agent or the like.
The solvent (B) is not particularly limited as long as it can dissolve the polymer (A). Among them, an organic solvent can be suitably used. Examples of the solvent (B) include aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, cyclohexane, methylcyclohexane, ethylcyclohexane, and the like; aromatic hydrocarbons such as toluene and xylene. Among these, toluene, cyclohexane, methylcyclohexane, and the like can be suitably used.
The composition (X) may further contain an antioxidant, a heat stabilizer, a weather stabilizer, an antistatic agent, a sliding agent, a leveling agent, a reinforcing agent, an antiblocking agent, an antifogging agent, a lubricant, a dye, a pigment, a natural oil, a synthetic oil, a wax, a filler, and the like as necessary within a range not impairing the object of the present invention.
As the antioxidant, a known antioxidant can be used. Specifically, a hindered phenol compound, a sulfur-based antioxidant, a lactone-based antioxidant, an organic phosphite compound, an organic phosphonite compound, or a combination of several thereof may be used.
Examples of the lubricant include sodium, calcium, and magnesium salts of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid, and stearic acid, and these may be used alone or in combination of 2 or more. The amount of the lubricant to be blended is usually about 0.1 to 3 parts by mass, preferably about 0.1 to 2 parts by mass, based on 100 parts by mass of the composition.
As the slip agent, amides of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid, stearic acid, erucic acid, behenic acid, or bisamides of these saturated or unsaturated fatty acids are preferably used. Among these, erucamide and ethylene bis stearamide are particularly preferable. These fatty acid amides are preferably blended in a range of 0.01 to 5 parts by mass relative to 100 parts by mass of the polymer (a).
Examples of the anti-blocking agent include fine powder silica, fine powder alumina, fine powder clay, powdered or liquid silicone resin, tetrafluoroethylene resin, fine powder crosslinked resin, crosslinked acrylic resin powder, methacrylic resin powder, and the like. Among these, fine powder silica and crosslinked acrylic and methacrylic resin powders are preferable.
In addition, as described later, when the composition (X) is used as a coating agent, it is also preferable to add a leveling agent to the composition (X). As the leveling agent for reducing the surface roughness of the film made of the composition (X), a fluorine-based nonionic surfactant, a special acrylic resin-based leveling agent, a silicone-based leveling agent, or the like can be used, and a leveling agent having good compatibility with a solvent is preferable, and the amount to be added is used in the range of 1 to 50,000ppm with respect to the polymer (a) in the composition (X).
As the reinforcing agent, 5 to 50 parts by mass of an oxide of a metal such as silicon, titanium, aluminum, zirconium, or the like, a polyfunctional alkoxy compound or an oligomer thereof, or a clay mineral may be blended with 100 parts by mass of the polymer (a) in the composition (X), and the hardness and elastic modulus of a film (also referred to as a coating layer in this case) produced using the composition (X) as a coating agent may be improved. When the amount is less than 5 parts by mass, the effect is too low, and when it exceeds 50 parts by mass, the transparency and mechanical strength of the coating may be impaired.
The method for producing the composition (X) is not particularly limited, and it can be produced by a method generally used. For example, the polymer (a) can be added to the solvent (B) and stirred at a temperature equal to or lower than the boiling point of the solvent (B) for a predetermined period of time.
The polymer (a) according to the embodiment 1 of the present invention is excellent in storage stability and solubility when dissolved in a solvent. The polymer (a) according to claim 2 of the present invention is excellent in storage stability and solubility in a solvent, and in appearance of a coating film when the coating film is stretched, for example, when the film is bent or used for flexibility. The polymer (a) according to the 3 rd aspect of the present invention is excellent in storage stability, heat resistance and solubility when dissolved in a solvent. Further, the polymer (A) has properties such as releasability, stretchability, electrical insulation and chemical resistance which are generally peculiar to 4-methyl-1-pentene polymers. Thus, the composition (X) comprising the polymer (A) can be suitably used for various purposes.
The composition (X) can be suitably used as a coating agent since it can produce a film having high heat resistance, particularly for various display devices such as liquid crystal display elements and electroluminescent display elements; a semiconductor device; optical members such as a light guide plate, a polarizing film, a light diffusion film, a retardation film, and an antireflection film; various coating agents for surface protection, insulation, planarization, heat resistance, light resistance, weather resistance, etc. of printed circuit boards and the like.
The composition (X) can be applied to an object to be coated and dried to obtain a thin film.
In particular, since the composition (X) can form a protective layer on a substrate having a complicated shape, it can be suitably used as a coating agent for forming a protective layer on the electrode surface of a printed wiring board or a capacitor. The composition (X) may be applied to another film and the solvent may be removed to thereby form a release film.
Examples
The present invention will be described in further detail with reference to examples. However, the present invention is not limited to these examples.
[ method for measuring various physical Properties ]
[ content of structural Unit in 4-methyl-1-pentene Polymer ]
The amount of the structural unit derived from 4-methyl-1-pentene (4-methyl-1-pentene content) and the amount of the structural unit derived from an alpha-olefin other than 4-methyl-1-pentene (alpha-olefin content) are determined by the following means and conditions 13 C-NMR spectrum.
The ECP500 type nuclear magnetic resonance apparatus manufactured by Nippon electronic Co., ltd.) was used, the solvent was o-dichlorobenzene/deuterated benzene (80/20% by volume) mixed solvent, the sample concentration was 55mg/0.6mL, the measurement temperature was 120 ℃, the observation core was 13C (125 MHz), the sequence was single pulse proton decoupling, the pulse width was 4.7. Mu.s (45℃pulse), the repetition time was 5.5 seconds, the cumulative number of times was 1 ten thousand times or more, and 27.50ppm was the base for chemical shift The standard value is measured. By the obtained 13 The composition of 4-methyl-1-pentene and α -olefin was quantified by C-NMR spectroscopy.
[ intrinsic viscosity [ eta ] ]
The intrinsic viscosity [ eta ] was measured at 135℃using a decalin solvent. That is, about 20mg of the polymer powder, pellet or resin block was dissolved in 15mL of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ℃. After adding 5mL of decalin solvent to the decalin solution and diluting, the specific viscosity ηsp was measured in the same manner. This dilution operation was further repeated 2 times, and the value of ηsp/C when the concentration (C) was extrapolated to 0 was obtained as the intrinsic viscosity (see the following formula).
[η]＝lim(ηsp/C)(C→0)
[ melting Point (Tm), crystallization temperature (Tc), endothermic end temperature (TmE), exothermic start temperature (TcS) ]
The exothermic and endothermic curves were obtained by using a DSC measuring device (DSC 220C) manufactured by Seiko Instruments, inc., according to ASTM D3418, and the melting point (Tm) and crystallization temperature (Tc) were obtained as follows.
About 5mg of the sample was put into an aluminum pan for measurement, and the temperature was raised from 20℃to 280℃at a heating rate of 10℃per minute, and after holding at 280℃for 5 minutes, the temperature was lowered to 20℃at a cooling rate of 10℃per minute, and after holding at 20℃for 5 minutes, the temperature was raised again from 20℃to 280℃at a heating rate of 10℃per minute. The crystallization peak developed at the 1 st cooling was set as the crystallization temperature (Tc). When a plurality of peaks are detected, the peak with the largest temperature is set as the crystallization temperature (Tc). The melting peak developed at the 2 nd temperature rise was set to the melting point (Tm). When a plurality of peaks are detected, the peak with the largest temperature is set as the melting point (Tm).
The temperature at the end of the heat absorption of the melting (heat absorption) curve is set as the heat absorption end temperature (TmE). The temperature at which the crystallization (exothermic) curve starts to emit heat is set as the exothermic start temperature (TcS).
The start and end points are points at which the heat amount becomes a constant base line with respect to the start or end of the heat absorption or heat release, and it can be confirmed that the curve deviates from the base line and the difference in the heat amount starts to occur.
[ storage stability ]
In the production of the composition described later, the polymer and the solvent were placed in a container equipped with a stirrer, stirred at 200rpm at 90℃for 1 hour, and after dissolving the polymer, the mixture was stored at room temperature for 24 hours. Then, the composition was visually evaluated under visible light, and the transparent condition was a, the condition that the composition appeared cloudy but fluidity was observed was B, the condition that the composition appeared cloudy and fluidity was not observed was C, and the results are shown in table 1.
[ contact Angle measurement of Water ]
Contact angle values at the time of dropping water drops on the films obtained in examples and comparative examples were measured using a DropMaster500 image processing type solid-liquid interface analysis system. The larger the contact angle value, the higher the degree of hydrophobicity, and the higher the releasability from a material having a high polarity.
[ normalized insulation breakdown Voltage ]
An insulation breakdown tester manufactured by Yamayo tester Co., ltd was used in accordance with ASTM-D149. The films obtained in examples and comparative examples were applied with a voltage at a step-up rate of 500V/sec, and the dielectric Breakdown Voltage (BVD) was measured to determine the withstand voltage characteristics. The thickness of the film having the above-mentioned dielectric breakdown voltage measured in the vicinity of the dielectric breakdown point was measured, and the value obtained by dividing the above-mentioned dielectric breakdown voltage by the above-mentioned thickness was set as the normalized dielectric breakdown voltage (kV/. Mu.m). The larger the normalized insulation breakdown voltage is, the higher the electrical insulation is.
[ appearance of coating film ]
Films obtained by coating the compositions obtained in examples and comparative examples on PET substrates were cut into 5mm X1 mm pieces, and the films were stretched at a speed of 10mm/min by a tensile tester (INSTRON 5982) at room temperature, and the coated films of the compositions were observed by a microscope (KEYENCE VK-X100). In table 1, the presence or absence of cracking is denoted as a, and the presence of cracking is denoted as B.
[ Heat resistance of coating film ]
The films obtained in examples and comparative examples were cut into square shapes of 50mm square, placed on a hot plate heated to 200℃and observed for changes in shape. In table 1, a case where the length change rate of the side having the largest change in length was 10% or less was a, a case where 10 to 20% was B, a case where 20% or more was observed, or a case where significant melting was observed in the film was C during 10 seconds.
Synthesis example 1
(8-octamethylfluoren-12' -yl- (2- (adamantan-1-yl) -8-methyl-3, 3b,4,5,6, 7a, 8-octahydrocyclopenta [ a ] indene)) zirconium dichloride was synthesized according to the method described in preliminary experiment 5 of International publication No. 2014/123212.
Synthesis example 2
Manufacture of olefin polymerization catalysts
In a 200mL three-necked flask equipped with a stirrer, which had been sufficiently replaced with nitrogen gas, 30mL of purified decane and solid polymethylaluminoxane (synthesized by the method described in International publication No. 2014/123212, hereinafter also referred to as "solid MAO") having a D50 of 28 μm and an aluminum atom content of 43 mass% were charged into a 200mL three-necked flask equipped with a stirrer, which had been sufficiently replaced with nitrogen gas, at 30℃under a nitrogen gas flow, and the contents were 14.65mmol in terms of aluminum atom to prepare a suspension. In this suspension, 50.0mg (0.0586 mmol) of zirconium dichloride (8-octamethylfluoren-12' -yl- (2- (adamantan-1-yl) -8-methyl-3, 3b,4,5,6, 7a, 8-octahydrocyclopenta [ a ] indene)) which is the transition metal compound described in Synthesis example 1 was prepared into a toluene solution of 4.58mmol/L, and added while stirring. After 1 hour, stirring was stopped, and the resultant mixture was washed with 100mL of decane by decantation, and decane was added thereto to prepare 50mL of slurry (Zr loading rate: 98%).
Synthesis example 3
Preparation of prepolymerized catalyst component
1.0mL of a decane solution of triisobutylaluminum (0.5 mmol/mL in terms of aluminum atom) was charged into the slurry prepared in Synthesis example 2 at 25℃under a nitrogen gas flow. After cooling to 15 ℃, 10mL of 4-methyl-1-pentene was charged into the reactor over 60 minutes. The start time of loading is set as the start of pre-polymerization. After 2.0 hours from the start of polymerization, stirring was stopped, and the resultant mixture was washed 3 times with decane 100mL by decantation. The catalyst component was prepolymerized to prepare decane slurry (9.5 g/L,0.56 mmol-Zr/L).
Example 1
(production of Polymer 1)
425mL of purified decane was charged into a SUS-made polymerizer having an internal volume of 1L and equipped with a stirrer, and the temperature was raised to 40℃under a nitrogen flow at room temperature. After reaching 40 ℃, 0.8mL (0.4 mmol in terms of aluminum atom) of a decane solution of triisobutylaluminum (0.5 mmol/mL in terms of aluminum atom) was charged, followed by charging a decane slurry of the previously prepared prepolymerized catalyst component of Synthesis example 3 in an amount of 0.002mmol in terms of zirconium atom. Hydrogen 16.25, 16.25NmL was charged, and then, a mixed solution of 234mL of 4-methyl-1-pentene and 18.5mL of an alpha-olefin mixture (trade name: linear 168, manufactured by Kagaku Co., ltd.) having 16 carbon atoms/18 carbon atoms was continuously charged into the polymerizer at a constant rate over 2 hours. The start of the loading was set to start the polymerization and the polymerization was maintained at 45℃for 4.5 hours. Hydrogen 16.25 was charged each after 1 hour and 2 hours from the start of polymerization, nmL. After 4.5 hours from the start of polymerization, the temperature was lowered to room temperature, and immediately after the depressurization, the polymerization solution containing a white solid was filtered to obtain a solid-like substance. The solid matter was dried at 80℃for 8 hours under reduced pressure to obtain a polymer 1. The yield was 124g. The 4-methyl-1-pentene content in the polymer 1 was 97.5mol%, and the α -olefin (1-hexadecene, 1-octadecene) content was 2.5mol%. The melting point (Tm) of the polymer 1 was 205℃and the intrinsic viscosity [ eta ] was 5.1dl/g.
Example 2
(production of Polymer 2)
A SUS-made polymerizer having an internal volume of 1L and a stirrer was charged with 425mL of purified decane at room temperature under a nitrogen flow, and cooled to 10 ℃. After reaching 10 ℃, 0.8mL (0.4 mmol in terms of aluminum atom) of a decane solution of triisobutylaluminum (0.5 mmol/mL in terms of aluminum atom) was charged, followed by charging a decane slurry of the previously prepared prepolymerized catalyst component of Synthesis example 3 in an amount of 0.006mmol in terms of zirconium atom. Hydrogen 22.5. 22.5NmL was charged, and then a mixed solution of 219mL of 4-methyl-1-pentene and 33.0mL of an alpha-olefin mixture (trade name; linear 168, manufactured by Kaiko Kaisha Co., ltd.) having 16 carbon atoms/18 carbon atoms was continuously charged into the polymerizer at a constant rate over 2 hours. The start of the loading was set to start the polymerization and the reaction was maintained at 10℃for 4.5 hours. Hydrogen 22.5. 22.5NmL was charged 1 hour and 2 hours after the start of polymerization, respectively. After 4.5 hours from the start of polymerization, the pressure was released, and immediately after that, the polymerization solution containing a white solid was filtered to obtain a solid-like substance. The solid matter was dried at 80℃for 8 hours under reduced pressure to obtain polymer 2. The yield was 162g. The 4-methyl-1-pentene content in the polymer 2 was 94.3mol%, and the α -olefin (1-hexadecene, 1-octadecene) content was 5.7mol%. Polymer 2 has a melting point (Tm) of 184℃and an intrinsic viscosity [ eta ] of 4.4dl/g.
Example 3
(production of Polymer 3)
425mL of purified heptane, 69mL of 4-methyl-1-pentene and 5.1mL of linear 168 (produced by Ningshi Co., ltd.) were charged into a SUS-made polymerizer having an inner volume of 1L and equipped with a stirrer at room temperature under a nitrogen flow, and the temperature was raised to 40 ℃. 0.43mL (0.43 mmol in terms of aluminum atom) of a toluene solution (1.0 mmol/mL in terms of aluminum atom) of triisobutylaluminum was charged. Next, 2.67mL of a toluene solution containing 0.189mmol of previously prepared methylaluminoxane and 0.00063mmol of (8-octamethylfluoren-12' -yl- (2- (adamantan-1-yl) -8-methyl-3, 3b,4,5,6, 7a, 8-octahydrocyclopenta [ a ] indene)) zirconium dichloride was charged. Next, hydrogen 31.25. 31.25NmL was charged to start polymerization. The start of the loading was set to start the polymerization, and the polymerization was kept at 45℃for 90 minutes. After 90 minutes from the start of polymerization, the pressure was released, and thereafter, the polymerization was stopped by exposure to air. The reaction solution was poured into acetone to which hydrochloric acid was added, and the entire amount of the polymer was precipitated, and after stirring, the polymer was filtered through filter paper to obtain a solid substance. The solid matter was dried at 80℃for 8 hours under reduced pressure to obtain a polymer 3. The yield was 35g. The 4-methyl-1-pentene content in the polymer 3 was 96.7mol%, and the α -olefin (1-hexadecene, 1-octadecene) content was 3.3mol%. Polymer 3 had a melting point (Tm) of 199℃and an intrinsic viscosity [ eta ] of 3.4dl/g.
Example 4
(production of Polymer 4)
In a SUS-made polymerizer with stirring blade having a capacity of 1.5L and sufficiently purged with nitrogen, 500mL of 4-methyl-1-pentene and 230mL of heptane were charged at 23 ℃. The autoclave was continuously charged with 20mL of linear 168 (produced by Niku-shi), and 0.3mL of a toluene solution of 1.0mmol/mL of Triisobutylaluminum (TIBAL), and stirring was started. Next, 140mL of hydrogen was charged, and the autoclave was heated to an internal temperature of 60 ℃. 2mL of a toluene solution containing 0.033mmol of previously prepared methylaluminoxane, (8-octamethylfluoren-12' -yl- (2- (adamantan-1-yl) -8-methyl-3, 3b,4,5,6, 7a, 8-octahydrocyclopenta [ a ] indene)) zirconium dichloride in terms of Al was introduced into an autoclave by pressing the solution into the autoclave with nitrogen, and polymerization was started. In the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave became 60 ℃. 13 minutes after the start of polymerization, 5mL of methanol was introduced into the autoclave with nitrogen, the polymerization was stopped, and the autoclave was depressurized to atmospheric pressure. The reaction solution was poured into acetone while stirring, and the polymer was precipitated. The resulting solvent-containing polymer was dried at 130℃under reduced pressure for 10 hours. The obtained polymer 4 was 68.4g, the content of 4-methyl-1-pentene in the polymer 4 was 97.6mol%, and the content of α -olefin (1-hexadecene, 1-octadecene) was 2.4mol%. Polymer 4 has a melting point (Tm) of 207℃and an intrinsic viscosity [ eta ] of 2.4dl/g.
Example 5
(production of Polymer 5)
In a SUS-made polymerizer with stirring blade having a capacity of 1.5L and sufficiently purged with nitrogen, 500mL of 4-methyl-1-pentene and 210mL of heptane were charged at 23 ℃. The autoclave was continuously charged with 45mL of linear 168 (produced by Niku-shi Co., ltd.) and 0.3mL of a toluene solution of 1.0mmol/mL of Triisobutylaluminum (TIBAL), and stirring was started. Next, 140mL of hydrogen was charged, and the autoclave was heated to an internal temperature of 60 ℃. 2mL of a toluene solution containing 0.033mmol of previously prepared methylaluminoxane, (8-octamethylfluoren-12' -yl- (2- (adamantan-1-yl) -8-methyl-3, 3b,4,5,6, 7a, 8-octahydrocyclopenta [ a ] indene)) zirconium dichloride in terms of Al was introduced into an autoclave by pressing the solution into the autoclave with nitrogen, and polymerization was started. In the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave became 60 ℃. 13 minutes after the start of polymerization, 5mL of methanol was introduced into the autoclave with nitrogen, the polymerization was stopped, and the autoclave was depressurized to atmospheric pressure. The reaction solution was poured into acetone while stirring, and the polymer was precipitated.
The obtained polymer containing a solvent was dried at 130℃under reduced pressure for 10 hours. The obtained polymer 5 was 68.6g, the content of 4-methyl-1-pentene in the polymer 5 was 94.6mol%, and the content of α -olefin (1-hexadecene, 1-octadecene) was 5.4mol%. The melting point (Tm) of the polymer 5 was 173℃and the intrinsic viscosity [ eta ] was 2.4dl/g.
Example 6
(production of Polymer 6)
In a SUS-made polymerizer with stirring blade having a capacity of 1.5L and sufficiently purged with nitrogen, 500mL of 4-methyl-1-pentene and 220mL of heptane were charged at 23 ℃. The autoclave was continuously charged with 30mL of 1-decene and 0.3mL of a toluene solution of 1.0mmol/mL of Triisobutylaluminum (TIBAL), and stirring was started. Next, 140mL of hydrogen was charged, and the autoclave was heated to an internal temperature of 60 ℃. 2mL of a toluene solution containing 0.039mmol of previously prepared methylaluminoxane, (8-octamethylfluoren-12' -yl- (2- (adamantan-1-yl) -8-methyl-3, 3b,4,5,6, 7a, 8-octahydrocyclopenta [ a ] indene)) zirconium dichloride in terms of Al was introduced into an autoclave by pressing the solution into the autoclave with nitrogen, and polymerization was started. In the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave became 60 ℃. After 10 minutes from the start of polymerization, 5mL of methanol was introduced into the autoclave with nitrogen, the polymerization was stopped, and the autoclave was depressurized to atmospheric pressure. The reaction solution was poured into acetone while stirring, and the polymer was precipitated. The resulting solvent-containing polymer was dried at 130℃under reduced pressure for 10 hours. The resulting polymer 6 was 66.5g, the content of 4-methyl-1-pentene in the polymer 6 was 94.1mol%, and the content of α -olefin (1-decene) was 5.9mol%. The melting point (Tm) of Polymer 6 was 190℃and the intrinsic viscosity [ eta ] was 2.3dl/g.
Example 7
(production of Polymer 7)
In a SUS-made polymerizer with stirring blade having a capacity of 1.5L and sufficiently purged with nitrogen, 500mL of 4-methyl-1-pentene and 230mL of heptane were charged at 23 ℃. The autoclave was continuously charged with 15mL of 1-decene and 0.3mL of a toluene solution of 1.0mmol/mL of Triisobutylaluminum (TIBAL), and stirring was started. Next, 140mL of hydrogen was charged, and the autoclave was heated to an internal temperature of 60 ℃. 2mL of a toluene solution containing 0.06mmol of previously prepared methylaluminoxane, (8-octamethylfluoren-12' -yl- (2- (adamantan-1-yl) -8-methyl-3, 3b,4,5,6, 7a, 8-octahydrocyclopenta [ a ] indene)) zirconium dichloride in terms of Al was introduced into an autoclave by pressure with nitrogen, and polymerization was started. In the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave became 60 ℃. After 30 minutes from the start of polymerization, 5mL of methanol was introduced into the autoclave with nitrogen, the polymerization was stopped, and the autoclave was depressurized to atmospheric pressure. The reaction solution was poured into acetone while stirring, and the polymer was precipitated. The resulting solvent-containing polymer was dried at 130℃under reduced pressure for 10 hours. The resulting polymer 7 was 35.6g, the content of 4-methyl-1-pentene in the polymer 7 was 96.7mol%, and the content of α -olefin (1-decene) was 3.3mol%. The melting point (Tm) of the polymer 7 was 212℃and the intrinsic viscosity [ eta ] was 2.3dl/g.
Example 8
(production of Polymer 8)
425mL of purified decane was charged into a SUS-made polymerizer having an internal volume of 1L and equipped with a stirrer, and the temperature was raised to 40℃under a nitrogen flow at room temperature. After reaching 40 ℃, 0.8mL (0.4 mmol in terms of aluminum atom) of a decane solution of triisobutylaluminum (0.5 mmol/mL in terms of aluminum atom) was charged, followed by charging a decane slurry of the previously prepared prepolymerized catalyst component of Synthesis example 3 in which 0.00075mmol in terms of zirconium atom was charged. Hydrogen 35, nmL was charged, and then a mixed solution of 238mL of 4-methyl-1-pentene and 13.6mL of 1-decene was continuously charged into the polymerizer at a constant rate over 2 hours. The start of the loading was set to start the polymerization and the polymerization was maintained at 45℃for 4.5 hours. Hydrogen 35NmL was charged 1 hour and 2 hours after the start of polymerization, respectively. After 4.5 hours from the start of polymerization, the temperature was lowered to room temperature, and immediately after the depressurization, the polymerization solution containing a white solid was filtered to obtain a solid-like substance. The solid matter was dried at 80℃for 8 hours under reduced pressure to obtain a polymer 8. The yield was 154g. The 4-methyl-1-pentene content in polymer 8 was 96.2mol%, and the α -olefin (1-decene content) was 3.8mol%. The melting point (Tm) of the polymer 8 was 207℃and the intrinsic viscosity [ eta ] was 2.2dl/g.
Example 9
(production of Polymer 9)
425mL of purified decane was charged into a SUS-made polymerizer having an internal volume of 1L and equipped with a stirrer, and the temperature was raised to 40℃under a nitrogen flow at room temperature. After reaching 40 ℃, 0.8mL (0.4 mmol in terms of aluminum atom) of a decane solution (0.5 mmol/mL in terms of aluminum atom) of Triisobutylaluminum (TIBAL) was charged, followed by charging a decane slurry of the prepolymerized catalyst component of the above-mentioned synthetic example 3 in an amount of 0.0020mmol in terms of zirconium atom. Hydrogen 16.25, 16.25NmL was charged, and then a mixture of 231mL of 4-methyl-1-pentene and 20.6mL of linear 168 (a mixture of 1-hexadecene and 1-octadecene produced by Wako-chemical industries, ltd.) was continuously charged into the polymerizer at a constant rate over 2 hours. The start of the loading of the above-mentioned mixed solution was set as the start of polymerization, and the mixture was kept at 45℃for 4.5 hours. Hydrogen 16.25. 16.25NmL was charged 1 hour and 2 hours after the start of polymerization, respectively. After 4.5 hours from the start of polymerization, the temperature was lowered to room temperature, and immediately after the depressurization, the polymerization solution containing a white solid was filtered to obtain a solid-like substance. The solid matter was dried at 80℃for 8 hours under reduced pressure to obtain a polymer 9. The yield was 128g. The 4-methyl-1-pentene content in the polymer 9 was 97.0mol%, and the α -olefin (1-hexadecene, 1-octadecene) content was 3.0mol%. The melting point (Tm) of the polymer 9 was 203℃and the intrinsic viscosity [ eta ] was 5.3dl/g.
Example 10
(production of Polymer 10)
425mL of purified decane was charged into a SUS-made polymerizer having an internal volume of 1L and equipped with a stirrer, and the temperature was raised to 40℃under a nitrogen flow at room temperature. After reaching 40 ℃, 0.8mL (0.4 mmol in terms of aluminum atom) of a decane solution (0.5 mmol/mL in terms of aluminum atom) of Triisobutylaluminum (TIBAL) was charged, followed by charging a decane slurry of the prepolymerized catalyst component of the above-mentioned synthetic example 3 in an amount of 0.00175mmol in terms of zirconium atom. Hydrogen 23.75 and NmL was charged, and then a mixture of 232mL of 4-methyl-1-pentene and 19.6mL of linear 168 (a mixture of 1-hexadecene and 1-octadecene produced in the light emitting system) was continuously charged into the polymerizer at a constant rate over 2 hours. The start of the loading of the above-mentioned mixed solution was set as the start of polymerization, and the mixture was kept at 45℃for 4.5 hours. Hydrogen 23.75NmL was charged 1 hour and 2 hours after the start of polymerization, respectively. After 4.5 hours from the start of polymerization, the temperature was lowered to room temperature, and immediately after the depressurization, the polymerization solution containing a white solid was filtered to obtain a solid-like substance. The solid matter was dried at 80℃for 8 hours under reduced pressure, to obtain a polymer 10. The yield was 146g. The 4-methyl-1-pentene content in the polymer 10 was 96.7mol%, and the α -olefin (1-hexadecene, 1-octadecene) content was 3.3mol%. The melting point (Tm) of the polymer 10 was 203℃and the intrinsic viscosity [ eta ] was 4.0dl/g.
Example 11
(production of Polymer 11)
425mL of purified decane was charged into a SUS-made polymerizer having an internal volume of 1L and equipped with a stirrer, and the temperature was raised to 40℃under a nitrogen flow at room temperature. After reaching 40 ℃, 0.8mL (0.4 mmol in terms of aluminum atom) of a decane solution (0.5 mmol/mL in terms of aluminum atom) of Triisobutylaluminum (TIBAL) was charged, followed by charging a decane slurry of the prepolymerized catalyst component of the above-mentioned synthetic example 3 in an amount of 0.00175mmol in terms of zirconium atom. Hydrogen 23.75 and NmL was charged, and then a mixture of 230mL of 4-methyl-1-pentene and 22.4mL of linear 168 (a mixture of 1-hexadecene and 1-octadecene produced in the light emitting system) was continuously charged into the polymerizer at a constant rate over 2 hours. The start of the loading of the above-mentioned mixed solution was set as the start of polymerization, and the mixture was kept at 45℃for 4.5 hours. Hydrogen 23.75NmL was charged 1 hour and 2 hours after the start of polymerization, respectively. After 4.5 hours from the start of polymerization, the temperature was lowered to room temperature, and immediately after the depressurization, the polymerization solution containing a white solid was filtered to obtain a solid-like substance. The solid matter was dried at 80℃for 8 hours under reduced pressure to obtain a polymer 11. The yield was 142g. The 4-methyl-1-pentene content in the polymer 11 was 96.5mol%, and the α -olefin (1-hexadecene, 1-octadecene) content was 3.5mol%. The melting point (Tm) of the polymer 11 was 201℃and the intrinsic viscosity [ eta ] was 4.2dl/g.
Example 12
(production of Polymer 12)
Polymer 9 (100 parts by mass), maleic anhydride 2 parts by mass, and 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexyne-3 (PERCEXYNE 25B, manufactured by Nippon Co., ltd.) as an organic peroxide were blended in an amount of 0.02 parts by mass, and kneaded at a resin temperature of 280℃and a screw speed of 150rpm using a mixer of a laboratory small kneader (Labo Plastomill) manufactured by Toyo Seisakusho Co., ltd.) to obtain polymer 12. The amount of the structural unit in the polymer 12 is the same as that of the polymer 9. The melting point (Tm) of the polymer 12 was 203℃and the intrinsic viscosity [ eta ] was 0.8dl/g, and the graft amount was 1.5 mass%.
Example 13
(production of Polymer 13)
Polymer 13 was obtained by producing the same as that of Polymer 12 except that Polymer 10 was used instead of Polymer 9.
The amount of structural units in polymer 13 is the same as that of polymer 10. The melting point (Tm) of the polymer 13 was 203℃and the intrinsic viscosity [ eta ] was 0.9dl/g, and the graft amount was 1.6 mass%.
Example 14
(production of Polymer 14)
Polymer 14 was obtained by producing the same as polymer 12 except that polymer 11 was used instead of polymer 9.
The amount of structural units in polymer 14 is the same as that of polymer 11. The melting point (Tm) of the polymer 14 was 201℃and the intrinsic viscosity [ eta ] was 0.9dl/g, and the graft amount was 1.5 mass%.
Example 15
(production of Polymer 15)
Polymer 9 (100 parts by mass), 1 part by mass of maleic anhydride and 0.01 part by mass of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexyne-3 (PERCEXYNE 25B, manufactured by Nikkin Co., ltd.) as an organic peroxide were blended, and kneaded at a resin temperature of 230℃and a screw rotation speed of 130rpm using a mixer of a small-sized laboratory kneader manufactured by Toyo Seisakusho Co., ltd.) to obtain polymer 15. The amount of the structural unit in the polymer 15 is the same as that of the polymer 9. The melting point (Tm) of the polymer 15 was 203℃and the intrinsic viscosity [ eta ] was 2.4dl/g, and the graft amount was 0.6 mass%.
Comparative example 1
(production of Polymer 16)
In a SUS-made polymerizer with stirring blades having a capacity of 1.5 liters and fully purged with nitrogen, 750ml of 4-methyl-1-pentene was charged at 23 ℃. The autoclave was charged with 0.75ml of a toluene solution of Triisobutylaluminum (TIBAL) at 1.0mmol/ml, and the stirrer was rotated.
Next, the autoclave was heated to an internal temperature of 60 ℃, and pressurized with propylene so that the total pressure became 0.15MPa (gauge pressure). Next, 0.34ml of a toluene solution containing 1mmol of methylaluminoxane and 0.003mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2, 7-di-t-butyl-fluorenyl) zirconium dichloride prepared in advance in terms of Al was introduced into an autoclave by pressing with nitrogen gas, and polymerization was started. In the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave became 60 ℃. After 5 minutes from the start of polymerization, 5mL of methanol was introduced into the autoclave with nitrogen, the polymerization was stopped, and the autoclave was depressurized to atmospheric pressure. Acetone was injected into the reaction solution while stirring. The resulting solvent-containing powdered polymer was dried at 130℃under reduced pressure for 12 hours. The resulting polymer 16 was 19.9g, and the content of 4-methyl-1-pentene in the polymer 16 was 92.0mol% and the content of propylene was 8.0mol%. The melting point Tm of the polymer 16 is 180℃and the intrinsic viscosity [ eta ] is 1.6dl/g.
Comparative example 2
(production of Polymer 17)
According to the polymerization method described in comparative example 9 of International publication No. 2006/054613, a 4-methyl-1-pentene polymer (polymer 17) described in Table 1 was obtained by changing the proportions of 4-methyl-1-pentene, other α -olefin (mass mixture such as 1-hexadecene and 1-octadecene), and hydrogen.
Example 16
To 10g of Polymer 1, 0.1% by weight of tris (2, 4-di-t-butylphenyl) phosphate as an antioxidant and 0.1% by weight of n-octadecyl-3- (4 ' -hydroxy-3 ',5' -di-t-butylphenyl) propionate as a heat stabilizer were added, and methylcyclohexane (manufactured by Wako pure chemical industries, ltd.) was added so that the solid content concentration became 5% by weight, and the mixture was stirred at 200rpm at 90℃for 1 hour, thereby producing a composition comprising Polymer 1. The composition was coated on a glass substrate at 25℃and uniformly spread using an applicator, and then dried at 25℃for 30 minutes and further dried at 80℃for 10 minutes, to obtain a film.
Further, in order to evaluate the appearance of the coating film, the above composition was coated on a PET (made by eastern corporation "lumirror") substrate at 25 ℃, uniformly spread with an applicator, and then dried at 25 ℃ for 30 minutes, and further dried at 80 ℃ for 10 minutes, to obtain the coating film.
Example 17
A composition, a film, and a coating film were obtained in the same manner as in example 16, except that the polymer 2 was used instead of the polymer 1.
Example 18
A composition, a film, and a coating film were obtained in the same manner as in example 16, except that the polymer 3 was used instead of the polymer 1.
Example 19
A composition, a film, and a coating film were obtained in the same manner as in example 16, except that the polymer 4 was used instead of the polymer 1.
Example 20
A composition, a film, and a coating film were obtained in the same manner as in example 16, except that the polymer 5 was used instead of the polymer 1.
Example 21
A composition, a film, and a coating film were obtained in the same manner as in example 16, except that the polymer 6 was used instead of the polymer 1.
Example 22
A composition, a film, and a coating film were obtained in the same manner as in example 16, except that the polymer 7 was used instead of the polymer 1.
Example 23
A composition, a film, and a coating film were obtained in the same manner as in example 16, except that the polymer 8 was used instead of the polymer 1.
Example 24
A composition, a film, and a coating film were obtained in the same manner as in example 16, except that the polymer 9 was used instead of the polymer 1.
Example 25
A composition, a film, and a coating film were obtained in the same manner as in example 16, except that the polymer 10 was used instead of the polymer 1.
Example 26
A composition, a film, and a coating film were obtained in the same manner as in example 16, except that the polymer 11 was used instead of the polymer 1.
Example 27
A composition, a film, and a coating film were obtained in the same manner as in example 16, except that the polymer 12 was used instead of the polymer 1.
Example 28
A composition, a film, and a coating film were obtained in the same manner as in example 16, except that the polymer 13 was used instead of the polymer 1.
Example 29
A composition, a film, and a coating film were obtained in the same manner as in example 16, except that the polymer 14 was used instead of the polymer 1.
Example 30
A composition, a film, and a coating film were obtained in the same manner as in example 16, except that the polymer 15 was used instead of the polymer 1.
Comparative example 3
A composition, a film, and a coating film were obtained in the same manner as in example 16, except that the polymer 16 was used instead of the polymer 1.
Comparative example 4
Polymer 17 was used instead of Polymer 1, and the mixture was stirred at 200rpm at 90℃for 1 hour in the same manner as in example 16, but most of Polymer 17 remained undissolved. Thus, the coating film was produced with a solution having a sufficient concentration, and thus a composition, a film and a coating film could not be obtained.
Table 1 shows the compositions and physical properties of the polymers of examples 1 to 30 and comparative examples 1 to 4, and the physical properties of the compositions, films and coating films. In addition, in comparative example 4, since the composition, film and coating film could not be obtained, evaluation of storage stability, contact angle of water, normalized insulation breakdown voltage and appearance of coating film could not be performed.
[ Table 1-1]
TABLE 1
[ tables 1-2]
Table 1 (subsequent)
The amount of the solvent contained in the films obtained in examples 16 to 30 and comparative examples 3 to 4 was 0.001 to 0.2 mass% based on 100 mass% of the film.
Claims (9)
1. A4-methyl-1-pentene polymer (A) which is a copolymer of 4-methyl-1-pentene and at least 1 selected from linear alpha-olefins having 6 to 20 carbon atoms and satisfies the following requirements (I) and (II),
(I) An endothermic end temperature TmE in a melting (endothermic) curve obtained by DSC measurement is 230 ℃ or lower,
(II) the exothermic onset temperature TcS in the crystallization (exothermic) curve obtained by DSC measurement is 210 ℃ or lower.
2. The 4-methyl-1-pentene polymer (A) according to claim 1, which has a melting point Tm of 170 to 242℃as measured by DSC.
3. The 4-methyl-1-pentene polymer (A) according to claim 1 or 2, which has an intrinsic viscosity [ eta ] of 1.7 to 5.5dl/g.
4. The 4-methyl-1-pentene polymer (A) according to claim 1, which has a melting point Tm of 200 to 242℃as measured by DSC.
5. The 4-methyl-1-pentene polymer (a) according to any one of claims 1 to 4, wherein the amount U1 of structural units derived from 4-methyl-1-pentene is 84.0 to 100 mol% and the total amount U2 of structural units derived from at least 1 selected from linear alpha-olefins having 6 to 20 carbon atoms is 16.0 to 0 mol%, and wherein the total of U1 and U2 is 100 mol%.
6. The 4-methyl-1-pentene polymer (a) according to any one of claims 1 to 5, which is not modified.
7. A composition (X) comprising 0.1 to 50% by mass of the 4-methyl-1-pentene polymer (A) according to any one of claims 1 to 6 and 50 to 99.9% by mass of the solvent (B).
8. The composition (X) according to claim 7, wherein the solvent (B) is an organic solvent.
9. A coating agent comprising the composition (X) according to claim 7 or 8.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-032478 | 2021-03-02 | ||
| JP2021032479 | 2021-03-02 | ||
| JP2021-032479 | 2021-03-02 | ||
| PCT/JP2022/007625 WO2022186044A1 (en) | 2021-03-02 | 2022-02-24 | 4-methyl-1-pentene polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116897172A true CN116897172A (en) | 2023-10-17 |
Family
ID=88312501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280018039.9A Pending CN116897172A (en) | 2021-03-02 | 2022-02-24 | 4-Methyl-1-pentene polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116897172A (en) |
-
2022
- 2022-02-24 CN CN202280018039.9A patent/CN116897172A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2222017A1 (en) | Blends and alloys of polycyclic polymers | |
| JP2009161743A (en) | Post curing resin composition and high frequency electrical insulating material using the same | |
| CN111777702B (en) | Modified cycloolefin random copolymer and preparation method thereof | |
| JP2007119660A (en) | Cycloolefin addition copolymer, process for producing the same and molding material | |
| JP2007084764A (en) | Coating material and method for producing the same | |
| JP4826242B2 (en) | Method for producing cyclic olefin-based addition polymer | |
| JPWO2007026527A1 (en) | Cyclic olefin addition polymer, composite and molded product thereof, and optical material | |
| JP7044521B2 (en) | Release film | |
| CN116897172A (en) | 4-Methyl-1-pentene polymer | |
| JP2005060639A (en) | Method for producing cycloolefin base addition polymer | |
| WO2007066712A1 (en) | Resin for thermal imprinting | |
| JP5840064B2 (en) | Composition, film, and method for producing said film | |
| JP5177335B2 (en) | Cross-linked body and cross-linking composition | |
| EP1862484A1 (en) | Norbornene addition copolymer and moldings | |
| JP5721913B2 (en) | Norbornene polymer solution | |
| TW202244077A (en) | 4-methyl-1-pentene polymer | |
| WO2005046964A1 (en) | Method for producing film or sheet having three-dimensional pattern on surface, and film or sheet having three-dimensional pattern on surface | |
| JP7365215B2 (en) | Olefin resin composition | |
| JP5331315B2 (en) | Thermal imprint method | |
| JP4626023B2 (en) | Cyclic olefin copolymer and optical material | |
| JP2005239975A (en) | Production method for aromatic-containing cycloolefin copolymer | |
| EP1725591A1 (en) | Method for preparing cyclic olefin polymer having high bulk density and cyclic olefin polymer prepared thereby | |
| JP2023051053A (en) | Laminate and method for manufacturing laminate | |
| WO2009139293A1 (en) | Cyclic olefin resin and film comprising the resin | |
| JP2004074662A (en) | Method for manufacturing cycloolefin addition polymer film or sheet and film or sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |