WO2022270375A1 - Composition - Google Patents
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- WO2022270375A1 WO2022270375A1 PCT/JP2022/023930 JP2022023930W WO2022270375A1 WO 2022270375 A1 WO2022270375 A1 WO 2022270375A1 JP 2022023930 W JP2022023930 W JP 2022023930W WO 2022270375 A1 WO2022270375 A1 WO 2022270375A1
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- WIPO (PCT)
- Prior art keywords
- polymer
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- 239000000203 mixture Substances 0.000 title claims abstract description 174
- 229920000642 polymer Polymers 0.000 claims abstract description 465
- 229920001721 polyimide Polymers 0.000 claims abstract description 207
- 239000002530 phenolic antioxidant Substances 0.000 claims abstract description 132
- 125000001424 substituent group Chemical group 0.000 claims abstract description 86
- 125000003118 aryl group Chemical group 0.000 claims abstract description 64
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 61
- 239000002904 solvent Substances 0.000 claims description 246
- 239000009719 polyimide resin Substances 0.000 claims description 185
- 125000004432 carbon atom Chemical group C* 0.000 claims description 160
- 125000000217 alkyl group Chemical group 0.000 claims description 49
- 239000000178 monomer Substances 0.000 claims description 42
- 125000005843 halogen group Chemical group 0.000 claims description 40
- 150000002430 hydrocarbons Chemical group 0.000 claims description 39
- 150000001925 cycloalkenes Chemical class 0.000 claims description 38
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 31
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- 125000002950 monocyclic group Chemical group 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 5
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 5
- 239000004760 aramid Substances 0.000 claims description 3
- 229920003235 aromatic polyamide Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 42
- 229920005989 resin Polymers 0.000 abstract description 42
- 239000004642 Polyimide Substances 0.000 abstract description 16
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 abstract 1
- -1 n-octyl group Chemical group 0.000 description 251
- 229920001577 copolymer Polymers 0.000 description 198
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 120
- 238000010521 absorption reaction Methods 0.000 description 94
- 239000006185 dispersion Substances 0.000 description 73
- 238000000034 method Methods 0.000 description 73
- 239000002131 composite material Substances 0.000 description 58
- 239000000243 solution Substances 0.000 description 55
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 51
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 46
- 230000015572 biosynthetic process Effects 0.000 description 43
- 229920002313 fluoropolymer Polymers 0.000 description 43
- 239000004811 fluoropolymer Substances 0.000 description 43
- 229920005575 poly(amic acid) Polymers 0.000 description 41
- 238000000576 coating method Methods 0.000 description 38
- 238000004519 manufacturing process Methods 0.000 description 38
- 239000011248 coating agent Substances 0.000 description 35
- 239000002245 particle Substances 0.000 description 33
- 239000000758 substrate Substances 0.000 description 33
- 230000001965 increasing effect Effects 0.000 description 31
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 30
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 28
- 239000003963 antioxidant agent Substances 0.000 description 27
- 230000003647 oxidation Effects 0.000 description 26
- 238000007254 oxidation reaction Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 25
- 238000011156 evaluation Methods 0.000 description 25
- 238000005259 measurement Methods 0.000 description 25
- 125000003545 alkoxy group Chemical group 0.000 description 24
- 239000011164 primary particle Substances 0.000 description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 23
- 238000010438 heat treatment Methods 0.000 description 23
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 22
- 125000000962 organic group Chemical group 0.000 description 22
- 230000002829 reductive effect Effects 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 19
- 238000001035 drying Methods 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 230000003078 antioxidant effect Effects 0.000 description 18
- 230000006866 deterioration Effects 0.000 description 18
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 17
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 17
- 239000011521 glass Substances 0.000 description 17
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 17
- 239000004810 polytetrafluoroethylene Substances 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 230000002776 aggregation Effects 0.000 description 16
- 238000004220 aggregation Methods 0.000 description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 239000005977 Ethylene Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 239000000523 sample Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 14
- 150000008282 halocarbons Chemical group 0.000 description 14
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 125000003277 amino group Chemical group 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000005227 gel permeation chromatography Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 125000001931 aliphatic group Chemical group 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 11
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 11
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 10
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 239000004793 Polystyrene Substances 0.000 description 10
- 238000005452 bending Methods 0.000 description 10
- 239000011889 copper foil Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 229920002223 polystyrene Polymers 0.000 description 10
- 239000002966 varnish Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 9
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 230000003993 interaction Effects 0.000 description 8
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 229910052723 transition metal Inorganic materials 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 125000004104 aryloxy group Chemical group 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 235000010290 biphenyl Nutrition 0.000 description 7
- 239000004305 biphenyl Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 125000001153 fluoro group Chemical group F* 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 125000001624 naphthyl group Chemical group 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 description 7
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- 230000036961 partial effect Effects 0.000 description 6
- 230000000737 periodic effect Effects 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 5
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 5
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 5
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- VYGUBTIWNBFFMQ-UHFFFAOYSA-N [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical group [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O VYGUBTIWNBFFMQ-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 150000001639 boron compounds Chemical class 0.000 description 4
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 150000001924 cycloalkanes Chemical class 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
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- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 description 1
- 125000005327 perimidinyl group Chemical group N1C(=NC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- AVRVTTKGSFYCDX-UHFFFAOYSA-N perylene-1,2,7,8-tetracarboxylic acid Chemical compound C1=CC(C2=C(C(C(=O)O)=CC=3C2=C2C=CC=3)C(O)=O)=C3C2=C(C(O)=O)C(C(O)=O)=CC3=C1 AVRVTTKGSFYCDX-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- RVRYJZTZEUPARA-UHFFFAOYSA-N phenanthrene-1,2,9,10-tetracarboxylic acid Chemical compound C1=CC=C2C(C(O)=O)=C(C(O)=O)C3=C(C(O)=O)C(C(=O)O)=CC=C3C2=C1 RVRYJZTZEUPARA-UHFFFAOYSA-N 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000036316 preload Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N pristane Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- RTHVZRHBNXZKKB-UHFFFAOYSA-N pyrazine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=NC(C(O)=O)=C(C(O)=O)N=C1C(O)=O RTHVZRHBNXZKKB-UHFFFAOYSA-N 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000005581 pyrene group Chemical group 0.000 description 1
- MIROPXUFDXCYLG-UHFFFAOYSA-N pyridine-2,5-diamine Chemical compound NC1=CC=C(N)N=C1 MIROPXUFDXCYLG-UHFFFAOYSA-N 0.000 description 1
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- YKWDNEXDHDSTCU-UHFFFAOYSA-N pyrrolidine-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C1NC(C(O)=O)C(C(O)=O)C1C(O)=O YKWDNEXDHDSTCU-UHFFFAOYSA-N 0.000 description 1
- MHOZZUICEDXVGD-UHFFFAOYSA-N pyrrolo[2,3-d]imidazole Chemical group C1=NC2=CC=NC2=N1 MHOZZUICEDXVGD-UHFFFAOYSA-N 0.000 description 1
- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical group C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 description 1
- GZTPJDLYPMPRDF-UHFFFAOYSA-N pyrrolo[3,2-c]pyrazole Chemical group N1=NC2=CC=NC2=C1 GZTPJDLYPMPRDF-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 125000005579 tetracene group Chemical group 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- 125000006337 tetrafluoro ethyl group Chemical group 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- ONCNIMLKGZSAJT-UHFFFAOYSA-N thieno[3,2-b]furan Chemical group S1C=CC2=C1C=CO2 ONCNIMLKGZSAJT-UHFFFAOYSA-N 0.000 description 1
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical group S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- LUEGQDUCMILDOJ-UHFFFAOYSA-N thiophene-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C=1SC(C(O)=O)=C(C(O)=O)C=1C(O)=O LUEGQDUCMILDOJ-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003852 triazoles Chemical group 0.000 description 1
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- NPHLURKGGOFSPO-UHFFFAOYSA-N tris(2,3,4,5-tetrafluorophenyl)borane Chemical compound FC1=C(F)C(F)=CC(B(C=2C(=C(F)C(F)=C(F)C=2)F)C=2C(=C(F)C(F)=C(F)C=2)F)=C1F NPHLURKGGOFSPO-UHFFFAOYSA-N 0.000 description 1
- BMKAZNZYKFHZCV-UHFFFAOYSA-N tris(2,3,4-trifluorophenyl)borane Chemical compound FC1=C(F)C(F)=CC=C1B(C=1C(=C(F)C(F)=CC=1)F)C1=CC=C(F)C(F)=C1F BMKAZNZYKFHZCV-UHFFFAOYSA-N 0.000 description 1
- GZQXROYFQLBBPK-UHFFFAOYSA-N tris(2,3,5,6-tetrafluorophenyl)borane Chemical compound FC1=CC(F)=C(F)C(B(C=2C(=C(F)C=C(F)C=2F)F)C=2C(=C(F)C=C(F)C=2F)F)=C1F GZQXROYFQLBBPK-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- LKNHGIFPRLUGEG-UHFFFAOYSA-N tris(3,4,5-trifluorophenyl)borane Chemical compound FC1=C(F)C(F)=CC(B(C=2C=C(F)C(F)=C(F)C=2)C=2C=C(F)C(F)=C(F)C=2)=C1 LKNHGIFPRLUGEG-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Definitions
- the present invention relates to a composition capable of forming a film that can be used as a substrate material compatible with high-frequency band printed circuit boards and antenna substrates, and the film.
- a copper-clad laminate called CCL has a structure in which copper foils are laminated on both surfaces of a resin layer via an adhesive. Since the transmission loss of the CCL can be suppressed by reducing the dielectric loss, particularly the dielectric loss tangent and the dielectric constant of the resin layer that serves as the transmission path, films with a low dielectric loss tangent are being studied.
- Patent Document 1 discloses a low dielectric resin composition containing a resin (A) such as a polyimide resin and a cyclic olefin (co)polymer (B), and a film having a low dielectric loss tangent formed from the composition. is disclosed.
- a resin (A) such as a polyimide resin and a cyclic olefin (co)polymer (B)
- an object of the present invention is to provide a composition capable of forming a film with excellent moisture absorption resistance and the film.
- the present inventors arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention includes the following preferred embodiments.
- the phenolic antioxidant has the formula (P): [In formula (P), R p , R q , R r and R s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms, and * represents a bond] wherein the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom has an aromatic ring which may have a substituent.
- composition according to [1] or [2], wherein the aromatic ring is a monocyclic aromatic hydrocarbon ring having 6 to 15 carbon atoms.
- the polymer (B) is particulate.
- the polymer (B) is at least one polymer selected from the group consisting of olefin-based polymers, polyimide-based polymers, fluorine-based polymers, silicone-based polymers, liquid-crystal polymers, aramid polymers, styrene-based polymers, and ether-based polymers.
- [8] The composition according to any one of [1] to [7], wherein the polymer (B) is a cycloolefin polymer.
- the cycloolefin-based polymer has the formula (I): [In formula (I), m represents an integer of 0 or more, R 7 to R 18 each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 11 to R When there are a plurality of 14 , they may be the same or different, and R 16 and R 17 may be bonded to each other to form a ring together with the carbon atom to which they are bonded.]
- the content of the monomer unit (I) in the cycloolefin-based polymer is 60 mol% or more relative to the total molar amount of repeating units constituting the cycloolefin-based polymer, according to [9].
- composition [11] containing a polyimide resin (A), a polymer (B) and a phenolic antioxidant,
- the phenolic antioxidant has the formula (P): [In formula (P), R p , R q , R r and R s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms, and * represents a bond]
- a film wherein the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom has an aromatic ring which may have a substituent.
- a composition capable of forming a film with excellent moisture absorption resistance and the film can be provided.
- the composition of the present invention comprises a polyimide resin (A), a polymer (B) and a phenolic antioxidant, wherein the phenolic antioxidant has the formula (P): [In the formula (P), R p , R q , R r and R s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms, and * represents a bond] Including a substituent P (sometimes referred to as a phenolic active site) represented by the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom is an aromatic that may have a substituent has a ring.
- a substituent P (sometimes referred to as a phenolic active site) represented by the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom is an aromatic that may have a substituent has a ring.
- the "film formed from the composition” may be simply referred to as "film”.
- the dielectric property means a property related to dielectric including dielectric loss, relative permittivity and dielectric loss tangent. It shows that the dielectric loss tangent is reduced.
- the present inventors have investigated the moisture absorption resistance of a film formed from a composition containing a polyimide resin (A), a polymer (B), and a solvent, and found that during film formation of the composition, for example, at high temperature It has been found that the polymer (B) is oxidized during the heat treatment of No. 2, resulting in the generation of polar groups, which may reduce the moisture absorption resistance of the film formed from the composition. Therefore, the present inventors focused on the oxidation of the polymer (B) and proceeded with further studies. It has been found that the use of a specific phenolic antioxidant possessed can effectively suppress the oxidation of the polymer (B) during film formation and improve the hygroscopic resistance of the formed film. Therefore, the composition of the present invention can form films having excellent resistance to moisture absorption.
- the composition of the present invention comprises a phenolic antioxidant, said phenolic antioxidant having the formula (P): [In formula (P), R p , R q , R r and R s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms, and * represents a bond]
- the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom is an aromatic ring optionally having a substituent (sometimes referred to as a substituent Q) (where the aromatic ring is different from the substituent P).
- the phenol-based antioxidant has the above aromatic ring as structure S, oxidation during film formation of the polymer (B) contained in the composition of the present invention and the formation of polar groups due to this can be effectively suppressed. A film with excellent hygroscopicity can be formed. Furthermore, even when the resulting film is exposed to a high-temperature environment, deterioration due to oxidation of the polymer (B) can be effectively suppressed, and excellent heat resistance can be exhibited. Although the reason for this is not clear, when the structure S excluding the phenolic active site has an aromatic ring which may have a substituent, in addition to improving the heat resistance of the antioxidant itself, It is presumed that this is because the affinity increases.
- R p , R q , R r and R s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms.
- alkyl groups having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Neopentyl group, n-hexyl group, n-octyl group, tert-amyl group and the like.
- the cycloalkyl group having 5 to 12 carbon atoms include cyclopentyl group, cyclohexyl group, cyclohexylmethyl group and the like.
- R p , R q , R r and R s are at least R p , R q , R r and R s from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the film.
- one is not a hydrogen atom, more preferably one of R p and R q is not a hydrogen atom, still more preferably at least one of R p , R q , R r and R s is a bulky substituent and more preferably at least one of R p and R q is a bulky substituent, and particularly preferably both R p and R q are a bulky substituent.
- the bulky substituent may be a tert-butyl group, a neopentyl group, a tert-amyl group, etc., preferably a tert-butyl group.
- the structures of the substituents P may be the same or different. That is, when there are multiple substituents P, R p , R q , R r and R s in each substituent P may be the same or different.
- R p and R q When at least one of R p and R q is not a hydrogen atom, preferably at least one of R p and R q is a bulky substituent, it reacts with unstable radicals such as carbon radicals and peroxy radicals, When converted to phenoxy radicals, the phenoxy radicals are further stabilized, so that the oxidation of the polymer (B) is easily suppressed, and the hygroscopic resistance and heat resistance of the obtained film are easily improved.
- unstable radicals such as carbon radicals and peroxy radicals
- the structure S in which the substituent P is substituted with a hydrogen atom has an aromatic ring that may have a substituent.
- the aromatic ring is different from the substituent P.
- the aromatic ring is preferably an aromatic ring having 5 to 20 carbon atoms.
- Aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles.
- aromatic hydrocarbon rings examples include monocyclic aromatic hydrocarbon rings, condensed polycyclic aromatic hydrocarbon rings, and ring-assembled aromatic hydrocarbon rings.
- the monocyclic aromatic hydrocarbon ring is preferably a monocyclic aromatic hydrocarbon ring having 6 to 15 carbon atoms, examples of which include a benzene ring.
- the condensed polycyclic aromatic hydrocarbon ring is preferably a condensed polycyclic aromatic hydrocarbon ring having 10 to 20 carbon atoms, examples of which include naphthalene ring, anthracene ring, phenanthrene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.
- the ring-assembled aromatic hydrocarbon ring is two or more monocyclic aromatic hydrocarbon rings, two or more condensed polycyclic aromatic hydrocarbon rings, or one or more monocyclic aromatic hydrocarbon rings and one or more and the condensed polycyclic aromatic hydrocarbon rings of are bonded to each other via a single bond, and ring-assembled aromatic hydrocarbon rings having 10 to 40 carbon atoms are preferred. Examples thereof include biphenyl ring, phenylnaphthyl ring, terphenyl ring, perylene ring and the like.
- a benzene ring, a naphthalene ring, a biphenyl ring and the like are preferable, and a benzene ring is more preferable, from the viewpoint of easily increasing the hygroscopic resistance and heat resistance of the film.
- aromatic heterocycles examples include monocyclic aromatic heterocycles, condensed polycyclic aromatic heterocycles, and ring-assembled aromatic heterocycles.
- the aromatic heterocycle also includes rings having tautomers, and even if the ring itself has no aromaticity, if the tautomers have aromaticity, the term " included in "aromatic heterocycle".
- the isocyanuric ring s-triazine-2,4,6-trione ring
- is s-triazine-2,4,6-triol which has an aromatic tautomer.
- the monocyclic aromatic heterocycle contains at least one heteroatom selected from a sulfur atom, a nitrogen atom and an oxygen atom, and is preferably an aromatic heterocycle having 5 to 15 carbon atoms and heteroatoms, examples of which include: pyrrole ring, pyrazole ring, imidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, isocyanuric ring, diazabenzene ring, furan ring, thiophene ring, azole ring, diazole ring, triazole ring, oxazole ring, oxazi An azole ring, a thiadiazole ring, and the like can be mentioned.
- the condensed polycyclic aromatic heterocycle contains at least one heteroatom selected from a sulfur atom, a nitrogen atom and an oxygen atom, and is preferably a condensed polycyclic aromatic heterocycle having 8 to 20 carbon atoms and heteroatoms, Examples thereof include azanaphthalene (quinoline) ring, diazanaphthalene ring, carbazole ring, dibenzofuran ring, dibenzothiophene ring, dibenzosilole ring, phenoxazine ring, phenothiazine ring, acridine ring, indole ring, pyrroloimidazole ring, pyrrolopyrazole ring.
- azanaphthalene (quinoline) ring diazanaphthalene ring
- carbazole ring dibenzofuran ring
- dibenzothiophene ring dibenzosilole ring
- phenoxazine ring phenothia
- pyrrolopyrrole ring thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, thiazole ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanth Lysine ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like.
- Ring-assembled aromatic heterocycles are two or more monocyclic aromatic heterocycles, two or more condensed polycyclic aromatic heterocycles, one or more monocyclic aromatic heterocycles and one or more condensed polycyclic aromatic rings. and one or more monocyclic aromatic hydrocarbon rings and one or more condensed polycyclic aromatic heterocycles, or one or more monocyclic rings It also includes those in which the formula aromatic heterocycle and one or more condensed polycyclic aromatic hydrocarbon rings are bonded to each other through a single bond.
- the ring-assembled aromatic heterocycle is preferably a ring-assembled aromatic heterocycle having 10 to 40 carbon atoms, and examples thereof include bipyridine ring, terpyridine ring and the like.
- a triazine ring, an isocyanuric ring, and the like are preferable, and a triazine ring is more preferable, from the viewpoint of easily increasing the hygroscopic resistance and heat resistance of the film.
- the structure S in the phenolic antioxidant may have one or more aromatic rings different from the substituent P.
- the aromatic ring may have a structure different from that of the substituent P, and may have a substituent other than the substituent P.
- Each aromatic ring may be linked by a divalent or higher valent hydrocarbon group, more preferably a divalent or trivalent hydrocarbon group, still more preferably an alkylene group.
- Examples of the alkylene group include groups obtained by removing one hydrogen atom from the above-exemplified alkyl groups having 1 to 12 carbon atoms.
- a carbon atom in the alkylene may be replaced with at least one selected from a sulfur atom, a nitrogen atom and an oxygen atom.
- aromatic hydrocarbon rings are preferable from the viewpoint of facilitating the enhancement of dielectric properties in addition to the hygroscopic resistance and heat resistance of the film.
- a cyclic aromatic hydrocarbon ring and/or a condensed polycyclic aromatic hydrocarbon ring is more preferable, a monocyclic aromatic hydrocarbon ring is more preferable, and a benzene ring is particularly preferable.
- Examples of the substituent Q that the aromatic ring may have include a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an alkylamino group, a cycloalkylamino group, an acyl group, and a mercapto group. , an amino group, a hydroxyl group, a group having an ester bond, and the like. These substituents Q can be used alone or in combination of two or more.
- the halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
- the alkyl group includes, for example, the above-exemplified alkyl groups having 1 to 12 carbon atoms.
- the cycloalkyl group includes, for example, the above-exemplified cycloalkyl groups having 5 to 12 carbon atoms.
- alkoxy groups include those having 1 to 12 carbon atoms such as methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butoxy, isobutoxy, tert-butoxy, pentyloxy and hexyloxy groups. An alkoxy group etc.
- Cycloalkoxy groups include, for example, cycloalkoxy groups having 5 to 12 carbon atoms such as cyclohexyloxy.
- alkylthio groups include alkylthio groups having 1 to 12 carbon atoms such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tert-butylthio, pentylthio and hexylthio. etc.
- the cycloalkylthio group includes, for example, cycloalkylthio groups having 5 to 12 carbon atoms such as cyclohexylthio group.
- alkylamino groups include monoalkylamino groups and dialkylamino groups in which the alkyl moiety is the above-exemplified alkyl group having 1 to 12 carbon atoms.
- examples of the cycloalkylamino group include monoalkylamino groups and dialkylamino groups in which the cycloalkyl moiety is the above-exemplified cycloalkyl group having 5 to 12 carbon atoms.
- substituents an alkyl group, an alkoxy group, or the like is preferable, an alkyl group is more preferable, and an alkyl group having 1 to 12 carbon atoms is even more preferable, from the viewpoint of easily increasing the moisture absorption resistance and heat resistance of the film.
- 1 to 4 alkyl groups are even more preferred, with methyl and/or ethyl groups being particularly preferred.
- the aromatic ring in structure S may or may not have a substituent, but from the viewpoint of easily increasing the moisture absorption resistance and heat resistance of the film, it has a substituent. is preferred.
- the number of substituents on the aromatic ring in structure S is not particularly limited, but is preferably 0 or more, more preferably 1 or more, still more preferably 2 or more, still more preferably 3 or more, particularly preferably 4 or more, and particularly preferably 4 or more.
- the number of substituents P is not particularly limited, but is 1 or more, preferably 2 or more, preferably 6 or less, more preferably 6 or less, from the viewpoint of easily increasing the moisture absorption resistance and heat resistance of the film. is 5 or less, more preferably 4 or less, and even more preferably 3.
- the structure of the phenolic antioxidant is a structure in which the bond of the substituent P is attached to the part of the structure S from which the hydrogen atoms have been removed.
- the structure S is an aromatic ring having a methyl group as the substituent Q
- it may be a structure in which a bond of the substituent P is attached to a portion obtained by removing one hydrogen atom from the methyl group, and from the aromatic ring
- a structure in which a bond of the substituent P is bonded to a portion from which one hydrogen atom has been removed may also be used.
- the substituent P may be bonded to the aromatic ring of the structure S, and bonded to a substituent obtained by removing one hydrogen atom from the substituent Q of the aromatic ring (also referred to as a substituent Q'). or if there are multiple substituents P, they may be bonded to both of them.
- the substituent P is preferably bonded to at least the substituent Q' of the aromatic ring.
- the case where the substituent P is bonded to the aromatic ring is meant to include the case where it is bonded to a heteroatom (for example, a nitrogen atom).
- the bonding position of the substituent P relative to the aromatic ring is not particularly limited.
- the aromatic ring is a benzene ring
- the substituents P are attached to It is preferably bonded to non-adjacent carbon atoms directly or via a substituent Q', and more preferably bonded directly or via a substituent Q' to the 1,3-position or 1,3,5-position.
- it is more preferably bonded to the 1, 3, and 5-positions via the substituent Q'.
- the substituent P is directly or via the substituent Q' at the 2,4-position or at the 2,4-position. It is more preferably bonded to the 6-position, and more preferably bonded to the 2-, 4-, and 6-positions via the substituent Q'.
- the aromatic ring is an isocyanuric ring
- the substituent P is directly or via the substituent Q 'at the 1,3-position or at the 1,3,5-position. is preferably bonded to the nitrogen atoms of , more preferably directly bonded to the nitrogen atoms at the 1, 3, and 5 positions.
- phenolic antioxidants include, for example, those having the following structures. [In each formula, R p , R q , R r and R s are the same as defined above] In the above structure, R p , R q , R r and R s in the substituent P may be the same or different in each phenolic antioxidant. With the structure as described above, the moisture absorption resistance and heat resistance of the film are likely to be improved.
- phenolic antioxidants include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6- trimethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert -butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4-[[4,6-bis(n-octylthio)-1,3 ,5-triazin-2-yl]amino]-2,6-di-tert-butylphenol, 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine, tris isocyanurate ( 4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) and the
- the content of the phenolic antioxidant contained in the composition of the present invention is preferably 0.01 parts by mass or more, more preferably 0 parts by mass with respect to 100 parts by mass of the polymer (B). 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.2 parts by mass or more, particularly preferably 0.5 parts by mass or more, and even more preferably 2 parts by mass or more.
- the content of the phenolic antioxidant is at least the above lower limit, the polymer (B) is easily covered with the phenolic antioxidant, and the oxidation of the polymer (B) is easily suppressed. Easy to improve heat resistance.
- the content of the phenolic antioxidant is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 7 parts by mass or less, and particularly preferably 5 parts by mass with respect to 100 parts by mass of the polymer (B). It is below. If the content of the phenolic antioxidant is equal to or less than the above upper limit, the dielectric properties of the film are likely to be enhanced.
- the polymer (B) is a polymer different from the polyimide resin (A).
- the polymer (B) may be a polyimide-based resin that differs in type from the polyimide-based resin (A), for example, the types and contents of the monomer units constituting the resin are different.
- the polymer (B) may be particulate, acicular or fibrous, preferably particulate.
- the polymer (B) is in the form of particles, the dispersibility of the polymer (B) in the composition and in the resulting film can be easily increased, and the hygroscopic resistance and heat resistance of the film can be easily improved.
- the "particle size of the particulate polymer (B)" may be simply referred to as "particle size”.
- the polymer (B) is not particularly limited, and examples thereof include olefin-based polymers, polyimide-based polymers, fluorine-based polymers, silicone-based polymers, liquid crystal polymers, aramid polymers, styrene-based polymers, and ether-based polymers.
- Polymer (B) can be used alone or in combination of two or more. When these are used as the polymer (B), the affinity with the phenolic antioxidant is improved, so that the phenolic antioxidant easily covers the periphery of the polymer (B). In addition, aggregation of the polymer (B) can be easily suppressed, and dispersibility of the polymer (B) can be easily improved.
- a film having excellent moisture absorption resistance and heat resistance can be formed.
- it is selected from the group consisting of olefin-based polymers, polyimide-based polymers, fluorine-based polymers, liquid crystal polymers, styrene-based polymers and ether-based polymers, from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the resulting film.
- At least one polymer is preferred, more preferably at least one polymer selected from the group consisting of olefinic polymers and fluoropolymers, more preferably olefinic polymers, polyethylene, high density polyethylene, polypropylene, polymethylpentene and cycloolefin At least one polymer selected from the group consisting of cycloolefin-based polymers is even more preferred, with cycloolefin-based polymers being particularly preferred.
- the cycloolefin-based polymer has formula (I) [In the formula (I), m represents an integer of 0 or more, R 7 to R 18 each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R 11 to R 14 are present, they are each independently the same may be different, and R 16 and R 17 may be bonded to each other to form a ring together with the carbon atom to which they are bonded] It preferably contains a cycloolefin-derived monomer unit (I) represented by
- m is an integer of 0 or more.
- the upper limit of m is preferably an integer of 3 or less, more preferably an integer of 2 or less, More preferably, it is an integer of 1 or less.
- hydrocarbon groups having 1 to 20 carbon atoms which are members of the substituents of R 7 to R 18 include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group and dodecyl group.
- Aryl groups such as phenyl group, tolyl group and naphthyl group; Aralkyl groups such as benzyl group and phenethyl group; mentioned.
- an alkyl group, an aryl group, or an aralkyl group is preferable from the viewpoint of easily improving the dispersibility of the polymer (B) and the hygroscopic resistance and heat resistance of the resulting film.
- R 7 to R 18 are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms. More preferably, it is an alkyl group having 1 to 10 carbon atoms.
- cycloolefins represented by formula (I) include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, and tricyclodecene. , tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene and the like.
- norbornene is preferable from the viewpoint of easy availability of raw material monomers, dispersibility of the polymer (B), and easiness in improving the hygroscopic resistance and heat resistance of the resulting film.
- the cycloolefins represented by formula (I) may be used alone or in combination of two or more.
- the cycloolefin-based polymer preferably contains a double chain structure of monomeric units (I).
- the heat resistance is likely to be improved as compared with a polymer having a similar content of the monomer unit (I).
- the presence or absence of a double-chain structure can be determined by 13 C-NMR spectrum analysis.
- signals derived from ethylene-tetracyclodecene-ethylene chains which are isolated chains of tetracyclodecene, appear near 54.7 ppm and 51.1 ppm, and endo-exo bonds
- the signal derived from the ethylene-tetracyclodecene-tetracyclodecene-ethylene chain which is the double chain of tetracyclodecene, is near 51.5 ppm and 50.8 ppm, and the ethylene-tetracyclodecene-tetracyclo Since the signals derived from the decene-ethylene chain appear near 55.3 ppm and 54.3 ppm, the pattern of signals near 55 ppm and 50 ppm can be determined.
- the two-chain structure of the monomer unit (I) includes a meso-type two-chain structure represented by the following structural formula (II-1) or the following structural formula (II-2), and/or the following structural formula (III- 1) or a racemo-type double linkage represented by the following structural formula (III-2).
- the ratio of the meso-type double chain to the racemo-type double chain is preferably 0.50 or less, more preferably 0.40 or less, and still more preferably It is 0.30 or less, particularly preferably 0.20 or less, preferably 0.01 or more, and more preferably 0.05 or more.
- the ratio of the meso-form bichain to the racemo-form bichain can be determined, for example, using 13 C-NMR, as described in RA Wendt, G.
- the content of the monomer unit (I) in the cycloolefin-based polymer is preferably 60 mol% or more, more preferably 65 mol% or more, relative to the total molar amount of repeating units constituting the cycloolefin-based polymer, It is more preferably 70 mol % or more, particularly preferably 75 mol % or more, preferably 100 mol % or less, more preferably 99 mol % or less, still more preferably 98 mol % or less.
- Tg glass transition temperature
- the content of the monomeric unit (I) is determined using 13 C-NMR, based on the assignment described in "RA Wendt, G. Fink, Macromol. Chem. Phys., 2001, 202, 3490.” For example, it can be calculated by the method described in Examples.
- the cycloolefin-based polymer consists of ethylene, a linear ⁇ -olefin having 3 to 20 carbon atoms, and an aromatic vinyl compound having 8 to 20 carbon atoms, from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the film. It preferably contains a monomeric unit (II) derived from at least one selected from the group.
- Linear ⁇ -olefins having 3 to 20 carbon atoms include, for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. be done. Among these, propylene, 1-butene, 1-hexene, or 1-octene is preferable, and propylene is more preferable, from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the film.
- Linear ⁇ -olefins having 3 to 20 carbon atoms may be used singly or in combination of two or more.
- the term "straight-chain ⁇ -olefin" refers to a straight-chain olefin having a carbon-carbon unsaturated double bond at the ⁇ -position.
- aromatic vinyl compounds having 8 to 20 carbon atoms include styrene, methylstyrene, dimethylstyrene, ethylstyrene, tert-butylstyrene, vinylnaphthalene, vinylanthracene, diphenylethylene, isopropenylbenzene, isopropenyltoluene, and isopropenyl.
- styrene methylstyrene, or dimethylstyrene is preferred, and styrene is more preferred, from the viewpoints of easy availability of raw material monomers and easy improvement of hygroscopic resistance and heat resistance of the film.
- the aromatic vinyl compounds having 8 to 20 carbon atoms may be used singly or in combination of two or more.
- the cycloolefin-based polymer is preferably selected from the group consisting of ethylene, propylene and styrene from the viewpoints of easy availability of raw material monomers and easy improvement of moisture absorption resistance and heat resistance of the film. It preferably contains monomer units (II) derived from at least one, more preferably monomer units (II) derived from at least one selected from the group consisting of ethylene and styrene.
- the content of the monomer unit (II) in the cycloolefin-based polymer is preferably 0 mol% or more, more preferably 0.01 mol%, relative to the total molar amount of repeating units constituting the cycloolefin-based polymer. More preferably 1 mol% or more, still more preferably 2 mol% or more, preferably 40 mol% or less, more preferably 35 mol% or less, still more preferably 30 mol% or less, particularly preferably 25 mol% It is below.
- the content of the monomer unit (II) is at least the above lower limit, mechanical properties such as bending resistance, workability, and moldability of the film can be easily improved.
- the content of the monomer unit (II) is equal to or less than the above upper limit, the hygroscopic resistance and heat resistance of the film are likely to be improved.
- the cycloolefin-based polymer is preferably a cycloolefin copolymer from the viewpoint of easily improving mechanical properties such as heat resistance, processability, and bending resistance, and moisture absorption resistance, and the formula (I ) and a cycloolefin-derived monomer unit (I) represented by ethylene, a linear ⁇ -olefin having 3 to 20 carbon atoms and an aromatic vinyl compound having 8 to 20 carbon atoms.
- the cycloolefin-based polymer contains at least one monomeric unit (II) derived from norbornene-derived monomeric unit (I) and ethylene-derived monomeric unit (II) or a styrene-norbornene copolymer containing monomeric units (I) derived from norbornene and monomeric units (II) derived from styrene.
- the cycloolefin-based polymer may contain other monomer units (III).
- Other monomers constituting the monomer unit (III) include, for example, conjugated dienes such as butadiene or isoprene; non-conjugated dienes such as 1,4-pentadiene; acrylic acid; methyl acrylate or acrylic acid; acrylic acid esters such as ethyl; methacrylic acid; methacrylic acid esters such as methyl methacrylate or ethyl methacrylate; and vinyl acetate.
- Other monomeric units (III) can be used singly or in combination of two or more.
- the polymer (B) can be used alone or in combination of two or more.
- the olefin-based polymer other than the cycloolefin-based polymer includes, for example, the monomer unit (II); the monomer unit (III); 3-methyl-1-butene, 3-methyl- at least one monomer unit selected from the group consisting of 1-pentene, 4-methyl-1-pentene and vinylcycloalkane; Polyethylene, polypropylene or polymethylpentene is preferable, and polypropylene or polymethylpentene is more preferable from the viewpoint of enhancing heat resistance.
- polyimide-based polymers include, for example, polyimide-based polymers that are soluble in the second solvent described later.
- the fluorine-based polymer is an olefin polymer containing fluorine or a modified product thereof.
- fluoroolefins such as tetrafluoroethylene, trifluoroethylene, chlorotrifluoro Polymers and copolymers containing at least one monomer unit selected from the group consisting of ethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, etc., such as polytetrafluoroethylene (PTFE), perfluoroalkoxyalkanes, perfluoroethylene propene copolymers, ethylene-tetrafluoroethylene copolymers, polyvinylidene fluoride, polychlorotrifluoroethylene, polyhexafluoropropylene and the like.
- PTFE polytetrafluoroethylene
- PTFE polytetrafluoroethylene
- perfluoroalkoxyalkanes perfluoroethylene propene copolymers
- the fluoropolymer is preferably a polymer having structural units derived from tetrafluoroethylene, and more preferably the molar ratio of the structural units derived from tetrafluoroethylene to the total of all structural units is 0.5. 25 or more, more preferably 0.30 or more, still more preferably 0.50 or more, and particularly preferably 0.75 or more.
- the molar ratio of each structural unit of the fluoropolymer can be obtained by NMR measurement. (HFP)-Tetrafluoroethylene (TFE)”, Macromolecules, 2015, Vol. 48, No. 11, p.3563-3576.
- liquid crystal polymers include polymers having repeating units such as aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, and aliphatic diols.
- monomers that give aromatic hydroxycarboxylic acid repeating units include parahydroxybenzoic acid, metahydroxybenzoic acid, orthohydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and 5-hydroxy-2-naphthoic acid.
- 3-hydroxy-2-naphthoic acid, 4′-hydroxyphenyl-4-benzoic acid, 3′-hydroxyphenyl-4-benzoic acid, 4′-hydroxyphenyl-3-benzoic acid and other aromatic hydroxycarboxylic acids, Alkyl-, alkoxy- or halogen-substituted products thereof, and ester-forming derivatives thereof are included.
- parahydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferred from the viewpoint of easily improving the moisture absorption resistance, mechanical properties and heat resistance of the film.
- monomers that provide aromatic dicarboxylic acid repeating units include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4 -naphthalenedicarboxylic acid, aromatic dicarboxylic acids such as 4,4′-dicarboxybiphenyl, alkyl-, alkoxy- or halogen-substituted products thereof, and ester-forming derivatives thereof.
- terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are preferable from the viewpoint of easily improving the moisture absorption resistance, mechanical properties and heat resistance of the film.
- monomers that give aromatic diol repeating units include hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4, Aromatic diols such as 4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl and 4,4'-dihydroxybiphenyl ether, their alkyl, alkoxy or halogen substituted products, and these and ester-forming derivatives of Among them, hydroquinone and 3,3'-dihydroxybiphenyl are preferable from the viewpoint of easily improving the moisture absorption resistance, mechanical properties and heat resistance of the film.
- monomers that provide aliphatic diol repeating units include aliphatic diols such as ethylene glycol, 1,4-butanediol and 1,6-hexanediol, and acylated products thereof.
- ethylene glycol is preferable from the viewpoint of easily improving the hygroscopic resistance, mechanical properties and heat resistance of the film.
- the styrenic polymer is a resin containing at least one styrene in the repeating structural unit.
- examples include polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AS resin (acrylonitrile - styrene copolymer) and the like.
- polystyrene is preferable from the viewpoint of easily increasing dielectric properties.
- a polymer having both a styrene-derived monomer unit and a cycloolefin-derived monomer unit as repeating structural units is classified as a cycloolefin-based polymer.
- the ether-based polymer is a resin containing at least one repeating unit containing an ether group in the main chain, such as polyetherimide, polyphenylene ether, polyethersulfone, polyetherketone, polyether ether ketone and the like.
- polyetherimide polyphenylene ether
- polyethersulfone polyetherketone
- polyether ether ketone polyether ketone
- polyphenylene ether, polyether sulfone, and polyether ether ketone are preferable from the viewpoint of easily improving the moisture absorption resistance, heat resistance, and dielectric properties of the film.
- At least one of the glass transition temperature and melting point of the polymer (B) is preferably 100°C or higher.
- the Tg of the polymer (B) is preferably 100° C. or higher, more preferably 140° C. or higher, still more preferably 160° C. or higher, even more preferably 180° C. or higher, particularly preferably 200° C. or higher, and particularly preferably 220° C. or higher. , particularly preferably 240° C. or higher, particularly more preferably 260° C. or higher, preferably 500° C. or lower, more preferably 400° C. or lower, and still more preferably 320° C. or lower.
- the melting point of the polymer (B) is preferably 100° C. or higher, more preferably 140° C. or higher, still more preferably 160° C. or higher, still more preferably 180° C. ° C. or higher, particularly preferably 200 ° C. or higher, particularly more preferably 220 ° C. or higher, even more preferably 240 ° C. or higher, most preferably 260 ° C. or higher, preferably 500 ° C. or lower, more preferably 400 ° C. or lower, further preferably is below 350°C.
- the CTE of the film is likely to be reduced, and mechanical properties such as wet water resistance, heat resistance and bending resistance are likely to be enhanced.
- the mechanical properties of the film particularly resistance to repeated bending, are likely to be enhanced.
- the Tg of polymer (B) is a softening temperature measured by TMA based on JIS K 7196, and can be measured, for example, by the method described in Examples.
- the method of adjusting the Tg and melting point of the polymer (B) is not particularly limited, but for example, a method of appropriately adjusting the content of the monomer unit (I), the Mw of the polymer (B), the degree of crystallinity, etc. mentioned.
- the Tg and melting point of the polymer (B) tend to increase as at least one selected from the group consisting of the content of the monomer unit (I), the Mw of the polymer (B), and the degree of crystallinity increases.
- the melting point of the polymer (B) can be determined, for example, by using a differential scanning calorimeter (DSC) and measuring the melting peak temperature from the resulting melting curve.
- DSC differential scanning calorimeter
- the DSC is not particularly limited, for example, a DSC manufactured by Hitachi High-Tech Science Co., Ltd. may be used.
- the weight average molecular weight of the polymer (B) (hereinafter the weight average molecular weight may be abbreviated as Mw) is preferably 10,000 or more, more preferably 15,000, and still more preferably 20. ,000 or more, still more preferably 30,000 or more, particularly preferably 50,000 or more, particularly more preferably 70,000 or more, particularly preferably 90,000 or more, preferably 2,000,000 or less, and more It is preferably 1,000,000 or less, more preferably 700,000 or less.
- Mw is at least the above lower limit, it is easy to increase the hygroscopic resistance and heat resistance of the film, and it is easy to improve the strength.
- the Mw is equal to or less than the above upper limit, the moisture absorption resistance, mechanical properties and moldability of the film are likely to be improved.
- the ratio (Mw/Mn) between the Mw and the number average molecular weight (hereinafter the number average molecular weight may be abbreviated as Mn) of the polymer (B) is preferably 2.0 in terms of polystyrene. 5 or less, more preferably 2.2 or less, still more preferably 2.0 or less, even more preferably 1.95 or less, particularly preferably 1.90 or less, preferably 1.30 or more, more preferably 1.90 or less. It is 50 or more, more preferably 1.60 or more, and particularly preferably 1.65 or more.
- Mw/Mn ratio When the Mw/Mn ratio is at most the above upper limit, the hygroscopic resistance, heat resistance, and mechanical properties of the film are likely to be enhanced, and at the above lower limit or above, the formability is likely to be enhanced.
- Mw and Mn can be obtained by performing gel permeation chromatography (hereinafter sometimes abbreviated as GPC) measurement and converting to standard polystyrene, for example, by the method described in Examples.
- GPC gel permeation chromatography
- the refractive index of the polymer (B) is preferably 1.600 or less, more preferably 1.570 or less, still more preferably 1.570 or less, from the viewpoint of easily obtaining a film with a reduced CTE. It is 550 or less, preferably 1.500 or more, more preferably 1.520 or more.
- the refractive index of the polymer (B) can be measured with a refractometer, for example, by the method described in Examples.
- the CTE of polymer (B) is preferably 58 ppm/K or less, more preferably 55 ppm/K or less, even more preferably 50 ppm/K or less, preferably 0 ppm/K or more, more preferably is 0.01 ppm/K or more, more preferably 1 ppm/K or more, and even more preferably 5 ppm/K or more.
- the CTE of the polymer (B) is equal to or less than the above upper limit, the CTE of the resulting film is likely to be reduced.
- the CTE of the film In the case of producing a copper-clad laminate by bonding with copper foil, it is preferable to adjust the CTE of the film to around 20 ppm/K from the viewpoint of preventing peeling of the laminate film.
- the polymer (B) with the optimum CTE can be selected.
- CTE can be measured, for example, by thermomechanical analysis (hereinafter sometimes referred to as TMA), and is determined by the method described in Examples.
- the median diameter of the particulate polymer (B) in the composition of the present invention is preferably 0.01 ⁇ m or more, more preferably 0.03 ⁇ m. More preferably 0.05 ⁇ m or more, preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 5 ⁇ m or less, even more preferably 3 ⁇ m or less, particularly preferably 1 ⁇ m or less, and particularly preferably 0.8 ⁇ m or less , and more preferably 0.5 ⁇ m or less.
- the median diameter of the particulate polymer (B) in the composition is at least the above lower limit, the dielectric properties of the film formed from the composition are likely to be enhanced, and the film is easily produced.
- the median diameter of the particulate polymer (B) in the composition is equal to or less than the above upper limit, the dispersibility of the polymer (B) in the composition and in the film is likely to be increased, and the resulting film has hygroscopic resistance and heat resistance. Easy to improve.
- the method for determining the median diameter of the particulate polymer (B) in the composition is not particularly limited, it can be determined, for example, using a centrifugal sedimentation particle size distribution analyzer or an ultrasonic attenuation particle size distribution analyzer.
- the polyimide resin (A) and the phenolic antioxidant are added to the particulate polymer (B) dispersion in an amount that does not affect the particle size of the particulate polymer (B) to form a composition.
- the median diameter of the particulate polymer (B) in the dispersion can be measured in advance and used as the median diameter of the particulate polymer (B) in the composition.
- the median diameter is also referred to as D50, and indicates a value at which the number of particles of the particulate polymer (B) on the side smaller than that value is equal to the number of particles on the larger side.
- the term "particle size” means the median size and/or average primary particle size of the particulate polymer (B), unless otherwise specified.
- the content of the polymer (B) contained in the composition of the present invention is usually 1% by mass or more with respect to the total mass of the polyimide resin (A) and the polymer (B), Preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 10% by mass or more, particularly preferably 20% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably is 35% by mass or less.
- the content of the polymer (B) contained in the composition is at least the above lower limit, the formation of aggregates of the polymer (B) is likely to be suppressed, and thus the dispersibility of the polymer (B) is likely to be enhanced.
- the content of the polymer (B) contained in the composition is equal to or less than the above upper limit, film formation is facilitated, which is advantageous from the viewpoint of film production. If the dispersibility of the polymer (B) in the film is high, the uniformity of thermal conductivity and CTE will be high. easier to suppress.
- Polymer (B) may be a commercially available product or may be produced by a conventional method.
- polymer (B) is preferably a cycloolefinic polymer.
- the method for producing the cycloolefin-based polymer is not particularly limited. at least one monomer selected from the group consisting of a cycloolefin represented by formula (I), the ethylene, a linear ⁇ -olefin having 3 to 20 carbon atoms and an aromatic vinyl compound having 8 to 20 carbon atoms; It is preferably prepared by polymerizing one monomer, and optionally said other monomers.
- transition metal complex ( ⁇ ) represented by the formula (IV) is used in the production of the cycloolefin-based polymer in the present invention, the content of the monomer unit (I) in the cycloolefin-based polymer is significantly increased. It is easy to adjust Tg within the above range.
- M represents a transition metal element in Group 4 of the periodic table of the elements
- Cp represents a group having a cyclopentadienyl skeleton
- A represents an atom of Group 16 of the Periodic Table of the Elements
- T represents an atom of Group 14 of the Periodic Table of the Elements
- D 1 and D 2 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon number It represents an aryloxy group having 6 to 20 carbon atoms or a disubstituted amino group having 2 to 20 carbon atoms, which may be the same or different.
- R 1 to R 6 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. represents an aryloxy group having 6 to 20 carbon atoms, a disubstituted amino group having 2 to 20 carbon atoms or a silyl group having 1 to 20 carbon atoms, which may be the same or different, and are optionally bonded may form a ring.
- M is a transition metal element in Group 4 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989), for example, titanium atom, zirconium atom, hafnium atom, and the like.
- Cp is a group having a cyclopentadienyl skeleton, such as cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl, substituted fluorenyl and the like.
- a cyclopentadienyl group such as cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl, substituted fluorenyl and the like.
- Specific examples include a cyclopentadienyl group, a methylcyclopentadienyl group, a tetramethylcyclopentadienyl group, an n-propylcyclopentadienyl group, an n-butylcyclopentadienyl group, and an isobutylcyclopentadienyl group.
- phenylcyclopentadienyl group indenyl group, methylindenyl group, n-propylindenyl group, n-butylindenyl group, isobutylindenyl group, phenylindenyl group, fluorenyl group, methylfluorenyl group, n -Propylfluorenyl group, phenylfluorenyl group, dimethylfluorenyl group and the like.
- cyclopentadienyl group methylcyclopentadienyl group, tetramethylcyclopentadienyl group, n-butylcyclopentadienyl group, isobutylcyclopentadienyl group, indenyl group and methylindenyl group are preferred. or a fluorenyl group.
- A is an atom of Group 16 of the periodic table of elements, and includes, for example, an oxygen atom and a sulfur atom. Among these, an oxygen atom is preferable.
- T is an atom of Group 14 of the periodic table of elements, and includes, for example, a carbon atom, a silicon atom, a germanium atom, and the like. Among these, a carbon atom or a silicon atom is preferred.
- D 1 and D 2 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or It is an aryloxy group having 6 to 20 carbon atoms or a disubstituted amino group having 2 to 20 carbon atoms, which may be the same or different.
- a halogen atom is preferable.
- D 1 and D 2 being halogen atoms include fluorine, chlorine, bromine and iodine atoms.
- D 1 and D 2 are hydrocarbon groups
- the number of carbon atoms is preferably 1-10.
- the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group and n-hexyl. group, n-octyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, naphthyl group, benzyl group and the like.
- D 1 and D 2 being halogenated hydrocarbon groups include fluoromethyl group, difluoromethyl group, 1-fluoroethyl group, 1,1-difluoroethyl group, 1,2-difluoroethyl group, 1,1,2-trifluoroethyl group, tetrafluoroethyl group, chloromethyl group, dichloromethyl group, 1-chloroethyl group, 1,1-dichloroethyl group, 1,2-dichloroethyl group, 1,1,2 -trichloroethyl group, 1,1,2,2-tetrachloroethyl group, bromomethyl group, dibromomethyl group, 1-bromoethyl group, 1,1-dibromoethyl group, 1,2-dibromoethyl group, 1,1,2 -tribromoethyl group, 1,1,2,2-tetrabromoethyl group, 2-fluoroph
- D 1 and D 2 being alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n- pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group and the like.
- D 1 and D 2 being aryloxy groups include phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy and naphthyloxy groups.
- the disubstituted amino group is an amino group in which two substituents are bonded.
- Specific examples thereof include a dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, diisobutylamino group, di-sec-butylamino group and di-tert-butyl.
- R 1 to R 6 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or represents an aryloxy group having 6 to 20 carbon atoms, a disubstituted amino group having 2 to 20 carbon atoms or a silyl group having 1 to 20 carbon atoms, which may be the same or different, and are optionally They may be combined to form a ring.
- hydrocarbon groups having 1 to 20 carbon atoms are preferred.
- R 1 to R 6 being halogen atoms include fluorine, chlorine, bromine and iodine atoms.
- R 1 to R 6 are hydrocarbon groups, they preferably have 1 to 10 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group and n-hexyl group.
- n-octyl group phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group , 2,6-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, pentamethylphenyl group and the like.
- R 1 to R 6 are a halogen atom, a halogenated hydrocarbon group, an alkoxy group, an aryloxy group, or a disubstituted amino group
- D 1 and D 2 being a halogen atom or a halogenated hydrocarbon group
- an alkoxy group, an aryloxy group, and a disubstituted amino group include those exemplified above.
- R 1 to R 6 are silyl groups include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, triisobutylsilyl group, tri -sec-butylsilyl group, tri-tert-butylsilyl group, triphenylsilyl group and the like.
- Such compounds represented by formula (IV) include isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(methylcyclo pentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(dimethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropyl Lidene (trimethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) ) titanium dichloride, isopropylidene (n-propylcyclopentadienyl) (3-tert-buty
- the transition metal complex ( ⁇ ) represented by formula (IV) above can be used as a catalyst for producing the polymer (B) according to one embodiment of the present invention in combination with various cocatalysts.
- a co-catalyst is a compound that interacts with the transition metal complex ( ⁇ ) to generate polymerization active species for cyclic olefins and alkenyl aromatic hydrocarbons. Examples thereof include organoaluminum compounds ( ⁇ ) and/or boron compounds ( ⁇ ) represented by any of the following formulas ( ⁇ 1) to ( ⁇ 3). The structure of the polymerization active species generated by this is not clear.
- B represents a boron atom in a trivalent state
- Q 1 to Q 4 each independently represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, or a silyl group having 1 to 20 carbon atoms.
- J + represents an inorganic or organic cation
- L represents a neutral Lewis base
- (LH) + represents a Bronsted acid.
- a known organoaluminum compound can be used as the organoaluminum compound ( ⁇ ).
- Specific examples include an organoaluminum compound represented by formula ( ⁇ 1), a cyclic aluminoxane having a structure represented by formula ( ⁇ 2), and a linear aluminoxane having a structure represented by formula ( ⁇ 3). , these can be used alone or in combination of two or more.
- E 1 , E 2 and E 3 each independently represent a hydrocarbon group having 1 to 8 carbon atoms, all E 1 , all E 2 and all E 3 may be the same or different, Z represents hydrogen or halogen, all Z may be the same or different, a represents an integer of 0 to 3 , b represents an integer of 2 or more, and c represents an integer of 1 or more.
- formula ( ⁇ 1) include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride; Dialkylaluminum chlorides such as dihexylaluminum chloride; Alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride; dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride , dialkylaluminum hydride such as dihexylaluminum, di
- E 2 and E 3 in formula ( ⁇ 2) and formula ( ⁇ 3) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group and neopentyl. and alkyl groups such as Among these, a methyl group or an isobutyl group is preferred.
- b is an integer of 2 or more, preferably an integer of 2-40.
- c is an integer of 1 or more, preferably an integer of 1-40.
- the above aluminoxanes are made by various methods.
- the method is not particularly limited, and it may be produced according to a known method.
- a method of contacting with a metal salt containing water of crystallization, such as copper sulfate hydrate, can be exemplified.
- any one of the boron compounds represented by formula ( ⁇ 1), formula ( ⁇ 2), or formula ( ⁇ 3) can be used.
- B represents a boron atom in a trivalent state
- Q 1 to Q 3 each independently represent a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, represents a halogenated hydrocarbon group, a substituted silyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a disubstituted amino group having 2 to 20 carbon atoms, which may be the same or different; good too.
- Q 1 to Q 3 are each independently preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.
- boron compound represented by formula ( ⁇ 1) include tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5- tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane, phenylbis(pentafluorophenyl)borane and the like, preferably tris (Pentafluorophenyl)borane can be mentioned.
- B represents a trivalent boron atom
- Q 1 to Q 4 are the same as Q 1 to Q 3 in formula ( ⁇ 1) above.
- J + represents an inorganic or organic cation.
- Inorganic cations in J + include ferrocenium cations, alkyl-substituted ferrocenium cations, silver cations, and the like.
- Examples of organic cations for J + include triphenylmethyl cations.
- (BQ 1 Q 2 Q 3 Q 4 ) - includes tetrakis(pentafluorophenyl)borate anion, tetrakis(2,3,5,6-tetrafluorophenyl)borate anion, tetrakis(2,3,4,5- tetrafluorophenyl)borate anion, tetrakis(3,4,5-trifluorophenyl)borate anion, tetrakis(2,2,4-trifluorophenyl)borate anion, phenylbis(pentafluorophenyl)borate anion, tetrakis(3 ,5-bistrifluoromethylphenyl)borate anion and the like.
- Specific combinations thereof include ferroceniumtetrakis(pentafluorophenyl)borate, 1,1'-dimethylferroceniumtetrakis(pentafluorophenyl)borate, silver tetrakis(pentafluorophenyl)borate, triphenylmethyltetrakis (Pentafluorophenyl)borate, triphenylmethyltetrakis(3,5-bistrifluoromethylphenyl)borate and the like, preferably triphenylmethyltetrakis(pentafluorophenyl)borate.
- B represents trivalent boron
- Q 1 to Q 4 are the same as Q 1 to Q 3 in formula ( ⁇ 1) above.
- L represents a neutral Lewis base and (LH) + represents a Bronsted acid.
- Bronsted acid (LH) + includes trialkyl-substituted ammonium cations, N,N-dialkylanilinium cations, dialkylammonium cations, and triarylphosphonium cations.
- (BQ 1 Q 2 Q 3 Q 4 ) - includes the same groups as those described above.
- the co-catalyst it is preferable to use the organoaluminum compound ( ⁇ ) and the compound ( ⁇ ) together.
- transition metal complex ( ⁇ ), organoaluminum compound ( ⁇ ) and/or compound ( ⁇ ) represented by formula (IV) can be used in any order during polymerization, but any of these compounds You may use the reactant obtained by contacting previously the combination of.
- the molar ratio of cocatalyst/transition metal complex ( ⁇ ) is preferably 0.01 to 10,000, more preferably 0.5 to 2,000.
- concentration of the transition metal complex ( ⁇ ) is preferably 0.0001-5 mmol/L, more preferably 0.001-1 mmol/L.
- the amount of catalyst component used is preferably 0.00001 to 1 mol %, more preferably 0.0001 to 0.1 mol %, based on the total amount of all monomers used.
- the polymerization method of the polymer (B) according to one embodiment of the present invention is not particularly limited. Any method such as a method or a slurry polymerization method can be adopted.
- solvents When using a solvent, various solvents can be used provided that they do not deactivate the catalyst.
- solvents include hydrocarbon solvents such as benzene, toluene, pentane, hexane, heptane, and cyclohexane; Examples thereof include halogenated hydrocarbon solvents such as dichloromethane and ethylene dichloride.
- the ethylene partial pressure in the system during polymerization is, for example, 50 to 400 kPa, preferably 50 to 300 kPa, and the hydrogen partial pressure is preferably 0 to 100 kPa.
- ethylene and hydrogen are introduced into the system, it is preferable to pressurize with the partial pressure of hydrogen and then pressurize with the partial pressure of ethylene.
- toluene may be added after charging the solution of the cycloolefin represented by the formula (I) into the polymerization reactor.
- the polymerization temperature is preferably 50°C or higher, more preferably 50 to 150°C, still more preferably 50 to 100°C.
- a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the polymer.
- the polyimide resin (A) is a resin containing a repeating structural unit containing an imide group (hereinafter sometimes referred to as a polyimide resin), and a resin containing a repeating structural unit containing both an imide group and an amide group (hereinafter (sometimes referred to as polyamide-imide resin), as well as precursors prior to production of polyimide-based resins by imidization.
- the precursor prior to manufacturing the polyimide resin is polyamic acid.
- a "repeating structural unit” may be called a "structural unit.”
- a "constituent unit derived from” may be simply referred to as a "unit”, and for example, a constituent unit derived from a compound may be referred to as a compound unit.
- the polyimide resin (A) has the formula (1): [In formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, and * represents a bond] It is preferable to have a structural unit represented by With such a polyimide resin, the dispersibility of the polymer (B) in the composition and film can be easily improved, and the hygroscopic resistance and heat resistance of the obtained film can be easily improved.
- Each X in formula (1) independently represents a divalent organic group, preferably a divalent organic group having 2 to 100 carbon atoms.
- the divalent organic group include a divalent aromatic group and a divalent aliphatic group.
- the divalent aliphatic group include a divalent acyclic aliphatic group and a divalent Cycloaliphatic groups are included.
- 2 Preferred are divalent cycloaliphatic groups and divalent aromatic groups, more preferred are divalent aromatic groups.
- a divalent aromatic group is a divalent organic group having an aromatic group, and may contain an aliphatic group or other substituents in part of its structure.
- a divalent aliphatic group is a divalent organic group having an aliphatic group, and may contain other substituents in part of its structure, but does not contain an aromatic group.
- the polyimide resin (A) may contain multiple types of X, and the multiple types of X may be the same or different.
- X in formula (1) includes, for example, groups (structures) represented by formulas (2) to (8); hydrogen atoms in groups represented by formulas (5) to (8) are methyl groups. , ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, fluoro group, chloro group or trifluoromethyl group.
- R a and R b are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a represents an aryl group, hydrogen atoms contained in R a and R b may be independently substituted with halogen atoms, and W is independently a single bond, —O—, —CH 2 — , -CH 2 -CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -COO-, -OOC-, -SO 2 -, -S -, -CO- or -N(R c )-, where R c represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom, n is 0 to is an integer of 4, t is an integer
- ring A represents a cycloalkane having 3 to 8 carbon atoms
- R d represents an alkyl group having 1 to 20 carbon atoms
- r is 0 or more (the number of carbon atoms in ring A is -2)
- S1 and S2 independently represent integers from 0 to 20, and * represents a bond.
- X in formula (1) examples include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, propylene group, 1,2-butanediyl group and 1,3-butanediyl group. , 1,12-dodecanediyl group, 2-methyl-1,2-propanediyl group, 2-methyl-1,3-propanediyl group and other linear or branched alkylene groups such as divalent acyclic Aliphatic groups are included. Hydrogen atoms in the divalent acyclic aliphatic group may be substituted with halogen atoms, and carbon atoms may be substituted with heteroatoms such as oxygen atoms, nitrogen atoms, and the like.
- the polyimide resin (A) in the present invention preferably contains a structure represented by formula (2) and/or a structure represented by formula (3) as X in formula (1), and formula (2 ) is more preferred.
- each benzene ring or cyclohexane ring are ortho-, meta- or para-positions, or ⁇ -, ⁇ - or ⁇ -positions relative to -W-. It may be bonded to any position, and from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the resulting film, it is preferably at the meta-position or para-position, or at the ⁇ -position or at the ⁇ -position, more preferably at the para-position or at the ⁇ -position.
- R a and R b each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
- alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2 -methyl-butyl group, 3-methylbutyl group, 2-ethyl-propyl group, n-hexyl group and the like.
- alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy and cyclohexyloxy groups. mentioned.
- Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, tolyl group, xylyl group, naphthyl group and biphenyl group.
- Hydrogen atoms contained in R a and R b may be independently substituted with halogen atoms, and examples of the halogen atoms include fluorine, chlorine, bromine and iodine atoms.
- R a and R b are each independently an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group having 1 to 6 carbon atoms, from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the resulting film.
- group more preferably an alkyl group having 1 to 3 carbon atoms or a fluorinated alkyl group having 1 to 3 carbon atoms, further preferably a methyl group or a trifluoromethyl group.
- t and u are independently integers of 0 to 4, and from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the resulting film, preferably 0 to 2. , more preferably 0 or 1.
- W is independently a single bond, —O—, —CH 2 —, —CH 2 —CH 2 —, —CH(CH 3 )—, —C(CH 3 ) represents 2 -, -C(CF 3 ) 2 -, -COO-, -OOC-, -SO 2 -, -S-, -CO- or -N(R c )-, and Single bonds, —O—, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 are preferred from the viewpoint of easily improving hygroscopicity, heat resistance and mechanical properties, especially bending resistance.
- R c represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom.
- Examples of monovalent hydrocarbon groups having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n- pentyl group, 2-methyl-butyl group, 3-methylbutyl group, 2-ethyl-propyl group, n-hexyl group, n-heptyl group, n-octyl group, tert-octyl group, n-nonyl group and n-decyl group etc., which may be substituted with a halogen atom.
- Halogen atoms include those mentioned above.
- n is an integer of 0 to 4, which facilitates increasing the dispersibility of the polymer (B) in the composition and film, and improves the moisture absorption resistance and heat resistance of the resulting film. It is preferably an integer of 0 to 3, more preferably 1 or 2, from the viewpoint of easy improvement.
- n is 2 or more, a plurality of W, R a , and t may be the same or different, and the position of the bond of each benzene ring relative to -W- is also the same. may be different.
- W, n, R a , R b , t and u may be independently the same as or different from W, n, R a , R b , t and u in formula (3) .
- ring A represents a cycloalkane having 3 to 8 carbon atoms.
- Cycloalkanes include, for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and cyclooctane, preferably cycloalkanes having 4 to 6 carbon atoms.
- each bond may or may not be adjacent to each other.
- the two bonds may have a positional relationship of ⁇ -position, ⁇ -position or ⁇ -position, preferably ⁇ -position or ⁇ -position.
- R d in formula (4) represents an alkyl group having 1 to 20 carbon atoms.
- the alkyl group having 1 to 20 carbon atoms include those exemplified above as the hydrocarbon group having 1 to 20 carbon atoms in R 7 to R 18 , preferably an alkyl group having 1 to 10 carbon atoms.
- r in formula (4) represents an integer of 0 or more and (the number of carbon atoms in ring A - 2) or less. r is 0 or more, preferably 4 or less.
- S1 and S2 in formula (4) each independently represent an integer of 0 to 20.
- S1 and S2 are each independently preferably 0 or more, more preferably 2 or more, and preferably 15 or less.
- X in formula (1) when X in formula (1) includes a structure represented by formula (2) and/or formula (3), X in formula (1) is represented by formula (2) and/or the proportion of the structural unit represented by formula (3) is preferably 30 mol% or more, more preferably 50 mol% or more, relative to the total molar amount of the structural units represented by formula (1), It is more preferably 70 mol % or more, particularly preferably 90 mol % or more, and preferably 100 mol % or less.
- the proportion of structural units represented by formula (2) and/or formula (3) for X in formula (1) is within the above range, the formation of aggregates of the polymer (B) is easily suppressed, and the polymer It is easy to improve the dispersibility of (B).
- the proportion of structural units in which Y in formula (1) is represented by formula (2) and/or formula (3) can be measured using, for example, 1 H-NMR, or calculated from the feed ratio of raw materials. You can also
- Y independently represents a tetravalent organic group, preferably a tetravalent organic group having 4 to 40 carbon atoms, more preferably a tetravalent organic group having 4 to 40 carbon atoms and having a cyclic structure. represents a valent organic group.
- Cyclic structures include alicyclic, aromatic and heterocyclic structures.
- a hydrogen atom in the organic group may be substituted with a halogen atom, a hydrocarbon group, an alkoxy group, or a halogenated hydrocarbon group. In this case, the number of carbon atoms in these groups is preferably 1 to 8. is.
- the polyimide resin (A) in the present invention may contain multiple types of Y, and the multiple types of Y may be the same or different.
- Y is a group (structure) represented by formulas (31) to (38); hydrogen atoms in the groups represented by formulas (34) to (38) are methyl group, ethyl group, n-propyl a group substituted with a group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, fluoro group, chloro group or trifluoromethyl group; tetravalent C1-8 chain formula A hydrocarbon group etc. are mentioned.
- R 19 to R 26 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a representing an aryl group, hydrogen atoms contained in R 19 to R 26 may be independently substituted with halogen atoms, V 1 and V 2 are each independently a single bond, —O—, —CH 2 —, —CH 2 —CH 2 —, —CH(CH 3 )—, —C(CH 3 ) 2 —, —C (CF 3 ) 2 -, -COO-, -OOC-, -SO 2 -, -S-, -CO-, -N(R j )-, formula (a) or formula (b) (In formula (a), R 27 to R 30 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Z is a single bond, —C(CH 3 )
- the polyimide resin in the present invention has the formula (1) Y in the above preferably contains at least one structure selected from the group consisting of a structure represented by formula (31), a structure represented by formula (32), or a structure represented by formula (33) , more preferably a structure represented by formula (31).
- R 19 to R 26 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. represents a group.
- the alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms and the aryl group having 6 to 12 carbon atoms are respectively the alkyl group having 1 to 6 carbon atoms and the carbon
- the alkoxy groups having 1 to 6 carbon atoms and the aryl groups having 6 to 12 carbon atoms are exemplified above.
- the hydrogen atoms contained in R 19 to R 26 may be independently substituted with halogen atoms, and the halogen atoms include those exemplified above.
- R 19 to R 26 are each independently hydrogen.
- An atom or an alkyl group having 1 to 6 carbon atoms is preferred, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is more preferred, and a hydrogen atom is even more preferred.
- V 1 and V 2 are each independently a single bond, —O—, —CH 2 —, —CH 2 —CH 2 —, —CH(CH 3 )—, —C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -COO-, -OOC-, -SO 2 -, -S-, -CO-, -N(R j )-, formula (a) or formula (b ), preferably a single bond, —O—, —CH 2 from the viewpoint of easily increasing the dispersibility of the polymer (B) in the composition and film and easily improving the moisture absorption resistance and heat resistance of the resulting film.
- R j represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include those exemplified above.
- e in formula (31) is 0, it indicates that formula (31) does not have -V 1 - (two benzene rings are not bonded at -V 1 -), and d is 0, it indicates that formula (31) does not have -V 2 - (the two benzene rings are not linked at -V 2 -).
- f represents an integer of 1 to 3, and from the viewpoint of easily improving the dispersibility of the polymer (B) in the composition and film and improving the hygroscopic resistance and heat resistance of the resulting film, Preferably 1 or 2, more preferably 1.
- f 2
- a structure in which R 23 and R 24 are bonded to a naphthalene ring is shown
- f 3
- a structure in which R 23 and R 24 are bonded to an anthracene ring is shown.
- R 27 to R 30 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- the alkyl group having 1 to 6 carbon atoms include those exemplified above as the alkyl group having 1 to 6 carbon atoms in the formulas (2) and (3).
- R 27 to R 30 are each independently hydrogen.
- An atom or an alkyl group having 1 to 3 carbon atoms is more preferred, a hydrogen atom or a methyl group is more preferred, and a hydrogen atom is even more preferred.
- Z represents a single bond, -C(CH 3 ) 2 - or -C(CF 3 ) 2 -.
- Z has such a structure, the dispersibility of the polymer (B) in the composition and film can be easily improved, and the hygroscopic resistance and heat resistance of the obtained film can be easily improved.
- i represents an integer of 1 to 3, preferably 1 or 2 from the viewpoint of easily increasing the dispersibility of the polymer (B) in the composition and film and easily improving the moisture absorption resistance and heat resistance of the resulting film. be.
- i is 2 or more, a plurality of Zs and R 27 to R 30 may be the same or different.
- Y in formula (1) contains at least one selected from the group consisting of structures represented by formulas (31) to (33)
- Y is represented by at least one selected from the group consisting of structures represented by formulas (31) to (33).
- the amount is preferably 30 mol % or more, more preferably 50 mol % or more, still more preferably 70 mol % or more, particularly preferably 90 mol % or more, and preferably 100 mol % or less.
- Y in formula (1) is selected from the group consisting of structures represented by formulas (31) to (33). It is easy to improve the dispersibility of the polymer (B) inside and in the film, and it is easy to improve the moisture absorption resistance and heat resistance of the obtained film.
- Y in formula ( 1 ) is represented by at least one selected from the group consisting of structures represented by formulas (31) to (33). It can be measured or calculated from the feed ratio of raw materials.
- the polyimide resin (A) in the present invention includes, in addition to the structural unit represented by formula (1), the structural unit represented by formula (52), the structural unit represented by formula (53), and the formula ( 54) may contain at least one selected from the group consisting of structural units represented by
- Y 1 represents a tetravalent organic group
- Y 2 represents a trivalent organic group
- X 1 and X 2 independently represent a divalent organic group
- * represents a bond
- G and X independently represent a divalent organic group
- * represents a bond
- Y 1 has the same meaning as Y in formula (1)
- X 1 and X 2 have the same meaning as X in formula (1).
- Y 2 in formula (53) is preferably a group in which one of the bonds of Y in formula (1) is replaced with a hydrogen atom.
- Y 2 is a group in which any one of the bonds (structures) of the groups (structures) represented by formulas (31) to (38) is replaced with a hydrogen atom; a trivalent chain hydrocarbon having 1 to 8 carbon atoms and the like.
- the polyimide resin may contain multiple types of Y 1 or Y 2 , and the multiple types of Y 1 or Y 2 may be the same or different.
- each G is independently a divalent organic group, preferably substituted with a hydrocarbon group having 1 to 8 carbon atoms or a fluorine-substituted hydrocarbon group having 1 to 8 carbon atoms. may be substituted with a divalent organic group having 2 to 100 carbon atoms, more preferably a hydrocarbon group having 1 to 8 carbon atoms or a fluorine-substituted hydrocarbon group having 1 to 8 carbon atoms. It represents a divalent organic group having 2 to 100 carbon atoms and having a cyclic structure. Cyclic structures include alicyclic, aromatic and heterocyclic structures.
- Examples of the organic group for G include, for example, a group in which two non-adjacent bonds among the bonds of the groups represented by formulas (31) to (38) are replaced with hydrogen atoms, and a divalent carbon chain having 6 or less carbon atoms. Examples thereof include hydrogen groups, and preferably groups in which two non-adjacent bonds of the groups represented by formulas (39) to (51) are replaced with hydrogen atoms.
- X in formula (54) is synonymous with X in formula (1), and when the polyimide resin contains a structural unit represented by formula (1) and a structural unit represented by formula (54), each X in the structural units may be the same or different.
- the polyimide resin may contain multiple types of X or G, and the multiple types of X or G may be the same or different.
- the polyimide resin (A) is a structural unit represented by formula (1), and optionally a structural unit represented by formula (52), represented by formula (53) It consists of at least one structural unit selected from structural units and structural units represented by formula (54).
- the polyimide resin (A) has the formula (1)
- the ratio of the structural units represented by all the structural units contained in the polyimide resin, for example, the structural unit represented by formula (1), and optionally the structural unit represented by formula (52), the formula (53) Based on the total molar amount of at least one structural unit selected from structural units represented by and structural units represented by formula (54), preferably 80 mol% or more, more preferably 90 mol% or more, and further Preferably, it is 95 mol % or more.
- the upper limit of the proportion of the structural unit represented by formula (1) is 100 mol % or less.
- the above ratio can be measured, for example, using 1 H-NMR, or can be calculated from the charging ratio of raw materials.
- the polyimide resin (A) in the present invention is preferably a polyimide from the viewpoint of easily improving the dispersibility of the polymer (B) in the composition and the film and easily improving the moisture absorption resistance and heat resistance of the resulting film. Resin.
- the polyimide-based resin (A) in the present invention may contain halogen atoms, preferably fluorine atoms, which can be introduced by, for example, the above halogen-containing atom substituents.
- halogen atoms preferably fluorine atoms
- the polyimide resin (A) contains a halogen atom, preferably a fluorine atom, it is easy to increase the dispersibility of the polymer (B) in the composition and the film, and the resulting film tends to be improved in hygroscopic resistance and heat resistance. In addition, it is easy to improve the optical characteristics.
- Preferred fluorine-containing substituents for allowing the polyimide resin (A) to contain fluorine atoms include, for example, a fluoro group and a trifluoromethyl group.
- the content of the halogen atoms in the polyimide resin (A) is preferably 0.1 to 40% by mass, based on the mass of the polyimide resin (A), More preferably 1 to 35 mass %, still more preferably 5 to 30 mass %.
- the halogen atom content is at least the above lower limit, the dispersibility of the polymer (B) in the composition and film is likely to be enhanced, and the hygroscopic resistance and heat resistance of the resulting film are likely to be enhanced.
- the halogen atom content is equal to or less than the above upper limit, the CTE of the film can be reduced, and synthesis is facilitated.
- the imidization rate of the polyimide resin (A) is preferably 90% or more, more preferably 93% or more, still more preferably 95% or more, and usually 100% or less. From the viewpoint of easily improving the dielectric properties, optical properties, moisture absorption resistance, and heat resistance of the film, the imidization rate is preferably at least the above lower limit.
- the imidization rate indicates the ratio of the molar amount of imide bonds in the polyimide resin (A) to twice the molar amount of the structural units derived from the tetracarboxylic acid compound in the polyimide resin (A).
- the polyimide resin (A) contains a tricarboxylic acid compound
- a value twice the molar amount of the structural unit derived from the tetracarboxylic acid compound in the polyimide resin (A), and derived from the tricarboxylic acid compound It shows the ratio of the molar amount of the imide bond in the polyimide resin (A) to the total of the molar amount of the constituent units.
- the imidization rate can be determined by IR method, NMR method, or the like.
- the polyimide resin (A) in the present invention includes a precursor before imidization of the polyimide resin, as described above.
- the polyimide resin (A) is a polyamic acid
- the polyamic acid has the formula (1′): [In formula (1′), Y and X respectively represent Y and X in formula (1)] Including the structural unit represented by.
- Tg of the polyimide resin (A) is preferably 100°C or higher, more preferably 150°C or higher, still more preferably 200°C or higher, still more preferably 220°C, particularly preferably 300°C or higher, and particularly preferably 350°C. above, preferably 550° C. or below.
- Tg of the polyimide resin (A) is at least the above lower limit, it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
- the Tg of the polyimide resin (A) is equal to or less than the above upper limit, the mechanical properties are likely to be improved.
- the Tg of the polyimide resin (A) can be obtained, for example, by performing dynamic viscoelasticity measurement (hereinafter sometimes abbreviated as DMA measurement), and can be measured by the method described in Examples.
- DMA measurement dynamic viscoelasticity measurement
- Mw of the polyimide resin (A) is preferably 50,000 or more, more preferably 100,000 or more, more preferably 150,000 or more, still more preferably 200,000 or more, still more preferably 250 in terms of polystyrene. ,000 or more, particularly preferably 300,000 or more, preferably 1,000,000 or less, more preferably 800,000 or less, even more preferably 700,000 or less, even more preferably 500,000 or less, particularly preferably is less than or equal to 450,000.
- Mw of the polyimide resin (A) is at least the above lower limit, it is easy to improve the hygroscopic resistance, heat resistance and mechanical properties of the resulting film.
- the Mw of the polyimide resin (A) is equal to or less than the above upper limit, the moldability is likely to be improved.
- the Mw of the polyimide resin (A) can be obtained, for example, by GPC measurement and standard polystyrene conversion, for example, by the method described in Examples.
- the content of the polyimide resin (A) contained in the composition of the present invention is preferably 50 mass with respect to the total mass of the polyimide resin (A) and the polymer (B). % or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 93% by mass or less, and even more preferably 90% by mass % or less, particularly preferably 80 mass % or less.
- the content of the polyimide resin (A) is at least the above lower limit, film formation is facilitated, which is advantageous from the viewpoint of film production.
- the content of the polyimide-based resin (A) is equal to or less than the above upper limit, the dispersibility of the polymer (B) in the composition is likely to be improved, and thus the hygroscopic resistance and heat resistance of the resulting film are likely to be improved.
- the method for producing the polyimide resin (A) is not particularly limited, but for example, it can be produced by a method including a step of reacting a diamine compound and a tetracarboxylic acid compound to obtain a polyamic acid, and a step of imidizing the polyamic acid. .
- a step of obtaining polyamic acid may be carried out.
- a dicarboxylic acid compound and a tricarboxylic acid compound may be reacted.
- the tetracarboxylic acid compound used in the synthesis of the polyimide resin (A) includes aromatic tetracarboxylic acid compounds such as aromatic tetracarboxylic dianhydride; and aliphatic tetracarboxylic acid compounds such as aliphatic tetracarboxylic dianhydride. acid compounds and the like.
- a tetracarboxylic acid compound may be used independently and may be used in combination of 2 or more type.
- the tetracarboxylic acid compound may be a dianhydride or a tetracarboxylic acid compound analog such as an acid chloride compound.
- tetracarboxylic acid compounds include pyromellitic anhydride (hereinafter sometimes abbreviated as PMDA), 4,4'-(4,4'-isopropylidenediphenoxy) diphthalic anhydride (hereinafter abbreviated as BPADA).
- PMDA pyromellitic anhydride
- BPADA 4,4'-(4,4'-isopropylidenediphenoxy) diphthalic anhydride
- 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride (hereinafter sometimes abbreviated as BPDA), 4,4'-(Hexafluoroisopropylidene)diphthalic dianhydride (hereinafter sometimes abbreviated as 6FDA), 4,4'-oxydiphthalic anhydride (hereinafter sometimes abbreviated as ODPA), 2,2 ',3,3'-, 2,3,3',4'- or 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic acid acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3',3,4'-diphenylethertetracarboxylic dianhydride, bis(2,3-dicarboxy
- PMDA BPDA
- 6FDA BPADA
- ODPA ODPA
- HPMDA HPMDA
- CBDA CBDA
- TAHQ tetracarboxylic acid compounds
- Diamine compounds used for synthesizing the polyimide resin (A) include, for example, aliphatic diamines, aromatic diamines, and mixtures thereof.
- the “aromatic diamine” represents a diamine having an aromatic ring, and may contain an aliphatic group or other substituents in a part of its structure.
- This aromatic ring may be a single ring or a condensed ring, and examples include, but are not limited to, benzene ring, naphthalene ring, anthracene ring, and fluorene ring. Among these, a benzene ring is preferred.
- the term "aliphatic diamine” refers to a diamine having an aliphatic group, which may contain other substituents in part of its structure, but does not have an aromatic ring.
- diamine compounds include 1,4-diaminocyclohexane, 4,4'-diamino-2,2'-dimethylbiphenyl (hereinafter sometimes referred to as m-TB), 4,4'-diamino- 3,3'-dimethylbiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl (hereinafter sometimes referred to as TFMB), 4,4'-diaminodiphenyl ether, 1,3 -bis(3-aminophenoxy)benzene (hereinafter sometimes abbreviated as 1,3-APB), 1,4-bis(4-aminophenoxy)benzene (hereinafter sometimes abbreviated as 1,4-APB) , 1,3-bis(4-aminophenoxy)benzene, 2,2′-bis[4-(4-aminophenoxy)phenyl]propane (hereinafter sometimes referred to as BAPP
- 1,4-diaminocyclohexane, 4,4'-diaminodiphenyl ether, TFMB, and 4 are preferred from the viewpoint of easily increasing the dispersibility of the polymer (B) and easily improving the moisture absorption resistance and heat resistance of the resulting film.
- the polyimide resin (A) in addition to the tetracarboxylic acid compound used in the resin synthesis, other tetracarboxylic acids, dicarboxylic acids and tricarboxylic acids and their Anhydrides and derivatives may be further reacted.
- tetracarboxylic acids include water adducts of the above tetracarboxylic acid compound anhydrides.
- dicarboxylic acid compounds include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, their analogous acid chloride compounds, acid anhydrides, and the like, which may be used alone or in combination of two or more. Specific examples include terephthalic acid; isophthalic acid; naphthalenedicarboxylic acid; 4,4′-biphenyldicarboxylic acid; 3,3′-biphenyldicarboxylic acid; compounds in which two benzoic acids are linked by a single bond, —O—, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —SO 2 — or a phenylene group, and their acid chloride compounds.
- tricarboxylic acid compounds include aromatic tricarboxylic acids, aliphatic tricarboxylic acids, their analogous acid chloride compounds, acid anhydrides, and the like, which may be used alone or in combination of two or more. Specific examples include anhydride of 1,2,4-benzenetricarboxylic acid; 2,3,6-naphthalenetricarboxylic acid-2,3-anhydride; a single bond between phthalic anhydride and benzoic acid; , —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —SO 2 — or compounds linked by a phenylene group.
- the amounts of the diamine compound, the tetracarboxylic acid compound, the dicarboxylic acid compound and the tricarboxylic acid compound to be used can be appropriately selected according to the desired ratio of each structural unit of the resin.
- the amount of the diamine compound used is preferably 0.94 mol or more, more preferably 0.96 mol or more, still more preferably 0.98 mol or more, and particularly It is preferably 0.99 mol or more, preferably 1.20 mol or less, more preferably 1.10 mol or less, still more preferably 1.05 mol or less, and particularly preferably 1.02 mol or less.
- the amount of the diamine compound used relative to the tetracarboxylic acid compound is within the above range, the dispersibility of the polymer (B) in the composition and the film is easily improved, and the moisture absorption resistance and heat resistance of the resulting film are easily improved.
- the reaction temperature of the diamine compound and the tetracarboxylic acid compound is not particularly limited, and may be, for example, 5 to 200° C.
- the reaction time is also not particularly limited, and may be, for example, about 0.5 to 72 hours.
- the reaction temperature is preferably 5-50° C., more preferably 10-40° C.
- the reaction time is preferably 3-24 hours. With such a reaction temperature and reaction time, it is easy to improve the dispersibility of the polymer (B) in the composition and the film, and it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
- the reaction between the diamine compound and the tetracarboxylic acid compound is preferably carried out in a solvent.
- the solvent is not particularly limited as long as it does not affect the reaction, but examples include water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, Alcohol solvents such as 2-butoxyethanol and propylene glycol monomethyl ether; Phenolic solvents such as phenol and cresol; Ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, ⁇ -butyrolactone (hereinafter sometimes referred to as GBL) , ⁇ -valerolactone, propylene glycol methyl ether acetate, ethyl lactate and other ester solvents; acetone, methyl ethyl ketone, cyclopentanone, cyclohexan
- the reaction between the diamine compound and the tetracarboxylic acid compound may be carried out under an inert atmosphere such as a nitrogen atmosphere or an argon atmosphere or under reduced pressure conditions, for example, an inert atmosphere such as a nitrogen atmosphere or an argon atmosphere. It is preferable to carry out with stirring in a strictly controlled dehydrated solvent.
- imidization may be performed using an imidization catalyst, imidization by heating, or a combination thereof.
- the imidization catalyst used in the imidization step include aliphatic amines such as tripropylamine, dibutylpropylamine and ethyldibutylamine; N-ethylpiperidine, N-propylpiperidine, N-butylpyrrolidine, N-butylpiperidine, and alicyclic amines (monocyclic) such as N-propylhexahydroazepine; azabicyclo[2.2.1]heptane, azabicyclo[3.2.1]octane, azabicyclo[2.2.2]octane, and Alicyclic amines (polycyclic) such as azabicyclo[3.2.2]nonane; and pyridine, 2-methylpyridine (2-picoline), 3-methylpyridine (3-picoline), 4-methylpyridine (4
- Acid anhydrides include conventional acid anhydrides used in imidization reactions, and specific examples thereof include aliphatic acid anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride, and aromatic acid anhydrides such as phthalic acid. and acid anhydrides.
- the imidization step by heating may be performed in a solvent in which the polyamic acid is dissolved, or may be performed in a film state as described later.
- the reaction temperature is usually 20 to 250°C, and the reaction time is preferably 0.5 to 24 hours, more preferably 1 to 12 hours.
- the polyimide resin (A) can be separated and purified by a conventional method such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination thereof.
- the resin can be isolated by adding a large amount of alcohol such as methanol to the reaction solution containing the resin to precipitate the resin, followed by concentration, filtration, drying, and the like.
- the composition of the present invention contains a polyimide resin (A), a polymer (B) and a phenolic antioxidant, the phenolic antioxidant contains a substituent P, and the substituent P in the phenolic antioxidant is
- the structure S in which the hydrogen atom is substituted has an aromatic ring which may have a substituent. Therefore, it is excellent in moisture absorption resistance, and can effectively suppress deterioration of dielectric properties due to moisture absorption of the film. In addition, it is excellent in heat resistance, and even if the film is placed in a high-temperature environment, deterioration due to oxidation of the polymer (B) can be effectively suppressed. Therefore, the film formed from the composition of the present invention can have both excellent moisture absorption resistance and excellent heat resistance.
- the specific phenolic antioxidant can effectively suppress the oxidation of the polymer (B) during film formation, which can reduce moisture resistance and the like.
- deterioration of moisture absorption resistance etc. can also occur due to deterioration of deposits adhering to the surface (for example, dispersants such as surfactants and protective materials). It is thought that the alteration of the
- the distance between the HSP values of the polymer (B) and the phenolic antioxidant is preferably 2.1 or more, more preferably 2.3 or more, still more preferably 2.5 or more, and More preferably 3.0 or more, particularly preferably 3.2 or more.
- the affinity between the phenolic antioxidant and the polymer (B) is not too high, and the phenolic antioxidant tends to uniformly cover the polymer (B). It is easy to suppress the oxidation of (B), and it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
- the distance between the HSP values of the phenolic antioxidant and the polymer (B) is preferably 16.0 or less, more preferably 12.0 or less, even more preferably 9.0 or less, still more preferably 6.0 or less, and even more preferably 6.0 or less. is preferably 5.5 or less, particularly preferably 5.0 or less, even more preferably 4.5 or less, and even more preferably 4.0 or less.
- the distance between the HSP values is equal to or less than the above upper limit, the phenolic antioxidant tends to approach or adsorb to the polymer (B), and tends to cover the polymer (B), thereby suppressing oxidation of the polymer (B). It is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
- the distance between HSP values between polymer (B) and structure S is preferably 1.5 or more, more preferably 2.0 or more, still more preferably 2.4 or more, still more preferably 2.6 or more.
- the affinity between the phenolic antioxidant and the polymer (B) is not too high, and the phenolic antioxidant tends to uniformly cover the polymer (B). It is easy to suppress the oxidation of (B), and it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
- the distance between the HSP values of structure S and polymer (B) is preferably 15.5 or less, more preferably 12.0 or less, still more preferably 10.0 or less, even more preferably 7.5 or less, even more preferably is 5.0 or less, particularly preferably 4.0 or less, particularly more preferably 3.5 or less, and even more preferably 3.0 or less.
- the phenolic antioxidant tends to approach or adsorb to the polymer (B), and tends to cover the polymer (B), thereby suppressing oxidation of the polymer (B). It is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
- the distance between the HSP values between the structure S and the polymer (B) is the HSP value between the phenolic antioxidant and the polymer (B) It is preferably smaller than the inter-HSP value distance (hereinafter also referred to as inter-HSP value distance (2)).
- inter-HSP value distance (2) the inter-HSP value distance
- the fact that the HSP value distance (1) is smaller than the HSP value distance (2) means that the portion of the structure S of the phenolic antioxidant has a particularly high affinity with the polymer (B), and oxidation Since the portion of the structure S of the inhibitor is easily adsorbed to the polymer (B) so that it is in contact with the polymer (B), the substituent P of the phenolic antioxidant tends to be uniformly present around the polymer (B), and as a result, the polymer ( The unstable radicals generated by the oxidation in B) are likely to be trapped by the substituent P. The radical of the substituent P generated by trapping the radical can further trap the radical of the polymer (B) and inactivate the polymer (B).
- the absolute value of the difference between the distance between HSP values (1) and the distance between HSP values (2) is preferably 0.1 or more, more preferably is 0.2 or more, more preferably 0.3 or more, even more preferably 0.4 or more, and particularly preferably 0.5 or more.
- the absolute value of the difference between the distance between HSP values (1) and the distance between HSP values (2) is such that the phenolic antioxidant easily adsorbs uniformly to the polymer (B), and the phenolic antioxidant Preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.0 or less, and even more preferably is 1.5 or less, particularly preferably 1.0 or less.
- the distance between the HSP values of the phenolic antioxidant and the polyimide resin (A) suppresses the oxidation of the polymer (B) because the phenolic antioxidant easily covers the polymer (B). from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the film, preferably 5.0 or more, more preferably 8.0 or more, still more preferably 8.5 or more, still more preferably 9.5 or more, It is particularly preferably 10.0 or more, and particularly more preferably 11.0 or more. Further, the distance between the HSP values of the phenolic antioxidant and the polyimide resin (A) is preferably 16.0 or less, from the viewpoint of easily preventing aggregation of the phenolic antioxidant in the composition or film. It is more preferably 15.0 or less, still more preferably 13.0 or less, and even more preferably 12.5 or less.
- the distance between the HSP values of the structure S and the polyimide resin (A) is preferably 5.0 or more, more preferably 7.0 or more, still more preferably 8.0 or more, and still more Preferably 9.0 or more, particularly preferably 10.0 or more, preferably 15.0 or less, more preferably 14.0 or less, still more preferably 13.0 or less, still more preferably 12.0 or less .
- the distance between HSP values is equal to or less than the upper limit or equal to or more than the lower limit, it is easy to suppress oxidation of the polymer (B), and it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
- the distance between the HSP values of the polyimide resin (A) and the polymer (B) is preferably 6.0 or more, more preferably 6.5 or more, still more preferably 7.0 or more, Even more preferably, it is 8.0 or more. If the distance between the HSP values of the polyimide resin (A) and the polymer (B) is at least the above lower limit, an interface is likely to form between the polymer (B) and the polyimide resin (A), so phenolic oxidation The inhibitor is easily adsorbed so as to cover the polymer (B), and the polymer (B) is easily prevented from being oxidized.
- the distance between the HSP values of the polyimide resin (A) and the polymer (B) is preferably 30.0 or less, more preferably 25.0 or less, still more preferably 20, from the viewpoint of affinity between the resin and the polymer. .0 or less, and even more preferably 15.0 or less.
- the composition of the present invention may further contain a solvent.
- the distance between the HSP values of the phenolic antioxidant and the solvent is preferably 12.0 or more.
- the polymer (B) contained in the composition of the present invention is hardly oxidized even during film formation, and the composition of the present invention is Easy to form a film with excellent moisture absorption resistance. This is because when the distance between the HSP values between the phenolic antioxidant and the solvent is 12.0 or more, the phenolic antioxidant is difficult to dissolve and disperse in the solvent, so the affinity with the polymer (B) is relatively high.
- the phenolic antioxidant becomes more likely to approach the polymer (B), and the phenolic antioxidant covers the polymer (B), so that the phenolic antioxidant can oxidize the polymer (B). It is considered that this is because the preventive effect increases. Furthermore, since the polymer (B) is formed into a film so as to cover the surroundings thereof, the polymer (B) is likely to exhibit a heat resistance function, and even when the resulting film is exposed to a high temperature environment, oxidation of the polymer (B) is likely to be suppressed.
- the distance between the HSP values of the phenolic antioxidant and the solvent is preferably 12.5 or more, more preferably 13.0 or more, still more preferably 14.0 or more, still more preferably 16 0.0 or more, particularly preferably 16.5 or more, and particularly more preferably 17.0 or more.
- the phenolic antioxidant tends to surround the polymer (B), and the phenolic antioxidant surrounds the polymer (B) to form a film. Therefore, oxidation of the polymer (B) is easily suppressed, and the hygroscopic resistance and heat resistance of the obtained film are easily improved.
- the upper limit of the distance between the HSP values of the phenolic antioxidant and the solvent is preferably 30 or less, more preferably 25 or less, still more preferably 20 or less.
- the phenolic antioxidant tends to disperse in the solvent, so that oxidation of the polymer (B) can be easily suppressed.
- the Hansen Solubility Parameters ⁇ D, ⁇ P, and ⁇ H can be calculated using HSPiP (Hansen Solubility Parameters in Practice), a program developed by Dr. Hansen's group who proposed the Hansen Solubility Parameters, according to the Hansen Solubility Sphere Method. For example, Ver. 4.1.07 and the like can be used. Details of the Hansen melting ball method are described below. A component of interest is dissolved in a solvent with a known HSP value, and the solubility of the component in a specific solvent is evaluated. Solubility evaluation is performed by visually judging whether or not each target component is dissolved in the solvent. This is done for multiple solvents.
- the HSP of the target component As for the types of solvents, it is preferable to use solvents having a wide range of different ⁇ t.
- the center coordinates ( ⁇ d, ⁇ p, ⁇ h) of the Hansen sphere obtained by inputting the obtained solubility evaluation results into HSPiP are used as the HSP of the target component.
- the HSP may be obtained by using, for example, numerical values in the HSPiP database or literature values, or may be determined from the structural formula using HSPiP.
- the value of the Hansen solubility parameter is referred to as the HSP value
- the HSP value represents the value at 25°C.
- the HSP value of the polyimide resin (A), the HSP value of the polymer (B), and the HSP value of the solvent may each be determined by any of the methods described above, for example, by the methods described in the Examples.
- the distance between the Hansen solubility parameters (hereinafter sometimes abbreviated as HSP) of two substances is called the distance between HSP values.
- the inter-HSP distance (Ra) is an index representing the affinity between both substances, and the smaller the value, the higher the affinity between the two substances. Conversely, the larger the Ra value, the lower the affinity between the two substances, that is, the less compatible they are.
- ⁇ A ( ⁇ DA, ⁇ PA, ⁇ HA)
- ⁇ B ( ⁇ DB, ⁇ PB, ⁇ HB)
- Ra [4 ⁇ ( ⁇ DA ⁇ DB) 2 +( ⁇ PA ⁇ PB) 2 +( ⁇ HA ⁇ HB) 2 ] 0.5
- Y can be calculated by
- the HSP value and the distance between HSP values are as defined above, and can be obtained according to the above method.
- the phenolic antioxidant preferably has a distance between the HSP values of the structure S and the solvent of 10.0 or more, more preferably 12.3 or more, and even more preferably 12.5. 12.7 or more, particularly preferably 13.0 or more, particularly more preferably 13.5 or more, even more preferably 14.0 or more, extremely preferably 15.0 or more, extremely more preferably 16.0 or higher, and very preferably 17.0 or higher.
- the distance between the HSP values is at least the above lower limit, the phenolic antioxidant is difficult to dissolve and disperse in the solvent and easily covers the polymer (B). It is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
- the upper limit of the distance between the HSP values of Structure S and the solvent is preferably 30.0 or less, more preferably 25.0 or less, and even more preferably 20.0 or less.
- the distance between the HSP values is equal to or less than the above upper limit, the phenolic antioxidant is prevented from aggregating in the composition, and the surroundings of the polymer (B) are easily covered, so oxidation of the polymer (B) is easily suppressed. .
- a solvent having an HSP value distance of 12.0 or more with a phenolic antioxidant (hereinafter sometimes referred to as a "first solvent”) is not particularly limited, and for example, N,N-dimethylacetamide (hereinafter , sometimes referred to as DMAc), amide solvents such as NN-dimethylformamide (hereinafter sometimes referred to as DMF); ⁇ -butyrolactone (hereinafter sometimes referred to as GBL), ⁇ - lactone solvents such as valerolactone; sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide and sulfolane; carbonate solvents such as ethylene carbonate and propylene carbonate; pyrrolidone solvents such as N-methylpyrrolidone; .
- DMAc N,N-dimethylacetamide
- DMF amide solvents
- GBL ⁇ -butyrolactone
- ⁇ - lactone solvents such as valerolactone
- sulfur-containing solvents
- amide-based solvents lactone-based solvents, and pyrrolidone-based solvents are preferred.
- the affinity between the phenolic antioxidant and the polymer (B) is relatively increased, the phenolic antioxidant is easily adsorbed to the polymer (B), and the polymer (B) Aggregation of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily improved, so that the moisture absorption resistance and heat resistance of the obtained film can be easily improved.
- the dispersibility of the polymer (B) in the composition increases, so the moisture absorption resistance, surface smoothness, dielectric properties and mechanical properties of the film tend to increase, and the film physical properties, such as variation in thermal conductivity of the film, coefficient of linear expansion (hereinafter referred to as CTE), and surface roughness of the film.
- CTE coefficient of linear expansion
- mechanical properties refer to mechanical properties including bending resistance and elastic modulus, and increasing or improving mechanical properties means, for example, increasing bending resistance and/or elastic modulus. show.
- a solvent can be used individually or in combination of 2 or more types.
- the distance between the HSP values of the first solvent and the polymer (B) is preferably 8.0 or more, more preferably 8.5 or more, even more preferably 9.0 or more, and particularly preferably is 10.0 or more, and more preferably 11.0 or more.
- the distance between the HSP values is at least the above lower limit, the affinity between the phenolic antioxidant and the polymer (B) is relatively increased, and the phenolic antioxidant is easily adsorbed to the polymer (B), and , when the polymer (B) is particulate, the dispersibility of the polymer (B) is likely to be enhanced.
- the upper limit of the distance between the HSP values between the first solvent and the polymer (B) is preferably 30.0 or less, more preferably 25.0 or less, still more preferably 20.0 or less.
- the distance between the HSP values of the first solvent and the polymer (B) is equal to or less than the above upper limit, aggregation of the polymer (B) is likely to be suppressed, and dispersibility of the polymer (B) is likely to be enhanced. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
- the first solvent is preferably a solvent in which the polymer (B) does not dissolve.
- a solvent in which the polymer (B) does not dissolve.
- an interface is easily formed, so the phenolic antioxidant is easily adsorbed to the polymer (B), and aggregation of the polymer (B) is easily suppressed, and the dispersibility of the polymer (B) is improved.
- Cheap it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
- the evaluation of whether “dissolves” or “does not dissolve” can be performed according to the method described in ⁇ Evaluation of Solubility> in Examples.
- the distance between the HSP values of the first solvent and polymer (B) is preferably larger than the interaction radius of polymer (B).
- the polymer (B) is less likely to be dissolved in the first solvent, so aggregation of the polymer (B) is easily suppressed and the dispersibility of the polymer (B) is easily improved.
- the interaction radius means a plurality of solvents capable of dissolving a specific polymer, that is, when the Hansen solubility parameters of good solvents are plotted in a three-dimensional HSP space, the plots of each good solvent are similar to each other.
- a solute with a large interaction radius is soluble in many solvents
- a solute with a small interaction radius is soluble in a small number of solvents, and is difficult to dissolve in a large number of solvents.
- a solubility test is conducted to determine whether various solvents are good solvents or poor solvents. A radius is calculated.
- the "interaction radius" is as defined above and can be determined according to the above method.
- the distance between the HSP values of the first solvent and the polyimide resin (A) is preferably 11.0 or less, more preferably 10.0 or less, still more preferably 9.5 or less, and more preferably 9.0 or less, particularly preferably 8.5 or less, preferably 0.01 or more, more preferably 0.1 or more, still more preferably 1.0 or more, still more preferably 3.0 or more, Especially preferably, it is 5.0 or more.
- the distance between the HSP values is the above upper limit or less, the affinity between the first solvent and the polyimide resin (A) can be improved, so that the dispersibility of the polymer (B) can be easily increased, and the resulting film It is easy to improve the moisture absorption resistance and heat resistance of
- the first solvent is preferably a solvent in which the polyimide resin (A) dissolves.
- a solvent facilitates dispersion of the polymer (B) in the resulting composition and film.
- the film tends to form a sea-island structure.
- the distance between the HSP values of the first solvent and the polyimide resin (A) is preferably smaller than the interaction radius of the polyimide resin (A).
- the content of the first solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more, relative to the mass of the composition of the present invention. Even more preferably 80% by mass or more, particularly preferably 90% by mass or more, preferably 99% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less.
- the content of the first solvent is within the above range, an interface is easily formed, so the phenolic antioxidant is easily adsorbed to the polymer (B), and aggregation of the polymer (B) is easily suppressed.
- the composition of the present invention may contain a second solvent in addition to the first solvent whose HSP value distance to the phenolic antioxidant is 12.0 or more.
- the composition contains the second solvent in addition to the first solvent, it is easy to prepare a composition containing the particulate polymer (B) with a reduced particle size.
- the second solvent examples include hydrocarbon solvents such as benzene, toluene, pentane, hexane, heptane, cyclohexane, and xylene; halogenated hydrocarbon solvents such as dichloromethane and ethylene dichloride; acetone, methyl ethyl ketone, cyclopentanone, and cyclohexanone. , 2-heptanone, and ketone solvents such as methyl isobutyl ketone.
- hydrocarbon-based solvents and/or ketone-based solvents are preferable, and hydrocarbon-based solvents are more preferable.
- a 2nd solvent can be used individually or in combination of 2 or more types.
- the distance between the HSP values of the second solvent and the phenolic antioxidant is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 1.0 or more, and even more preferably Preferably it is 1.5 or more.
- the upper limit of the distance between the HSP values of the second solvent and the phenolic antioxidant is usually 15 or less, preferably 10 or less, more preferably 8.0 or less, even more preferably 5.0 or less, and even more preferably 2.5 or less, particularly preferably 2.0 or less.
- the phenolic antioxidant is likely to be adsorbed to the polymer (B), and the hygroscopic resistance and heat resistance of the resulting film are likely to be improved.
- the distance between the HSP values of the second solvent and the polymer (B) is preferably 8.0 or less, more preferably 7.0 or less, even more preferably 6.0 or less, even more preferably is 5.0 or less, particularly preferably 4.0 or less, particularly more preferably 3.0 or less, and even more preferably 2.5 or less.
- the distance between the HSP values is equal to or less than the above upper limit, the solubility of the polymer (B) in the second solvent is increased, so that the dispersibility of the polymer (B) is likely to be increased.
- the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
- the lower limit of the distance between HSP values is usually greater than zero.
- the second solvent is preferably a solvent in which the polymer (B) dissolves.
- a solvent tends to improve the dispersibility of the polymer (B).
- the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
- the distance between the HSP values of the second solvent and the polymer (B) is preferably smaller than the interaction radius of the polymer (B). Such a relationship facilitates dissolution of the polymer (B) in the second solvent, thereby enhancing the dispersibility of the polymer (B). In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
- the distance between the HSP values of the second solvent and the polyimide resin (A) is preferably 4.0 or more, more preferably 5.0 or more, still more preferably 6.0 or more, and further It is more preferably 7.0 or higher, particularly preferably 8.0 or higher, and particularly preferably 9.0 or higher.
- the distance between the HSP values is at least the above lower limit, the polyimide resin (A) is difficult to dissolve in the second solvent, so the formation of aggregates of the polymer (B) is easily suppressed, and the polymer (B) is dispersed. easy to enhance. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
- the upper limit of the distance between the HSP values of the second solvent and the polyimide resin (A) is preferably 30.0 or less, more preferably 27.0 or less, still more preferably 25.0 or less, and even more preferably 23.0 or less. , and particularly preferably 21.0 or less.
- the distance between the HSP values of the second solvent and the polyimide resin (A) is the above upper limit or less, aggregation of the polymer (B) is easily suppressed, so the dispersibility of the polymer (B) is easily increased, and It is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
- the second solvent is preferably a solvent in which the polyimide resin (A) does not dissolve.
- a solvent tends to enhance the dispersibility of the polymer (B).
- the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
- the distance between the HSP values of the second solvent and the polyimide resin (A) is preferably larger than the interaction radius of the polyimide resin (A).
- the polyimide resin (A) is less likely to be dissolved in the second solvent, so the formation of aggregates of the polymer (B) is easily suppressed, and the dispersibility of the polymer (B) is easily enhanced.
- the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
- the solubility of polymer (B) in the second solvent is preferably greater than the solubility of polymer (B) in the first solvent.
- Such a relationship tends to suppress the formation of aggregates of the polymer (B), and tends to increase the dispersibility of the polymer (B).
- the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
- the solubility of the polymer (B) in solvents can be measured by the following method. 1000 mg of polymer (B) and 3 mL of solvent are added to a sample bottle and stirred at room temperature for 2 hours.
- the solubility in the second solvent is clearly is large, it is not necessary to measure the solubility.
- the content of the second solvent that can be contained in the composition of the present invention is preferably 120 parts by mass or less, more preferably 100 parts by mass with respect to 100 parts by mass of the content of the first solvent. parts or less, more preferably 60 parts by mass or less, even more preferably 45 parts by mass or less, particularly preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, even more preferably 30 parts by mass or less, and even more preferably is less than 30 parts by mass, extremely preferably 25 parts by mass or less, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and still more preferably 0.1 parts by mass or more.
- the content of the second solvent is equal to or less than the above upper limit, the formation of aggregates of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily enhanced. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. It is easy to prepare a composition as content of a 2nd solvent is more than said minimum.
- the composition of the present invention may contain a solvent other than the first solvent and the second solvent within a range that does not impair the effects of the present invention.
- solvents are not particularly limited, and commonly used solvents can be used.
- the total content of the first solvent, the second solvent and other solvents that can be contained in the composition of the present invention is preferably 50% by mass or more, based on the mass of the composition. More preferably 60% by mass or more, still more preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, preferably 99% by mass or less, more preferably 97% by mass or less, More preferably, it is 95% by mass or less.
- the total content is within the above range, the formation of aggregates of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily improved. Furthermore, it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
- the total weight of the first solvent and the second solvent is preferably 50% by weight based on the total weight of the first solvent, the second solvent and other solvents that may be included in the composition. Above, more preferably 70% by mass or more, still more preferably 90% by mass or more, even more preferably 95% by mass or more, and preferably 100% by mass or less.
- the total mass of the first solvent and the second solvent is within the above range, the formation of aggregates of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily improved. Furthermore, it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
- the composition of the present invention preferably further contains a secondary antioxidant.
- a secondary antioxidant By including the secondary antioxidant in addition to the phenolic antioxidant which is the primary antioxidant, it is easy to suppress oxidation of the polymer (B) and improve the hygroscopic resistance and heat resistance of the resulting film.
- Secondary antioxidants include phosphorus antioxidants, sulfur antioxidants, and the like, and these secondary antioxidants can be used alone or in combination of two or more.
- phosphorus-based antioxidants include, for example, tris(2,4-di-tert-butylphenyl)phosphite, triphenylphosphite, tris(nonylphenyl)phosphite, trilaurylphosphite.
- trioctadecyl phosphite distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-Butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl) ) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4′-diphenylenediphosphonite, 2,2′-methylene
- sulfur-based antioxidants include, for example, dilauryl 3,3'-thiodipropionate, tridecyl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3,3'-thiodipropionate, neopentanetetrayl tetrakis(3-laurylthiopropionate) and the like.
- sulfur antioxidants can be used alone or in combination of two or more.
- the content of the secondary antioxidant that can be contained in the composition of the present invention is preferably 0.002 parts by mass or more, more preferably 100 parts by mass of the polymer (B) 0.01 parts by mass or more, more preferably 0.04 parts by mass or more, still more preferably 0.1 parts by mass or more, and particularly preferably 1 part by mass or more.
- the content of the secondary antioxidant is at least the above lower limit, the oxidation of the polymer (B) can be sufficiently suppressed, and the hygroscopic resistance and heat resistance of the film can be easily improved.
- the content of the secondary antioxidant is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and still more preferably 7 parts by mass with respect to 100 parts by mass of the polymer (B). parts or less, particularly preferably 5 parts by mass or less.
- the content of the secondary antioxidant is equal to or less than the above upper limit, the dielectric properties of the film are likely to be enhanced.
- the content of the secondary antioxidant that can be contained in the composition of the present invention is preferably 5 parts by mass or more, more preferably 10 parts by mass with respect to 100 parts by mass of the phenolic antioxidant. It is at least 15 parts by mass, more preferably at least 20 parts by mass, particularly preferably at least 30 parts by mass.
- the content of the secondary antioxidant is at least the above lower limit, the oxidation of the polymer (B) can be sufficiently suppressed, and the hygroscopic resistance and heat resistance of the film can be easily improved.
- the content of the secondary antioxidant is preferably 1000 parts by mass or less, more preferably 700 parts by mass or less, still more preferably 600 parts by mass or less, still more preferably 500 parts by mass or less, relative to 100 parts by mass of the phenolic antioxidant. Part by mass or less, particularly preferably 200 parts by mass or less, particularly more preferably 150 parts by mass or less, and even more preferably 100 parts by mass or less.
- the content of the secondary antioxidant is equal to or less than the above upper limit, the dielectric properties of the film are likely to be enhanced.
- the composition of the present invention may contain additives as necessary within a range that does not impair the effects of the present invention.
- additives include flame retardants, cross-linking agents, surfactants, compatibilizers, imidization catalysts, weathering agents, lubricants, anti-blocking agents, antistatic agents, anti-fogging agents, anti-drip agents, pigments, fillers, etc. is mentioned.
- Additives can be used alone or in combination of two or more.
- the composition of the present invention effectively suppresses the formation of aggregates of the polymer (B) even without containing a compatibilizer, and the polymer (B) exhibits high dispersibility.
- the content of the compatibilizing agent is preferably 5 parts by mass or less, more preferably 1 part by mass or less, further preferably 0.1 part by mass or less, with respect to 100 parts by mass of the polyimide resin (A). 1 part by mass or less, still more preferably less than 0.1 part by mass, particularly preferably 0.05 part by mass or less, particularly more preferably 0.01 part by mass or less, and even more preferably 0.001 part by mass or less, Even more preferably, it may be 0 parts by mass.
- the polyimide resin (A) is a polyimide resin precursor such as polyamic acid and thermal imidization is required during film production, inhibition of imidization by a compatibilizing agent or compatibilization by heating
- the content of the compatibilizing agent is preferably less than 0.1 parts by mass within the above range from the viewpoint of preventing deterioration of the properties of the film due to deterioration of the agent.
- the content of the compatibilizer may be based on 100 parts by mass of the polyimide resin (A) and the polymer (B) in place of 100 parts by mass of the polyimide resin (A).
- the total mass of the polyimide resin (A) and polymer (B) contained in the composition is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass. It is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less.
- the total mass of the polyimide resin (A) and the polymer (B) contained in the composition is within the above range, it is easy to suppress the formation of aggregates of the polymer (B), and the dispersibility of the polymer (B) is increased. Cheap.
- the phenol-based antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
- the method for producing the composition of the present invention is not particularly limited, for example, polyimide resin (A), polymer (B), phenolic antioxidant, and optionally solvent, secondary antioxidant, and additives etc., but in one preferred embodiment of the invention in which the polymer (B) is particulate, the following steps: Step (I) of preparing a dispersion containing particulate polymer (B) (hereinafter sometimes referred to as particulate polymer (B) dispersion); ) Step (II) of adding and preferably produced by a method of adding a phenolic antioxidant in the step (I) and/or the step (II).
- Step (I) is a step of preparing a dispersion containing particulate polymer (B).
- step (I) comprises, for example, the following steps: Step (1) of dissolving polymer (B) in a second solvent to obtain a polymer (B) solution; and after contacting the polymer (B) solution with the first solvent, distilling off the second solvent, Step (2) of obtaining a particulate polymer (B) dispersion
- Step (1) of dissolving polymer (B) in a second solvent to obtain a polymer (B) solution
- Step (2) of obtaining a particulate polymer (B) dispersion It is preferable that the step of preparing a particulate polymer (B) dispersion is performed by a method comprising: When such a step is included, aggregation of the particles of the polymer (B) can be suppressed, so that the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
- Step (1) is a step of dissolving polymer (B) in a second solvent to obtain a polymer (B) solution.
- the form of the polymer (B) dissolved in the second solvent is not particularly limited, and may be, for example, particulate, fibrous, sheet-like, or pellet-like.
- the polymer (B) solution preferably contains 0.01 to 20% by mass of polymer (B) relative to the mass of the solution.
- the content of the polymer (B) in the polymer (B) solution is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass, relative to the mass of the solution. % or more, more preferably 0.5 mass % or more, preferably 20 mass % or less, more preferably 10 mass % or less, and even more preferably 5 mass % or less.
- the content of the polymer (B) in the solution is at least the above lower limit, it is easy to adjust the composition.
- the content of the polymer (B) in the solution is equal to or less than the above upper limit, the formation of aggregates of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
- the method of dissolving the polymer (B) in the second solvent is not particularly limited.
- the second solvent may be added to the polymer (B), or the polymer (B) may be added to the second solvent. or both. Also, depending on the solubility of the second solvent in the polymer (B), it may be dissolved by heating or the like.
- the step (2) is a step of bringing the polymer (B) solution into contact with the first solvent and then distilling off the second solvent to obtain a dispersion containing the particulate polymer (B).
- the method of bringing the polymer (B) solution into contact with the first solvent is not particularly limited, but an example thereof includes a method of mixing the polymer (B) solution and the first solvent. Specifically, a method of adding the polymer (B) solution to the first solvent and a method of adding the first solvent to the polymer (B) solution can be exemplified. By such contact, the particulate polymer (B) having a small particle size can be precipitated or dispersed in the mixture of the first solvent and the second solvent. A small amount of the resin (A) and other additives may be added at any timing during the step (2) as long as the particulate polymer (B) does not aggregate.
- the amount of the polymer (B) solution to be brought into contact with the first solvent is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 1 part by mass of the first solvent used. is 0.3 parts by mass or more, particularly preferably 0.7 parts by mass or more, preferably 100 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 3 parts by mass or less, particularly preferably 1.5 parts by mass It is below the department.
- the amount of the polymer (B) solution to be brought into contact with the first solvent is within the above range, the formation of aggregates of the polymer (B) is easily suppressed, and the particle size is easily reduced, so the dispersibility is enhanced. Cheap.
- step (2) after the polymer (B) solution is brought into contact with the first solvent, the second solvent is distilled off.
- the second solvent By distilling off the second solvent, the dispersion stability of the particulate polymer (B) can be enhanced. Further, the polymer (B) may be further precipitated by distilling off the second solvent.
- the second solvent may be at least partially distilled or removed, and the second solvent may remain in the particulate polymer (B) dispersion. From the standpoints of facilitating the suppression of aggregation of the polymer (B) and the facilitating preparation of the dispersion, it is preferred that the second solvent partially remain or partly be contained in the dispersion of the particulate polymer (B).
- step (2) the method of distilling off the second solvent is not particularly limited, and a method of distilling off under reduced pressure using an evaporator or the like is exemplified.
- the pressure and temperature during distillation can be appropriately selected according to the characteristics such as the boiling points of the second solvent and the first solvent.
- the second solvent is distilled off from the mixture of the second solvent and the first solvent, so the boiling point of the second solvent is usually lower than that of the first solvent. In this way, a particulate polymer (B) dispersion in which the polymer (B) is dispersed without containing aggregates of the polymer (B) can be obtained.
- the content of the second solvent contained in the particulate polymer (B) dispersion obtained after distilling off the second solvent is preferably 120 parts by mass or less, more preferably 120 parts by mass or less with respect to 100 parts by mass of the first solvent.
- the content of the second solvent is equal to or less than the above upper limit, the formation of aggregates of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. Moreover, when the content of the second solvent is at least the above lower limit, it is easy to prepare a dispersion.
- step (I) is, for example, the following steps: Step (1′) of mixing particulate polymer (B) and solvent It may be a step of preparing a particulate polymer (B) dispersion by a method comprising When such a step is included, aggregation of the particles of the polymer (B) can be suppressed, so that the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
- the step (1') is a step of mixing the particulate polymer (B) and a solvent to obtain a particulate polymer (B) dispersion.
- the particulate polymer (B) used in step (1′) can be obtained, for example, by pulverizing the polymer (B) with a pulverizer, and if necessary, using a classifier, the particulate polymer (B ) may be adjusted within a desired range.
- the particulate polymer (B) taken out from the particulate polymer (B) dispersion obtained by the steps (1) and (2) may be used.
- the median diameter of the particulate polymer (B) used in step (1′) is preferably 0.01 ⁇ m or more, more preferably 0.03 ⁇ m or more, still more preferably 0.05 ⁇ m or more, and preferably 15 ⁇ m or less. It is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
- the median diameter of the particulate polymer (B) to be added is at least the above lower limit, the dielectric properties of the film formed from the composition are likely to be enhanced, and the film is easily produced.
- the median diameter of the particulate polymer (B) is equal to or less than the above upper limit, the hygroscopic resistance and heat resistance of the film formed from the composition are likely to be improved.
- the solvent to be mixed with the particulate polymer (B) is preferably a solvent containing the first solvent, from the viewpoint that the phenolic antioxidant easily adsorbs to the particulate polymer (B), More preferably, it is the first solvent.
- the particulate polymer (B) dispersion obtained in step (I) contains a solvent other than the first solvent and the second solvent within a range that does not impair the effects of the present invention.
- solvents are not particularly limited, and commonly used solvents can be used.
- the total content of the first solvent, the second solvent and other solvents that can be contained in the particulate polymer (B) dispersion obtained in step (I) is On the other hand, it is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, particularly preferably 95% by mass or more, preferably 99.99% by mass or less, more preferably 99.9% by mass or more. It is 9% by mass or less, more preferably 99% by mass or less, and particularly preferably 95% by mass or less.
- the content of the solvent is within the above range, aggregation of the polymer (B) is likely to be suppressed, and dispersibility of the polymer (B) is likely to be enhanced. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
- the total mass of the first solvent and the second solvent is the first solvent, the second solvent and other
- the total mass of the solvent is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and preferably 100% by mass or less.
- the total mass of the second solvent and the first solvent is within the above range, aggregation of the polymer (B) is likely to be suppressed, and dispersibility of the polymer (B) is likely to be improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
- the content of the particulate polymer (B) contained in the particulate polymer (B) dispersion obtained in step (I) is, relative to the mass of the polymer (B) dispersion, Preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more, preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 10% by mass Below, it is 5 mass % or less especially preferably.
- the content of the particulate polymer (B) is within the above range, aggregation of the polymer (B) is likely to be suppressed, and dispersibility of the polymer (B) is likely to be enhanced. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
- the polyimide resin (A) to be added when added in the form of varnish in step (II) described later, it is contained in the particulate polymer (B) dispersion obtained in step (I).
- the content of the particulate polymer (B) is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more, relative to the mass of the polymer (B) dispersion, It is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 15% by mass or less.
- the median diameter of the particulate polymer (B) contained in the particulate polymer (B) dispersion can be selected from the same range as the median diameter of the particulate polymer (B) in the composition of the present invention.
- the median diameter of the particulate polymer (B) in the dispersion is at least the above lower limit, the dielectric properties of the film formed from the composition are likely to be enhanced, and the film is easily produced.
- the median diameter of the particulate polymer (B) in the dispersion is equal to or less than the above upper limit, it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
- the median diameter of the particulate polymer (B) contained in the particulate polymer (B) dispersion can be determined by scattering particle size distribution measurement using laser diffraction, for example, by the method described in Examples. be able to.
- Step (II) is a step of adding the polyimide resin (A) to the particulate polymer (B) dispersion.
- the polyimide resin (A) to be added may be in the form of a solid, preferably powder, or in the form of a varnish obtained by dissolving the polyimide resin (A) in a predetermined solvent, such as the first solvent.
- a predetermined solvent such as the first solvent.
- the polyimide resin or polyamic acid can be added in solid, preferably powder form or in varnish form.
- the amount of the polyimide resin (A) added in the varnish is preferably 0.1% by mass or more, more preferably 1% by mass, based on the mass of the varnish.
- the polyimide resin (A) added in step (II) is preferably 50% by mass or more, more preferably 60% by mass or more, based on the total mass of the polyimide resin (A) and the polymer (B). It is preferably 65% by mass or more, preferably 95% by mass or less, more preferably 93% by mass or less, and even more preferably 90% by mass or less.
- the content of the polyimide-based resin (A) to be added is at least the above lower limit, film formation is facilitated, which is advantageous from the viewpoint of film production.
- the content of the polyimide resin (A) is equal to or less than the above upper limit, it is easy to improve the moisture absorption resistance and heat resistance of the obtained film, and it is easy to improve the dielectric properties of the film.
- the method of adding the polyimide resin (A) to the particulate polymer (B) dispersion is not particularly limited. It may be added in batches.
- the composition of the present invention can be produced by adding a phenolic antioxidant in the step (I) and/or the step (II). Addition of the phenolic antioxidant may be performed in either step (I) or step (II), or may be performed in both step (I) and step (II).
- the method of adding the phenolic antioxidant is not particularly limited, and the phenolic antioxidant may be added at once or may be added in multiple portions.
- step (I) when the step (I) is a step including the step (1) and the step (2), the phenolic antioxidant is easily dispersed, and the polymer (B) is easily adsorbed uniformly. Therefore, it is preferable to add the phenolic antioxidant in step (I). Further, in one embodiment of the present invention, when the step (I) is a step including the step (1 '), the phenolic antioxidant is easily dispersed and uniformly adsorbed on the polymer (B). Addition of the phenolic antioxidant is preferably carried out in step (I).
- step (I) When adding a phenolic antioxidant in step (I), it may be performed in any of steps (1), (2), and step (1′), but the phenolic antioxidant is dispersed. It is preferable to carry out in step (2) or step (1′), particularly step (1′), from the viewpoint of easy and uniform adsorption on the polymer (B).
- the order of addition of the phenolic antioxidant and the polyimide resin (A) is not particularly limited, and the polyimide resin ( A) may be added, or the phenolic antioxidant may be added after adding the polyimide resin (A).
- the phenolic antioxidant is easily dispersed and uniformly adsorbed on the polymer (B)
- the phenolic antioxidant added in step (I) and/or step (II) is preferably 0.01 part per 100 parts by mass of the polymer (B) in the particulate polymer (B) dispersion or composition. Part by mass or more, more preferably 0.05 part by mass or more, still more preferably 0.1 part by mass or more, still more preferably 0.2 part by mass or more, particularly preferably 1 part by mass or more, particularly more preferably 2 parts by mass That's it.
- the amount of the phenolic antioxidant added is at least the above lower limit, the polymer (B) is easily covered with the phenolic antioxidant, and the oxidation of the polymer (B) is easily suppressed. Easy to improve heat resistance.
- the content of the phenolic antioxidant is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and still more preferably 7 parts by mass with respect to 100 parts by mass of the polymer (B). parts or less, particularly preferably 5 parts by mass or less.
- the content of the phenolic antioxidant is equal to or less than the above upper limit, the dielectric properties of the film are likely to be enhanced.
- the above production method in the present invention may include steps other than steps (I) and (II) within a range that does not impair the effects of the present invention, other than the above-described polyimide resin (A) and polymer (B) polymers, secondary antioxidants or additives may be added.
- Additives include those described above.
- the polyimide resin (A) is added to the polymer (B) dispersion. good too.
- the varnish of the polyimide resin (A) may be obtained by dissolving the polyimide resin (A) in a predetermined solvent, for example, the first solvent, or the polyimide resin It may be a resin solution used when synthesizing the precursor of (A), such as a polyamic acid solution (a solution containing at least polyamic acid and a synthesis solvent).
- the present invention comprises a polyimide resin (A), a polymer (B) and a phenolic antioxidant, wherein the phenolic antioxidant has the formula (P): [In the formula (P), R p , R q , R r and R s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms, and * represents a bond]
- the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom includes a film having an aromatic ring which may have a substituent.
- the aromatic ring is an aromatic ring different from the substituent P.
- the film of the present invention has excellent moisture absorption resistance and heat resistance, when the film of the present invention is used for the resin layer of the CCL, it is easy to improve the dielectric properties and suppress the dielectric loss and transmission loss.
- the polymer (B) contained in the film of the present invention is preferably particulate.
- the dispersibility of the polymer (B) is likely to be enhanced, and the hygroscopic resistance and heat resistance of the film are likely to be improved.
- the average primary particle size of the particulate polymer (B) is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less. , still more preferably 3 ⁇ m or less, particularly preferably 1 ⁇ m or less, particularly more preferably 0.8 ⁇ m or less, even more preferably 0.5 ⁇ m or less, preferably 0.01 ⁇ m or more, more preferably 0.03 ⁇ m or more, and further It is preferably 0.05 ⁇ m or more.
- the average primary particle size of the particulate polymer (B) is at least the above lower limit, the mechanical properties of the film are likely to be enhanced.
- the average primary particle size of the particulate polymer (B) can be determined by image analysis of images taken with an electron microscope. For example, the cross section of the film is observed using a scanning transmission electron microscope (STEM), the particle diameters of 50 or more particles are measured from the observed image, and the average value thereof is the average primary particle diameter of the particulate cycloolefin copolymer. and can be measured, for example, by the method described in Examples.
- STEM scanning transmission electron microscope
- the film of the present invention is preferably a composite film in which the polymer (B) is dispersed, preferably uniformly dispersed, in the polyimide resin (A).
- the composite film preferably has a sea-island structure, wherein the polyimide resin (A) is the sea and the polymer (B) is the islands.
- Such a composite film tends to improve moisture absorption resistance and heat resistance.
- the film of the present invention is preferably formed from the composition of the present invention. Since such a film is preferably formed by removing the solvent from the composition of the present invention, components contained in the film of the present invention, such as polyimide resin (A), polymer (B), phenolic antioxidant The descriptions regarding the agent, secondary antioxidant, etc. are the same as those described in the section [Composition].
- the film of the present invention contains a solvent, the type of the solvent and the distance between the HSP values between each component contained in the film of the present invention and the solvent are described in [Composition Item].
- the total mass of the polyimide resin (A) and polymer (B) contained in the film is preferably 40% by mass or more, more preferably 60% by mass or more, relative to the mass of the film. , more preferably 80% by mass or more, particularly preferably 90% by mass or more, and preferably 100% by mass or less.
- the total mass of the polyimide resin (A) and the polymer (B) contained in the film is at least the above lower limit, the dispersibility of the polymer (B) is easily increased, and the hygroscopic resistance and heat resistance of the film are easily improved. .
- the thickness of the film of the present invention can be appropriately selected depending on the application, and is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably 20 ⁇ m or more, preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, and still more preferably. 100 ⁇ m or less, particularly preferably 80 ⁇ m or less.
- the thickness of the film can be measured using a film thickness meter or the like, for example, by the method described in Examples.
- the above thickness represents the average thickness of the single layer portion.
- the moisture absorption rate of the film is preferably 0.64% by mass or less, more preferably 0.60% by mass or less, even more preferably 0.57% by mass or less, and even more preferably 0.54% by mass. % by mass or less, particularly preferably 0.52 mass % or less, particularly preferably 0.50 mass % or less.
- the moisture absorption rate is equal to or less than the above upper limit, excellent moisture absorption resistance can be exhibited. Therefore, when the film of the present invention is used for the resin layer of CCL, it is easy to improve the dielectric properties and to suppress dielectric loss and transmission loss.
- the moisture absorption rate of the film of the present invention may generally be 0.01% by mass or more.
- the moisture absorption rate of the film of the present invention can be determined by exposing the film to an environment with a temperature of 23° C. and a humidity of 50% for a certain period of time and measuring the moisture content of the film after the exposure with a moisture meter. It can be measured by the method described in .
- the heat resistance of the film of the present invention may be evaluated by the IR peak retention rate of polymer (B) before and after the heat deterioration test.
- the retention rate of the IR peak is derived from the cycloolefin-based polymer when annealed at 360° C. for 5 minutes in air (that is, before and after the heat deterioration test). It may be a peak retention rate in the range of 2500 to 3500 cm ⁇ 1 , preferably 2900 to 3000 cm ⁇ 1 .
- IR peak retention rate [(peak intensity of cycloolefin polymer after deterioration test) / (peak intensity of polyimide resin after deterioration test)] ⁇ [(peak intensity of cycloolefin polymer before deterioration test) / (degradation test Peak intensity of the previous polyimide resin)]
- the cycloolefin polymer peak intensity is 2500 to 3500 cm -1 , preferably 2900 to 3000 cm -1 peak top intensity
- the polyimide resin peak intensity is 1450 to 1550 cm -1 , preferably 1480 to 1520 cm shows a peak top intensity of -1
- the peak top intensity of 2500 to 3500 cm -1 indicates the stretching vibration of C-H contained in the cycloolefin-based polymer
- the peak top intensity of 1450 to 1550 cm -1 is benzen
- the IR peak retention rate of the polymer (B) is preferably 50% or higher, more preferably 60% or higher, even more preferably 70% or higher, still more preferably 80% or higher, particularly preferably 85% or more, particularly preferably 90% or more.
- the upper limit of the IR peak retention rate is not particularly limited, and is usually 100% or less.
- the film of the present invention may be a single layer film or a multilayer film containing at least one layer made of the film of the present invention.
- the multilayer film can contain other layers (or other films). Even in such a case, the film including all layers is referred to as the film of the present invention.
- Other layers include, for example, functional layers. Examples of the functional layer include a primer layer, a gas barrier layer, an adhesive layer, and a protective layer.
- a functional layer can be used individually or in combination of 2 or more types.
- the film of the present invention may be subjected to surface treatment such as corona discharge treatment, flame treatment, plasma treatment, ozone treatment, etc., by a method commonly employed industrially.
- composition and film of the present invention are not limited to the above embodiments, and various modifications are possible without departing from the gist of the present invention.
- the configurations, methods, etc. of the embodiments other than the above may be arbitrarily adopted and combined, and the configurations, methods, etc. according to the above one embodiment are applied to the configurations, methods, etc. according to the above other embodiments. You may
- a film according to an embodiment of the present invention has excellent moisture absorption resistance and dielectric properties. Therefore, it can be suitably used as a substrate material compatible with printed circuit boards and antenna substrates for high frequency bands.
- CCL has a structure in which copper foils are laminated on both surfaces of a resin layer via an adhesive.
- transmission loss can be reduced because of its excellent moisture absorption resistance and low dielectric loss.
- the film of the present invention is used as the resin layer, it has excellent heat resistance, so that it can maintain excellent dielectric properties even when exposed to a high-temperature environment.
- the film of the present invention is used as the resin layer, the surface smoothness is high, and the variation in physical properties and CTE are reduced.
- the film of the present invention is also suitably used for industrial materials such as automobile parts and electric/electronic parts; optical materials such as lenses, prisms, optical fibers, and recording media.
- the method for producing the film of the present invention is not particularly limited, but for example the following steps: (a) a composition preparation step of preparing a composition comprising a polyimide resin (A), a polymer (B), a phenolic antioxidant and optionally a solvent; (b) a coating step of applying the composition to a substrate to form a coating film; and (c) a film forming step of drying the applied liquid (coating film) to form a film.
- a step of completing the imidization reaction may be included.
- composition preparation step for example, the composition may be prepared by mixing the polyimide resin (A), the polymer (B), the phenolic antioxidant, optionally the solvent, and the additives. It is preferred to use the composition of the invention, in particular the composition obtained by using the above-described process for producing the composition of the invention.
- the composition of the present invention By using the composition of the present invention, a film having excellent dispersibility of the polymer (B) in the film, moisture absorption resistance and heat resistance can be formed.
- the application step is a step of applying the composition obtained in the composition preparation step to a substrate to form a coating film.
- a coating film is formed by coating the composition on the substrate by a known coating method.
- Known coating methods include, for example, wire bar coating, reverse coating, roll coating such as gravure coating, die coating, comma coating, lip coating, spin coating, screen coating, fountain coating, dipping, A spray method, a curtain coating method, a slot coating method, a casting method, and the like can be mentioned.
- base materials include copper plates (including copper foil), SUS plates (including SUS foil and SUS belts), glass substrates, PET films, PEN films, other polyimide resin films, and polyamide resin films.
- SUS plate, glass substrate, PET film, PEN film, etc. are preferable from the viewpoint of excellent heat resistance, and SUS plate, glass substrate, PET film, etc. are more preferable from the viewpoint of adhesion to the film and cost. is mentioned.
- the coating can be dried and optionally peeled from the substrate to form a film.
- the base material is a copper foil
- a film is formed without peeling the coating film from the copper foil, and the obtained laminate is a copper-clad laminate in which the film is laminated on the copper foil. It can also be used for laminates.
- a drying process for further drying the film may be performed after peeling.
- the composition is applied to a substrate to form a film, the surface of the coating film on the substrate side is almost flat, but the surface opposite to the substrate side (hereinafter also referred to as the air surface).
- the thickness may vary and the surface smoothness of the film may be impaired.
- the use of the composition of the present invention effectively suppresses the formation of such surface roughness. Therefore, a film having excellent surface smoothness can be formed.
- Drying of the coating film can be appropriately selected depending on the heat resistance of the polyimide resin (A), etc., and is usually carried out at a temperature of 50 to 450°C, preferably 55 to 400°C, more preferably 70 to 380°C. can be carried out, and in another embodiment of the invention, it can be carried out at a temperature of 50-400°C, preferably 70-360°C. In a preferred embodiment of the invention, the drying is preferably done in stages.
- the composition can be dried uniformly, and the moisture absorption resistance and heat resistance of the resulting film can be easily improved.
- it may be heated to 200 to 450°C, preferably 200 to 400°C, more preferably 200 to 350°C.
- the drying or heating time is preferably 5 minutes to 10 hours, more preferably 10 minutes to 5 hours. Heating from a low temperature to a high temperature stepwise within such a range tends to improve the hygroscopic resistance, heat resistance, uniformity of thermal conductivity or thermal diffusivity, optical properties, and Tg of the resulting film.
- the coating film may be dried under inert atmosphere conditions such as nitrogen or argon, under vacuum or reduced pressure conditions, and/or under ventilation.
- inert atmosphere conditions such as nitrogen or argon, under vacuum or reduced pressure conditions, and/or under ventilation.
- drying of the coating film may be continued, and after all drying is completed, the coating film ( film) may be peeled off.
- the coating film may be peeled off from the substrate and the second and subsequent drying stages may be performed, or after all the drying stages are completed, the coating film (film) may be peeled off from the substrate. good. Note that the drying in the first stage may be pre-drying.
- the film may be peeled off from the copper foil as the base material by etching away the copper foil with a ferric chloride solution or the like.
- the composition when the polyimide resin (A) in the composition is a polyimide resin precursor, such as polyamic acid, and the polyimide resin is produced during film production, the composition is applied to the substrate. After that, it is preferable to thermally imidize by heating. By the heating, drying for removing the solvent and thermal imidization can be performed at the same time.
- the drying and imidization temperature is usually in the range of 50 to 450° C., and from the viewpoint of easily obtaining a smooth film having excellent moisture absorption resistance, it is preferable to carry out heating in stages. For example, after removing the solvent by heating at a relatively low temperature of 50 to 150°C, it may be heated stepwise to a temperature in the range of 300 to 450°C.
- the heating time can be selected, for example, from the same range as the above range.
- the film of the present invention is a multilayer film
- it can be produced by a multilayer film forming method such as coextrusion processing, extrusion lamination, heat lamination, and dry lamination.
- HSP Hansen solubility parameter
- HSP Hansen solubility parameter
- the Hansen Solubility Parameters (HSP) of the phenolic antioxidant, solvent, cycloolefin copolymer, polyimide resin and fluoropolymer, and the distance between the HSP values were obtained as follows.
- HSP Heansen Solubility Parameter
- the HSP value of the structure S of the phenolic antioxidant was calculated from the structural formula using HSPiP .
- Structure S of Sumilizer GA80 had ⁇ D of 16.7 MPa 0.5 , ⁇ P of 5.0 MPa 0.5 and ⁇ H of 4.5 MPa 0.5 .
- the HSP value of the solvent is 18.0 MPa 0.5 for GBL, 16.6 MPa 0.5 for ⁇ P, 7.4 MPa 0.5 for ⁇ H , and 16 for DMAc. 8 MPa 0.5 , ⁇ P is 11.5 MPa 0.5 , ⁇ H is 9.4 MPa 0.5 and toluene has ⁇ D of 18.0 MPa 0.5 , ⁇ P of 1.4 MPa 0.5 , ⁇ H of 2.0 MPa 0.5 .
- Acetone had a ⁇ D of 15.5 MPa 0.5 , a ⁇ P of 10.4 MPa 0.5 and a ⁇ H of 7.0 MPa 0.5 .
- HSP of cycloolefin copolymer The solubility of cycloolefin copolymers in various solvents was evaluated. Solubility evaluation was carried out using solvents with known solubility parameters in a transparent container (see HSPiP database, solvents used: 2-(1-cyclohexenyl)cyclohexanone, 6-tert-butyl-2,4-xylenol, Methyl chloride, 1,4-dioxane, 1,4-dichlorobenzene, chloroform, toluene, 1-phenyloctane, p-xylene, styrene, ethanol, 1-butanol, N,N-dimethylformamide, dimethylsulfoxide, GBL, N -methylformamide, acetic acid) and 0.1 g of a cycloolefin copolymer were added to prepare a mixed solution.
- the resulting mixture was subjected to ultrasonic treatment for a total of 6 hours.
- the appearance of the mixed solution after ultrasonic treatment was visually observed, and the solubility of each resin in the solvent was evaluated based on the following evaluation criteria based on the obtained observation results.
- evaluation criteria 2 At room temperature, the appearance of the mixed solution is cloudy and precipitation occurs, but when heated to 50° C. and stirred with a stirrer for 30 minutes, the appearance of the mixed solution becomes transparent.
- 1 Appearance of mixture is transparent at room temperature.
- 0 At room temperature, the appearance of the mixture is cloudy and precipitation occurs, and even after heating to 50° C. and stirring with a stirrer for 30 minutes, the appearance of the mixture does not become clear.
- the HSP value was calculated by the above-mentioned Hansen dissolving sphere method using HSPiP.
- HSP of polyimide resin The solubility of the polyimide resin in various solvents was evaluated. Solubility evaluation was carried out using solvents with known solubility parameters in a transparent container (see HSPiP database, solvents used acetone, toluene, ethanol, tetrahydrofuran, N,N-dimethylformamide, dimethylsulfoxide, hexane, GBL, ethyl acetate , methyl ethyl ketone, propylene glycol monomethyl ether, 1-butanol, N-methylformamide, 1-methylnaphthalene, bromobenzene, 1-methylimidazole, pyrazole, acetic acid) and 0.1 g of polyimide resin were added to prepare a mixed solution.
- HSPiP Hansen dissolving sphere method from the evaluation results of the solubility of the obtained polyimide resin in the solvent.
- HSP of fluoropolymer 1 THV221AZ
- THV solubility of fluoropolymer 1 in various solvents
- Solubility evaluation was carried out using solvents with known solubility parameters in a transparent container (see HSPiP database, solvents used: acetone, tetrahydrofuran, N,N-dimethylformamide, dimethylsulfoxide, GBL, methyl ethyl ketone, 1-butanol, acetic acid Butyl, DMAc, methanol, hexyl acetate, ethyl acetoacetate, 2-propanol) (10 mL) and 0.1 g of fluoropolymer were added to prepare a mixed solution.
- the HSP value was calculated by the above-mentioned Hansen dissolving sphere method using HSPiP.
- HSP of fluoropolymer 2 (PTFE)
- PTFE fluoropolymer 2
- ⁇ D was 17.1 MPa 0.5
- ⁇ P was 8.1 MPa 0.5
- ⁇ h was 1.3 MPa 0.5 .
- NB content The content of norbornene-derived monomer units (also referred to as “NB content”) in the cycloolefin copolymer was measured using 13 C-NMR.
- the 13 C-NMR measurement conditions are as follows.
- Apparatus Bruker AVANCE600, 10 mm cryoprobe Measurement temperature: 135°C Measurement method: proton decoupling method Concentration: 100 mg/mL Number of times of integration: 1024 times Pulse width: 45 degrees Pulse repetition time: 4 seconds Chemical shift value standard: Tetramethylsilane Solvent: 1,2-dichlorobenzene-d4 and 1,1,2,2 - tetrachloroethane - d2 The NB content in the cycloolefin copolymer is based on 1,2-dichlorobenzene (127.68 ppm) and is calculated according to RA Wendt, G. Fink, Macromol. , 2001, 202, 3490”.
- ⁇ Meso type double chain/racemo type double chain The ratio of the meso-type double chain and the racemo-type double chain of the norbornene double chain of the cycloolefin copolymer (meso-type double chain/racemo-type double chain) is measured using 13 C-NMR under the same conditions as the measurement of the NB content. Measured at The meso-type double chain/racemo-type double chain of the norbornene double chain is based on 1,1,2,2-tetrachloroethane (74.24 ppm), and is described in RA Wendt, G. Fink, Macromol. Chem.
- meso-type two-chain/racemo-type two chains are observed at chemical shift values of 27.5-28.4 ppm in a spectrum chart measured using 13 C-NMR: signal integral value: IC5 , C6 -m (derived from carbon atoms at positions 5 and 6 of the norbornene ring of the meso-type double chain), signal integral values observed at chemical shift values 28.4-29.6 ppm: I C5, C6 -r (racemo type derived from carbon atoms at positions 5 and 6 of a double-chained norbornene ring), it was obtained from the following formula.
- Meso-type bilinkage/racemo-type bilinkage I C5,C6 ⁇ m/I C5,C6 ⁇ r
- the refractive index of the cycloolefin copolymer was obtained by measuring under the following conditions using a sheet-like sample molded to a thickness of 100 ⁇ m with a vacuum press.
- ⁇ CTE> The CTE of the cycloolefin copolymer was measured using TMA under the following conditions, and the CTE at 50°C to 100°C was calculated.
- Apparatus TMA/SS6200 manufactured by Hitachi High-Tech Science Co., Ltd. Indenter (probe) diameter: 3.5 mm Load: 38.5 mN
- Temperature program Temperature rise from 20°C to 130°C at a rate of 5°C/min Test piece: 10 mm x 10 mm x 1 mm rectangular parallelepiped
- Tg of cycloolefin copolymer The Tg of the cycloolefin copolymer was obtained by measuring the softening temperature by TMA based on JIS K 7196. Specifically, a sample (thickness: 1.0 mm) obtained by molding a cycloolefin copolymer into a sheet with a vacuum press was measured under the following conditions, and the softening temperature was defined as the onset of the displacement when the indenter sinks into the sample. did. Apparatus: "TMA/SS6200" manufactured by Hitachi High-Tech Science Co., Ltd. Indenter diameter: 1mm Load: 780mN Temperature program: Temperature rise from 20°C to 380°C at a rate of 5°C/min
- Tg of polyimide resin The Tg of the polyimide resin was determined by the following measurements. Using TA Instrument Co., Ltd., "DMA Q800", measured under the following samples and conditions to obtain a tan ⁇ curve, which is the ratio of the values of loss modulus and storage modulus, and then the peak of the tan ⁇ curve. Tg was calculated from the highest peak.
- ⁇ Mw and Mn of cycloolefin copolymer> The polystyrene equivalent Mw and Mn of the cycloolefin copolymer were measured using GPC. GPC measurement was performed under the following conditions, and peaks were designated by defining a baseline on the chromatogram based on the description of ISO16014-1.
- GPC column TSKgel GMH6-HT inner diameter 7.8 mm ⁇ length 300 mm (manufactured by Tosoh Corporation) 3 columns connected Mobile phase: ortho-dichlorobenzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade) with 0.1 g of BHT /100 mL was added for use.
- Sample solution concentration 1 mg/mL
- Automatic shaker for dissolution DF-8020 (manufactured by Tosoh Corporation)
- Dissolution conditions 5 mg of sample is enclosed in a 1,000 mesh SUS wire mesh bag, the wire mesh bag containing the sample is placed in a test tube, 5 mL of orthodichlorobenzene having the same composition as the mobile phase is added, and the test tube is The test tube was covered with aluminum foil, set in DF-8020, and stirred at 140° C. for 120 minutes at a stirring rate of 60 reciprocations/minute. GPC measurement was performed using the stirred solution as a sample.
- ⁇ Mw of polyimide resin and polyamic acid The polystyrene equivalent Mw of the polyimide resin and polyamic acid was measured using GPC. GPC measurement was performed under the following conditions. GPC measurement (1) Pretreatment method A DMF eluent (10 mmol/L lithium bromide-added DMF solution) was added to the sample to a concentration of 2 mg/mL, heated at 80°C for 30 minutes with stirring, and cooled. A measurement solution was obtained by filtration through a 0.45 ⁇ m membrane filter.
- ⁇ Particle size of particulate cycloolefin copolymer and particulate fluoropolymer in dispersion and composition> (The particle size of the particulate cycloolefin copolymer in the particulate cycloolefin copolymer dispersion obtained using the cycloolefin copolymer solutions obtained in Production Examples 1 and 3, and the particle size in the particulate fluoropolymer dispersion Particle size of fluoropolymer)
- the median diameter of the particulate cycloolefin copolymers in the dispersions of the particulate cycloolefin copolymers obtained in Examples 1, 3, 5, 9, 10, 12 and Comparative Examples 1 and 3, and the median sizes obtained in Examples 7 and 8 The median diameter of the particulate fluoropolymer in the obtained particulate fluoropolymer dispersion was determined by scattering particle size distribution measurement using laser diffraction.
- the particulate cycloolefin copolymer dispersion obtained in Examples 1, 3, 5, 9, 10, 12 and Comparative Examples 1 and 3, or Example 7 was placed in a glass cell having a capacity of 3.5 mL.
- add the particulate fluoropolymer dispersion obtained in 8 further add GBL or DMAc (using the same solvent as the dispersion) to dilute 1000 times, and contain particulate cycloolefin copolymer or particulate fluoropolymer A dispersion sample was obtained.
- Each dispersion sample obtained was measured using a laser diffraction/scattering particle size distribution analyzer (manufactured by Malvern Panalytical, model: NanoZS, refractive index: 1.70-0.20i), and the particulate cycloolefin copolymer and the median diameter of the particulate fluoropolymer were determined.
- the polyimide resin was used in an amount within a range not affecting the particle size of the particulate cycloolefin copolymer or the particulate fluoropolymer.
- the median size of the particulate cycloolefin copolymer in the dispersion and the median size of the particulate fluoropolymer in the dispersion were used.
- the particulate cycloolefin copolymer obtained in Production Examples 2 and 4 was dispersed in isopropanol to obtain a dispersion liquid sample containing the particulate cycloolefin copolymer.
- Each dispersion sample obtained was measured using a laser diffraction/scattering particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., model: MT3300EX II) to determine the median diameter of each particulate cycloolefin copolymer.
- polyamic acid was added to the dispersion in an amount within a range not affecting the particle size of the particulate cycloolefin copolymer to form the composition. did. Also, particulate cycloolefin copolymers are not soluble in isopropanol, DMAc and GBL. Therefore, the median diameter of the particulate cycloolefin copolymer in the dispersion sample was used as the median diameter of the particulate cycloolefin copolymer in the composition.
- ⁇ Thickness of composite film> The thickness of the composite films obtained in Examples and Comparative Examples was measured using a digimatic indicator (manufactured by Mitutoyo Co., Ltd., "ID-C112XBS"), and measuring the thickness at five or more arbitrary points of the film. Their average value was taken as the thickness of the composite film.
- ⁇ Moisture absorption rate of composite film> The moisture absorption of the composite films obtained in Examples 1, 2, 5 to 9 and Comparative Examples 1 and 2 was measured with a Karl Fischer moisture meter (evaporation type). Specifically, a film cut into a size of 20 mm ⁇ 20 mm is put in a vial bottle for a moisture vaporizer, and the temperature is 23 ° C. and the humidity is 50% (hereinafter also referred to as “23 ° C. 50%”) for 24 hours. more exposed. After that, the vial was sealed in the same environment, and the water content in the film was measured under the conditions shown below.
- Moisture absorption rate [(moisture content in film) - (moisture content in blank measurement)] ⁇ (film mass after exposure for 24 hours or more at 23 ° C. 50% environment) ⁇ 100
- ⁇ ATR unit Specac silver gate ATR evolution (germanium flat plate)
- ⁇ Measurement surface The surface on the glass substrate side when the composite film was peeled from the glass substrate
- ⁇ Measurement conditions 32 integration times, wave number resolution 4 cm ⁇ 1 , scan speed 5 kHz
- Calculation of IR peak retention rate Calculated from the following formula.
- Toluene is dehydrated using molecular sieves 13X (manufactured by Union Showa Co., Ltd.) and activated alumina ("NKHD-24" manufactured by Sumitomo Chemical Co., Ltd.), and then nitrogen gas is blown to remove dissolved oxygen. It was used.
- NB is dissolved in toluene, dehydrated using molecular sieves 13X (manufactured by Union Showa Co., Ltd.) and activated alumina ("NKHD-24" manufactured by Sumitomo Chemical Co., Ltd.), and then nitrogen gas is blown. (hereinafter referred to as "NB solution”).
- NB solution The NB concentration in the NB solution was measured using gas chromatography.
- the NB content is 82.5 mol%
- the Tg is 297°C
- the Mw is 343,000
- the Mw/Mn is 1.79
- the CTE is 47.0 ppm/ was K.
- the cycloolefin copolymer had a ⁇ D of 17.4 MPa 0.5 , a ⁇ P of 1.6 MPa 0.5 , a ⁇ H of 3.8 MPa 0.5 and a meso/racemo bilink of 0.5 . 11 and the refractive index was 1.54.
- Table 2 shows the synthesis conditions of Synthesis Example 1.
- the cycloolefin copolymer had a ⁇ D of 17.4 MPa 0.5, a ⁇ P of 1.6 MPa 0.5 and a ⁇ H of 3.8 MPa 0.5 .
- Table 3 shows the synthesis conditions of Synthesis Example 2.
- cycloolefin copolymer solution 1 Production of cycloolefin copolymer solution 1> A cycloolefin copolymer solution 1 was obtained by dissolving the cycloolefin copolymer obtained in Synthesis Example 1 in toluene at a concentration of 2% by mass.
- ⁇ Production Example 2 Production of crushed cycloolefin copolymer powder 1>
- the cycloolefin copolymer obtained in Synthesis Example 1 was pulverized with a counter jet mill manufactured by Kitamura Co., Ltd. and classified by a filter to obtain crushed cycloolefin copolymer powder 1 having a median diameter of 2.6 ⁇ m. .
- cycloolefin copolymer solution 2 was obtained by dissolving the cycloolefin copolymer obtained in Synthesis Example 2 in toluene at a concentration of 2% by mass.
- ⁇ Production Example 4 Production of crushed cycloolefin copolymer powder 2>
- the cycloolefin copolymer obtained in Synthesis Example 2 was pulverized with a counter jet mill manufactured by Kitamura Co., Ltd. and classified by a filter to obtain crushed cycloolefin copolymer powder 2 having a median diameter of 2.7 ⁇ m. rice field.
- the resulting polyimide resin had a ⁇ D of 18.1 MPa 0.5, a ⁇ P of 8.3 MPa 0.5 , and a ⁇ H of 9.3 MPa 0.5 .
- the polyimide resin had an Mw of 334,300 and a Tg of 361°C.
- the distance between the HSP values of the polyimide resin and the cycloolefin copolymer obtained in Production Example 1 was 8.8.
- a reactor was prepared by attaching a silica gel tube, a stirrer and a thermometer to a separable flask. After creating a nitrogen atmosphere in the flask using dry nitrogen, 399.20 g of DMAc and 16.00 g (0.148 mol) of p-PDA were added, followed by stirring at room temperature to dissolve p-PDA in DMAc. rice field. To this was added 21.2869 g (0.0724 mol) of BPDA and 33.1603 g (0.0724 mol) of TAHQ while stirring at 400 rpm. After that, the mixture was stirred at room temperature for 3 hours to obtain a polyamic acid solution.
- Example 1 100.0 g of the cycloolefin copolymer solution 1 obtained in Production Example 1 and 98.0 g of GBL were mixed and distilled under reduced pressure at 50 hPa and 80° C. so that the toluene content was 7 parts by mass with respect to 100 parts by mass of GBL. toluene was distilled off to obtain a particulate cycloolefin copolymer dispersion.
- the median diameter of the particulate cycloolefin copolymer in the dispersion and composition measured by the above method was 0.14 ⁇ m.
- Adekastab AO-330 manufactured by ADEKA Corporation; (1,3,5-tris(3,5-di-tert-butyl-4 -Hydroxyphenylmethyl)-2,4,6-trimethylbenzene) 0.0487 g was added and stirred, and then 2.0 g of the polyimide resin obtained above was added to obtain a polyimide-cycloolefin copolymer mixture, A composition was obtained.
- the content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer.
- the resulting composition was cast on a glass substrate to form a coating film at a line speed of 0.4 m/min. After heating the coating film at 70 ° C. for 60 minutes and peeling the film from the glass substrate, the film was fixed with a metal frame and further heated at 360 ° C. for 15 minutes in the atmosphere to obtain a polyimide-cycloolefin having a thickness of 50 ⁇ m. A copolymer composite film was obtained.
- the content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
- the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.16 ⁇ m.
- the distance between the HSP values between the cycloolefin copolymer and the polyimide resin used in Example 1 is 8.8, the distance between the HSP values between the cycloolefin copolymer and toluene is 2.2, and the distance between the polyimide resin and toluene is 8.8.
- the distance between HSP values is 10.0, the distance between HSP values between the cycloolefin copolymer and GBL is 15.5, the distance between HSP values between polyimide resin and GBL is 8.5, and AO-330
- the distance between HSP values between and GBL is 17.7, the distance between HSP values between structure S of AO-330 and GBL is 17.6, and the distance between HSP values between AO-330 and cycloolefin copolymer is 3.4, and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8.
- the distance between the HSP values between AO-330 and the polyimide resin is 11.7
- the distance between the HSP values between the structure S of AO-330 and the polyimide resin is 11.5
- the distance between AO-330 and toluene was 1.7.
- the cycloolefin copolymer used in Example 1 dissolved in toluene but did not dissolve in GBL.
- the polyimide resin dissolved in GBL but did not dissolve in toluene.
- Example 2 7.31 g of crushed cycloolefin copolymer powder 1, 52.03 g of DMAc and 0.365 g of AO-330 were mixed and stirred to obtain a dispersion. 100 g of polyamic acid solution (15% by mass of polyamic acid) was added to the resulting dispersion to obtain a composition as a polyamic acid-cycloolefin copolymer mixed solution. The content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer. The resulting composition was cast on a glass substrate to form a coating film at a line speed of 0.4 m/min. After heating the coating film at 50° C.
- the film was fixed with a metal frame and further heated at 360° C. for 15 minutes in the atmosphere to obtain a polyamic film.
- the acid was imidized to obtain a 50 ⁇ m thick polyimide-cycloolefin copolymer composite film.
- the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer.
- the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 ⁇ m.
- the distance between the HSP values between the cycloolefin copolymer and the polyamic acid used in Example 2 is 6.0 or more, the distance between the HSP values between the cycloolefin copolymer and DMAc is 11.4, and AO-330 and DMAc
- the distance between HSP values of AO-330 is 14.4, the distance between HSP values between Structure S of AO-330 and DMAc is 14.0, and the distance between HSP values between AO-330 and cycloolefin copolymer is 3.4. and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8.
- the distance between the HSP values of the cycloolefin copolymer used in Example 2 and the polyimide resin obtained by imidating the polyamic acid was 6.0 or more. According to the above solubility evaluation method, the polyamic acid used in Example 2 dissolved in DMAc but did not dissolve in toluene.
- the content of the particulate cycloolefin copolymer was 32.8% by weight based on the total weight of the polyimide resin and the particulate cycloolefin copolymer.
- the average primary particle size was 0.16 ⁇ m.
- the distance between the HSP values between the cycloolefin copolymer and the polyimide resin used in Comparative Example 1 was 8.8, the distance between the HSP values between the cycloolefin copolymer and toluene was 2.2, and the cycloolefin copolymer and GBL
- the distance between HSP values is 15.5, the distance between HSP values between polyimide resin and toluene is 10.0, the distance between HSP values between polyimide resin and GBL is 8.5, and Sumilizer GA80 and
- the distance between HSP values with GBL is 15.3, the distance between HSP values between Structure S of Sumilizer GA80 and GBL is 12.2, and the distance between HSP values between Sumilizer GA80 and cycloolefin copolymer is 2.0.
- the distance between the HSP values of Structure S of Sumilizer GA80 and the cycloolefin copolymer was 3.7. Further, the distance between the HSP values between Sumilizer GA80 and the polyimide resin is 8.1, the distance between the HSP values between the structure S of Sumilizer GA80 and the polyimide resin is 6.5, and the distance between the HSP values between Sumilizer GA80 and toluene The distance was 2.8.
- Example 2 A composition as a polyamic acid-cycloolefin copolymer mixture and a thickness of 50 ⁇ m were prepared in the same manner as in Example 2, except that 0.365 g of Sumilizer GA80 manufactured by Sumitomo Chemical Co., Ltd. was added instead of AO-330. A polyimide-cycloolefin copolymer composite film was obtained. The content of Sumilizer GA80 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer.
- the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer.
- the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 ⁇ m.
- the distance between the HSP values between the cycloolefin copolymer used in Comparative Example 2 and DMAc was 11.4, the distance between the HSP values between Sumilizer GA80 and DMAc was 11.4, and the distance between Structure S of Sumilizer GA80 and DMAc was 11.4.
- the HSP value distance is 8.1, the HSP value distance between Sumilizer GA80 and the cycloolefin copolymer is 2.0, and the HSP value distance between Structure S of Sumilizer GA80 and the cycloolefin copolymer is 3.7. there were.
- Example 3 A composition prepared in the same manner as in Example 1 was cast on a glass substrate to form a coating film at a line speed of 0.4 m/min. After heating the coating film at 70 ° C. for 60 minutes, peeling the film from the glass substrate, fixing the film with a metal frame, and further heating at 200 ° C. for 60 minutes in a nitrogen atmosphere, a 50 ⁇ m thick polyimide- A cycloolefin copolymer composite film was obtained. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.16 ⁇ m.
- Example 4 A coating film was prepared from the composition prepared in the same manner as in Example 2 by casting on a glass substrate at a line speed of 0.4 m/min. The coating film was heated at 50°C for 80 minutes, the polyamic acid-cycloolefin copolymer composite film was peeled off from the glass substrate, the film was fixed with a metal frame, and the temperature was increased stepwise to 360°C in a nitrogen atmosphere. The polyamic acid was imidized by heating at 360° C. for 5 minutes to obtain a polyimide-cycloolefin copolymer composite film having a thickness of 50 ⁇ m.
- the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer.
- the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 ⁇ m.
- Example 3 A polyimide-cycloolefin copolymer composite film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 3, except that the composition prepared in the same manner as in Comparative Example 1 was used.
- the content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
- the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.16 ⁇ m.
- Example 4 A polyimide-cycloolefin copolymer composite film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 4 except that the composition prepared in the same manner as in Comparative Example 2 was used.
- the content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
- the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 ⁇ m.
- Example 5 100.0 g of the cycloolefin copolymer solution 2 obtained in Production Example 3 and 98.0 g of DMAc were mixed, and the toluene content was 0.6 parts by mass with respect to 100 parts by mass of DMAc at 50 hPa and 80 ° C. Toluene was distilled off under reduced pressure to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the dispersion and composition measured by the above method was 0.13 ⁇ m.
- Adekastab AO-330 manufactured by ADEKA Corporation; (1,3,5-tris(3,5-di-tert-butyl-4 -Hydroxyphenylmethyl)-2,4,6-trimethylbenzene) 0.03 g was added and stirred, and then 8.0 g of the polyamic acid solution obtained above (polyamic acid 15% by mass) was added to obtain a polyamic.
- a composition was obtained as an acid-cycloolefin copolymer mixed solution.
- the content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer.
- a polyimide-cycloolefin copolymer composite film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 4, except that the composition obtained above was used.
- the content of the particulate cycloolefin copolymer was 33.3% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer.
- the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.15 ⁇ m.
- the distance between the HSP values between the cycloolefin copolymer and polyamic acid used in Example 5 is 6.0 or more, the distance between the HSP values between the cycloolefin copolymer and toluene is 2.2, and the cycloolefin copolymer and DMAc
- the distance between HSP values is 11.4, the distance between HSP values between AO-330 and DMAc is 14.4, and the distance between HSP values between structure S of AO-330 and DMAc is 14.0.
- the distance between the HSP values of AO-330 and the cycloolefin copolymer was 3.4, and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8. Further, the distance between the HSP values of the cycloolefin copolymer used in Example 9 and the polyimide resin obtained by imidating the polyamic acid was 6.0 or more. According to the above solubility evaluation method, the cycloolefin copolymer used in Example 5 dissolved in toluene but did not dissolve in DMAc. Polyamic acid dissolved in DMAc but did not dissolve in toluene.
- Example 6 A composition as a polyamic acid-cycloolefin copolymer mixed solution was prepared in the same manner as in Example 2 except that the cycloolefin copolymer crushed powder 2 obtained in Production Example 4 was added instead of the cycloolefin copolymer crushed powder 1. and a polyimide-cycloolefin copolymer composite film with a thickness of 50 ⁇ m.
- the content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer.
- the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer.
- the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 ⁇ m.
- the distance between the HSP values between the cycloolefin copolymer and the polyamic acid used in Example 6 is 6.0 or more, the distance between the HSP values between the cycloolefin copolymer and DMAc is 11.4, and AO-330 and DMAc
- the distance between HSP values of AO-330 is 14.4, the distance between HSP values between Structure S of AO-330 and DMAc is 14.0, and the distance between HSP values between AO-330 and cycloolefin copolymer is 3.4. and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8.
- the distance between the HSP values of the cycloolefin copolymer used in Example 6 and the polyimide resin obtained by imidating the polyamic acid was 6.0 or more. According to the solubility evaluation method described above, the cycloolefin copolymer used in Example 10 dissolved in toluene but did not dissolve in DMAc. Polyamic acid dissolved in DMAc but did not dissolve in toluene.
- Example 7 Fluorine polymer (manufactured by 3M, THV221AZ (tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, molar ratio of tetrafluoroethylene structural units: 0.35, Mw: 384,000, melting point: 120° C.)) 2 g and 98 g of acetone were mixed to obtain a fluoropolymer solution. 100 g of the obtained fluoropolymer solution and 98.0 g of GBL were mixed and distilled under reduced pressure at 50 hPa and 40° C. for 2 hours to remove acetone and obtain a particulate fluoropolymer dispersion.
- the acetone content of the resulting dispersion was 0.6 parts by weight per 100 parts by weight of GBL.
- the median diameter of the fluoropolymer in the particulate fluoropolymer dispersion measured by the above method was 0.11 ⁇ m.
- Adekastab AO-330 manufactured by ADEKA Corporation; (1,3,5-tris(3,5-di-tert -Butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene) 0.03 g was added and stirred, and then 1.2 g of the polyimide resin obtained above was added to obtain a polyimide-fluoropolymer.
- a composition was obtained as a mixed solution.
- the content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the fluoropolymer. No fluoropolymer aggregates larger than 1 mm were observed in the resulting composition.
- the resulting composition was cast on a glass substrate to form a coating film at a line speed of 0.4 m/min. After heating the coating film at 70 ° C. for 60 minutes, peeling the film from the glass substrate, fixing the film with a metal frame, and further heating at 360 ° C. for 15 minutes in the atmosphere, a polyimide-fluoropolymer having a thickness of 50 ⁇ m. A composite film was obtained.
- the content of the particulate fluoropolymer in the obtained composite film was 33.3% by mass with respect to the total mass of the polyimide resin and the particulate fluoropolymer.
- the average primary particle size of the particulate fluoropolymer in the obtained composite film was 0.13 ⁇ m.
- the HSP value distance between the fluoropolymer and polyimide used in Example 7 was 11.2, the HSP value distance between the fluoropolymer and acetone was 5.2, and the HSP value between the fluoropolymer and GBL.
- the inter-HSP value distance between AO-330 and acetone is 12.9, and the inter-HSP value distance between AO-330 and fluoropolymer is 15.9.
- the distance between HSP values between structure S and fluoropolymer is 15.3, the distance between HSP values between polyimide resin and acetone is 6.1, and the distance between HSP values between polyimide resin and GBL is 8.5. there were.
- the fluoropolymer used in Example 7 dissolved in acetone, but did not dissolve in GBL.
- the polyimide used in Example 7 was dissolved in GBL and acetone.
- Example 8 5.69 g of particulate PTFE (manufactured by Polysciences Inc., melting point: 320° C., Mw: 20,000) and 42.1 g of DMAc were mixed and stirred to obtain a particulate PTFE dispersion.
- Adekastab AO-330 manufactured by ADEKA Corporation; (1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6- After adding 0.2845 g of trimethylbenzene and stirring, 100 g of the polyamic acid solution obtained above (15% by mass of polyamic acid) was added to obtain a composition as a polyamic acid-PTFE mixed solution.
- the content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the fluoropolymer. No fluoropolymer aggregates larger than 1 mm were observed in the resulting composition.
- a polyimide-PTFE composite film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 4, except that the composition obtained above was used.
- the content of particulate PTFE was 27.5% by mass with respect to the total mass of the polyimide resin and PTFE.
- the average primary particle size of the particulate PTFE in the obtained composite film was 3 ⁇ m.
- the distance between the HSP values between PTFE and polyamic acid used in Example 8 is 6.0 or more, the distance between the HSP values between PTFE and DMAc is 8.8, and the distance between the HSP values between AO-330 and PTFE The distance was 8.2, and the distance between the HSP values of Structure S of AO-330 and PTFE was 8.0. Further, the distance between the HSP values of the PTFE used in Example 8 and the polyimide resin obtained by imidizing the polyamic acid was 6.0 or more.
- the PTFE used in Example 8 did not dissolve in DMAc by the above solubility evaluation method. Polyamic acid dissolved in DMAc but did not dissolve in toluene.
- Example 9 100.0 g of the cycloolefin copolymer solution 1 obtained in Production Example 1 and 98.0 g of DMAc were mixed and distilled under reduced pressure at 50 hPa and 80° C. so that the toluene content was 7 parts by mass with respect to 100 parts by mass of DMAc. toluene was distilled off to obtain a particulate cycloolefin copolymer dispersion.
- the median diameter of the particulate cycloolefin copolymer in the dispersion and composition measured by the above method was 0.13 ⁇ m.
- a polyimide-cycloolefin copolymer composite film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 1, except that the particulate cycloolefin copolymer dispersion prepared above was used.
- the content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
- the average primary particle size of the particulate cycloolefin copolymer in the obtained composite film was 0.14 ⁇ m.
- the distance between the HSP values between the cycloolefin copolymer used in Example 9 and toluene was 2.2, the distance between the HSP values between the cycloolefin copolymer and DMAc was 11.4, and the distance between AO-330 and DMAc was The inter-HSP value distance was 14.4, and the inter-HSP value distance between structure S of AO-330 and DMAc was 14.0.
- the cycloolefin copolymer used in Example 9 dissolved in toluene but did not dissolve in DMAc.
- the polyimide resin dissolved in DMAc but did not dissolve in toluene.
- Example 10 A polyimide-cycloolefin copolymer composite film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 4, except that the composition prepared in the same manner as in Example 5 was used.
- the content of the particulate cycloolefin copolymer in the resulting composite film was 33.3% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
- the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.15 ⁇ m.
- Example 11 A polyimide-cycloolefin copolymer composite film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 4 except that a composition prepared in the same manner as in Example 6 was used.
- the content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
- the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 ⁇ m.
- Example 12 A polyimide-cycloolefin copolymer composite film having a thickness of 50 ⁇ m was obtained in the same manner as in Example 3 except that a composition prepared in the same manner as in Example 9 was used.
- the content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
- the average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.15 ⁇ m.
- the moisture absorption rate of the polyimide-cycloolefin copolymer composite films obtained in Examples 1, 2, 5 to 9 and Comparative Examples 1 and 2 was measured according to the above method. The results obtained are shown in Table 43.
- the IR peak retention rate of the polyimide-cycloolefin copolymer composite films obtained in Examples 3, 4, 10 to 12 and Comparative Examples 3 and 4 was measured according to the above method. The results obtained are shown in Table 54.
- the films obtained in Examples 1, 2, 5 to 9 had lower moisture absorption rates and superior water absorption resistance than Comparative Examples 1 and 2.
- the films obtained in Examples 3, 4, and 10 to 12 had higher COC IR peak retention rates and superior heat resistance than Comparative Examples 3 and 4.
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Abstract
A composition comprising a polyimide-based resin (A), a polymer (B), and a phenolic antioxidant, wherein the phenolic antioxidant contains a substituent P represented by formula (P) [wherein Rp, Rq, Rr, and Rs each independently represent a hydrogen atom, a C1-C12 alkyl group, or a C5-C12 cycloalkyl group and * indicates a linking bond] and a structure S formed by replacing the substituent P of the phenolic antioxidant with a hydrogen atom has an optionally substituted aromatic ring.
Description
本発明は、高周波帯域用のプリント回路基板やアンテナ基板に対応可能な基板材料などに利用できるフィルムを形成可能な組成物、及び該フィルムに関する。
The present invention relates to a composition capable of forming a film that can be used as a substrate material compatible with high-frequency band printed circuit boards and antenna substrates, and the film.
5Gと称される第5世代移動通信システムの本格的な普及に伴い、高周波帯域に対応できるプリント回路やアンテナに利用可能なプリント配線基板などが要求されている。しかし、高周波帯域になると基板材料由来の伝送損失が顕著に影響してくるため、伝送損失を抑制可能な基板材料の選択が重要となる。例えば、CCLと称される銅張積層板は樹脂層の両表面に接着剤を介して銅箔が積層された構造等を有する。該CCLの伝送損失は、伝送路となる樹脂層の誘電損失、特に誘電正接や比誘電率を低減することにより抑制し得るため、誘電正接の低いフィルムが検討されている。例えば、特許文献1には、ポリイミド樹脂等の樹脂(A)と環状オレフィン(共)重合体(B)とを含む低誘電性樹脂組成物、及び該組成物から形成された誘電正接が低いフィルムが開示されている。
With the full-scale spread of the 5th generation mobile communication system called 5G, there is a demand for printed circuits that can handle high frequency bands and printed wiring boards that can be used for antennas. However, since the transmission loss derived from the substrate material has a significant effect in a high frequency band, it is important to select a substrate material capable of suppressing the transmission loss. For example, a copper-clad laminate called CCL has a structure in which copper foils are laminated on both surfaces of a resin layer via an adhesive. Since the transmission loss of the CCL can be suppressed by reducing the dielectric loss, particularly the dielectric loss tangent and the dielectric constant of the resin layer that serves as the transmission path, films with a low dielectric loss tangent are being studied. For example, Patent Document 1 discloses a low dielectric resin composition containing a resin (A) such as a polyimide resin and a cyclic olefin (co)polymer (B), and a film having a low dielectric loss tangent formed from the composition. is disclosed.
しかしながら、高周波帯域に対応可能なCCL中の樹脂層は吸湿すると誘電特性が悪化することが知られているため、優れた耐吸湿性も要求される。
However, it is known that the dielectric properties of the resin layer in CCL, which is compatible with high-frequency bands, deteriorate when it absorbs moisture, so excellent moisture absorption resistance is also required.
したがって、本発明の目的は、耐吸湿性に優れたフィルムを形成可能な組成物及び該フィルムを提供することにある。
Therefore, an object of the present invention is to provide a composition capable of forming a film with excellent moisture absorption resistance and the film.
本発明者らは、上記課題を解決するために鋭意検討した結果、本発明に到達した。すなわち本発明は、以下の好適な態様を包含する。
The present inventors arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention includes the following preferred embodiments.
[1]ポリイミド系樹脂(A)、ポリマー(B)及びフェノール系酸化防止剤を含み、
フェノール系酸化防止剤は式(P):
[式(P)中、Rp、Rq、Rr及びRsは、互いに独立に、水素原子、炭素数1~12のアルキル基又は炭素数5~12のシクロアルキル基を表し、*は結合手を表す]
で表される置換基Pを含み、フェノール系酸化防止剤中の置換基Pを水素原子に置換した構造Sは、置換基を有していてもよい芳香環を有する、組成物。
[2]ポリマー(B)とフェノール系酸化防止剤とのHSP値間距離は16.0以下である、[1]に記載の組成物。
[3]芳香環は、炭素数6~15の単環式芳香族炭化水素環である、[1]又は[2]に記載の組成物。
[4]さらに溶媒を含み、構造Sと溶媒とのHSP値間距離は10.0以上である、[1]~[3]のいずれかに記載の組成物。
[5]ポリマー(B)は粒子状である、[1]~[4]のいずれかに記載の組成物。
[6]ポリマー(B)は、オレフィン系ポリマー、ポリイミド系ポリマー、フッ素系ポリマー、シリコーン系ポリマー、液晶ポリマー、アラミドポリマー、スチレン系ポリマー及びエーテル系ポリマーからなる群から選択される少なくとも1つのポリマーである、[1]~[5]のいずれかに記載の組成物。
[7]ポリマー(B)のガラス転移温度は100℃以上である、[1]~[6]のいずれかに記載の組成物。
[8]ポリマー(B)は、シクロオレフィン系ポリマーである、[1]~[7]のいずれかに記載の組成物。
[9]シクロオレフィン系ポリマーは、式(I):
[式(I)中、mは0以上の整数を表し、R7~R18は、互いに独立に、水素原子、ハロゲン原子又は炭素原子数1~20の炭化水素基を表し、R11~R14が複数存在する場合、それらは同一であってもよく、異なっていてもよく、R16とR17とは互いに結合し、それらが結合する炭素原子とともに環を形成してもよい]
で表されるシクロオレフィン由来の単量体単位(I)を含む、[8]に記載の組成物。
[10]シクロオレフィン系ポリマーにおける前記単量体単位(I)の含有量は、シクロオレフィン系ポリマーを構成する繰り返し単位の合計モル量に対して、60モル%以上である、[9]に記載の組成物。
[11]ポリイミド系樹脂(A)、ポリマー(B)及びフェノール系酸化防止剤を含み、
フェノール系酸化防止剤は式(P):
[式(P)中、Rp、Rq、Rr及びRsは、互いに独立に、水素原子、炭素数1~12のアルキル基又は炭素数5~12のシクロアルキル基を表し、*は結合手を表す]
で表される置換基Pを含み、フェノール系酸化防止剤中の置換基Pを水素原子に置換した構造Sは、置換基を有していてもよい芳香環を有する、フィルム。 [1] containing a polyimide resin (A), a polymer (B) and a phenolic antioxidant,
The phenolic antioxidant has the formula (P):
[In formula (P), R p , R q , R r and R s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms, and * represents a bond]
wherein the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom has an aromatic ring which may have a substituent.
[2] The composition according to [1], wherein the distance between the HSP values of the polymer (B) and the phenolic antioxidant is 16.0 or less.
[3] The composition according to [1] or [2], wherein the aromatic ring is a monocyclic aromatic hydrocarbon ring having 6 to 15 carbon atoms.
[4] The composition according to any one of [1] to [3], further comprising a solvent, wherein the distance between the HSP values of Structure S and the solvent is 10.0 or more.
[5] The composition according to any one of [1] to [4], wherein the polymer (B) is particulate.
[6] The polymer (B) is at least one polymer selected from the group consisting of olefin-based polymers, polyimide-based polymers, fluorine-based polymers, silicone-based polymers, liquid-crystal polymers, aramid polymers, styrene-based polymers, and ether-based polymers. The composition according to any one of [1] to [5].
[7] The composition according to any one of [1] to [6], wherein the polymer (B) has a glass transition temperature of 100° C. or higher.
[8] The composition according to any one of [1] to [7], wherein the polymer (B) is a cycloolefin polymer.
[9] The cycloolefin-based polymer has the formula (I):
[In formula (I), m represents an integer of 0 or more, R 7 to R 18 each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 11 to R When there are a plurality of 14 , they may be the same or different, and R 16 and R 17 may be bonded to each other to form a ring together with the carbon atom to which they are bonded.]
The composition according to [8], comprising a cycloolefin-derived monomer unit (I) represented by
[10] The content of the monomer unit (I) in the cycloolefin-based polymer is 60 mol% or more relative to the total molar amount of repeating units constituting the cycloolefin-based polymer, according to [9]. composition.
[11] containing a polyimide resin (A), a polymer (B) and a phenolic antioxidant,
The phenolic antioxidant has the formula (P):
[In formula (P), R p , R q , R r and R s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms, and * represents a bond]
A film wherein the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom has an aromatic ring which may have a substituent.
フェノール系酸化防止剤は式(P):
で表される置換基Pを含み、フェノール系酸化防止剤中の置換基Pを水素原子に置換した構造Sは、置換基を有していてもよい芳香環を有する、組成物。
[2]ポリマー(B)とフェノール系酸化防止剤とのHSP値間距離は16.0以下である、[1]に記載の組成物。
[3]芳香環は、炭素数6~15の単環式芳香族炭化水素環である、[1]又は[2]に記載の組成物。
[4]さらに溶媒を含み、構造Sと溶媒とのHSP値間距離は10.0以上である、[1]~[3]のいずれかに記載の組成物。
[5]ポリマー(B)は粒子状である、[1]~[4]のいずれかに記載の組成物。
[6]ポリマー(B)は、オレフィン系ポリマー、ポリイミド系ポリマー、フッ素系ポリマー、シリコーン系ポリマー、液晶ポリマー、アラミドポリマー、スチレン系ポリマー及びエーテル系ポリマーからなる群から選択される少なくとも1つのポリマーである、[1]~[5]のいずれかに記載の組成物。
[7]ポリマー(B)のガラス転移温度は100℃以上である、[1]~[6]のいずれかに記載の組成物。
[8]ポリマー(B)は、シクロオレフィン系ポリマーである、[1]~[7]のいずれかに記載の組成物。
[9]シクロオレフィン系ポリマーは、式(I):
で表されるシクロオレフィン由来の単量体単位(I)を含む、[8]に記載の組成物。
[10]シクロオレフィン系ポリマーにおける前記単量体単位(I)の含有量は、シクロオレフィン系ポリマーを構成する繰り返し単位の合計モル量に対して、60モル%以上である、[9]に記載の組成物。
[11]ポリイミド系樹脂(A)、ポリマー(B)及びフェノール系酸化防止剤を含み、
フェノール系酸化防止剤は式(P):
で表される置換基Pを含み、フェノール系酸化防止剤中の置換基Pを水素原子に置換した構造Sは、置換基を有していてもよい芳香環を有する、フィルム。 [1] containing a polyimide resin (A), a polymer (B) and a phenolic antioxidant,
The phenolic antioxidant has the formula (P):
wherein the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom has an aromatic ring which may have a substituent.
[2] The composition according to [1], wherein the distance between the HSP values of the polymer (B) and the phenolic antioxidant is 16.0 or less.
[3] The composition according to [1] or [2], wherein the aromatic ring is a monocyclic aromatic hydrocarbon ring having 6 to 15 carbon atoms.
[4] The composition according to any one of [1] to [3], further comprising a solvent, wherein the distance between the HSP values of Structure S and the solvent is 10.0 or more.
[5] The composition according to any one of [1] to [4], wherein the polymer (B) is particulate.
[6] The polymer (B) is at least one polymer selected from the group consisting of olefin-based polymers, polyimide-based polymers, fluorine-based polymers, silicone-based polymers, liquid-crystal polymers, aramid polymers, styrene-based polymers, and ether-based polymers. The composition according to any one of [1] to [5].
[7] The composition according to any one of [1] to [6], wherein the polymer (B) has a glass transition temperature of 100° C. or higher.
[8] The composition according to any one of [1] to [7], wherein the polymer (B) is a cycloolefin polymer.
[9] The cycloolefin-based polymer has the formula (I):
The composition according to [8], comprising a cycloolefin-derived monomer unit (I) represented by
[10] The content of the monomer unit (I) in the cycloolefin-based polymer is 60 mol% or more relative to the total molar amount of repeating units constituting the cycloolefin-based polymer, according to [9]. composition.
[11] containing a polyimide resin (A), a polymer (B) and a phenolic antioxidant,
The phenolic antioxidant has the formula (P):
A film wherein the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom has an aromatic ring which may have a substituent.
本発明によれば、耐吸湿性に優れたフィルムを形成可能な組成物及び該フィルムを提供できる。
According to the present invention, a composition capable of forming a film with excellent moisture absorption resistance and the film can be provided.
〔組成物〕
本発明の組成物は、ポリイミド系樹脂(A)、ポリマー(B)及びフェノール系酸化防止剤を含み、フェノール系酸化防止剤は式(P):
[式(P)中、Rp、Rq、Rr及びRsは、互いに独立に、水素原子、炭素数1~12のアルキル基又は炭素数5~12のシクロアルキル基を表し、*は結合手を表す]
で表される置換基P(フェノール系活性部位ということがある)を含み、フェノール系酸化防止剤中の置換基Pを水素原子に置換した構造Sは、置換基を有していてもよい芳香環を有する。本明細書において、「組成物から形成されたフィルム」を単に「フィルム」ということがある。また、本明細書において、誘電特性とは、誘電損失、比誘電率及び誘電正接を含む誘電に関する特性を意味し、誘電特性が高まる又は向上するとは、例えば、誘電損失、比誘電率及び/又は誘電正接が低減することを示す。 〔Composition〕
The composition of the present invention comprises a polyimide resin (A), a polymer (B) and a phenolic antioxidant, wherein the phenolic antioxidant has the formula (P):
[In the formula (P), R p , R q , R r and R s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms, and * represents a bond]
Including a substituent P (sometimes referred to as a phenolic active site) represented by the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom is an aromatic that may have a substituent has a ring. In this specification, the "film formed from the composition" may be simply referred to as "film". In this specification, the dielectric property means a property related to dielectric including dielectric loss, relative permittivity and dielectric loss tangent. It shows that the dielectric loss tangent is reduced.
本発明の組成物は、ポリイミド系樹脂(A)、ポリマー(B)及びフェノール系酸化防止剤を含み、フェノール系酸化防止剤は式(P):
で表される置換基P(フェノール系活性部位ということがある)を含み、フェノール系酸化防止剤中の置換基Pを水素原子に置換した構造Sは、置換基を有していてもよい芳香環を有する。本明細書において、「組成物から形成されたフィルム」を単に「フィルム」ということがある。また、本明細書において、誘電特性とは、誘電損失、比誘電率及び誘電正接を含む誘電に関する特性を意味し、誘電特性が高まる又は向上するとは、例えば、誘電損失、比誘電率及び/又は誘電正接が低減することを示す。 〔Composition〕
The composition of the present invention comprises a polyimide resin (A), a polymer (B) and a phenolic antioxidant, wherein the phenolic antioxidant has the formula (P):
Including a substituent P (sometimes referred to as a phenolic active site) represented by the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom is an aromatic that may have a substituent has a ring. In this specification, the "film formed from the composition" may be simply referred to as "film". In this specification, the dielectric property means a property related to dielectric including dielectric loss, relative permittivity and dielectric loss tangent. It shows that the dielectric loss tangent is reduced.
本発明者らは、ポリイミド系樹脂(A)、ポリマー(B)及び溶媒を含む組成物から形成されるフィルムの耐吸湿性について検討を進めたところ、該組成物の製膜時、例えば高温での熱処理時にポリマー(B)が酸化し、それにより極性基が生成することにより、該組成物から形成されるフィルムの耐吸湿性が低下する場合があることがわかった。そこで、本発明者らはポリマー(B)の酸化に着目してさらに検討を進めたところ、フェノール系活性部位を水素原子に置換した構造Sが、置換基を有していてもよい芳香環を有する特定のフェノール系酸化防止剤を用いると、製膜時のポリマー(B)の酸化を有効に抑制でき、形成されるフィルムの耐吸湿性を向上できることを見出した。したがって、本発明の組成物は、優れた耐吸湿性を有するフィルムを形成できる。
The present inventors have investigated the moisture absorption resistance of a film formed from a composition containing a polyimide resin (A), a polymer (B), and a solvent, and found that during film formation of the composition, for example, at high temperature It has been found that the polymer (B) is oxidized during the heat treatment of No. 2, resulting in the generation of polar groups, which may reduce the moisture absorption resistance of the film formed from the composition. Therefore, the present inventors focused on the oxidation of the polymer (B) and proceeded with further studies. It has been found that the use of a specific phenolic antioxidant possessed can effectively suppress the oxidation of the polymer (B) during film formation and improve the hygroscopic resistance of the formed film. Therefore, the composition of the present invention can form films having excellent resistance to moisture absorption.
<フェノール系酸化防止剤>
本発明の組成物はフェノール系酸化防止剤を含み、該フェノール系酸化防止剤は式(P):
[式(P)中、Rp、Rq、Rr及びRsは、互いに独立に、水素原子、炭素数1~12のアルキル基又は炭素数5~12のシクロアルキル基を表し、*は結合手を表す]
で表される置換基Pを含み、フェノール系酸化防止剤中の置換基Pを水素原子に置換した構造Sは、置換基(置換基Qということがある)を有していてもよい芳香環(但し、該芳香環は、置換基Pと異なる。)を有する。該フェノール系酸化防止剤が構造Sとして上記芳香環を有すると、本発明の組成物に含まれるポリマー(B)の製膜時における酸化及びこれによる極性基の生成を有効に抑制できるため、耐吸湿性に優れたフィルムを形成できる。さらに、得られるフィルムは高温環境下に曝露されても、ポリマー(B)の酸化による劣化を有効に抑制でき、優れた耐熱性を発現できる。これは、理由は定かではないが、フェノール系活性部位を除く構造Sが置換基を有していてもよい芳香環を有すると、酸化防止剤自体の耐熱向上に加え、ポリマー(B)との親和性が高まるためだと推定される。 <Phenolic antioxidant>
The composition of the present invention comprises a phenolic antioxidant, said phenolic antioxidant having the formula (P):
[In formula (P), R p , R q , R r and R s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms, and * represents a bond]
The structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom is an aromatic ring optionally having a substituent (sometimes referred to as a substituent Q) (where the aromatic ring is different from the substituent P). When the phenol-based antioxidant has the above aromatic ring as structure S, oxidation during film formation of the polymer (B) contained in the composition of the present invention and the formation of polar groups due to this can be effectively suppressed. A film with excellent hygroscopicity can be formed. Furthermore, even when the resulting film is exposed to a high-temperature environment, deterioration due to oxidation of the polymer (B) can be effectively suppressed, and excellent heat resistance can be exhibited. Although the reason for this is not clear, when the structure S excluding the phenolic active site has an aromatic ring which may have a substituent, in addition to improving the heat resistance of the antioxidant itself, It is presumed that this is because the affinity increases.
本発明の組成物はフェノール系酸化防止剤を含み、該フェノール系酸化防止剤は式(P):
で表される置換基Pを含み、フェノール系酸化防止剤中の置換基Pを水素原子に置換した構造Sは、置換基(置換基Qということがある)を有していてもよい芳香環(但し、該芳香環は、置換基Pと異なる。)を有する。該フェノール系酸化防止剤が構造Sとして上記芳香環を有すると、本発明の組成物に含まれるポリマー(B)の製膜時における酸化及びこれによる極性基の生成を有効に抑制できるため、耐吸湿性に優れたフィルムを形成できる。さらに、得られるフィルムは高温環境下に曝露されても、ポリマー(B)の酸化による劣化を有効に抑制でき、優れた耐熱性を発現できる。これは、理由は定かではないが、フェノール系活性部位を除く構造Sが置換基を有していてもよい芳香環を有すると、酸化防止剤自体の耐熱向上に加え、ポリマー(B)との親和性が高まるためだと推定される。 <Phenolic antioxidant>
The composition of the present invention comprises a phenolic antioxidant, said phenolic antioxidant having the formula (P):
The structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom is an aromatic ring optionally having a substituent (sometimes referred to as a substituent Q) (where the aromatic ring is different from the substituent P). When the phenol-based antioxidant has the above aromatic ring as structure S, oxidation during film formation of the polymer (B) contained in the composition of the present invention and the formation of polar groups due to this can be effectively suppressed. A film with excellent hygroscopicity can be formed. Furthermore, even when the resulting film is exposed to a high-temperature environment, deterioration due to oxidation of the polymer (B) can be effectively suppressed, and excellent heat resistance can be exhibited. Although the reason for this is not clear, when the structure S excluding the phenolic active site has an aromatic ring which may have a substituent, in addition to improving the heat resistance of the antioxidant itself, It is presumed that this is because the affinity increases.
式(P)において、Rp、Rq、Rr及びRsは、互いに独立に、水素原子、炭素数1~12のアルキル基又は炭素数5~12のシクロアルキル基を表す。炭素数1~12のアルキル基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、ネオペンチル基、n-ヘキシル基、n-オクチル基、tert-アミル基等が挙げられる。炭素数5~12のシクロアルキル基としては、例えば、シクロペンチル基、シクロヘキシル基、シクロヘキシルメチル基等が挙げられる。
In formula (P), R p , R q , R r and R s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms. Examples of alkyl groups having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Neopentyl group, n-hexyl group, n-octyl group, tert-amyl group and the like. Examples of the cycloalkyl group having 5 to 12 carbon atoms include cyclopentyl group, cyclohexyl group, cyclohexylmethyl group and the like.
本発明の一実施形態において、Rp、Rq、Rr及びRsは、フィルムの耐吸湿性及び耐熱性を向上しやすい観点から、Rp、Rq、Rr及びRsのうち少なくとも1つが水素原子でないことが好ましく、より好ましくはRp及びRqのいずれかは水素原子ではなく、さらに好ましくはRp、Rq、Rr及びRsのうち少なくとも1つが嵩高い置換基であり、さらにより好ましくはRp及びRqの少なくとも一方が嵩高い置換基であり、特に好ましくはRp及びRqがいずれも嵩高い置換基である。前記嵩高い置換基は、tert-ブチル基、ネオペンチル基、tert-アミル基等であってよく、好ましくはtert-ブチル基である。フェノール系酸化防止剤が置換基Pを複数有する場合、置換基Pの構造は同一又は異なっていてもよい。すなわち、置換基Pを複数有する場合、各置換基P中のRp、Rq、Rr及びRsは、それぞれ同一であっても、異なっていてもよい。Rp及びRqの少なくとも一方が水素原子ではなく、好ましくはRp及びRqの少なくとも一方が嵩高い置換基であると、不安定なラジカル、例えば炭素ラジカルやパーオキシラジカルと反応して、フェノキシラジカルとなった際に、フェノキシラジカルがより安定化されるため、ポリマー(B)の酸化を抑制しやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, R p , R q , R r and R s are at least R p , R q , R r and R s from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the film. preferably one is not a hydrogen atom, more preferably one of R p and R q is not a hydrogen atom, still more preferably at least one of R p , R q , R r and R s is a bulky substituent and more preferably at least one of R p and R q is a bulky substituent, and particularly preferably both R p and R q are a bulky substituent. The bulky substituent may be a tert-butyl group, a neopentyl group, a tert-amyl group, etc., preferably a tert-butyl group. When the phenolic antioxidant has multiple substituents P, the structures of the substituents P may be the same or different. That is, when there are multiple substituents P, R p , R q , R r and R s in each substituent P may be the same or different. When at least one of R p and R q is not a hydrogen atom, preferably at least one of R p and R q is a bulky substituent, it reacts with unstable radicals such as carbon radicals and peroxy radicals, When converted to phenoxy radicals, the phenoxy radicals are further stabilized, so that the oxidation of the polymer (B) is easily suppressed, and the hygroscopic resistance and heat resistance of the obtained film are easily improved.
フェノール系酸化防止剤は、置換基Pを水素原子に置換した構造Sが、置換基を有していてもよい芳香環を有する。但し、該芳香環は、置換基Pとは異なる。芳香環は、炭素数5~20の芳香環であることが好ましい。芳香環としては、芳香族炭化水素環又は芳香族複素環が挙げられる。
In the phenolic antioxidant, the structure S in which the substituent P is substituted with a hydrogen atom has an aromatic ring that may have a substituent. However, the aromatic ring is different from the substituent P. The aromatic ring is preferably an aromatic ring having 5 to 20 carbon atoms. Aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles.
芳香族炭化水素環としては、例えば、単環式芳香族炭化水素環、縮合多環式芳香族炭化水素環又は環集合芳香族炭化水素環が挙げられる。
Examples of aromatic hydrocarbon rings include monocyclic aromatic hydrocarbon rings, condensed polycyclic aromatic hydrocarbon rings, and ring-assembled aromatic hydrocarbon rings.
単環式芳香族炭化水素環は、炭素数6~15の単環式芳香族炭化水素環が好ましく、その例としては、ベンゼン環等が挙げられる。縮合多環式芳香族炭化水素環は、炭素数10~20の縮合多環式芳香族炭化水素環が好ましく、その例としては、ナフタレン環、アントラセン環、フェナントレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環等が挙げられる。環集合芳香族炭化水素環は、2以上の単環式芳香族炭化水素環、2以上の縮合多環式芳香族炭化水素環、又は、1以上の単環式芳香族炭化水素環と1以上の縮合多環式芳香族炭化水素環とが互いに単結合を介して結合しているものを意味し、炭素数10~40の環集合芳香族炭化水素環が好ましい。その例としては、ビフェニル環、フェニルナフチル環、テルフェニル環、ペリレン環等が挙げられる。芳香族炭化水素環の中でも、フィルムの耐吸湿性及び耐熱性を高めやすい観点から、ベンゼン環、ナフタレン環、ビフェニル環等が好ましく、ベンゼン環がより好ましい。
The monocyclic aromatic hydrocarbon ring is preferably a monocyclic aromatic hydrocarbon ring having 6 to 15 carbon atoms, examples of which include a benzene ring. The condensed polycyclic aromatic hydrocarbon ring is preferably a condensed polycyclic aromatic hydrocarbon ring having 10 to 20 carbon atoms, examples of which include naphthalene ring, anthracene ring, phenanthrene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like. The ring-assembled aromatic hydrocarbon ring is two or more monocyclic aromatic hydrocarbon rings, two or more condensed polycyclic aromatic hydrocarbon rings, or one or more monocyclic aromatic hydrocarbon rings and one or more and the condensed polycyclic aromatic hydrocarbon rings of are bonded to each other via a single bond, and ring-assembled aromatic hydrocarbon rings having 10 to 40 carbon atoms are preferred. Examples thereof include biphenyl ring, phenylnaphthyl ring, terphenyl ring, perylene ring and the like. Among the aromatic hydrocarbon rings, a benzene ring, a naphthalene ring, a biphenyl ring and the like are preferable, and a benzene ring is more preferable, from the viewpoint of easily increasing the hygroscopic resistance and heat resistance of the film.
芳香族複素環としては、例えば、単環式芳香族複素環、縮合多環式芳香族複素環又は環集合芳香族複素環が挙げられる。本明細書において、芳香族複素環には、互変異性体を有する環も含まれ、その環自体に芳香族性がなくても、その互変異性体に芳香族性があれば、用語「芳香族複素環」に含まれる。例えば、イソシアヌル環(s-トリアジン-2,4,6-トリオン環)は、互変異性体が芳香族性のあるs-トリアジン-2,4,6-トリオールであるため、本明細書においては、芳香族複素環に含まれる。単環式芳香族複素環は、硫黄原子、窒素原子及び酸素原子から選択される少なくとも1つのヘテロ原子を含み、炭素及びヘテロ原子数5~15の芳香族複素環が好ましく、その例としては、ピロール環、ピラゾール環、イミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、イソシアヌル環、ジアザベンゼン環、フラン環、チオフェン環、アゾール環、ジアゾール環、トリアゾール環、オキサゾール環、オキサジアゾール環、チアジアゾール環等が挙げられる。縮合多環式芳香族複素環は、硫黄原子、窒素原子及び酸素原子から選択される少なくとも1つのヘテロ原子を含み、炭素及びヘテロ原子数8~20の縮合多環式芳香族複素環が好ましく、その例としては、アザナフタレン(キノリン)環、ジアザナフタレン環、カルバゾール環、ジベンゾフラン環、ジベンゾチオフェン環、ジベンゾシロール環、フェノキサジン環、フェノチアジン環、アクリジン環、インドール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、チアゾール環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環等が挙げられる。環集合芳香族複素環は、2以上の単環式芳香族複素環、2以上の縮合多環式芳香族複素環、1以上の単環式芳香族複素環と1以上の縮合多環式芳香族複素環とが互いに単結合を介して結合しているものに加え、1以上の単環式芳香族炭化水素環と1以上の縮合多環式芳香族複素環、又は、1以上の単環式芳香族複素環と1以上の縮合多環式芳香族炭化水素環が互いに単結合を介して結合しているものも含む。環集合芳香族複素環は、炭素数10~40の環集合芳香族複素環が好ましく、その例としては、ビピリジン環、テルピリジン環等が挙げられる。芳香族複素環の中でも、フィルムの耐吸湿性及び耐熱性を高めやすい観点から、トリアジン環、イソシアヌル環等が好ましく、トリアジン環がより好ましい。
Examples of aromatic heterocycles include monocyclic aromatic heterocycles, condensed polycyclic aromatic heterocycles, and ring-assembled aromatic heterocycles. As used herein, the aromatic heterocycle also includes rings having tautomers, and even if the ring itself has no aromaticity, if the tautomers have aromaticity, the term " included in "aromatic heterocycle". For example, the isocyanuric ring (s-triazine-2,4,6-trione ring) is s-triazine-2,4,6-triol, which has an aromatic tautomer. , included in aromatic heterocycles. The monocyclic aromatic heterocycle contains at least one heteroatom selected from a sulfur atom, a nitrogen atom and an oxygen atom, and is preferably an aromatic heterocycle having 5 to 15 carbon atoms and heteroatoms, examples of which include: pyrrole ring, pyrazole ring, imidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, isocyanuric ring, diazabenzene ring, furan ring, thiophene ring, azole ring, diazole ring, triazole ring, oxazole ring, oxazi An azole ring, a thiadiazole ring, and the like can be mentioned. The condensed polycyclic aromatic heterocycle contains at least one heteroatom selected from a sulfur atom, a nitrogen atom and an oxygen atom, and is preferably a condensed polycyclic aromatic heterocycle having 8 to 20 carbon atoms and heteroatoms, Examples thereof include azanaphthalene (quinoline) ring, diazanaphthalene ring, carbazole ring, dibenzofuran ring, dibenzothiophene ring, dibenzosilole ring, phenoxazine ring, phenothiazine ring, acridine ring, indole ring, pyrroloimidazole ring, pyrrolopyrazole ring. ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, thiazole ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanth Lysine ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like. Ring-assembled aromatic heterocycles are two or more monocyclic aromatic heterocycles, two or more condensed polycyclic aromatic heterocycles, one or more monocyclic aromatic heterocycles and one or more condensed polycyclic aromatic rings. and one or more monocyclic aromatic hydrocarbon rings and one or more condensed polycyclic aromatic heterocycles, or one or more monocyclic rings It also includes those in which the formula aromatic heterocycle and one or more condensed polycyclic aromatic hydrocarbon rings are bonded to each other through a single bond. The ring-assembled aromatic heterocycle is preferably a ring-assembled aromatic heterocycle having 10 to 40 carbon atoms, and examples thereof include bipyridine ring, terpyridine ring and the like. Among the aromatic heterocycles, a triazine ring, an isocyanuric ring, and the like are preferable, and a triazine ring is more preferable, from the viewpoint of easily increasing the hygroscopic resistance and heat resistance of the film.
フェノール系酸化防止剤中の構造Sは、置換基Pとは異なる芳香環を1又は2以上有していてもよい。前記芳香環は、置換基Pと異なる構造であればよく、置換基P以外の置換基を有していてもよい。各芳香環は、2価以上の炭化水素基、より好ましくは2価又は3価の炭化水素基、さらに好ましくはアルキレン基で連結されていてもよい。アルキレン基としては、上記に例示の炭素数1~12のアルキル基のうち、1つの水素原子を取り除いた基が挙げられる。該アルキレン中の炭素原子は、硫黄原子、窒素原子及び酸素原子から選択される少なくとも1つと置き換わっていてもよい。
The structure S in the phenolic antioxidant may have one or more aromatic rings different from the substituent P. The aromatic ring may have a structure different from that of the substituent P, and may have a substituent other than the substituent P. Each aromatic ring may be linked by a divalent or higher valent hydrocarbon group, more preferably a divalent or trivalent hydrocarbon group, still more preferably an alkylene group. Examples of the alkylene group include groups obtained by removing one hydrogen atom from the above-exemplified alkyl groups having 1 to 12 carbon atoms. A carbon atom in the alkylene may be replaced with at least one selected from a sulfur atom, a nitrogen atom and an oxygen atom.
芳香環の中でも、フィルムの耐吸湿性及び耐熱性に加え、誘電特性を高めやすい観点からは、芳香族炭化水素環が好ましく、フィルムの耐吸湿性及び耐熱性をより向上しやすい観点から、単環式芳香族炭化水素環及び/又は縮合多環式芳香族炭化水素環がより好ましく、単環式芳香族炭化水素環がさらに好ましく、ベンゼン環が特に好ましい。
Among the aromatic rings, aromatic hydrocarbon rings are preferable from the viewpoint of facilitating the enhancement of dielectric properties in addition to the hygroscopic resistance and heat resistance of the film. A cyclic aromatic hydrocarbon ring and/or a condensed polycyclic aromatic hydrocarbon ring is more preferable, a monocyclic aromatic hydrocarbon ring is more preferable, and a benzene ring is particularly preferable.
芳香環が有し得る置換基Qとしては、ハロゲン原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アルキルチオ基、シクロアルキルチオ基、アルキルアミノ基、シクロアルキルアミノ基、アシル基、メルカプト基、アミノ基、ヒドロキシル基、エステル結合を有する基などが挙げられる。これらの置換基Qは単独又は二種以上組合せて使用できる。
Examples of the substituent Q that the aromatic ring may have include a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an alkylamino group, a cycloalkylamino group, an acyl group, and a mercapto group. , an amino group, a hydroxyl group, a group having an ester bond, and the like. These substituents Q can be used alone or in combination of two or more.
ハロゲン原子としては、例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。アルキル基としては、例えば、上記に例示の炭素数1~12のアルキル基等が挙げられる。シクロアルキル基としては、例えば、上記に例示の炭素数5~12のシクロアルキル基等が挙げられる。アルコキシ基としては、例えばメトキシ基、エトキシ基、n-プロピルオキシ基、イソプロピルオキシ基、n-ブトキシ基、イソブトキシ基、tert-ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基等の炭素数1~12のアルコキシ基などが挙げられる。シクロアルコキシ基としては、例えばシクロヘキシルオキシ等の炭素数5~12のシクロアルコキシ基などが挙げられる。アルキルチオ基としては、例えばメチルチオ基、エチルチオ基、n-プロピルチオ基、イソプロピルチオ基、n-ブチルチオ基、イソブチルチオ基、tert-ブチルチオ基、ペンチルチオ基、ヘキシルチオ基等の炭素数1~12のアルキルチオ基などが挙げられる。シクロアルキルチオ基としては、例えばシクロヘキシルチオ基等の炭素数5~12のシクロアルキルチオ基などが挙げられる。アルキルアミノ基としては、アルキル部位が上記に例示の炭素数1~12のアルキル基であるモノアルキルアミノ基又はジアルキルアミノ基などが挙げられる。シクロアルキルアミノ基としては、シクロアルキル部位が上記に例示の炭素数5~12のシクロアルキル基であるモノアルキルアミノ基又はジアルキルアミノ基などが挙げられる。これらの置換基の中でも、フィルムの耐吸湿性及び耐熱性を高めやすい観点から、アルキル基、アルコキシ基等が好ましく、アルキル基がより好ましく、炭素数1~12のアルキル基がさらに好ましく、炭素数1~4のアルキル基がさらにより好ましく、メチル基及び/又はエチル基が特に好ましい。
The halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. The alkyl group includes, for example, the above-exemplified alkyl groups having 1 to 12 carbon atoms. The cycloalkyl group includes, for example, the above-exemplified cycloalkyl groups having 5 to 12 carbon atoms. Examples of alkoxy groups include those having 1 to 12 carbon atoms such as methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butoxy, isobutoxy, tert-butoxy, pentyloxy and hexyloxy groups. An alkoxy group etc. are mentioned. Cycloalkoxy groups include, for example, cycloalkoxy groups having 5 to 12 carbon atoms such as cyclohexyloxy. Examples of alkylthio groups include alkylthio groups having 1 to 12 carbon atoms such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tert-butylthio, pentylthio and hexylthio. etc. The cycloalkylthio group includes, for example, cycloalkylthio groups having 5 to 12 carbon atoms such as cyclohexylthio group. Examples of alkylamino groups include monoalkylamino groups and dialkylamino groups in which the alkyl moiety is the above-exemplified alkyl group having 1 to 12 carbon atoms. Examples of the cycloalkylamino group include monoalkylamino groups and dialkylamino groups in which the cycloalkyl moiety is the above-exemplified cycloalkyl group having 5 to 12 carbon atoms. Among these substituents, an alkyl group, an alkoxy group, or the like is preferable, an alkyl group is more preferable, and an alkyl group having 1 to 12 carbon atoms is even more preferable, from the viewpoint of easily increasing the moisture absorption resistance and heat resistance of the film. 1 to 4 alkyl groups are even more preferred, with methyl and/or ethyl groups being particularly preferred.
構造S中の芳香環は、置換基を有していても、置換基を有していなくてもよいが、フィルムの耐吸湿性及び耐熱性を高めやすい観点から、置換基を有していることが好ましい。構造S中の芳香環の置換基の数は、特に限定されないが、好ましくは0以上、より好ましくは1以上、さらに好ましくは2以上、さらにより好ましくは3以上、特に好ましくは4以上、特により好ましくは5以上であり、好ましくは12以下、より好ましくは11以下、さらに好ましくは10以下、さらにより好ましくは9以下、特に好ましくは8以下、特により好ましくは7以下であり、特にさらに好ましくは6である。
The aromatic ring in structure S may or may not have a substituent, but from the viewpoint of easily increasing the moisture absorption resistance and heat resistance of the film, it has a substituent. is preferred. The number of substituents on the aromatic ring in structure S is not particularly limited, but is preferably 0 or more, more preferably 1 or more, still more preferably 2 or more, still more preferably 3 or more, particularly preferably 4 or more, and particularly preferably 4 or more. Preferably 5 or more, preferably 12 or less, more preferably 11 or less, still more preferably 10 or less, still more preferably 9 or less, particularly preferably 8 or less, particularly more preferably 7 or less, and even more preferably is 6.
フェノール系酸化防止剤において、置換基Pの数は、特に限定されないが、フィルムの耐吸湿性及び耐熱性を高めやすい観点から、1以上、好ましくは2以上であり、好ましくは6以下、より好ましくは5以下、さらに好ましくは4以下であり、さらにより好ましくは3である。
In the phenolic antioxidant, the number of substituents P is not particularly limited, but is 1 or more, preferably 2 or more, preferably 6 or less, more preferably 6 or less, from the viewpoint of easily increasing the moisture absorption resistance and heat resistance of the film. is 5 or less, more preferably 4 or less, and even more preferably 3.
フェノール系酸化防止剤の構造は、構造S中の水素原子を取り除いた部分に置換基Pの結合手が結合した構造である。例えば、構造Sが置換基Qとしてメチル基を有する芳香環である場合、メチル基から1つの水素原子を取り除いた部分に置換基Pの結合手が結合した構造であってもよく、芳香環から1つの水素原子を取り除いた部分に置換基Pの結合手が結合した構造であってもよい。このように、置換基Pは、構造Sの芳香環に結合していてもよく、芳香環が有する置換基Qから1つの水素原子を取り除いた置換基(置換基Q’ともいう)に結合していてもよく、置換基Pが複数ある場合には、その両方に結合していてもよい。フィルムの耐吸湿性及び耐熱性を向上しやすい観点からは、置換基Pは少なくとも芳香環が有する置換基Q’に結合していることが好ましい。なお、置換基Pが芳香環に結合する場合は、ヘテロ原子(例えば窒素原子)に結合する場合を含む意味である。
The structure of the phenolic antioxidant is a structure in which the bond of the substituent P is attached to the part of the structure S from which the hydrogen atoms have been removed. For example, when the structure S is an aromatic ring having a methyl group as the substituent Q, it may be a structure in which a bond of the substituent P is attached to a portion obtained by removing one hydrogen atom from the methyl group, and from the aromatic ring A structure in which a bond of the substituent P is bonded to a portion from which one hydrogen atom has been removed may also be used. Thus, the substituent P may be bonded to the aromatic ring of the structure S, and bonded to a substituent obtained by removing one hydrogen atom from the substituent Q of the aromatic ring (also referred to as a substituent Q'). or if there are multiple substituents P, they may be bonded to both of them. From the viewpoint of easily improving the moisture absorption resistance and heat resistance of the film, the substituent P is preferably bonded to at least the substituent Q' of the aromatic ring. In addition, the case where the substituent P is bonded to the aromatic ring is meant to include the case where it is bonded to a heteroatom (for example, a nitrogen atom).
芳香環を基準にした置換基Pの結合位置は、特に限定されないが、例えば芳香環がベンゼン環である場合、フィルムの耐吸湿性及び耐熱性を向上しやすい観点から、置換基Pは、互いに隣接しない炭素原子に直接又は置換基Q’を介して結合していることが好ましく、直接又は置換基Q’を介して1,3位又は1,3,5位に結合していることがより好ましく、置換基Q’を介して1,3,5位に結合していることがさらに好ましい。また、例えば芳香環がトリアジン環である場合、フィルムの耐吸湿性及び耐熱性を向上しやすい観点から、置換基Pは、直接又は置換基Q’を介して2,4位又は2,4,6位に結合していることがより好ましく、置換基Q’を介して2,4,6位に結合していることがさらに好ましい。例えば芳香環がイソシアヌル環である場合、フィルムの耐吸湿性及び耐熱性を向上しやすい観点から、置換基Pは、直接又は置換基Q’を介して1,3位又は1,3,5位の窒素原子に結合していることが好ましく、直接1,3,5位の窒素原子に結合していることがより好ましい。
The bonding position of the substituent P relative to the aromatic ring is not particularly limited. For example, when the aromatic ring is a benzene ring, the substituents P are attached to It is preferably bonded to non-adjacent carbon atoms directly or via a substituent Q', and more preferably bonded directly or via a substituent Q' to the 1,3-position or 1,3,5-position. Preferably, it is more preferably bonded to the 1, 3, and 5-positions via the substituent Q'. Further, for example, when the aromatic ring is a triazine ring, from the viewpoint of easily improving the hygroscopic resistance and heat resistance of the film, the substituent P is directly or via the substituent Q' at the 2,4-position or at the 2,4-position. It is more preferably bonded to the 6-position, and more preferably bonded to the 2-, 4-, and 6-positions via the substituent Q'. For example, when the aromatic ring is an isocyanuric ring, from the viewpoint of easily improving the hygroscopic resistance and heat resistance of the film, the substituent P is directly or via the substituent Q 'at the 1,3-position or at the 1,3,5-position. is preferably bonded to the nitrogen atoms of , more preferably directly bonded to the nitrogen atoms at the 1, 3, and 5 positions.
本発明の一実施形態において、フェノール系酸化防止剤としては、例えば以下の構造を有するものが挙げられる。
[各式中、Rp、Rq、Rr及びRsは、上記に示した定義と同じである]
なお、上記構造中、各フェノール系酸化防止剤において、置換基P中のRp、Rq、Rr及びRsは、それぞれ同一であっても、異なっていてもよい。上記のような構造であると、フィルムの耐吸湿性及び耐熱性を向上しやすい。 In one embodiment of the present invention, phenolic antioxidants include, for example, those having the following structures.
[In each formula, R p , R q , R r and R s are the same as defined above]
In the above structure, R p , R q , R r and R s in the substituent P may be the same or different in each phenolic antioxidant. With the structure as described above, the moisture absorption resistance and heat resistance of the film are likely to be improved.
[各式中、Rp、Rq、Rr及びRsは、上記に示した定義と同じである]
なお、上記構造中、各フェノール系酸化防止剤において、置換基P中のRp、Rq、Rr及びRsは、それぞれ同一であっても、異なっていてもよい。上記のような構造であると、フィルムの耐吸湿性及び耐熱性を向上しやすい。 In one embodiment of the present invention, phenolic antioxidants include, for example, those having the following structures.
[In each formula, R p , R q , R r and R s are the same as defined above]
In the above structure, R p , R q , R r and R s in the substituent P may be the same or different in each phenolic antioxidant. With the structure as described above, the moisture absorption resistance and heat resistance of the film are likely to be improved.
本発明の一実施形態において、フェノール系酸化防止剤の具体例としては、1,3,5-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシフェニルメチル)-2,4,6-トリメチルベンゼン、2,4,6-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシベンジル)-1,3,5-トリアジン、1,3,5-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシベンジル)-1,3,5-トリアジン-2,4,6(1H、3H、5H)-トリオン、4-[[4,6-ビス(n-オクチルチオ)-1,3,5-トリアジン-2-イル]アミノ]-2,6-ジ-tert-ブチルフェノール、2,4,6-トリス(2,4-ジヒドロキシフェニル)-1,3,5-トリアジン、イソシアヌル酸トリス(4-tert-ブチル-3-ヒドロキシ-2,6-ジメチルベンジル)などが挙げられる。これらの中でも、フィルムの耐吸湿性及び耐熱性を向上しやすい観点から、1,3,5-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシフェニルメチル)-2,4,6-トリメチルベンゼンが好ましい。
In one embodiment of the present invention, specific examples of phenolic antioxidants include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6- trimethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert -butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4-[[4,6-bis(n-octylthio)-1,3 ,5-triazin-2-yl]amino]-2,6-di-tert-butylphenol, 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine, tris isocyanurate ( 4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) and the like. Among these, from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the film, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6- Trimethylbenzene is preferred.
本発明の一実施形態において、本発明の組成物に含まれるフェノール系酸化防止剤の含有量は、ポリマー(B)100質量部に対して、好ましくは0.01質量部以上、より好ましくは0.05質量部以上、さらに好ましくは0.1質量部以上、さらにより好ましくは0.2質量部以上、特に好ましくは0.5質量部以上、特により好ましくは2質量部以上である。フェノール系酸化防止剤の含有量が上記下限以上であると、フェノール系酸化防止剤によりポリマー(B)を覆いやすく、ポリマー(B)の酸化を十分に抑制しやすいため、フィルムの耐吸湿性及び耐熱性を向上しやすい。フェノール系酸化防止剤の含有量は、ポリマー(B)100質量部に対して、好ましくは20質量部以下、より好ましくは10質量部以下、さらに好ましくは7質量部以下、特に好ましくは5質量部以下である。フェノール系酸化防止剤の含有量が上記上限以下であると、フィルムの誘電特性を高めやすい。
In one embodiment of the present invention, the content of the phenolic antioxidant contained in the composition of the present invention is preferably 0.01 parts by mass or more, more preferably 0 parts by mass with respect to 100 parts by mass of the polymer (B). 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.2 parts by mass or more, particularly preferably 0.5 parts by mass or more, and even more preferably 2 parts by mass or more. When the content of the phenolic antioxidant is at least the above lower limit, the polymer (B) is easily covered with the phenolic antioxidant, and the oxidation of the polymer (B) is easily suppressed. Easy to improve heat resistance. The content of the phenolic antioxidant is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 7 parts by mass or less, and particularly preferably 5 parts by mass with respect to 100 parts by mass of the polymer (B). It is below. If the content of the phenolic antioxidant is equal to or less than the above upper limit, the dielectric properties of the film are likely to be enhanced.
<ポリマー(B)>
ポリマー(B)はポリイミド系樹脂(A)とは異なるポリマーである。ポリマー(B)がポリイミド系樹脂である場合は、ポリイミド系樹脂(A)とは異なる種類、例えば樹脂を構成する単量体単位の種類やその含有量等が異なるポリイミド系樹脂であればよい。 <Polymer (B)>
The polymer (B) is a polymer different from the polyimide resin (A). When the polymer (B) is a polyimide-based resin, it may be a polyimide-based resin that differs in type from the polyimide-based resin (A), for example, the types and contents of the monomer units constituting the resin are different.
ポリマー(B)はポリイミド系樹脂(A)とは異なるポリマーである。ポリマー(B)がポリイミド系樹脂である場合は、ポリイミド系樹脂(A)とは異なる種類、例えば樹脂を構成する単量体単位の種類やその含有量等が異なるポリイミド系樹脂であればよい。 <Polymer (B)>
The polymer (B) is a polymer different from the polyimide resin (A). When the polymer (B) is a polyimide-based resin, it may be a polyimide-based resin that differs in type from the polyimide-based resin (A), for example, the types and contents of the monomer units constituting the resin are different.
本発明の一実施形態において、ポリマー(B)は粒子状、針状または繊維状であってもよく、粒子状であることが好ましい。ポリマー(B)が粒子状であると、組成物中及び得られるフィルム中のポリマー(B)の分散性を高めやすく、フィルムの耐吸湿性及び耐熱性を向上しやすい。本明細書において、「粒子状ポリマー(B)の粒子径」を単に「粒子径」ということがある。
In one embodiment of the present invention, the polymer (B) may be particulate, acicular or fibrous, preferably particulate. When the polymer (B) is in the form of particles, the dispersibility of the polymer (B) in the composition and in the resulting film can be easily increased, and the hygroscopic resistance and heat resistance of the film can be easily improved. In this specification, the "particle size of the particulate polymer (B)" may be simply referred to as "particle size".
ポリマー(B)としては、特に限定されず、例えばオレフィン系ポリマー、ポリイミド系ポリマー、フッ素系ポリマー、シリコーン系ポリマー、液晶ポリマー、アラミドポリマー、スチレン系ポリマー及びエーテル系ポリマーなどが挙げられる。ポリマー(B)は単独又は二種以上組合せて使用できる。これらをポリマー(B)として用いると、フェノール系酸化防止剤との親和性が向上するため、フェノール系酸化防止剤がポリマー(B)の周囲を覆いやすくなる。また、ポリマー(B)の凝集を抑制しやすく、ポリマー(B)の分散性を高めやすい。その結果、耐吸湿性及び耐熱性に優れたフィルムを形成できる。これらの中でも、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい観点から、オレフィン系ポリマー、ポリイミド系ポリマー、フッ素系ポリマー、液晶ポリマー、スチレン系ポリマー及びエーテル系ポリマーからなる群から選択される少なくとも1つのポリマーが好ましく、オレフィン系ポリマー及びフッ素系ポリマーからなる群から選択される少なくとも1つのポリマーがより好ましく、オレフィン系ポリマーがさらに好ましく、ポリエチレン、高密度ポリエチレン、ポリプロピレン、ポリメチルペンテン及びシクロオレフィン系ポリマーからなる群から選択される少なくとも1つのポリマーがさらにより好ましく、シクロオレフィン系ポリマーが特に好ましい。
The polymer (B) is not particularly limited, and examples thereof include olefin-based polymers, polyimide-based polymers, fluorine-based polymers, silicone-based polymers, liquid crystal polymers, aramid polymers, styrene-based polymers, and ether-based polymers. Polymer (B) can be used alone or in combination of two or more. When these are used as the polymer (B), the affinity with the phenolic antioxidant is improved, so that the phenolic antioxidant easily covers the periphery of the polymer (B). In addition, aggregation of the polymer (B) can be easily suppressed, and dispersibility of the polymer (B) can be easily improved. As a result, a film having excellent moisture absorption resistance and heat resistance can be formed. Among these, it is selected from the group consisting of olefin-based polymers, polyimide-based polymers, fluorine-based polymers, liquid crystal polymers, styrene-based polymers and ether-based polymers, from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the resulting film. At least one polymer is preferred, more preferably at least one polymer selected from the group consisting of olefinic polymers and fluoropolymers, more preferably olefinic polymers, polyethylene, high density polyethylene, polypropylene, polymethylpentene and cycloolefin At least one polymer selected from the group consisting of cycloolefin-based polymers is even more preferred, with cycloolefin-based polymers being particularly preferred.
本発明の好適な実施形態において、シクロオレフィン系ポリマーは、式(I)
[式(I)中、mは0以上の整数を表し、
R7~R18は、互いに独立に、水素原子、ハロゲン原子又は炭素数1~20の炭化水素基を表し、R11~R14が複数存在する場合、それらは互いに独立に、同一であってもよく、異なっていてもよく、R16とR17とは互いに結合し、それらが結合する炭素原子とともに環を形成してもよい]
で表されるシクロオレフィン由来の単量体単位(I)を含むことが好ましい。 In a preferred embodiment of the invention, the cycloolefin-based polymer has formula (I)
[In the formula (I), m represents an integer of 0 or more,
R 7 to R 18 each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R 11 to R 14 are present, they are each independently the same may be different, and R 16 and R 17 may be bonded to each other to form a ring together with the carbon atom to which they are bonded]
It preferably contains a cycloolefin-derived monomer unit (I) represented by
R7~R18は、互いに独立に、水素原子、ハロゲン原子又は炭素数1~20の炭化水素基を表し、R11~R14が複数存在する場合、それらは互いに独立に、同一であってもよく、異なっていてもよく、R16とR17とは互いに結合し、それらが結合する炭素原子とともに環を形成してもよい]
で表されるシクロオレフィン由来の単量体単位(I)を含むことが好ましい。 In a preferred embodiment of the invention, the cycloolefin-based polymer has formula (I)
R 7 to R 18 each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R 11 to R 14 are present, they are each independently the same may be different, and R 16 and R 17 may be bonded to each other to form a ring together with the carbon atom to which they are bonded]
It preferably contains a cycloolefin-derived monomer unit (I) represented by
式(I)において、mは0以上の整数である。ポリマー(B)の分散性、並びにフィルムの耐吸湿性及び耐熱性を向上しやすく、入手も容易である観点からは、mの上限は好ましくは3以下の整数、より好ましくは2以下の整数、さらに好ましくは1以下の整数である。
In formula (I), m is an integer of 0 or more. From the viewpoint of easy improvement of dispersibility of the polymer (B), moisture absorption resistance and heat resistance of the film, and easy availability, the upper limit of m is preferably an integer of 3 or less, more preferably an integer of 2 or less, More preferably, it is an integer of 1 or less.
R7~R18の置換基の一員である炭素原子数1~20の炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、オクチル基、ドデシル基等のアルキル基;フェニル基、トリル基、ナフチル基等のアリール基;ベンジル基、フェネチール基等のアラルキル基;上記アルキル基、アリール基及びアラルキル基の水素原子の一部がハロゲン原子で置換された基等が挙げられる。これらの中でも、ポリマー(B)の分散性、並びに得られるフィルムの耐吸湿性及び耐熱性を向上しやすい観点から、アルキル基、アリール基又はアラルキル基であることが好ましい。すなわち、R7~R18は、水素原子、炭素原子数1~20のアルキル基、炭素原子数6~20のアリール基又は炭素原子数7~20のアラルキル基であることが好ましく、水素原子又は炭素原子数1~10のアルキル基であることがより好ましい。
Examples of hydrocarbon groups having 1 to 20 carbon atoms which are members of the substituents of R 7 to R 18 include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group and dodecyl group. Aryl groups such as phenyl group, tolyl group and naphthyl group; Aralkyl groups such as benzyl group and phenethyl group; mentioned. Among these, an alkyl group, an aryl group, or an aralkyl group is preferable from the viewpoint of easily improving the dispersibility of the polymer (B) and the hygroscopic resistance and heat resistance of the resulting film. That is, R 7 to R 18 are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms. More preferably, it is an alkyl group having 1 to 10 carbon atoms.
式(I)で表されるシクロオレフィンとしては、例えば、ノルボルネン、5-メチルノルボルネン、5-エチルノルボルネン、5-ブチルノルボルネン、5-フェニルノルボルネン、5-ベンジルノルボルネン、テトラシクロドデセン、トリシクロデセン、トリシクロウンデセン、ペンタシクロペンタデセン、ペンタシクロヘキサデセン、8-メチルテトラシクロドデセン、8-エチルテトラシクロドデセン等が挙げられる。これらの中でも、原料モノマーの入手容易性、ポリマー(B)の分散性、並びに得られるフィルムの耐吸湿性及び耐熱性を向上しやすい観点から、ノルボルネンであることが好ましい。式(I)で表されるシクロオレフィンは、1種を単独で用いてもよいし、2種以上を併用してもよい。
Examples of cycloolefins represented by formula (I) include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, and tricyclodecene. , tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene and the like. Among these, norbornene is preferable from the viewpoint of easy availability of raw material monomers, dispersibility of the polymer (B), and easiness in improving the hygroscopic resistance and heat resistance of the resulting film. The cycloolefins represented by formula (I) may be used alone or in combination of two or more.
本発明の一実施形態において、シクロオレフィン系ポリマーは、単量体単位(I)の二連鎖構造を含むことが好ましい。該二連鎖構造を含むことにより、単量体単位(I)の含有量が同程度のポリマーに比べて、耐熱性を向上しやすい。なお、二連鎖構造の有無は、13C-NMRスペクトル分析により判定することができる。例えば、テトラシクロデセン-エチレン共重合体の場合、テトラシクロデセンの孤立鎖であるエチレン-テトラシクロデセン-エチレン連鎖由来のシグナルは、54.7ppm付近及び51.1ppm付近に現れ、endo-exo結合のテトラシクロデセンの二連鎖であるエチレン-テトラシクロデセン-テトラシクロデセン-エチレン連鎖由来のシグナルは、51.5ppm付近及び50.8ppm付近に、exo-exo結合のエチレン-テトラシクロデセン-テトラシクロデセン-エチレン連鎖由来のシグナルは、55.3ppm付近及び54.3ppm付近に現れるので、55ppm近辺及び50ppm近辺のシグナルのパターンで判定することができる。
In one embodiment of the present invention, the cycloolefin-based polymer preferably contains a double chain structure of monomeric units (I). By including the two-chain structure, the heat resistance is likely to be improved as compared with a polymer having a similar content of the monomer unit (I). The presence or absence of a double-chain structure can be determined by 13 C-NMR spectrum analysis. For example, in the case of tetracyclodecene-ethylene copolymer, signals derived from ethylene-tetracyclodecene-ethylene chains, which are isolated chains of tetracyclodecene, appear near 54.7 ppm and 51.1 ppm, and endo-exo bonds The signal derived from the ethylene-tetracyclodecene-tetracyclodecene-ethylene chain, which is the double chain of tetracyclodecene, is near 51.5 ppm and 50.8 ppm, and the ethylene-tetracyclodecene-tetracyclo Since the signals derived from the decene-ethylene chain appear near 55.3 ppm and 54.3 ppm, the pattern of signals near 55 ppm and 50 ppm can be determined.
単量体単位(I)の二連鎖構造には、下記構造式(II-1)又は下記構造式(II-2)で表されるメソ型二連鎖、及び/又は、下記構造式(III-1)又は下記構造式(III-2)で表されるラセモ型二連鎖が含まれる。
The two-chain structure of the monomer unit (I) includes a meso-type two-chain structure represented by the following structural formula (II-1) or the following structural formula (II-2), and/or the following structural formula (III- 1) or a racemo-type double linkage represented by the following structural formula (III-2).
メソ型二連鎖とラセモ型二連鎖との比(以下、メソ型二連鎖/ラセモ型二連鎖と称することがある)は、好ましくは0.50以下、より好ましくは0.40以下、さらに好ましくは0.30以下、特に好ましくは0.20以下であり、好ましくは0.01以上、より好ましくは0.05以上である。メソ型二連鎖とラセモ型二連鎖との比が上記範囲であると、フィルムの機械的特性及び耐熱性を高めやすい。メソ型二連鎖とラセモ型二連鎖との比は、例えば13C-NMRを用いて、「R.A.Wendt,G.Fink,Macromol.Chem.Phys.,2001,202,3490」及び「特開2008-285656号公報」に記載の帰属に基づいて算出でき、具体的には実施例に記載の方法により算出できる。なお、メソ型二連鎖とラセモ型二連鎖を上記範囲に調整する方法としては、モノマーの嵩高さに対して、適切な配位子の広さを持った触媒を選択する方法等がある。前記触媒としては、例えば、特開平9-183809号公報に記載された触媒を用いることができる。
The ratio of the meso-type double chain to the racemo-type double chain (hereinafter sometimes referred to as meso-type double chain/racemo-type double chain) is preferably 0.50 or less, more preferably 0.40 or less, and still more preferably It is 0.30 or less, particularly preferably 0.20 or less, preferably 0.01 or more, and more preferably 0.05 or more. When the ratio of the meso-type two-chain to the racemo-type two-chain is within the above range, the mechanical properties and heat resistance of the film are likely to be improved. The ratio of the meso-form bichain to the racemo-form bichain can be determined, for example, using 13 C-NMR, as described in RA Wendt, G. Fink, Macromol. JP-A-2008-285656", specifically, it can be calculated by the method described in Examples. As a method for adjusting the meso-type double chain and the racemo-type double chain within the above ranges, there is a method of selecting a catalyst having an appropriate ligand width with respect to the bulkiness of the monomer. As the catalyst, for example, the catalyst described in JP-A-9-183809 can be used.
シクロオレフィン系ポリマーにおける前記単量体単位(I)の含有量は、シクロオレフィン系ポリマーを構成する繰り返し単位の合計モル量に対して、好ましくは60モル%以上、より好ましくは65モル%以上、さらに好ましくは70モル%以上、特に好ましくは75モル%以上であり、好ましくは100モル%以下、より好ましくは99モル%以下、さらに好ましくは98モル%以下である。単量体単位(I)の含有量が上記の下限以上であると、ガラス転移温度(以下、Tgと称することがある)を高めやすいため、フィルムのCTEを低減しやすく、また、フィルムの耐吸湿性を向上しやすい。さらに、フィルムの耐熱性及び屈曲耐性等の機械的特性を向上しやすい。単量体単位(I)の含有量が上記の上限以下であると、屈曲耐性等の機械的特性を高めやすい。単量体単位(I)の含有量は、13C-NMRを用いて、「R.A.Wendt,G.Fink,Macromol.Chem.Phys.,2001,202,3490」に記載の帰属に基づいて算出でき、例えば実施例に記載の方法により算出できる。
The content of the monomer unit (I) in the cycloolefin-based polymer is preferably 60 mol% or more, more preferably 65 mol% or more, relative to the total molar amount of repeating units constituting the cycloolefin-based polymer, It is more preferably 70 mol % or more, particularly preferably 75 mol % or more, preferably 100 mol % or less, more preferably 99 mol % or less, still more preferably 98 mol % or less. When the content of the monomer unit (I) is at least the above lower limit, the glass transition temperature (hereinafter sometimes referred to as Tg) tends to increase, so the CTE of the film tends to decrease, and the resistance of the film increases. Easy to improve moisture absorption. Furthermore, it is easy to improve mechanical properties such as heat resistance and bending resistance of the film. When the content of the monomeric unit (I) is equal to or less than the above upper limit, mechanical properties such as bending resistance are likely to be enhanced. The content of the monomer unit (I) is determined using 13 C-NMR, based on the assignment described in "RA Wendt, G. Fink, Macromol. Chem. Phys., 2001, 202, 3490." For example, it can be calculated by the method described in Examples.
シクロオレフィン系ポリマーは、フィルムの耐吸湿性及び耐熱性を向上しやすい観点から、エチレン、炭素原子数3~20の直鎖状α-オレフィン、及び炭素数8~20の芳香族ビニル化合物からなる群から選択される少なくとも1つに由来する単量体単位(II)を含むことが好ましい。
The cycloolefin-based polymer consists of ethylene, a linear α-olefin having 3 to 20 carbon atoms, and an aromatic vinyl compound having 8 to 20 carbon atoms, from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the film. It preferably contains a monomeric unit (II) derived from at least one selected from the group.
炭素原子数3~20の直鎖状α-オレフィンとしては、例えば、プロピレン、1-ブテン、1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン、1-ノネン、1-デセン等が挙げられる。これらの中でも、フィルムの耐吸湿性及び耐熱性を向上しやすい観点から、プロピレン、1-ブテン、1-ヘキセン又は1-オクテンであることが好ましく、プロピレンであることがより好ましい。炭素原子数3~20の直鎖状α-オレフィンは、1種を単独で用いてもよいし、2種以上を併用してもよい。なお、「直鎖状α-オレフィン」とは、α位に炭素-炭素不飽和二重結合を有する直鎖状のオレフィンをいう。
Linear α-olefins having 3 to 20 carbon atoms include, for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. be done. Among these, propylene, 1-butene, 1-hexene, or 1-octene is preferable, and propylene is more preferable, from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the film. Linear α-olefins having 3 to 20 carbon atoms may be used singly or in combination of two or more. The term "straight-chain α-olefin" refers to a straight-chain olefin having a carbon-carbon unsaturated double bond at the α-position.
炭素数8~20の芳香族ビニル化合物としては、例えば、スチレン、メチルスチレン、ジメチルスチレン、エチルスチレン、tert-ブチルスチレン、ビニルナフタレン、ビニルアントラセン、ジフェニルエチレン、イソプロペニルベンゼン、イソプロペニルトルエン、イソプロペニルエチルベンゼン、イソプロペニルプロピルベンゼン、イソプロペニルブチルベンゼン、イソプロペニルペンチルベンゼン、イソプロペニルヘキシルベンゼン、イソプロペニルオクチルベンゼン、イソプロペニルナフタレン、イソプロペニルアントラセン等が挙げられる。これらの中でも、原料モノマーの入手容易性、フィルムの耐吸湿性及び耐熱性を向上しやすい観点から、好ましくはスチレン、メチルスチレン又はジメチルスチレン、より好ましくはスチレンである。炭素数8~20の芳香族ビニル化合物は、1種を単独で用いてもよいし、2種以上を併用してもよい。
Examples of aromatic vinyl compounds having 8 to 20 carbon atoms include styrene, methylstyrene, dimethylstyrene, ethylstyrene, tert-butylstyrene, vinylnaphthalene, vinylanthracene, diphenylethylene, isopropenylbenzene, isopropenyltoluene, and isopropenyl. ethylbenzene, isopropenylpropylbenzene, isopropenylbutylbenzene, isopropenylpentylbenzene, isopropenylhexylbenzene, isopropenyloctylbenzene, isopropenylnaphthalene, isopropenylanthracene and the like. Among these, styrene, methylstyrene, or dimethylstyrene is preferred, and styrene is more preferred, from the viewpoints of easy availability of raw material monomers and easy improvement of hygroscopic resistance and heat resistance of the film. The aromatic vinyl compounds having 8 to 20 carbon atoms may be used singly or in combination of two or more.
本発明の一実施形態において、シクロオレフィン系ポリマーは、原料モノマーの入手容易性、フィルムの耐吸湿性及び耐熱性を向上しやすい観点から、好ましくはエチレン、プロピレン及びスチレンからなる群から選択される少なくとも1つに由来する単量体単位(II)、より好ましくはエチレン及びスチレンからなる群から選択される少なくとも1つに由来する単量体単位(II)を含むことが好ましい。
In one embodiment of the present invention, the cycloolefin-based polymer is preferably selected from the group consisting of ethylene, propylene and styrene from the viewpoints of easy availability of raw material monomers and easy improvement of moisture absorption resistance and heat resistance of the film. It preferably contains monomer units (II) derived from at least one, more preferably monomer units (II) derived from at least one selected from the group consisting of ethylene and styrene.
シクロオレフィン系ポリマーにおける前記単量体単位(II)の含有量は、シクロオレフィン系ポリマーを構成する繰り返し単位の合計モル量に対して、好ましくは0モル%以上、より好ましくは0.01モル%以上、さらに好ましくは1モル%以上、さらにより好ましくは2モル%以上であり、好ましくは40モル%以下、より好ましくは35モル%以下、さらに好ましくは30モル%以下、特に好ましくは25モル%以下である。単量体単位(II)の含有量が上記の下限以上であると、フィルムの屈曲耐性等の機械的特性、加工性及び成形性を高めやすい。単量体単位(II)の含有量が上記の上限以下であると、フィルムの耐吸湿性及び耐熱性を向上しやすい。
The content of the monomer unit (II) in the cycloolefin-based polymer is preferably 0 mol% or more, more preferably 0.01 mol%, relative to the total molar amount of repeating units constituting the cycloolefin-based polymer. More preferably 1 mol% or more, still more preferably 2 mol% or more, preferably 40 mol% or less, more preferably 35 mol% or less, still more preferably 30 mol% or less, particularly preferably 25 mol% It is below. When the content of the monomer unit (II) is at least the above lower limit, mechanical properties such as bending resistance, workability, and moldability of the film can be easily improved. When the content of the monomer unit (II) is equal to or less than the above upper limit, the hygroscopic resistance and heat resistance of the film are likely to be improved.
本発明の一実施形態において、耐熱性、加工性、屈曲耐性等の機械的特性及び耐吸湿性を向上しやすい観点から、シクロオレフィン系ポリマーは、シクロオレフィンコポリマーであることが好ましく、式(I)で表されるシクロオレフィン由来の単量体単位(I)とエチレン、炭素原子数3~20の直鎖状α-オレフィン及び炭素数8~20の芳香族ビニル化合物からなる群から選択される少なくとも1つに由来する単量体単位(II)とを含むシクロオレフィン系ポリマーであることがより好ましく、ノルボルネンに由来する単量体単位(I)とエチレンに由来する単量体単位(II)とを含むエチレン-ノルボルネン共重合体、又はノルボルネンに由来する単量体単位(I)とスチレンに由来する単量体単位(II)とを含むスチレン-ノルボルネン共重合体であることがさらに好ましい。
In one embodiment of the present invention, the cycloolefin-based polymer is preferably a cycloolefin copolymer from the viewpoint of easily improving mechanical properties such as heat resistance, processability, and bending resistance, and moisture absorption resistance, and the formula (I ) and a cycloolefin-derived monomer unit (I) represented by ethylene, a linear α-olefin having 3 to 20 carbon atoms and an aromatic vinyl compound having 8 to 20 carbon atoms. It is more preferable that the cycloolefin-based polymer contains at least one monomeric unit (II) derived from norbornene-derived monomeric unit (I) and ethylene-derived monomeric unit (II) or a styrene-norbornene copolymer containing monomeric units (I) derived from norbornene and monomeric units (II) derived from styrene.
シクロオレフィン系ポリマーは、その他の単量体単位(III)を含んでいてもよい。その他の単量体単位(III)を構成するその他の単量体としては、例えば、ブタジエン又はイソプレン等の共役ジエン;1,4-ペンタジエン等の非共役ジエン;アクリル酸;アクリル酸メチル又はアクリル酸エチル等のアクリル酸エステル;メタクリル酸;メタクリル酸メチル又はメタクリル酸エチル等のメタクリル酸エステル;酢酸ビニル等が挙げられる。その他の単量体単位(III)は単独又は二種以上組合せて使用できる。
なお、ポリマー(B)は単独又は二種以上組合せて使用できる。 The cycloolefin-based polymer may contain other monomer units (III). Other monomers constituting the monomer unit (III) include, for example, conjugated dienes such as butadiene or isoprene; non-conjugated dienes such as 1,4-pentadiene; acrylic acid; methyl acrylate or acrylic acid; acrylic acid esters such as ethyl; methacrylic acid; methacrylic acid esters such as methyl methacrylate or ethyl methacrylate; and vinyl acetate. Other monomeric units (III) can be used singly or in combination of two or more.
Incidentally, the polymer (B) can be used alone or in combination of two or more.
なお、ポリマー(B)は単独又は二種以上組合せて使用できる。 The cycloolefin-based polymer may contain other monomer units (III). Other monomers constituting the monomer unit (III) include, for example, conjugated dienes such as butadiene or isoprene; non-conjugated dienes such as 1,4-pentadiene; acrylic acid; methyl acrylate or acrylic acid; acrylic acid esters such as ethyl; methacrylic acid; methacrylic acid esters such as methyl methacrylate or ethyl methacrylate; and vinyl acetate. Other monomeric units (III) can be used singly or in combination of two or more.
Incidentally, the polymer (B) can be used alone or in combination of two or more.
本発明の一実施形態において、シクロオレフィン系ポリマー以外のオレフィン系ポリマーとしては、例えば、前記単量体単位(II);前記単量体単位(III);3-メチルー1-ブテン、3-メチルー1-ペンテン、4-メチルー1-ペンテン及びビニルシクロアルカンからなる群から選択される少なくとも1つの単量体単位;並びにそれらの誘導体等を含む重合体又は共重合体が挙げられ、ポリエチレン、高密度ポリエチレン、ポリプロピレン又はポリメチルペンテンが好ましく、中でも耐熱性を高める観点から、ポリプロピレン又はポリメチルペンテンがより好ましい。
In one embodiment of the present invention, the olefin-based polymer other than the cycloolefin-based polymer includes, for example, the monomer unit (II); the monomer unit (III); 3-methyl-1-butene, 3-methyl- at least one monomer unit selected from the group consisting of 1-pentene, 4-methyl-1-pentene and vinylcycloalkane; Polyethylene, polypropylene or polymethylpentene is preferable, and polypropylene or polymethylpentene is more preferable from the viewpoint of enhancing heat resistance.
本発明の一実施形態において、ポリイミド系ポリマーとしては、例えば、後述の第2溶媒に可溶なポリイミド系ポリマーが挙げられる。
In one embodiment of the present invention, polyimide-based polymers include, for example, polyimide-based polymers that are soluble in the second solvent described later.
本発明の一実施形態において、フッ素系ポリマーとしては、フッ素を含むオレフィンの重合体又はその変性物であり、具体的には、フルオロオレフィン類、例えば、テトラフルオロエチレン、トリフルオロエチレン、クロロトリフルオロエチレン、ヘキサフルオロプロピレン、フッ化ビニリデン、フッ化ビニル等からなる群から選択される少なくとも1つの単量体単位を含む重合体及び共重合体が挙げられ、例えば、ポリテトラフルオロエチレン(PTFE)、パーフルオロアルコキシアルカン、パーフルオロエチレンプロペンコポリマー、エチレン-テトラフルオロエチレンコポリマー、ポリビニリデンフルオライド、ポリクロロトリフルオロエチレン、ポリヘキサフルオロプロピレン等が挙げられる。フィルムの誘電特性を高める観点からは、フッ素ポリマーは好ましくはテトラフルオロエチレン由来の構成単位を有するポリマーであり、より好ましくは全構成単位の合計に対するテトラフルオロエチレン由来の構成単位のモル比が0.25以上、さらに好ましくは前記モル比が0.30以上、さらにより好ましくは0.50以上、特に好ましくは0.75以上である。フッ素ポリマーの各構成単位のモル比は、NMR測定により求めることができ、モル比の算出に当たっては、例えばEric B. Twum et al., “Multidimensional 19F NMR Analyses of Terpolymers from Vinylidene Fluoride (VDF)-Hexafluoropropylene(HFP)-Tetrafluoroethylene (TFE)”, Macromolecules、2015年, 48巻, 11号, p.3563-3576を参照することができる。また、後述の第2溶媒への溶解性を高める観点から、ビニルエーテル類、ビニルエステル類及びアリルエーテル類からなる群から選択される少なくとも1つと前記単量体単位との共重合体であってもよい。
In one embodiment of the present invention, the fluorine-based polymer is an olefin polymer containing fluorine or a modified product thereof. Specifically, fluoroolefins such as tetrafluoroethylene, trifluoroethylene, chlorotrifluoro Polymers and copolymers containing at least one monomer unit selected from the group consisting of ethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, etc., such as polytetrafluoroethylene (PTFE), perfluoroalkoxyalkanes, perfluoroethylene propene copolymers, ethylene-tetrafluoroethylene copolymers, polyvinylidene fluoride, polychlorotrifluoroethylene, polyhexafluoropropylene and the like. From the viewpoint of enhancing the dielectric properties of the film, the fluoropolymer is preferably a polymer having structural units derived from tetrafluoroethylene, and more preferably the molar ratio of the structural units derived from tetrafluoroethylene to the total of all structural units is 0.5. 25 or more, more preferably 0.30 or more, still more preferably 0.50 or more, and particularly preferably 0.75 or more. The molar ratio of each structural unit of the fluoropolymer can be obtained by NMR measurement. (HFP)-Tetrafluoroethylene (TFE)”, Macromolecules, 2015, Vol. 48, No. 11, p.3563-3576. Further, from the viewpoint of increasing the solubility in the second solvent described later, even if it is a copolymer of at least one selected from the group consisting of vinyl ethers, vinyl esters and allyl ethers and the above-mentioned monomer units good.
本発明の一実施形態において、液晶ポリマーとしては、芳香族ヒドロキシカルボン酸、芳香族ジカルボン酸、芳香族ジオール及び脂肪族ジオールなどを繰り返し単位として有するポリマー等が挙げられる。
芳香族ヒドロキシカルボン酸繰り返し単位を与える単量体の具体例としては、パラヒドロキシ安息香酸、メタヒドロキシ安息香酸、オルトヒドロキシ安息香酸、6-ヒドロキシ-2-ナフトエ酸、5-ヒドロキシ-2-ナフトエ酸、3-ヒドロキシ-2-ナフトエ酸、4’-ヒドロキシフェニル-4-安息香酸、3’-ヒドロキシフェニル-4-安息香酸、4’-ヒドロキシフェニル-3-安息香酸等の芳香族ヒドロキシカルボン酸、これらのアルキル、アルコキシ又はハロゲン置換体、ならびにこれらのエステル形成性誘導体が挙げられる。中でも、フィルムの耐吸湿性、機械的特性及び耐熱性を高めやすい観点から、パラヒドロキシ安息香酸及び6-ヒドロキシ-2-ナフトエ酸が好ましい。 In one embodiment of the present invention, liquid crystal polymers include polymers having repeating units such as aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, and aliphatic diols.
Specific examples of monomers that give aromatic hydroxycarboxylic acid repeating units include parahydroxybenzoic acid, metahydroxybenzoic acid, orthohydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and 5-hydroxy-2-naphthoic acid. , 3-hydroxy-2-naphthoic acid, 4′-hydroxyphenyl-4-benzoic acid, 3′-hydroxyphenyl-4-benzoic acid, 4′-hydroxyphenyl-3-benzoic acid and other aromatic hydroxycarboxylic acids, Alkyl-, alkoxy- or halogen-substituted products thereof, and ester-forming derivatives thereof are included. Among them, parahydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferred from the viewpoint of easily improving the moisture absorption resistance, mechanical properties and heat resistance of the film.
芳香族ヒドロキシカルボン酸繰り返し単位を与える単量体の具体例としては、パラヒドロキシ安息香酸、メタヒドロキシ安息香酸、オルトヒドロキシ安息香酸、6-ヒドロキシ-2-ナフトエ酸、5-ヒドロキシ-2-ナフトエ酸、3-ヒドロキシ-2-ナフトエ酸、4’-ヒドロキシフェニル-4-安息香酸、3’-ヒドロキシフェニル-4-安息香酸、4’-ヒドロキシフェニル-3-安息香酸等の芳香族ヒドロキシカルボン酸、これらのアルキル、アルコキシ又はハロゲン置換体、ならびにこれらのエステル形成性誘導体が挙げられる。中でも、フィルムの耐吸湿性、機械的特性及び耐熱性を高めやすい観点から、パラヒドロキシ安息香酸及び6-ヒドロキシ-2-ナフトエ酸が好ましい。 In one embodiment of the present invention, liquid crystal polymers include polymers having repeating units such as aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, and aliphatic diols.
Specific examples of monomers that give aromatic hydroxycarboxylic acid repeating units include parahydroxybenzoic acid, metahydroxybenzoic acid, orthohydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and 5-hydroxy-2-naphthoic acid. , 3-hydroxy-2-naphthoic acid, 4′-hydroxyphenyl-4-benzoic acid, 3′-hydroxyphenyl-4-benzoic acid, 4′-hydroxyphenyl-3-benzoic acid and other aromatic hydroxycarboxylic acids, Alkyl-, alkoxy- or halogen-substituted products thereof, and ester-forming derivatives thereof are included. Among them, parahydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferred from the viewpoint of easily improving the moisture absorption resistance, mechanical properties and heat resistance of the film.
芳香族ジカルボン酸繰返し単位を与える単量体の具体例としては、テレフタル酸、イソフタル酸、2,6-ナフタレンジカルボン酸、1,6-ナフタレンジカルボン酸、2,7-ナフタレンジカルボン酸、1,4-ナフタレンジカルボン酸、4,4’-ジカルボキシビフェニル等の芳香族ジカルボン酸、これらのアルキル、アルコキシ又はハロゲン置換体、ならびにこれらのエステル形成性誘導体が挙げられる。中でも、フィルムの耐吸湿性、機械的特性及び耐熱性を高めやすい観点から、テレフタル酸、イソフタル酸、及び2,6-ナフタレンジカルボン酸が好ましい。
Specific examples of monomers that provide aromatic dicarboxylic acid repeating units include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4 -naphthalenedicarboxylic acid, aromatic dicarboxylic acids such as 4,4′-dicarboxybiphenyl, alkyl-, alkoxy- or halogen-substituted products thereof, and ester-forming derivatives thereof. Among them, terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are preferable from the viewpoint of easily improving the moisture absorption resistance, mechanical properties and heat resistance of the film.
芳香族ジオール繰返し単位を与える単量体の具体例としては、ハイドロキノン、レゾルシン、2,6-ジヒドロキシナフタレン、2,7-ジヒドロキシナフタレン、1,6-ジヒドロキシナフタレン、1,4-ジヒドロキシナフタレン、4,4’-ジヒドロキシビフェニル、3,3’-ジヒドロキシビフェニル、3,4’-ジヒドロキシビフェニル、4,4’-ジヒドロキシビフェニルエ-テル等の芳香族ジオール、これらのアルキル、アルコキシ又はハロゲン置換体、ならびにこれらのエステル形成性誘導体が挙げられる。中でも、フィルムの耐吸湿性、機械的特性及び耐熱性を高めやすい観点から、ハイドロキノン及び3,3’-ジヒドロキシビフェニルが好ましい。
Specific examples of monomers that give aromatic diol repeating units include hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4, Aromatic diols such as 4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl and 4,4'-dihydroxybiphenyl ether, their alkyl, alkoxy or halogen substituted products, and these and ester-forming derivatives of Among them, hydroquinone and 3,3'-dihydroxybiphenyl are preferable from the viewpoint of easily improving the moisture absorption resistance, mechanical properties and heat resistance of the film.
脂肪族ジオール繰返し単位を与える単量体の具体例としては、エチレングリコール、1,4-ブタンジオール、1,6-ヘキサンジオール等の脂肪族ジオール、ならびにこれらのアシル化物が挙げられる。中でも、フィルムの耐吸湿性、機械的特性及び耐熱性を高めやすい観点から、エチレングリコールが好ましい。
Specific examples of monomers that provide aliphatic diol repeating units include aliphatic diols such as ethylene glycol, 1,4-butanediol and 1,6-hexanediol, and acylated products thereof. Among them, ethylene glycol is preferable from the viewpoint of easily improving the hygroscopic resistance, mechanical properties and heat resistance of the film.
本発明の一実施形態において、スチレン系ポリマーとしては、繰り返し構造単位にスチレンを少なくとも1つ含有する樹脂であり、例えば、ポリスチレン、ABS樹脂(アクリロニトリル・ブタジエン・スチレン共重合体)、AS樹脂(アクリロニトリル・スチレン共重合体)等が挙げられる。中でも、誘電特性を高めやすい観点から、ポリスチレンが好ましい。なお、本明細書において、繰り返し構造単位に、スチレンに由来する単量体単位とシクロオレフィン由来の単量体単位とをともに有するポリマーは、シクロオレフィン系ポリマーとして分類する。
In one embodiment of the present invention, the styrenic polymer is a resin containing at least one styrene in the repeating structural unit. Examples include polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AS resin (acrylonitrile - styrene copolymer) and the like. Among them, polystyrene is preferable from the viewpoint of easily increasing dielectric properties. In this specification, a polymer having both a styrene-derived monomer unit and a cycloolefin-derived monomer unit as repeating structural units is classified as a cycloolefin-based polymer.
本発明の一実施形態において、エーテル系ポリマーとしては、主鎖にエーテル基を含む繰り返し単位を少なくとも1つ含有する樹脂であり、例えば、ポリエーテルイミド、ポリフェニレンエーテル、ポリエーテルスルホン、ポリエーテルケトン、ポリエーテルエーテルケトン等が挙げられる。中でも、フィルムの耐吸湿性、耐熱性及び誘電特性を高めやすい観点から、ポリフェニレンエーテル、ポリエーテルスルホン、ポリエーテルエーテルケトンが好ましい。
In one embodiment of the present invention, the ether-based polymer is a resin containing at least one repeating unit containing an ether group in the main chain, such as polyetherimide, polyphenylene ether, polyethersulfone, polyetherketone, polyether ether ketone and the like. Among them, polyphenylene ether, polyether sulfone, and polyether ether ketone are preferable from the viewpoint of easily improving the moisture absorption resistance, heat resistance, and dielectric properties of the film.
本発明の一実施形態において、ポリマー(B)のガラス転移温度及び融点の少なくともいずれか一方は100℃以上であることが好ましい。ポリマー(B)のTgは、好ましくは100℃以上、より好ましくは140℃以上、さらに好ましくは160℃以上、さらにより好ましくは180℃以上、特に好ましくは200℃以上、特により好ましくは220℃以上、とりわけ好ましくは240℃以上、とりわけより好ましくは260℃以上であり、好ましくは500℃以下、より好ましくは400℃以下、さらに好ましくは320℃以下である。また、ポリマー(B)が融点を有する結晶性ポリマーである場合、ポリマー(B)の融点が、好ましくは100℃以上、より好ましくは140℃以上、さらに好ましくは160℃以上、さらにより好ましくは180℃以上、特に好ましくは200℃以上、特により好ましくは220℃以上、特にさらに好ましくは240℃以上、最も好ましくは260℃以上であり、好ましくは500℃以下、より好ましくは400℃以下、さらに好ましくは350℃以下である。ポリマー(B)のTg及び融点の少なくともいずれか一方が上記の下限以上であると、フィルムのCTEを低減しやすく、かつ耐湿水性、耐熱性及び屈曲耐性等の機械的特性をより高めやすい。ポリマー(B)のTg及び融点の少なくともいずれか一方が上記の上限以下であると、フィルムの機械的特性、特に反復屈曲耐性が高めやすい。ポリマー(B)のTgは、JIS K 7196に基づき、TMAにより測定した軟化温度であり、例えば実施例に記載の方法により測定できる。なお、ポリマー(B)のTg及び融点を調整する方法は、特に限定されないが、例えば単量体単位(I)の含有量、ポリマー(B)のMw、結晶化度等を適宜調整する方法が挙げられる。単量体単位(I)の含有量、ポリマー(B)のMw、及び結晶化度からなる群から選択される少なくとも1つが大きくなるほど、ポリマー(B)のTg及び融点が高くなる傾向がある。ポリマー(B)の融点は、例えば示差走査熱量計(DSC)を用いて、これにより得られる融解曲線から融解ピーク温度を測定することにより求めることができる。DSCは、特に限定されないが、例えば株式会社日立ハイテクサイエンス製のDSCを使用してもよい。
In one embodiment of the present invention, at least one of the glass transition temperature and melting point of the polymer (B) is preferably 100°C or higher. The Tg of the polymer (B) is preferably 100° C. or higher, more preferably 140° C. or higher, still more preferably 160° C. or higher, even more preferably 180° C. or higher, particularly preferably 200° C. or higher, and particularly preferably 220° C. or higher. , particularly preferably 240° C. or higher, particularly more preferably 260° C. or higher, preferably 500° C. or lower, more preferably 400° C. or lower, and still more preferably 320° C. or lower. Further, when the polymer (B) is a crystalline polymer having a melting point, the melting point of the polymer (B) is preferably 100° C. or higher, more preferably 140° C. or higher, still more preferably 160° C. or higher, still more preferably 180° C. ° C. or higher, particularly preferably 200 ° C. or higher, particularly more preferably 220 ° C. or higher, even more preferably 240 ° C. or higher, most preferably 260 ° C. or higher, preferably 500 ° C. or lower, more preferably 400 ° C. or lower, further preferably is below 350°C. When at least one of the Tg and melting point of the polymer (B) is at least the above lower limit, the CTE of the film is likely to be reduced, and mechanical properties such as wet water resistance, heat resistance and bending resistance are likely to be enhanced. When at least one of the Tg and melting point of the polymer (B) is equal to or less than the above upper limit, the mechanical properties of the film, particularly resistance to repeated bending, are likely to be enhanced. The Tg of polymer (B) is a softening temperature measured by TMA based on JIS K 7196, and can be measured, for example, by the method described in Examples. The method of adjusting the Tg and melting point of the polymer (B) is not particularly limited, but for example, a method of appropriately adjusting the content of the monomer unit (I), the Mw of the polymer (B), the degree of crystallinity, etc. mentioned. The Tg and melting point of the polymer (B) tend to increase as at least one selected from the group consisting of the content of the monomer unit (I), the Mw of the polymer (B), and the degree of crystallinity increases. The melting point of the polymer (B) can be determined, for example, by using a differential scanning calorimeter (DSC) and measuring the melting peak temperature from the resulting melting curve. Although the DSC is not particularly limited, for example, a DSC manufactured by Hitachi High-Tech Science Co., Ltd. may be used.
本発明の一実施形態において、ポリマー(B)の重量平均分子量(以下、重量平均分子量をMwと略すことがある)は、好ましくは10,000以上、より好ましくは15,000、さらに好ましくは20,000以上、さらにより好ましくは30,000以上、特に好ましくは50,000以上、特により好ましくは70,000以上、特に好ましくは90,000以上であり、好ましくは2,000,000以下、より好ましくは1,000,000以下、さらに好ましくは700,000以下である。Mwが上記の下限以上であると、フィルムの耐吸湿性及び耐熱性を高めやすく、また強度を向上しやすい。Mwが上記の上限以下であると、フィルムの耐吸湿性、機械的特性及び成形性を高めやすい。
In one embodiment of the present invention, the weight average molecular weight of the polymer (B) (hereinafter the weight average molecular weight may be abbreviated as Mw) is preferably 10,000 or more, more preferably 15,000, and still more preferably 20. ,000 or more, still more preferably 30,000 or more, particularly preferably 50,000 or more, particularly more preferably 70,000 or more, particularly preferably 90,000 or more, preferably 2,000,000 or less, and more It is preferably 1,000,000 or less, more preferably 700,000 or less. When the Mw is at least the above lower limit, it is easy to increase the hygroscopic resistance and heat resistance of the film, and it is easy to improve the strength. When the Mw is equal to or less than the above upper limit, the moisture absorption resistance, mechanical properties and moldability of the film are likely to be improved.
本発明の一実施形態において、ポリマー(B)のMwと数平均分子量(以下、数平均分子量をMnと略すことがある)との比(Mw/Mn)は、ポリスチレン換算で、好ましくは2.5以下、より好ましくは2.2以下、さらに好ましくは2.0以下、さらにより好ましくは1.95以下、特に好ましくは1.90以下であり、好ましくは1.30以上、より好ましくは1.50以上、さらに好ましくは1.60以上、特に好ましくは1.65以上である。Mw/Mn比が上記の上限以下であると、フィルムの耐吸湿性、耐熱性及び機械的特性を高めやすく、また上記の下限以上であると成形性を高めやすい。なお、Mw及びMnは、ゲルパーミエーションクロマトグラフィー(以下、GPCと略すことがある)測定を行い、標準ポリスチレン換算により求めることができ、例えば実施例に記載の方法により求められる。
In one embodiment of the present invention, the ratio (Mw/Mn) between the Mw and the number average molecular weight (hereinafter the number average molecular weight may be abbreviated as Mn) of the polymer (B) is preferably 2.0 in terms of polystyrene. 5 or less, more preferably 2.2 or less, still more preferably 2.0 or less, even more preferably 1.95 or less, particularly preferably 1.90 or less, preferably 1.30 or more, more preferably 1.90 or less. It is 50 or more, more preferably 1.60 or more, and particularly preferably 1.65 or more. When the Mw/Mn ratio is at most the above upper limit, the hygroscopic resistance, heat resistance, and mechanical properties of the film are likely to be enhanced, and at the above lower limit or above, the formability is likely to be enhanced. In addition, Mw and Mn can be obtained by performing gel permeation chromatography (hereinafter sometimes abbreviated as GPC) measurement and converting to standard polystyrene, for example, by the method described in Examples.
本発明の一実施形態において、CTEが低減されたフィルムを得られやすい観点から、ポリマー(B)の屈折率は、好ましくは1.600以下、より好ましくは1.570以下、さらに好ましくは1.550以下であり、好ましくは1.500以上、より好ましくは1.520以上である。ポリマー(B)の屈折率は屈折計により測定でき、例えば実施例に記載の方法により測定できる。
In one embodiment of the present invention, the refractive index of the polymer (B) is preferably 1.600 or less, more preferably 1.570 or less, still more preferably 1.570 or less, from the viewpoint of easily obtaining a film with a reduced CTE. It is 550 or less, preferably 1.500 or more, more preferably 1.520 or more. The refractive index of the polymer (B) can be measured with a refractometer, for example, by the method described in Examples.
本発明の一実施形態において、ポリマー(B)のCTEは、好ましくは58ppm/K以下、より好ましくは55ppm/K以下、さらに好ましくは50ppm/K以下であり、好ましくは0ppm/K以上、より好ましくは0.01ppm/K以上、さらに好ましくは1ppm/K以上、さらにより好ましくは5ppm/K以上である。ポリマー(B)のCTEが上記の上限以下であると、得られるフィルムのCTEを低減しやすい。また、銅箔と貼り合せて銅張積層板を作製する場合には、積層フィルムの剥がれ防止の観点から、フィルムのCTEを20ppm/K前後に調整することが好ましい。混合する樹脂のCTEに応じて、最適なCTEを有するポリマー(B)を選択することができる。なお、CTEは、例えば熱機械分析(以下、TMAと称することがある)により測定でき、実施例に記載の方法により求められる。
In one embodiment of the present invention, the CTE of polymer (B) is preferably 58 ppm/K or less, more preferably 55 ppm/K or less, even more preferably 50 ppm/K or less, preferably 0 ppm/K or more, more preferably is 0.01 ppm/K or more, more preferably 1 ppm/K or more, and even more preferably 5 ppm/K or more. When the CTE of the polymer (B) is equal to or less than the above upper limit, the CTE of the resulting film is likely to be reduced. In the case of producing a copper-clad laminate by bonding with copper foil, it is preferable to adjust the CTE of the film to around 20 ppm/K from the viewpoint of preventing peeling of the laminate film. Depending on the CTE of the resin to be mixed, the polymer (B) with the optimum CTE can be selected. CTE can be measured, for example, by thermomechanical analysis (hereinafter sometimes referred to as TMA), and is determined by the method described in Examples.
本発明の一実施形態において、ポリマー(B)が粒子状である場合、本発明における組成物中の粒子状ポリマー(B)のメジアン径は、好ましくは0.01μm以上、より好ましくは0.03μm以上、さらに好ましくは0.05μm以上であり、好ましくは15μm以下、より好ましくは10μm以下、さらに好ましくは5μm以下、さらにより好ましくは3μm以下、特に好ましくは1μm以下、特により好ましくは0.8μm以下、特にさらに好ましくは0.5μm以下である。組成物中の粒子状ポリマー(B)のメジアン径が上記の下限以上であると、組成物から形成されるフィルムの誘電特性を高めやすく、またフィルムを製造しやすい。組成物中の粒子状ポリマー(B)のメジアン径が上記の上限以下であると、組成物中及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。組成物中の粒子状ポリマー(B)のメジアン径を求める方法は特に限定されないが、例えば遠心沈式粒度分布測定装置や超音波減衰式粒度分布測定装置により求めることができる。また、粒子状ポリマー(B)の粒子径に影響を及ぼさない範囲の量で、ポリイミド系樹脂(A)やフェノール系酸化防止剤を粒子状ポリマー(B)分散液に添加して組成物を形成する場合、予め、該分散液中の粒子状ポリマー(B)のメジアン径を測定し、これを該組成物中の粒子状ポリマー(B)のメジアン径とすることができる。なお、本明細書において、メジアン径とはD50とも称され、その値よりもサイズの小さい側の粒子状ポリマー(B)の粒子数と、大きい側の粒子数とが等しくなる値を示す。また、本明細書において、「粒子径」は、特記しない限り、粒子状ポリマー(B)のメジアン径及び/又は平均一次粒子径を含む意味である。
In one embodiment of the present invention, when the polymer (B) is particulate, the median diameter of the particulate polymer (B) in the composition of the present invention is preferably 0.01 μm or more, more preferably 0.03 μm. More preferably 0.05 μm or more, preferably 15 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, even more preferably 3 μm or less, particularly preferably 1 μm or less, and particularly preferably 0.8 μm or less , and more preferably 0.5 μm or less. When the median diameter of the particulate polymer (B) in the composition is at least the above lower limit, the dielectric properties of the film formed from the composition are likely to be enhanced, and the film is easily produced. When the median diameter of the particulate polymer (B) in the composition is equal to or less than the above upper limit, the dispersibility of the polymer (B) in the composition and in the film is likely to be increased, and the resulting film has hygroscopic resistance and heat resistance. Easy to improve. Although the method for determining the median diameter of the particulate polymer (B) in the composition is not particularly limited, it can be determined, for example, using a centrifugal sedimentation particle size distribution analyzer or an ultrasonic attenuation particle size distribution analyzer. In addition, the polyimide resin (A) and the phenolic antioxidant are added to the particulate polymer (B) dispersion in an amount that does not affect the particle size of the particulate polymer (B) to form a composition. In this case, the median diameter of the particulate polymer (B) in the dispersion can be measured in advance and used as the median diameter of the particulate polymer (B) in the composition. In this specification, the median diameter is also referred to as D50, and indicates a value at which the number of particles of the particulate polymer (B) on the side smaller than that value is equal to the number of particles on the larger side. In the present specification, the term "particle size" means the median size and/or average primary particle size of the particulate polymer (B), unless otherwise specified.
本発明の一実施形態において、本発明の組成物に含まれるポリマー(B)の含有量は、ポリイミド系樹脂(A)とポリマー(B)との合計質量に対して、通常1質量%以上、好ましくは5質量%以上、より好ましくは7質量%以上、さらに好ましくは10質量%以上、特に好ましくは20質量%以上であり、好ましくは50質量%以下、より好ましくは40質量%以下、さらに好ましくは35質量%以下である。該組成物に含まれるポリマー(B)の含有量が上記の下限以上であると、ポリマー(B)の凝集体の形成を抑制しやすいことからポリマー(B)の分散性を高めやすい。また、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。また、該組成物に含まれるポリマー(B)の含有量が上記の上限以下であると、膜形成が容易となるため、フィルム製造の観点から有利である。なお、フィルム中のポリマー(B)の分散性が高いと熱伝導率及びCTEの均一性が高くなるため、例えばCCLの樹脂層として該フィルムを使用した場合に、フィルムと銅箔との剥がれを抑制しやすくなる。
In one embodiment of the present invention, the content of the polymer (B) contained in the composition of the present invention is usually 1% by mass or more with respect to the total mass of the polyimide resin (A) and the polymer (B), Preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 10% by mass or more, particularly preferably 20% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably is 35% by mass or less. When the content of the polymer (B) contained in the composition is at least the above lower limit, the formation of aggregates of the polymer (B) is likely to be suppressed, and thus the dispersibility of the polymer (B) is likely to be enhanced. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. Further, when the content of the polymer (B) contained in the composition is equal to or less than the above upper limit, film formation is facilitated, which is advantageous from the viewpoint of film production. If the dispersibility of the polymer (B) in the film is high, the uniformity of thermal conductivity and CTE will be high. easier to suppress.
<ポリマー(B)の製造方法>
ポリマー(B)は、市販品を用いてもよく、慣用の方法により製造してもよい。本発明の一実施形態では、ポリマー(B)はシクロオレフィン系ポリマーであることが好ましい。シクロオレフィン系ポリマーの製造方法は特に限定されないが、例えば、式(IV)で表される遷移金属錯体(α)を一成分として使用してなる触媒の存在下、シクロオレフィン系ポリマーを形成する単量体、例えば式(I)で表されるシクロオレフィン、前記エチレン、炭素数3~20の直鎖状α-オレフィン及び炭素数8~20の芳香族ビニル化合物からなる群から選択される少なくとも1つの単量体、及び任意に前記その他の単量体を重合させることにより製造することが好ましい。本発明におけるシクロオレフィン系ポリマーの製造では、式(IV)で表される遷移金属錯体(α)を用いるため、シクロオレフィン系ポリマー中の単量体単位(I)の含有量を顕著に増加させやすく、Tgを上記範囲内に調整しやすい。 <Method for producing polymer (B)>
Polymer (B) may be a commercially available product or may be produced by a conventional method. In one embodiment of the invention, polymer (B) is preferably a cycloolefinic polymer. The method for producing the cycloolefin-based polymer is not particularly limited. at least one monomer selected from the group consisting of a cycloolefin represented by formula (I), the ethylene, a linear α-olefin having 3 to 20 carbon atoms and an aromatic vinyl compound having 8 to 20 carbon atoms; It is preferably prepared by polymerizing one monomer, and optionally said other monomers. Since the transition metal complex (α) represented by the formula (IV) is used in the production of the cycloolefin-based polymer in the present invention, the content of the monomer unit (I) in the cycloolefin-based polymer is significantly increased. It is easy to adjust Tg within the above range.
ポリマー(B)は、市販品を用いてもよく、慣用の方法により製造してもよい。本発明の一実施形態では、ポリマー(B)はシクロオレフィン系ポリマーであることが好ましい。シクロオレフィン系ポリマーの製造方法は特に限定されないが、例えば、式(IV)で表される遷移金属錯体(α)を一成分として使用してなる触媒の存在下、シクロオレフィン系ポリマーを形成する単量体、例えば式(I)で表されるシクロオレフィン、前記エチレン、炭素数3~20の直鎖状α-オレフィン及び炭素数8~20の芳香族ビニル化合物からなる群から選択される少なくとも1つの単量体、及び任意に前記その他の単量体を重合させることにより製造することが好ましい。本発明におけるシクロオレフィン系ポリマーの製造では、式(IV)で表される遷移金属錯体(α)を用いるため、シクロオレフィン系ポリマー中の単量体単位(I)の含有量を顕著に増加させやすく、Tgを上記範囲内に調整しやすい。 <Method for producing polymer (B)>
Polymer (B) may be a commercially available product or may be produced by a conventional method. In one embodiment of the invention, polymer (B) is preferably a cycloolefinic polymer. The method for producing the cycloolefin-based polymer is not particularly limited. at least one monomer selected from the group consisting of a cycloolefin represented by formula (I), the ethylene, a linear α-olefin having 3 to 20 carbon atoms and an aromatic vinyl compound having 8 to 20 carbon atoms; It is preferably prepared by polymerizing one monomer, and optionally said other monomers. Since the transition metal complex (α) represented by the formula (IV) is used in the production of the cycloolefin-based polymer in the present invention, the content of the monomer unit (I) in the cycloolefin-based polymer is significantly increased. It is easy to adjust Tg within the above range.
Cpはシクロペンタジエニル骨格を有する基を表し、
Aは元素の周期律表の第16族の原子を表し、
Tは元素の周期律表の第14族の原子を表し、
D1及びD2は、互いに独立に、水素原子、ハロゲン原子、炭素数1~20の炭化水素基、炭素数1~20のハロゲン化炭化水素基、炭素数1~20のアルコキシ基、炭素数6~20のアリールオキシ基又は炭素数2~20の2置換アミノ基を表し、それらは同一であってもよく、異なってもよい。
R1~R6は、互いに独立に、水素原子、ハロゲン原子、炭素数1~20の炭化水素基、炭素数1~20のハロゲン化炭化水素基、炭素数1~20のアルコキシ基、炭素数6~20のアリールオキシ基、炭素数2~20の2置換アミノ基又は炭素数1~20のシリル基を表し、それらは同一であってもよく、異なってもよく、さらにそれらは任意に結合して環を形成してもよい。]
Cp represents a group having a cyclopentadienyl skeleton,
A represents an atom of Group 16 of the Periodic Table of the Elements;
T represents an atom of Group 14 of the Periodic Table of the Elements;
D 1 and D 2 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon number It represents an aryloxy group having 6 to 20 carbon atoms or a disubstituted amino group having 2 to 20 carbon atoms, which may be the same or different.
R 1 to R 6 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. represents an aryloxy group having 6 to 20 carbon atoms, a disubstituted amino group having 2 to 20 carbon atoms or a silyl group having 1 to 20 carbon atoms, which may be the same or different, and are optionally bonded may form a ring. ]
Mは、元素の周期律表(IUPAC無機化学命名法改訂版1989)の第4族の遷移金属元素であり、例えば、チタニウム原子、ジルコニウム原子、ハフニウム原子等が挙げられる。
M is a transition metal element in Group 4 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989), for example, titanium atom, zirconium atom, hafnium atom, and the like.
Cpは、シクロペンタジエニル骨格を有する基であり、例えば、シクロペンタジエニル、置換シクロペンタジエニル、インデニル、置換インデニル、フルオレニル、置換フルオレニル等が挙げられる。具体例としては、シクロペンタジエニル基、メチルシクロペンタジエニル基、テトラメチルシクロペンタジエニル基、n-プロピルシクロペンタジエニル基、n-ブチルシクロペンタジエニル基、イソブチルシクロペンタジエニル基、フェニルシクロペンタジエニル基、インデニル基、メチルインデニル基、n-プロピルインデニル基、n-ブチルインデニル基、イソブチルインデニル基、フェニルインデニル基、フルオレニル基、メチルフルオレニル基、n-プロピルフルオレニル基、フェニルフルオレニル基、ジメチルフルオレニル基等が挙げられる。これらの中でも、好ましくはシクロペンタジエニル基、メチルシクロペンタジエニル基、テトラメチルシクロペンタジエニル基、n-ブチルシクロペンタジエニル基、イソブチルシクロペンタジエニル基、インデニル基、メチルインデニル基又はフルオレニル基が挙げられる。
Cp is a group having a cyclopentadienyl skeleton, such as cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl, substituted fluorenyl and the like. Specific examples include a cyclopentadienyl group, a methylcyclopentadienyl group, a tetramethylcyclopentadienyl group, an n-propylcyclopentadienyl group, an n-butylcyclopentadienyl group, and an isobutylcyclopentadienyl group. , phenylcyclopentadienyl group, indenyl group, methylindenyl group, n-propylindenyl group, n-butylindenyl group, isobutylindenyl group, phenylindenyl group, fluorenyl group, methylfluorenyl group, n -Propylfluorenyl group, phenylfluorenyl group, dimethylfluorenyl group and the like. Among these, cyclopentadienyl group, methylcyclopentadienyl group, tetramethylcyclopentadienyl group, n-butylcyclopentadienyl group, isobutylcyclopentadienyl group, indenyl group and methylindenyl group are preferred. or a fluorenyl group.
Aは、元素の周期律表の第16族の原子であり、例えば、酸素原子、硫黄原子等が挙げられる。これらの中でも、酸素原子であることが好ましい。
A is an atom of Group 16 of the periodic table of elements, and includes, for example, an oxygen atom and a sulfur atom. Among these, an oxygen atom is preferable.
Tは、元素の周期律表の第14族の原子であり、例えば、炭素原子、ケイ素原子、ゲルマニウム原子等が挙げられる。これらの中でも、炭素原子又はケイ素原子であることが好ましい。
T is an atom of Group 14 of the periodic table of elements, and includes, for example, a carbon atom, a silicon atom, a germanium atom, and the like. Among these, a carbon atom or a silicon atom is preferred.
D1、D2は、互いに独立に、水素原子、ハロゲン原子、炭素数1~20の炭化水素基、炭素数1~20のハロゲン化炭化水素基、炭素数1~20のアルコキシ基、炭素数6~20のアリールオキシ基又は炭素数2~20の2置換アミノ基であり、それらは同一であってもよく、異なってもよい。これらの中でも、ハロゲン原子であることが好ましい。
D 1 and D 2 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or It is an aryloxy group having 6 to 20 carbon atoms or a disubstituted amino group having 2 to 20 carbon atoms, which may be the same or different. Among these, a halogen atom is preferable.
D1、D2がハロゲン原子である場合の具体例としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
Specific examples of D 1 and D 2 being halogen atoms include fluorine, chlorine, bromine and iodine atoms.
D1、D2が炭化水素基である場合、その炭素数は好ましくは1~10である。前記炭化水素基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、ネオペンチル基、n-ヘキシル基、n-オクチル基、フェニル基、2-メチルフェニル基、3-メチルフェニル基、4-メチルフェニル基、ナフチル基、ベンジル基等が挙げられる。
When D 1 and D 2 are hydrocarbon groups, the number of carbon atoms is preferably 1-10. Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group and n-hexyl. group, n-octyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, naphthyl group, benzyl group and the like.
D1、D2がハロゲン化炭化水素基である場合の具体例としては、フルオロメチル基、ジフルオロメチル基、1-フルオロエチル基、1,1-ジフルオロエチル基、1,2-ジフルオロエチル基、1,1,2-トリフルオロエチル基、テトラフルオロエチル基、クロロメチル基、ジクロロメチル基、1-クロロエチル基、1,1-ジクロロエチル基、1,2-ジクロロエチル基、1,1,2-トリクロロエチル基、1,1,2,2-テトラクロロエチル基、ブロモメチル基、ジブロモメチル基、1-ブロモエチル基、1,1-ジブロモエチル基、1,2-ジブロモエチル基、1,1,2-トリブロモエチル基、1,1,2,2-テトラブロモエチル基、2-フルオロフェニル基、3-フルオロフェニル基、4-フルオロフェニル基、2,3-ジフルオロフェニル基、2,4-ジフルオロフェニル基、2,5-ジフルオロフェニル基、2,6-ジフルオロフェニル基、2,3,4-トリフルオロフェニル基、2,3,5-トリフルオロフェニル基、2,3,6-トリフルオロフェニル基、2,3,4,5-テトラフルオロフェニル基、2,3,4,6-テトラフルオロフェニル基、ペンタフルオロフェニル基、2-クロロフェニル基、3-クロロフェニル基、4-クロロフェニル基、2,3-ジクロロフェニル基、2,4-ジクロロフェニル基、2,5-ジクロロフェニル基、2,6-ジクロロフェニル基、2,3,4-トリクロロフェニル基、2,3,5-トリクロロフェニル基、2,3,6-トリクロロフェニル基、2,3,4,5-テトラクロロフェニル基、2,3,4,6-テトラクロロフェニル基、ペンタクロロフェニル基、2-ブロモフェニル基、3-ブロモフェニル基、4-ブロモフェニル基、2,3-ジブロモフェニル基、2,4-ジブロモフェニル基、2,5-ジブロモフェニル基、2,6-ジブロモフェニル基、2,3,4-トリブロモフェニル基、2,3,5-トリブロモフェニル基、2,3,6-トリブロモフェニル基、2,3,4,5-テトラブロモフェニル基、2,3,4,6-テトラブロモフェニル基、ペンタブロモフェニル基等が挙げられる。
Specific examples of D 1 and D 2 being halogenated hydrocarbon groups include fluoromethyl group, difluoromethyl group, 1-fluoroethyl group, 1,1-difluoroethyl group, 1,2-difluoroethyl group, 1,1,2-trifluoroethyl group, tetrafluoroethyl group, chloromethyl group, dichloromethyl group, 1-chloroethyl group, 1,1-dichloroethyl group, 1,2-dichloroethyl group, 1,1,2 -trichloroethyl group, 1,1,2,2-tetrachloroethyl group, bromomethyl group, dibromomethyl group, 1-bromoethyl group, 1,1-dibromoethyl group, 1,2-dibromoethyl group, 1,1,2 -tribromoethyl group, 1,1,2,2-tetrabromoethyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluoro phenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,3,6-trifluorophenyl group, 2,3,4,5-tetrafluorophenyl group, 2,3,4,6-tetrafluorophenyl group, pentafluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2, 3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 2,3,4-trichlorophenyl group, 2,3,5-trichlorophenyl group, 2,3, 6-trichlorophenyl group, 2,3,4,5-tetrachlorophenyl group, 2,3,4,6-tetrachlorophenyl group, pentachlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2,3-dibromophenyl group, 2,4-dibromophenyl group, 2,5-dibromophenyl group, 2,6-dibromophenyl group, 2,3,4-tribromophenyl group, 2,3,5 -tribromophenyl group, 2,3,6-tribromophenyl group, 2,3,4,5-tetrabromophenyl group, 2,3,4,6-tetrabromophenyl group, pentabromophenyl group and the like. be done.
D1、D2がアルコキシ基である場合の具体例としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、n-ブトキシ基、イソブトキシ基、sec-ブトキシ基、tert-ブトキシ基、n-ペントキシ基、ネオペントキシ基、n-ヘキソキシ基、n-オクトキシ基等が挙げられる。
Specific examples of D 1 and D 2 being alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n- pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group and the like.
D1、D2がアリールオキシ基である場合の具体例としては、フェノキシ基、2-メチルフェノキシ基、3-メチルフェノキシ基、4-メチルフェノキシ基、ナフチルオキシ基等が挙げられる。
Specific examples of D 1 and D 2 being aryloxy groups include phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy and naphthyloxy groups.
D1、D2が2置換アミノ基である場合の2置換アミノ基とは、置換基が2個結合したアミノ基である。その具体例としては、ジメチルアミノ基、ジエチルアミノ基、ジ-n-プロピルアミノ基、ジイソプロピルアミノ基、ジ-n-ブチルアミノ基、ジイソブチルアミノ基、ジ-sec-ブチルアミノ基、ジ-tert-ブチルアミノ基、ジ-n-ヘキシルアミノ基、ジ-n-オクチルアミノ基、ジフェニルアミノ基等が挙げられる。
When D 1 and D 2 are disubstituted amino groups, the disubstituted amino group is an amino group in which two substituents are bonded. Specific examples thereof include a dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, diisobutylamino group, di-sec-butylamino group and di-tert-butyl. Amino group, di-n-hexylamino group, di-n-octylamino group, diphenylamino group and the like.
R1~R6は、互いに独立に、水素原子、ハロゲン原子、炭素数1~20の炭化水素基、炭素数1~20のハロゲン化炭化水素基、炭素数1~20のアルコキシ基、炭素数6~20のアリールオキシ基、炭素数2~20の2置換アミノ基又は炭素原子数1~20のシリル基を表し、それらは同一であってもよく、異なってもよく、さらにそれらは任意に結合して環を形成してもよい。これらの中でも、炭素数1~20の炭化水素基であることが好ましい。
R 1 to R 6 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or represents an aryloxy group having 6 to 20 carbon atoms, a disubstituted amino group having 2 to 20 carbon atoms or a silyl group having 1 to 20 carbon atoms, which may be the same or different, and are optionally They may be combined to form a ring. Among these, hydrocarbon groups having 1 to 20 carbon atoms are preferred.
R1~R6がハロゲン原子である場合の具体例としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
Specific examples of R 1 to R 6 being halogen atoms include fluorine, chlorine, bromine and iodine atoms.
R1~R6が炭化水素基である場合、炭素数は1~10であることが好ましい。その具体例としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、ネオペンチル基、n-ヘキシル基、n-オクチル基、フェニル基、2-メチルフェニル基、3-メチルフェニル基、4-メチルフェニル基、2,3-ジメチルフェニル基、2,4-ジメチルフェニル基、2,5-ジメチルフェニル基、2,6-ジメチルフェニル基、2,3,4-トリメチルフェニル基、2,3,5-トリメチルフェニル基、2,3,6-トリメチルフェニル基、2,3,4,5-テトラメチルフェニル基、2,3,4,6-テトラメチルフェニル基、ペンタメチルフェニル基等が挙げられる。
When R 1 to R 6 are hydrocarbon groups, they preferably have 1 to 10 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group and n-hexyl group. , n-octyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group , 2,6-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, pentamethylphenyl group and the like.
R1~R6がハロゲン原子、ハロゲン化炭化水素基、アルコキシ基、アリールオキシ基、及び2置換アミノ基である場合の具体例としては、D1、D2がハロゲン原子、ハロゲン化炭化水素基、アルコキシ基、アリールオキシ基、及び2置換アミノ基である場合の具体例として上記に例示したものが挙げられる。
Specific examples where R 1 to R 6 are a halogen atom, a halogenated hydrocarbon group, an alkoxy group, an aryloxy group, or a disubstituted amino group include D 1 and D 2 being a halogen atom or a halogenated hydrocarbon group. , an alkoxy group, an aryloxy group, and a disubstituted amino group include those exemplified above.
R1~R6がシリル基である場合の具体例としては、トリメチルシリル基、トリエチルシリル基、トリ-n-プロピルシリル基、トリイソプロピルシリル基、トリ-n-ブチルシリル基、トリイソブチルシリル基、トリ-sec-ブチルシリル基、トリtert-ブチルシリル基、トリフェニルシリル基等が挙げられる。
Specific examples when R 1 to R 6 are silyl groups include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, triisobutylsilyl group, tri -sec-butylsilyl group, tri-tert-butylsilyl group, triphenylsilyl group and the like.
このような、式(IV)で表される化合物の具体例としては、イソプロピリデン(シクロペンタジエニル)(3-tert-ブチル-5-メチル-2-フェノキシ)チタニウムジクロライド、イソプロピリデン(メチルシクロペンタジエニル)(3-tert-ブチル-5-メチル-2-フェノキシ)チタニウムジクロライド、イソプロピリデン(ジメチルシクロペンタジエニル)(3-tert-ブチル-5-メチル-2-フェノキシ)チタニウムジクロライド、イソプロピリデン(トリメチルシクロペンタジエニル)(3-tert-ブチル-5-メチル-2-フェノキシ)チタニウムジクロライド、イソプロピリデン(テトラメチルシクロペンタジエニル)(3-tert-ブチル-5-メチル-2-フェノキシ)チタニウムジクロライド、イソプロピリデン(n-プロピルシクロペンタジエニル)(3-tert-ブチル-5-メチル-2-フェノキシ)チタニウムジクロライド、イソプロピリデン(n-ブチルシクロペンタジエニル)(3-tert-ブチル-5-メチル-2-フェノキシ)チタニウムジクロライド、イソプロピリデン(イソブチルシクロペンタジエニル)(3-tert-ブチル-5-メチル-2-フェノキシ)チタニウムジクロライド、イソプロピリデン(フェニルシクロペンタジエニル)(3-tert-ブチル-5-メチル-2-フェノキシ)チタニウムジクロライド、イソプロピリデン(シクロペンタジエニル)(3-tert-ブチル-2-フェノキシ)チタニウムジクロライド、イソプロピリデン(メチルシクロペンタジエニル)(3-tert-ブチル-2-フェノキシ)チタニウムジクロライド、イソプロピリデン(ジメチルシクロペンタジエニル)(3-tert-ブチル-2-フェノキシ)チタニウムジクロライド、イソプロピリデン(トリメチルシクロペンタジエニル)(3-tert-ブチル-2-フェノキシ)チタニウムジクロライド、イソプロピリデン(テトラメチルシクロペンタジエニル)(3-tert-ブチル-2-フェノキシ)チタニウムジクロライド、イソプロピリデン(n-プロピルシクロペンタジエニル)(3-tert-ブチル-2-フェノキシ)チタニウムジクロライド、イソプロピリデン(n-ブチルシクロペンタジエニル)(3-tert-ブチル-2-フェノキシ)チタニウムジクロライド、イソプロピリデン(イソブチルシクロペンタジエニル)(3-tert-ブチル-2-フェノキシ)チタニウムジクロライド、イソプロピリデン(フェニルシクロペンタジエニル)(3-tert-ブチル-2-フェノキシ)チタニウムジクロライド、イソプロピリデン(シクロペンタジエニル)(2-フェノキシ)チタニウムジクロライド、イソプロピリデン(メチルシクロペンタジエニル)(2-フェノキシ)チタニウムジクロライド、イソプロピリデン(ジメチルシクロペンタジエニル)(2-フェノキシ)チタニウムジクロライド、イソプロピリデン(トリメチルシクロペンタジエニル)(2-フェノキシ)チタニウムジクロライド、イソプロピリデン(テトラメチルシクロペンタジエニル)(2-フェノキシ)チタニウムジクロライド、イソプロピリデン(n-プロピルシクロペンタジエニル)(2-フェノキシ)チタニウムジクロライド、イソプロピリデン(n-ブチルシクロペンタジエニル)(2-フェノキシ)チタニウムジクロライド、イソプロピリデン(イソブチルシクロペンタジエニル)(2-フェノキシ)チタニウムジクロライド、イソプロピリデン(フェニルシクロペンタジエニル)(2-フェノキシ)チタニウムジクロライド等が挙げられる。
Specific examples of such compounds represented by formula (IV) include isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(methylcyclo pentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(dimethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropyl Lidene (trimethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) ) titanium dichloride, isopropylidene (n-propylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (n-butylcyclopentadienyl) (3-tert-butyl -5-methyl-2-phenoxy) titanium dichloride, isopropylidene (isobutylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (phenylcyclopentadienyl) (3 -tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3- tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (dimethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylcyclopentadienyl) (3-tert-butyl- 2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (n-propylcyclopentadienyl) (3-tert-butyl-2 -phenoxy) titanium dichloride, isopropylidene (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (isobutylcyclope pentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, isopropylidene(phenylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, isopropylidene(cyclopentadienyl)(2- phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, isopropylidene (dimethylcyclopentadienyl) (2-phenoxy) titanium dichloride, isopropylidene (trimethylcyclopentadienyl) (2 -phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, isopropylidene (n-propylcyclopentadienyl) (2-phenoxy) titanium dichloride, isopropylidene (n-butylcyclo pentadienyl)(2-phenoxy)titanium dichloride, isopropylidene(isobutylcyclopentadienyl)(2-phenoxy)titanium dichloride, isopropylidene(phenylcyclopentadienyl)(2-phenoxy)titanium dichloride and the like.
また、上記の具体例におけるチタニウムをジルコニウムあるいはハフニウムに変更した化合物、及び、それらを含めイソプロピリデンをジメチルシリレン、ジフェニルシリレン、メチレンに変更した化合物についても同様に例示できる。更に、ジクロライドをジブロマイド、ジアイオダイド、ジメチル、ジベンジル、ジメトキシド、ジエトキシドに変更した化合物についても、同様に例示することができる。
Also, compounds in which titanium in the above specific examples is changed to zirconium or hafnium, and compounds in which isopropylidene is changed to dimethylsilylene, diphenylsilylene, and methylene can be similarly exemplified. Furthermore, compounds in which dichloride is changed to dibromide, diiodide, dimethyl, dibenzyl, dimethoxide and diethoxide can be similarly exemplified.
上記の式(IV)で表される遷移金属錯体(α)は、種々の助触媒と組合せて、本発明の一実施形態に係るポリマー(B)を製造するための触媒として使用できる。助触媒とは、遷移金属錯体(α)と相互作用をして、環状オレフィン、アルケニル芳香族炭化水素に対する重合活性種を生成せしめる化合物のことである。その例としては、有機アルミニウム化合物(β)及び/又は下記式(γ1)~式(γ3)のいずれかで表されるホウ素化合物(γ)を挙げることができるが、これらの助触媒を使用することにより生成する重合活性種の構造は明らかではない。
The transition metal complex (α) represented by formula (IV) above can be used as a catalyst for producing the polymer (B) according to one embodiment of the present invention in combination with various cocatalysts. A co-catalyst is a compound that interacts with the transition metal complex (α) to generate polymerization active species for cyclic olefins and alkenyl aromatic hydrocarbons. Examples thereof include organoaluminum compounds (β) and/or boron compounds (γ) represented by any of the following formulas (γ1) to (γ3). The structure of the polymerization active species generated by this is not clear.
式(γ1) BQ1Q2Q3
式(γ2) J+(BQ1Q2Q3Q4)-
式(γ3) (L-H)+(BQ1Q2Q3Q4)-
[式(γ1)~式(γ3)中、Bは3価の原子価状態のホウ素原子を表し、
Q1~Q4は、互いに独立に、ハロゲン原子、炭素数1~20の炭化水素基、炭素数1~20のハロゲン化炭化水素基、炭素数1~20の置換シリル基、炭素数1~20のアルコキシ基又は炭素数2~20の2置換アミノ基を表し、
J+は、無機又は有機のカチオンを表し、
Lは、中性ルイス塩基を表し、(L-H)+はブレンステッド酸を表す。] Formula (γ1) BQ 1 Q 2 Q 3
Formula (γ2) J + (BQ 1 Q 2 Q 3 Q 4 ) −
Formula (γ3) (L−H) + (BQ 1 Q 2 Q 3 Q 4 ) −
[In the formulas (γ1) to (γ3), B represents a boron atom in a trivalent state,
Q 1 to Q 4 each independently represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, or a silyl group having 1 to 20 carbon atoms. represents a 20 alkoxy group or a disubstituted amino group having 2 to 20 carbon atoms,
J + represents an inorganic or organic cation,
L represents a neutral Lewis base and (LH) + represents a Bronsted acid. ]
式(γ2) J+(BQ1Q2Q3Q4)-
式(γ3) (L-H)+(BQ1Q2Q3Q4)-
[式(γ1)~式(γ3)中、Bは3価の原子価状態のホウ素原子を表し、
Q1~Q4は、互いに独立に、ハロゲン原子、炭素数1~20の炭化水素基、炭素数1~20のハロゲン化炭化水素基、炭素数1~20の置換シリル基、炭素数1~20のアルコキシ基又は炭素数2~20の2置換アミノ基を表し、
J+は、無機又は有機のカチオンを表し、
Lは、中性ルイス塩基を表し、(L-H)+はブレンステッド酸を表す。] Formula (γ1) BQ 1 Q 2 Q 3
Formula (γ2) J + (BQ 1 Q 2 Q 3 Q 4 ) −
Formula (γ3) (L−H) + (BQ 1 Q 2 Q 3 Q 4 ) −
[In the formulas (γ1) to (γ3), B represents a boron atom in a trivalent state,
Q 1 to Q 4 each independently represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, or a silyl group having 1 to 20 carbon atoms. represents a 20 alkoxy group or a disubstituted amino group having 2 to 20 carbon atoms,
J + represents an inorganic or organic cation,
L represents a neutral Lewis base and (LH) + represents a Bronsted acid. ]
前記有機アルミニウム化合物(β)としては、公知の有機アルミニウム化合物が使用できる。具体的には、式(β1)で表される有機アルミニウム化合物、式(β2)で表される構造を有する環状のアルミノキサン及び式(β3)で表される構造を有する線状のアルミノキサンが挙げられ、これらは単独でも、あるいは2種以上を混合して用いることができる。
A known organoaluminum compound can be used as the organoaluminum compound (β). Specific examples include an organoaluminum compound represented by formula (β1), a cyclic aluminoxane having a structure represented by formula (β2), and a linear aluminoxane having a structure represented by formula (β3). , these can be used alone or in combination of two or more.
式(β1) E1
aAlZ3-a
式(β2) {-Al(E2)-O-}b
式(β3) E3{-Al(E3)-O-}cAlE3 2
[式(β1)~式(β3)中、E1、E2及びE3は、互いに独立に、炭素数1~8の炭化水素基を表し、全てのE1、全てのE2及び全てのE3は同一であってもよく、異なっていてもよく、Zは水素又はハロゲンを表し、全てのZは同一であってもよく、異なっていてもよく、aは0~3の整数を表し、bは2以上の整数を表し、cは1以上の整数を表す。] Formula (β1) E 1 a AlZ 3-a
Formula (β2) {-Al(E 2 )-O-} b
Formula (β3) E 3 {-Al(E 3 )-O-} c AlE 3 2
[In formulas (β1) to (β3), E 1 , E 2 and E 3 each independently represent a hydrocarbon group having 1 to 8 carbon atoms, all E 1 , all E 2 and all E 3 may be the same or different, Z represents hydrogen or halogen, all Z may be the same or different, a represents an integer of 0 to 3 , b represents an integer of 2 or more, and c represents an integer of 1 or more. ]
式(β2) {-Al(E2)-O-}b
式(β3) E3{-Al(E3)-O-}cAlE3 2
[式(β1)~式(β3)中、E1、E2及びE3は、互いに独立に、炭素数1~8の炭化水素基を表し、全てのE1、全てのE2及び全てのE3は同一であってもよく、異なっていてもよく、Zは水素又はハロゲンを表し、全てのZは同一であってもよく、異なっていてもよく、aは0~3の整数を表し、bは2以上の整数を表し、cは1以上の整数を表す。] Formula (β1) E 1 a AlZ 3-a
Formula (β2) {-Al(E 2 )-O-} b
Formula (β3) E 3 {-Al(E 3 )-O-} c AlE 3 2
[In formulas (β1) to (β3), E 1 , E 2 and E 3 each independently represent a hydrocarbon group having 1 to 8 carbon atoms, all E 1 , all E 2 and all E 3 may be the same or different, Z represents hydrogen or halogen, all Z may be the same or different, a represents an integer of 0 to 3 , b represents an integer of 2 or more, and c represents an integer of 1 or more. ]
式(β1)の具体例としては、トリメチルアルミニウム、トリエチルアルミニウム、トリプロピルアルミニウム、トリイソブチルアルミニウム、トリヘキシルアルミニウム等のトリアルキルアルミニウム;ジメチルアルミニウムクロライド、ジエチルアルミニウムクロライド、ジプロピルアルミニウムクロライド、ジイソブチルアルミニウムクロライド、ジヘキシルアルミニウムクロライド等のジアルキルアルミニウムクロライド;メチルアルミニウムジクロライド、エチルアルミニウムジクロライド、プロピルアルミニウムジクロライド、イソブチルアルミニウムジクロライド、ヘキシルアルミニウムジクロライド等のアルキルアルミニウムジクロライド;ジメチルアルミニウムハイドライド、ジエチルアルミニウムハイドライド、ジプロピルアルミニウムハイドライド、ジイソブチルアルミニウムハイドライド、ジヘキシルアルミニウムハイドライド等のジアルキルアルミニウムハイドライドなどが挙げられる。これらの中でも、好ましくはトリアルキルアルミニウムが挙げられ、より好ましくはトリエチルアルミニウム又はトリイソブチルアルミニウムが挙げられる。
Specific examples of formula (β1) include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride; Dialkylaluminum chlorides such as dihexylaluminum chloride; Alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride; dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride , dialkylaluminum hydride such as dihexylaluminum hydride. Among these, trialkylaluminum is preferred, and triethylaluminum or triisobutylaluminum is more preferred.
式(β2)、式(β3)における、E2、E3の具体例としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、n-ペンチル基、ネオペンチル基等のアルキル基が挙げられる。これらの中でも、好ましくはメチル基又はイソブチル基が挙げられる。bは2以上の整数であり、好ましくは2~40の整数である。cは1以上の整数であり、好ましくは1~40の整数である。
Specific examples of E 2 and E 3 in formula (β2) and formula (β3) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group and neopentyl. and alkyl groups such as Among these, a methyl group or an isobutyl group is preferred. b is an integer of 2 or more, preferably an integer of 2-40. c is an integer of 1 or more, preferably an integer of 1-40.
上記のアルミノキサンは各種の方法で作られる。その方法については特に限定されず、公知の方法に準じて作ればよい。例えば、トリアルキルアルミニウム、例えば、トリメチルアルミニウム等を適当な有機溶剤、例えば、ベンゼン、脂肪族炭化水素などに溶かした溶液を水と接触させて作る方法、トリアルキルアルミニウム、例えば、トリメチルアルミニウム等を、結晶水を含んでいる金属塩、例えば、硫酸銅水和物等に接触させて作る方法が例示できる。
The above aluminoxanes are made by various methods. The method is not particularly limited, and it may be produced according to a known method. For example, a method in which a solution of a trialkylaluminum such as trimethylaluminum dissolved in an appropriate organic solvent such as benzene or an aliphatic hydrocarbon is brought into contact with water; A method of contacting with a metal salt containing water of crystallization, such as copper sulfate hydrate, can be exemplified.
ホウ素化合物(γ)としては、式(γ1)、式(γ2)又は式(γ3)で表されるホウ素化合物のいずれかを用いることができる。
As the boron compound (γ), any one of the boron compounds represented by formula (γ1), formula (γ2), or formula (γ3) can be used.
式(γ1)において、Bは3価の原子価状態のホウ素原子を表し、Q1~Q3は、互いに独立に、ハロゲン原子、炭素数1~20の炭化水素基、炭素数1~20のハロゲン化炭化水素基、炭素数1~20の置換シリル基、炭素数1~20のアルコキシ基又は炭素数2~20の2置換アミノ基を表し、それらは同一であってもよく、異なっていてもよい。Q1~Q3は、互いに独立に、好ましくはハロゲン原子、炭素数1~20の炭化水素基、又は、炭素数1~20のハロゲン化炭化水素基である。
In formula (γ1), B represents a boron atom in a trivalent state, Q 1 to Q 3 each independently represent a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, represents a halogenated hydrocarbon group, a substituted silyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a disubstituted amino group having 2 to 20 carbon atoms, which may be the same or different; good too. Q 1 to Q 3 are each independently preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.
式(γ1)で表されるホウ素化合物の具体例としては、トリス(ペンタフルオロフェニル)ボラン、トリス(2,3,5,6-テトラフルオロフェニル)ボラン、トリス(2,3,4,5-テトラフルオロフェニル)ボラン、トリス(3,4,5-トリフルオロフェニル)ボラン、トリス(2,3,4-トリフルオロフェニル)ボラン、フェニルビス(ペンタフルオロフェニル)ボラン等が挙げられ、好ましくはトリス(ペンタフルオロフェニル)ボランが挙げられる。
Specific examples of the boron compound represented by formula (γ1) include tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5- tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane, phenylbis(pentafluorophenyl)borane and the like, preferably tris (Pentafluorophenyl)borane can be mentioned.
式(γ2)において、Bは3価の原子価状態のホウ素原子を表し、Q1~Q4は上記の式(γ1)におけるQ1~Q3と同様である。また、J+は無機又は有機のカチオンを表す。
In formula (γ2), B represents a trivalent boron atom, and Q 1 to Q 4 are the same as Q 1 to Q 3 in formula (γ1) above. Also, J + represents an inorganic or organic cation.
J+における無機のカチオンとしては、フェロセニウムカチオン、アルキル置換フェロセニウムカチオン、銀陽イオン等が挙げられる。
J+における有機のカチオンとしては、トリフェニルメチルカチオン等が挙げられる。
(BQ1Q2Q3Q4)-としては、テトラキス(ペンタフルオロフェニル)ボレートアニオン、テトラキス(2,3,5,6-テトラフルオロフェニル)ボレートアニオン、テトラキス(2,3,4,5-テトラフルオロフェニル)ボレートアニオン、テトラキス(3,4,5-トリフルオロフェニル)ボレートアニオン、テトラキス(2,2,4-トリフルオロフェニル)ボレートアニオン、フェニルビス(ペンタフルオロフェニル)ボレートアニオン、テトラキス(3,5-ビストリフルオロメチルフェニル)ボレートアニオン等が挙げられる。 Inorganic cations in J + include ferrocenium cations, alkyl-substituted ferrocenium cations, silver cations, and the like.
Examples of organic cations for J + include triphenylmethyl cations.
(BQ 1 Q 2 Q 3 Q 4 ) - includes tetrakis(pentafluorophenyl)borate anion, tetrakis(2,3,5,6-tetrafluorophenyl)borate anion, tetrakis(2,3,4,5- tetrafluorophenyl)borate anion, tetrakis(3,4,5-trifluorophenyl)borate anion, tetrakis(2,2,4-trifluorophenyl)borate anion, phenylbis(pentafluorophenyl)borate anion, tetrakis(3 ,5-bistrifluoromethylphenyl)borate anion and the like.
J+における有機のカチオンとしては、トリフェニルメチルカチオン等が挙げられる。
(BQ1Q2Q3Q4)-としては、テトラキス(ペンタフルオロフェニル)ボレートアニオン、テトラキス(2,3,5,6-テトラフルオロフェニル)ボレートアニオン、テトラキス(2,3,4,5-テトラフルオロフェニル)ボレートアニオン、テトラキス(3,4,5-トリフルオロフェニル)ボレートアニオン、テトラキス(2,2,4-トリフルオロフェニル)ボレートアニオン、フェニルビス(ペンタフルオロフェニル)ボレートアニオン、テトラキス(3,5-ビストリフルオロメチルフェニル)ボレートアニオン等が挙げられる。 Inorganic cations in J + include ferrocenium cations, alkyl-substituted ferrocenium cations, silver cations, and the like.
Examples of organic cations for J + include triphenylmethyl cations.
(BQ 1 Q 2 Q 3 Q 4 ) - includes tetrakis(pentafluorophenyl)borate anion, tetrakis(2,3,5,6-tetrafluorophenyl)borate anion, tetrakis(2,3,4,5- tetrafluorophenyl)borate anion, tetrakis(3,4,5-trifluorophenyl)borate anion, tetrakis(2,2,4-trifluorophenyl)borate anion, phenylbis(pentafluorophenyl)borate anion, tetrakis(3 ,5-bistrifluoromethylphenyl)borate anion and the like.
これらの具体的な組合せとしては、フェロセニウムテトラキス(ペンタフルオロフェニル)ボレート、1,1’-ジメチルフェロセニウムテトラキス(ペンタフルオロフェニル)ボレート、銀テトラキス(ペンタフルオロフェニル)ボレート、トリフェニルメチルテトラキス(ペンタフルオロフェニル)ボレート、トリフェニルメチルテトラキス(3,5-ビストリフルオロメチルフェニル)ボレート等が挙げられ、好ましくはトリフェニルメチルテトラキス(ペンタフルオロフェニル)ボレートが挙げられる。
Specific combinations thereof include ferroceniumtetrakis(pentafluorophenyl)borate, 1,1'-dimethylferroceniumtetrakis(pentafluorophenyl)borate, silver tetrakis(pentafluorophenyl)borate, triphenylmethyltetrakis (Pentafluorophenyl)borate, triphenylmethyltetrakis(3,5-bistrifluoromethylphenyl)borate and the like, preferably triphenylmethyltetrakis(pentafluorophenyl)borate.
式(γ3)において、Bは3価の原子価状態のホウ素を表し、Q1~Q4は上記の式(γ1)におけるQ1~Q3と同様である。また、Lは中性ルイス塩基を表し、(L-H)+はブレンステッド酸を表す。
In formula (γ3), B represents trivalent boron, and Q 1 to Q 4 are the same as Q 1 to Q 3 in formula (γ1) above. Also, L represents a neutral Lewis base and (LH) + represents a Bronsted acid.
式(γ3)において、ブレンステッド酸である(L-H)+としては、トリアルキル置換アンモニウムカチオン、N,N-ジアルキルアニリニウムカチオン、ジアルキルアンモニウムカチオン、トリアリ-ルホスホニウムカチオン等が挙げられる。
(BQ1Q2Q3Q4)-としては、前述と同様のものが挙げられる。 In formula (γ3), Bronsted acid (LH) + includes trialkyl-substituted ammonium cations, N,N-dialkylanilinium cations, dialkylammonium cations, and triarylphosphonium cations.
(BQ 1 Q 2 Q 3 Q 4 ) - includes the same groups as those described above.
(BQ1Q2Q3Q4)-としては、前述と同様のものが挙げられる。 In formula (γ3), Bronsted acid (LH) + includes trialkyl-substituted ammonium cations, N,N-dialkylanilinium cations, dialkylammonium cations, and triarylphosphonium cations.
(BQ 1 Q 2 Q 3 Q 4 ) - includes the same groups as those described above.
これらの具体的な組合せとしては、トリエチルアンモニウムテトラキス(ペンタフルオロフェニル)ボレート、トリプロピルアンモニウムテトラキス(ペンタフルオロフェニル)ボレート、トリ(n-ブチル)アンモニウムテトラキス(ペンタフルオロフェニル)ボレート、トリ(n-ブチル)アンモニウムテトラキス(3,5-ビストリフルオロメチルフェニル)ボレート、N,N-ジメチルアニリニウムテトラキス(ペンタフルオロフェニル)ボレート、N,N-ジエチルアニリニウムテトラキス(ペンタフルオロフェニル)ボレート、N,N-2,4,6-ペンタメチルアニリニウムテトラキス(ペンタフルオロフェニル)ボレート、N,N-ジメチルアニリニウムテトラキス(3,5-ビストリフルオロメチルフェニル)ボレート、ジ-iso-プロピルアンモニウムテトラキス(ペンタフルオロフェニル)ボレート、ジシクロヘキシルアンモニウムテトラキス(ペンタフルオロフェニル)ボレート、トリフェニルホスホニウムテトラキス(ペンタフルオロフェニル)ボレート、トリ(メチルフェニル)ホスホニウムテトラキス(ペンタフルオロフェニル)ボレート、トリ(ジメチルフェニル)ホスホニウムテトラキス(ペンタフルオロフェニル)ボレート等が挙げられる。これらの中でも、トリ(n-ブチル)アンモニウムテトラキス(ペンタフルオロフェニル)ボレート、又は、N,N-ジメチルアニリニウムテトラキス(ペンタフルオロフェニル)ボレートであることが好ましい。
Specific combinations thereof include triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl) ) ammonium tetrakis(3,5-bistrifluoromethylphenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-2 , 4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bistrifluoromethylphenyl)borate, di-iso-propylammonium tetrakis(pentafluorophenyl)borate , dicyclohexylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, tri(methylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, tri(dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, etc. are mentioned. Among these, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate are preferred.
助触媒としては、有機アルミニウム化合物(β)及び化合物(γ)を併用することが好ましい。
As the co-catalyst, it is preferable to use the organoaluminum compound (β) and the compound (γ) together.
式(IV)で表される遷移金属錯体(α)、有機アルミニウム化合物(β)及び/又は化合物(γ)は、重合時に任意の順序で投入し使用することができるが、それらの任意の化合物の組合せを予め接触させて得られた反応物を用いてもよい。
The transition metal complex (α), organoaluminum compound (β) and/or compound (γ) represented by formula (IV) can be used in any order during polymerization, but any of these compounds You may use the reactant obtained by contacting previously the combination of.
助触媒/遷移金属錯体(α)のモル比は、好ましくは0.01~10,000、より好ましくは0.5~2,000である。触媒成分を溶液状態で使用する場合、遷移金属錯体(α)の濃度は、好ましくは0.0001~5mmol/L、より好ましくは0.001~1mmol/Lである。触媒成分の使用量は、使用される全モノマーの合計量に対して、好ましくは0.00001~1mol%、より好ましくは0.0001~0.1mol%である。
The molar ratio of cocatalyst/transition metal complex (α) is preferably 0.01 to 10,000, more preferably 0.5 to 2,000. When the catalyst component is used in solution, the concentration of the transition metal complex (α) is preferably 0.0001-5 mmol/L, more preferably 0.001-1 mmol/L. The amount of catalyst component used is preferably 0.00001 to 1 mol %, more preferably 0.0001 to 0.1 mol %, based on the total amount of all monomers used.
本発明の一実施形態に係るポリマー(B)の重合法としては、特に限定されず、例えば、バッチ式又は連続式の気相重合法、塊状重合法、適当な溶媒を使用しての溶液重合法あるいはスラリー重合法等、任意の方法を採用することができる。
The polymerization method of the polymer (B) according to one embodiment of the present invention is not particularly limited. Any method such as a method or a slurry polymerization method can be adopted.
溶媒を使用する場合、触媒を失活させないという条件の各種の溶媒が使用可能であり、このような溶媒の例としては、ベンゼン、トルエン、ペンタン、ヘキサン、ヘプタン、シクロヘキサン等の炭化水素系溶媒;ジクロロメタン、二塩化エチレン等のハロゲン化炭化水素系溶媒などが挙げられる。
When using a solvent, various solvents can be used provided that they do not deactivate the catalyst. Examples of such solvents include hydrocarbon solvents such as benzene, toluene, pentane, hexane, heptane, and cyclohexane; Examples thereof include halogenated hydrocarbon solvents such as dichloromethane and ethylene dichloride.
また、溶媒を使用する場合、重合中の系内のエチレン分圧は、例えば50~400kPa、好ましくは50~300kPaであり、水素分圧は好ましくは0~100kPaである。なお、系内にエチレン及び水素を投入する場合、水素分圧での加圧を実施した後、エチレン分圧での加圧を実施することが好ましい。また、式(I)で表されるシクロオレフィンの溶液を重合反応槽に投入した後、さらにトルエンを投入してもよい。
When using a solvent, the ethylene partial pressure in the system during polymerization is, for example, 50 to 400 kPa, preferably 50 to 300 kPa, and the hydrogen partial pressure is preferably 0 to 100 kPa. When ethylene and hydrogen are introduced into the system, it is preferable to pressurize with the partial pressure of hydrogen and then pressurize with the partial pressure of ethylene. Alternatively, toluene may be added after charging the solution of the cycloolefin represented by the formula (I) into the polymerization reactor.
重合温度は、好ましくは50℃以上、より好ましくは50~150℃、さらに好ましくは50~100℃である。なお、重合体の分子量を調節するために水素等の連鎖移動剤を添加することもできる。
The polymerization temperature is preferably 50°C or higher, more preferably 50 to 150°C, still more preferably 50 to 100°C. A chain transfer agent such as hydrogen may be added to adjust the molecular weight of the polymer.
<ポリイミド系樹脂(A)>
ポリイミド系樹脂(A)とは、イミド基を含む繰返し構造単位を含有する樹脂(以下、ポリイミド樹脂ということがある)、及びイミド基及びアミド基の両方を含む繰り返し構造単位を含有する樹脂(以下、ポリアミドイミド樹脂ということがある)、並びにイミド化によりポリイミド系樹脂を製造する前の前駆体を含む意味である。該ポリイミド樹脂を製造する前の前駆体はポリアミック酸である。なお、本明細書において、「繰り返し構造単位」を「構成単位」ということがある。また、「由来の構成単位」を単に「単位」ということがあり、例えば化合物由来の構成単位を化合物単位などということがある。 <Polyimide resin (A)>
The polyimide resin (A) is a resin containing a repeating structural unit containing an imide group (hereinafter sometimes referred to as a polyimide resin), and a resin containing a repeating structural unit containing both an imide group and an amide group (hereinafter (sometimes referred to as polyamide-imide resin), as well as precursors prior to production of polyimide-based resins by imidization. The precursor prior to manufacturing the polyimide resin is polyamic acid. In addition, in this specification, a "repeating structural unit" may be called a "structural unit." In addition, a "constituent unit derived from" may be simply referred to as a "unit", and for example, a constituent unit derived from a compound may be referred to as a compound unit.
ポリイミド系樹脂(A)とは、イミド基を含む繰返し構造単位を含有する樹脂(以下、ポリイミド樹脂ということがある)、及びイミド基及びアミド基の両方を含む繰り返し構造単位を含有する樹脂(以下、ポリアミドイミド樹脂ということがある)、並びにイミド化によりポリイミド系樹脂を製造する前の前駆体を含む意味である。該ポリイミド樹脂を製造する前の前駆体はポリアミック酸である。なお、本明細書において、「繰り返し構造単位」を「構成単位」ということがある。また、「由来の構成単位」を単に「単位」ということがあり、例えば化合物由来の構成単位を化合物単位などということがある。 <Polyimide resin (A)>
The polyimide resin (A) is a resin containing a repeating structural unit containing an imide group (hereinafter sometimes referred to as a polyimide resin), and a resin containing a repeating structural unit containing both an imide group and an amide group (hereinafter (sometimes referred to as polyamide-imide resin), as well as precursors prior to production of polyimide-based resins by imidization. The precursor prior to manufacturing the polyimide resin is polyamic acid. In addition, in this specification, a "repeating structural unit" may be called a "structural unit." In addition, a "constituent unit derived from" may be simply referred to as a "unit", and for example, a constituent unit derived from a compound may be referred to as a compound unit.
本発明の好適な実施形態において、ポリイミド系樹脂(A)は、式(1):
[式(1)中、Xは2価の有機基を表し、Yは4価の有機基を表し、*は結合手を表す]
で表される構成単位を有することが好ましい。このようなポリイミド系樹脂であると、組成物及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。 In a preferred embodiment of the present invention, the polyimide resin (A) has the formula (1):
[In formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, and * represents a bond]
It is preferable to have a structural unit represented by With such a polyimide resin, the dispersibility of the polymer (B) in the composition and film can be easily improved, and the hygroscopic resistance and heat resistance of the obtained film can be easily improved.
で表される構成単位を有することが好ましい。このようなポリイミド系樹脂であると、組成物及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。 In a preferred embodiment of the present invention, the polyimide resin (A) has the formula (1):
It is preferable to have a structural unit represented by With such a polyimide resin, the dispersibility of the polymer (B) in the composition and film can be easily improved, and the hygroscopic resistance and heat resistance of the obtained film can be easily improved.
式(1)中のXは、互いに独立に2価の有機基を表し、好ましくは炭素数2~100の2価の有機基を表す。2価の有機基としては、例えば2価の芳香族基、2価の脂肪族基等が挙げられ、2価の脂肪族基としては、例えば2価の非環式脂肪族基又は2価の環式脂肪族基が挙げられる。これらの中でも、ポリマー(B)の凝集体の形成を抑制しやすく、ポリマー(B)の分散性を高めやすい観点、並びに、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい観点から、2価の環式脂肪族基及び2価の芳香族基が好ましく、2価の芳香族基がより好ましい。2価の有機基は、有機基中の水素原子がハロゲン原子、炭化水素基、アルコキシ基又はハロゲン化炭化水素基で置換されていてもよく、その場合、これらの基の炭素数は好ましくは1~8である。なお、本明細書において、2価の芳香族基は芳香族基を有する2価の有機基であり、その構造の一部に脂肪族基又はその他の置換基を含んでいてもよい。また、2価の脂肪族基は脂肪族基を有する2価の有機基であり、その構造の一部にその他の置換基を含んでいてもよいが、芳香族基は含まない。
Each X in formula (1) independently represents a divalent organic group, preferably a divalent organic group having 2 to 100 carbon atoms. Examples of the divalent organic group include a divalent aromatic group and a divalent aliphatic group. Examples of the divalent aliphatic group include a divalent acyclic aliphatic group and a divalent Cycloaliphatic groups are included. Among these, from the viewpoint of easily suppressing the formation of aggregates of the polymer (B) and easily increasing the dispersibility of the polymer (B), and from the viewpoint of easily improving the hygroscopic resistance and heat resistance of the resulting film, 2 Preferred are divalent cycloaliphatic groups and divalent aromatic groups, more preferred are divalent aromatic groups. In the divalent organic group, hydrogen atoms in the organic group may be substituted with a halogen atom, a hydrocarbon group, an alkoxy group or a halogenated hydrocarbon group, in which case the number of carbon atoms in these groups is preferably 1 ~8. In this specification, a divalent aromatic group is a divalent organic group having an aromatic group, and may contain an aliphatic group or other substituents in part of its structure. A divalent aliphatic group is a divalent organic group having an aliphatic group, and may contain other substituents in part of its structure, but does not contain an aromatic group.
本発明の一実施形態において、ポリイミド系樹脂(A)は、複数種のXを含み得、複数種のXは、互いに同一であってもよく、異なっていてもよい。式(1)中のXとしては、例えば式(2)~式(8)で表される基(構造);式(5)~式(8)で表される基中の水素原子がメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、フルオロ基、クロロ基又はトリフルオロメチル基で置換された基などが挙げられる。
In one embodiment of the present invention, the polyimide resin (A) may contain multiple types of X, and the multiple types of X may be the same or different. X in formula (1) includes, for example, groups (structures) represented by formulas (2) to (8); hydrogen atoms in groups represented by formulas (5) to (8) are methyl groups. , ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, fluoro group, chloro group or trifluoromethyl group.
式(4)中、環Aは炭素数3~8のシクロアルカンを表し、Rdは炭素数1~20のアルキル基を表し、rは0以上であって(環Aの炭素数-2)以下の整数を表し、S1及びS2は、互いに独立に、0~20の整数を表し、*は結合手を表す。]
In formula (4), ring A represents a cycloalkane having 3 to 8 carbon atoms, R d represents an alkyl group having 1 to 20 carbon atoms, r is 0 or more (the number of carbon atoms in ring A is -2) The following integers are represented, S1 and S2 independently represent integers from 0 to 20, and * represents a bond. ]
式(1)中のXの他の例としては、例えば、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、プロピレン基、1,2-ブタンジイル基、1,3-ブタンジイル基、1,12-ドデカンジイル基、2-メチル-1,2-プロパンジイル基、2-メチル-1,3-プロパンジイル基等の直鎖状又は分岐鎖状アルキレン基などの2価の非環式脂肪族基が挙げられる。2価の非環式脂肪族基中の水素原子は、ハロゲン原子で置換されていてもよく、炭素原子はヘテロ原子、例えば酸素原子、窒素原子等で置換されていてもよい。
Other examples of X in formula (1) include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, propylene group, 1,2-butanediyl group and 1,3-butanediyl group. , 1,12-dodecanediyl group, 2-methyl-1,2-propanediyl group, 2-methyl-1,3-propanediyl group and other linear or branched alkylene groups such as divalent acyclic Aliphatic groups are included. Hydrogen atoms in the divalent acyclic aliphatic group may be substituted with halogen atoms, and carbon atoms may be substituted with heteroatoms such as oxygen atoms, nitrogen atoms, and the like.
これらの中でも、ポリマー(B)の凝集体の形成を抑制しやすく、ポリマー(B)の分散性を高めやすい観点、並びに、得られるフィルムの高い耐吸湿性及び耐熱性を達成しやすい観点から、本発明におけるポリイミド系樹脂(A)は、式(1)中のXとして、式(2)で表される構造及び/又は式(3)で表される構造を含むことが好ましく、式(2)で表される構造を含むことがより好ましい。
Among these, from the viewpoint of easily suppressing the formation of aggregates of the polymer (B) and easily increasing the dispersibility of the polymer (B), and from the viewpoint of easily achieving high moisture absorption resistance and heat resistance of the obtained film, The polyimide resin (A) in the present invention preferably contains a structure represented by formula (2) and/or a structure represented by formula (3) as X in formula (1), and formula (2 ) is more preferred.
式(2)及び式(3)において、各ベンゼン環又はシクロヘキサン環の結合手は、-W-を基準に、それぞれ、オルト位、メタ位又はパラ位、もしくはα位、β位又はγ位のいずれに結合していてもよく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい観点から、好ましくはメタ位又はパラ位、もしくはβ位又はγ位、より好ましくはパラ位、もしくはγ位に結合することができる。Ra及びRbは、互いに独立に、ハロゲン原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、又は炭素数6~12のアリール基を表す。炭素数1~6のアルキル基としては、例えばメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、2-メチル-ブチル基、3-メチルブチル基、2-エチル-プロピル基、n-ヘキシル基等が挙げられる。炭素数1~6のアルコキシ基としては、例えばメトキシ基、エトキシ基、プロピルオキシ基、イソプロピルオキシ基、ブトキシ基、イソブトキシ基、tert-ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基及びシクロヘキシルオキシ基等が挙げられる。炭素数6~12のアリール基としては、例えばフェニル基、トリル基、キシリル基、ナフチル基及びビフェニル基等が挙げられる。Ra及びRbに含まれる水素原子は、互いに独立に、ハロゲン原子で置換されていてもよく、該ハロゲン原子としては、例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。これらの中でも、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい観点から、Ra及びRbは、互いに独立に、炭素数1~6のアルキル基又は炭素数1~6のフッ化アルキル基であることが好ましく、炭素数1~3のアルキル基又は炭素数1~3のフッ化アルキル基であることがより好ましく、メチル基又はトリフルオロメチル基であることがさらに好ましい。
In formulas (2) and (3), the bonds of each benzene ring or cyclohexane ring are ortho-, meta- or para-positions, or α-, β- or γ-positions relative to -W-. It may be bonded to any position, and from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the resulting film, it is preferably at the meta-position or para-position, or at the β-position or at the γ-position, more preferably at the para-position or at the γ-position. can be bound to R a and R b each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2 -methyl-butyl group, 3-methylbutyl group, 2-ethyl-propyl group, n-hexyl group and the like. Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy and cyclohexyloxy groups. mentioned. Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, tolyl group, xylyl group, naphthyl group and biphenyl group. Hydrogen atoms contained in R a and R b may be independently substituted with halogen atoms, and examples of the halogen atoms include fluorine, chlorine, bromine and iodine atoms. Among these, R a and R b are each independently an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group having 1 to 6 carbon atoms, from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the resulting film. group, more preferably an alkyl group having 1 to 3 carbon atoms or a fluorinated alkyl group having 1 to 3 carbon atoms, further preferably a methyl group or a trifluoromethyl group.
式(2)及び式(3)において、t及びuは、互いに独立に、0~4の整数であり、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい観点から、好ましくは0~2の整数、より好ましくは0又は1である。
In formulas (2) and (3), t and u are independently integers of 0 to 4, and from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the resulting film, preferably 0 to 2. , more preferably 0 or 1.
式(2)及び式(3)において、Wは、互いに独立に、単結合、-O-、-CH2-、-CH2-CH2-、-CH(CH3)-、-C(CH3)2-、-C(CF3)2-、-COO-、-OOC-、-SO2-、-S-、-CO-又は-N(Rc)-を表し、得られるフィルムの耐吸湿性、耐熱性及び機械的特性、特に屈曲耐性を向上しやすい観点から、好ましくは単結合、-O-、-CH2-、-C(CH3)2-、-C(CF3)2-、-COO-、-OOC-又は-CO-を表し、より好ましくは単結合、-O-、-CH2-、-C(CH3)2-又は-C(CF3)2-を表す。Rcは水素原子、ハロゲン原子で置換されていてもよい炭素数1~12の一価の炭化水素基を表す。炭素数1~12の1価の炭化水素基としては、例えばメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、2-メチル-ブチル基、3-メチルブチル基、2-エチル-プロピル基、n-ヘキシル、n-ヘプチル基、n-オクチル基、tert-オクチル基、n-ノニル基及びn-デシル基等が挙げられ、これらはハロゲン原子で置換されていてもよい。ハロゲン原子としては、上記と同様のものが挙げられる。
In formulas (2) and (3), W is independently a single bond, —O—, —CH 2 —, —CH 2 —CH 2 —, —CH(CH 3 )—, —C(CH 3 ) represents 2 -, -C(CF 3 ) 2 -, -COO-, -OOC-, -SO 2 -, -S-, -CO- or -N(R c )-, and Single bonds, —O—, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 are preferred from the viewpoint of easily improving hygroscopicity, heat resistance and mechanical properties, especially bending resistance. represents -, -COO-, -OOC- or -CO-, more preferably represents a single bond, -O-, -CH 2 -, -C(CH 3 ) 2 - or -C(CF 3 ) 2 - . R c represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Examples of monovalent hydrocarbon groups having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n- pentyl group, 2-methyl-butyl group, 3-methylbutyl group, 2-ethyl-propyl group, n-hexyl group, n-heptyl group, n-octyl group, tert-octyl group, n-nonyl group and n-decyl group etc., which may be substituted with a halogen atom. Halogen atoms include those mentioned above.
式(2)及び式(3)において、nは、0~4の整数であり、組成物及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい観点から、好ましくは0~3の整数、より好ましくは1又は2である。nが2以上の場合、複数のW、Ra、及びtは互いに同一であってもよく、異なっていてもよく、-W-を基準とした各ベンゼン環の結合手の位置も同一であってもよく、異なっていてもよい。
In formulas (2) and (3), n is an integer of 0 to 4, which facilitates increasing the dispersibility of the polymer (B) in the composition and film, and improves the moisture absorption resistance and heat resistance of the resulting film. It is preferably an integer of 0 to 3, more preferably 1 or 2, from the viewpoint of easy improvement. When n is 2 or more, a plurality of W, R a , and t may be the same or different, and the position of the bond of each benzene ring relative to -W- is also the same. may be different.
本発明におけるポリイミド系樹脂(A)が、式(1)中のXとして、式(2)で表される構造と式(3)で表される構造の両方を含む場合、式(2)におけるW、n、Ra、Rb、t及びuは、互いに独立に、式(3)におけるW、n、Ra、Rb、t及びuと同一であってもよく、異なっていてもよい。
When the polyimide resin (A) in the present invention contains both the structure represented by the formula (2) and the structure represented by the formula (3) as X in the formula (1), in the formula (2) W, n, R a , R b , t and u may be independently the same as or different from W, n, R a , R b , t and u in formula (3) .
式(4)において、環Aは炭素数3~8のシクロアルカンを表す。シクロアルカンとしては、例えばシクロプロパン、シクロブタン、シクロペンタン、シクロヘキサン、シクロヘプタン、シクロオクタンが挙げられ、好ましくは炭素数4~6のシクロアルカンが挙げられる。環Aにおいて、各結合手は、互いに隣接していてもよいし、隣接していなくてもよい。例えば、環Aがシクロヘキサンである場合、2つの結合手はα位、β位又はγ位の位置関係にあってもよく、好ましくはβ位又はγ位の位置関係にあってもよい。
In formula (4), ring A represents a cycloalkane having 3 to 8 carbon atoms. Cycloalkanes include, for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and cyclooctane, preferably cycloalkanes having 4 to 6 carbon atoms. In ring A, each bond may or may not be adjacent to each other. For example, when ring A is cyclohexane, the two bonds may have a positional relationship of α-position, β-position or γ-position, preferably β-position or γ-position.
式(4)中のRdは炭素数1~20のアルキル基を表す。炭素数1~20のアルキル基としては、R7~R18における炭素数1~20の炭化水素基として上記に例示のものが挙げられ、好ましくは炭素数1~10のアルキル基を表す。式(4)中のrは0以上であって(環Aの炭素数-2)以下の整数を表す。rは0以上であり、好ましくは4以下である。式(4)中のS1及びS2は、互いに独立に、0~20の整数を表す。S1及びS2は、互いに独立に、好ましくは0以上、より好ましくは2以上であり、好ましくは15以下である。
R d in formula (4) represents an alkyl group having 1 to 20 carbon atoms. Examples of the alkyl group having 1 to 20 carbon atoms include those exemplified above as the hydrocarbon group having 1 to 20 carbon atoms in R 7 to R 18 , preferably an alkyl group having 1 to 10 carbon atoms. r in formula (4) represents an integer of 0 or more and (the number of carbon atoms in ring A - 2) or less. r is 0 or more, preferably 4 or less. S1 and S2 in formula (4) each independently represent an integer of 0 to 20. S1 and S2 are each independently preferably 0 or more, more preferably 2 or more, and preferably 15 or less.
式(2)~式(4)で表される構造の具体例としては、式(4’)及び式(9)~式(30)で表される構造が挙げられる。なお、これらの式中、*は結合手を表す。
Specific examples of structures represented by formulas (2) to (4) include structures represented by formula (4') and formulas (9) to (30). In these formulas, * represents a bond.
本発明の好適な実施形態において、式(1)中のXとして、式(2)及び/又は式(3)で表される構造を含む場合、式(1)中のXが式(2)及び/又は式(3)で表される構成単位の割合は、式(1)で表される構成単位の総モル量に対して、好ましくは30モル%以上、より好ましくは50モル%以上、さらに好ましくは70モル%以上、特に好ましくは90モル%以上であり、好ましくは100モル%以下である。式(1)中のXが式(2)及び/又は式(3)で表される構成単位の割合が上記の範囲であると、ポリマー(B)の凝集体の形成を抑制しやすく、ポリマー(B)の分散性を高めやすい。また、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。式(1)中のYが式(2)及び/又は式(3)で表される構成単位の割合は、例えば1H-NMRを用いて測定することができ、又は原料の仕込み比から算出することもできる。
In a preferred embodiment of the present invention, when X in formula (1) includes a structure represented by formula (2) and/or formula (3), X in formula (1) is represented by formula (2) and/or the proportion of the structural unit represented by formula (3) is preferably 30 mol% or more, more preferably 50 mol% or more, relative to the total molar amount of the structural units represented by formula (1), It is more preferably 70 mol % or more, particularly preferably 90 mol % or more, and preferably 100 mol % or less. When the proportion of structural units represented by formula (2) and/or formula (3) for X in formula (1) is within the above range, the formation of aggregates of the polymer (B) is easily suppressed, and the polymer It is easy to improve the dispersibility of (B). In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. The proportion of structural units in which Y in formula (1) is represented by formula (2) and/or formula (3) can be measured using, for example, 1 H-NMR, or calculated from the feed ratio of raw materials. You can also
式(1)において、Yは、互いに独立に4価の有機基を表し、好ましくは炭素数4~40の4価の有機基を表し、より好ましくは環状構造を有する炭素数4~40の4価の有機基を表す。環状構造としては、脂環、芳香環、ヘテロ環構造が挙げられる。前記有機基は、有機基中の水素原子がハロゲン原子、炭化水素基、アルコキシ基又はハロゲン化炭化水素基で置換されていてもよく、その場合、これらの基の炭素数は好ましくは1~8である。本発明におけるポリイミド系樹脂(A)は、複数種のYを含み得、複数種のYは、互いに同一であってもよく、異なっていてもよい。Yとしては、式(31)~式(38)で表される基(構造);式(34)~式(38)で表される基中の水素原子がメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、フルオロ基、クロロ基又はトリフルオロメチル基で置換された基;4価の炭素数1~8の鎖式炭化水素基などが挙げられる。
In formula (1), Y independently represents a tetravalent organic group, preferably a tetravalent organic group having 4 to 40 carbon atoms, more preferably a tetravalent organic group having 4 to 40 carbon atoms and having a cyclic structure. represents a valent organic group. Cyclic structures include alicyclic, aromatic and heterocyclic structures. A hydrogen atom in the organic group may be substituted with a halogen atom, a hydrocarbon group, an alkoxy group, or a halogenated hydrocarbon group. In this case, the number of carbon atoms in these groups is preferably 1 to 8. is. The polyimide resin (A) in the present invention may contain multiple types of Y, and the multiple types of Y may be the same or different. Y is a group (structure) represented by formulas (31) to (38); hydrogen atoms in the groups represented by formulas (34) to (38) are methyl group, ethyl group, n-propyl a group substituted with a group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, fluoro group, chloro group or trifluoromethyl group; tetravalent C1-8 chain formula A hydrocarbon group etc. are mentioned.
V1及びV2は、互いに独立に、単結合、-O-、-CH2-、-CH2-CH2-、-CH(CH3)-、-C(CH3)2-、-C(CF3)2-、-COO-、-OOC-、-SO2-、-S-、-CO-、-N(Rj)-、式(a)又は式(b)
を表し、Rjは、水素原子、又はハロゲン原子で置換されていてもよい炭素数1~12の一価の炭化水素基を表し、e及びdは、互いに独立に、0~3の整数を表し(但し、e+dは0ではない)、fは1~3の整数を表し、g及びhは、互いに独立に、0~4の整数を表し、*は結合手を表す]
V 1 and V 2 are each independently a single bond, —O—, —CH 2 —, —CH 2 —CH 2 —, —CH(CH 3 )—, —C(CH 3 ) 2 —, —C (CF 3 ) 2 -, -COO-, -OOC-, -SO 2 -, -S-, -CO-, -N(R j )-, formula (a) or formula (b)
represents, R j represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom, e and d are each independently an integer of 0 to 3 (where e + d is not 0), f represents an integer of 1 to 3, g and h independently represent an integer of 0 to 4, * represents a bond]
これらの中でも、組成物及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい観点から、本発明におけるポリイミド系樹脂は、式(1)中のYとして、式(31)で表される構造、式(32)で表される構造又は式(33)で表される構造からなる群から選択される少なくとも1つの構造を含むことが好ましく、式(31)で表される構造を含むことがより好ましい。
Among these, from the viewpoint of easily improving the dispersibility of the polymer (B) in the composition and film and easily improving the hygroscopic resistance and heat resistance of the resulting film, the polyimide resin in the present invention has the formula (1) Y in the above preferably contains at least one structure selected from the group consisting of a structure represented by formula (31), a structure represented by formula (32), or a structure represented by formula (33) , more preferably a structure represented by formula (31).
式(31)~式(33)において、R19~R26は、互いに独立に、水素原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基又は炭素数6~12のアリール基を表す。炭素数1~6のアルキル基、炭素数1~6のアルコキシ基及び炭素数6~12のアリール基としてはそれぞれ、式(2)及び式(3)における炭素数1~6のアルキル基、炭素数1~6のアルコキシ基及び炭素数6~12のアリール基として上記に例示のものが挙げられる。R19~R26に含まれる水素原子は、互いに独立に、ハロゲン原子で置換されていてもよく、ハロゲン原子としては上記に例示のものが挙げられる。これらの中でも、組成物及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい観点から、R19~R26は、互いに独立に、水素原子又は炭素数1~6のアルキル基が好ましく、水素原子又は炭素数1~3のアルキル基がより好ましく、水素原子がさらに好ましい。
In formulas (31) to (33), R 19 to R 26 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. represents a group. The alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms and the aryl group having 6 to 12 carbon atoms are respectively the alkyl group having 1 to 6 carbon atoms and the carbon The alkoxy groups having 1 to 6 carbon atoms and the aryl groups having 6 to 12 carbon atoms are exemplified above. The hydrogen atoms contained in R 19 to R 26 may be independently substituted with halogen atoms, and the halogen atoms include those exemplified above. Among these, from the viewpoint of easily increasing the dispersibility of the polymer (B) in the composition and film and easily improving the moisture absorption resistance and heat resistance of the resulting film, R 19 to R 26 are each independently hydrogen. An atom or an alkyl group having 1 to 6 carbon atoms is preferred, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is more preferred, and a hydrogen atom is even more preferred.
式(31)において、V1及びV2は、互いに独立に、単結合、-O-、-CH2-、-CH2-CH2-、-CH(CH3)-、-C(CH3)2-、-C(CF3)2-、-COO-、-OOC-、-SO2-、-S-、-CO-、-N(Rj)-、式(a)又は式(b)を表し、組成物及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい観点から、好ましくは単結合、-O-、-CH2-、-C(CH3)2-、-C(CF3)2-、-COO-、-OOC-又は-CO-を表し、より好ましくは単結合、-COO-、-O-、-C(CH3)2-又は-C(CF3)2-を表す。Rjは水素原子、ハロゲン原子で置換されていてもよい炭素数1~12の一価の炭化水素基を表す。炭素数1~12の一価の炭化水素基としては、上記に例示のものが挙げられる。
In formula (31), V 1 and V 2 are each independently a single bond, —O—, —CH 2 —, —CH 2 —CH 2 —, —CH(CH 3 )—, —C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -COO-, -OOC-, -SO 2 -, -S-, -CO-, -N(R j )-, formula (a) or formula (b ), preferably a single bond, —O—, —CH 2 from the viewpoint of easily increasing the dispersibility of the polymer (B) in the composition and film and easily improving the moisture absorption resistance and heat resistance of the resulting film. represents -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -COO-, -OOC- or -CO-, more preferably a single bond, -COO-, -O-, -C represents (CH 3 ) 2 - or -C(CF 3 ) 2 -; R j represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include those exemplified above.
式(31)において、e及びdは、互いに独立に、0~3の整数を表し、組成物及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい観点から、好ましくは0又は1であり、より好ましくはe+d=1であってもよく、e及びdは好ましくは3であってもよい。なお、式(31)中のeが0のときは、式(31)は-V1-を有していない(2つのベンゼン環は-V1-で結合していない)ことを示し、dが0のときは、式(31)は-V2-を有していない(2つのベンゼン環は-V2-で結合していない)ことを示す。
In formula (31), e and d independently represent an integer of 0 to 3, which facilitates increasing the dispersibility of the polymer (B) in the composition and film, and the resulting film's hygroscopic resistance and heat resistance is preferably 0 or 1, more preferably e+d=1, and e and d are preferably 3. Note that when e in formula (31) is 0, it indicates that formula (31) does not have -V 1 - (two benzene rings are not bonded at -V 1 -), and d is 0, it indicates that formula (31) does not have -V 2 - (the two benzene rings are not linked at -V 2 -).
式(32)において、fは1~3の整数を表し、組成物及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい観点から、好ましくは1又は2、より好ましくは1である。なお、fが2のときは、ナフタレン環にR23及びR24が結合した構造を示し、fが3のときは、アントラセン環にR23及びR24が結合した構造を示す。
In formula (32), f represents an integer of 1 to 3, and from the viewpoint of easily improving the dispersibility of the polymer (B) in the composition and film and improving the hygroscopic resistance and heat resistance of the resulting film, Preferably 1 or 2, more preferably 1. When f is 2, a structure in which R 23 and R 24 are bonded to a naphthalene ring is shown, and when f is 3, a structure in which R 23 and R 24 are bonded to an anthracene ring is shown.
式(33)において、g及びhは、互いに独立に、0~4の整数を表し、組成物及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい観点から、好ましくは0~2の整数であり、より好ましくは0又は1であり、さらに好ましくはg+h=0~2の整数である。
In formula (33), g and h independently represent an integer of 0 to 4, which facilitates increasing the dispersibility of the polymer (B) in the composition and film, and the resulting film's hygroscopic resistance and heat resistance is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably g + h = an integer of 0 to 2.
式(a)において、R27~R30は、互いに独立に、水素原子又は炭素数1~6のアルキル基を表す。炭素数1~6のアルキル基としては、式(2)及び(3)における炭素数1~6のアルキル基として上記に例示のものが挙げられる。これらの中でも、組成物及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい観点から、R27~R30は、互いに独立に、水素原子又は炭素数1~3のアルキル基がより好ましく、水素原子又はメチル基がさらに好ましく、水素原子がさらにより好ましい。
In formula (a), R 27 to R 30 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include those exemplified above as the alkyl group having 1 to 6 carbon atoms in the formulas (2) and (3). Among these, from the viewpoint of easily increasing the dispersibility of the polymer (B) in the composition and film and easily improving the moisture absorption resistance and heat resistance of the resulting film, R 27 to R 30 are each independently hydrogen. An atom or an alkyl group having 1 to 3 carbon atoms is more preferred, a hydrogen atom or a methyl group is more preferred, and a hydrogen atom is even more preferred.
式(a)において、Zは単結合、-C(CH3)2-又は-C(CF3)2-を表す。Zがこのような構造であると、組成物及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。iは1~3の整数を表し、組成物及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい観点から、好ましくは1又は2である。iが2以上の場合、複数のZ及びR27~R30は互いに同一であってもよく、異なっていてもよい。
In formula (a), Z represents a single bond, -C(CH 3 ) 2 - or -C(CF 3 ) 2 -. When Z has such a structure, the dispersibility of the polymer (B) in the composition and film can be easily improved, and the hygroscopic resistance and heat resistance of the obtained film can be easily improved. i represents an integer of 1 to 3, preferably 1 or 2 from the viewpoint of easily increasing the dispersibility of the polymer (B) in the composition and film and easily improving the moisture absorption resistance and heat resistance of the resulting film. be. When i is 2 or more, a plurality of Zs and R 27 to R 30 may be the same or different.
式(31)~式(33)で表される構造の具体例としては、式(39)~式(51)で表される構造が挙げられる。なお、これらの式中、*は結合手を表す。
Specific examples of structures represented by formulas (31) to (33) include structures represented by formulas (39) to (51). In these formulas, * represents a bond.
本発明の一実施形態において、式(1)中のYとして、式(31)~式(33)で表される構造からなる群から選択される少なくとも1つを含む場合、式(1)中のYが式(31)~式(33)で表される構造からなる群から選択される少なくとも1つで表される構成単位の割合は、式(1)で表される構成単位の総モル量に対して、好ましくは30モル%以上、より好ましくは50モル%以上、さらに好ましくは70モル%以上、特に好ましくは90モル%以上であり、好ましくは100モル%以下である。式(1)中のYが式(31)~式(33)で表される構造からなる群から選択される少なくとも1つで表される構成単位の割合が上記の範囲であると、組成物中及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。式(1)中のYが式(31)~式(33)で表される構造からなる群から選択される少なくとも1つで表される構成単位の割合は、例えば1H-NMRを用いて測定することができ、又は原料の仕込み比から算出することもできる。
In one embodiment of the present invention, when Y in formula (1) contains at least one selected from the group consisting of structures represented by formulas (31) to (33), in formula (1) Y is represented by at least one selected from the group consisting of structures represented by formulas (31) to (33). The amount is preferably 30 mol % or more, more preferably 50 mol % or more, still more preferably 70 mol % or more, particularly preferably 90 mol % or more, and preferably 100 mol % or less. Y in formula (1) is selected from the group consisting of structures represented by formulas (31) to (33). It is easy to improve the dispersibility of the polymer (B) inside and in the film, and it is easy to improve the moisture absorption resistance and heat resistance of the obtained film. Y in formula ( 1 ) is represented by at least one selected from the group consisting of structures represented by formulas (31) to (33). It can be measured or calculated from the feed ratio of raw materials.
本発明におけるポリイミド系樹脂(A)は、式(1)で表される構成単位の他に、式(52)で表される構成単位、式(53)で表される構成単位、及び式(54)で表される構成単位からなる群から選択される少なくとも1つを含んでいてもよい。
The polyimide resin (A) in the present invention includes, in addition to the structural unit represented by formula (1), the structural unit represented by formula (52), the structural unit represented by formula (53), and the formula ( 54) may contain at least one selected from the group consisting of structural units represented by
Y2は3価の有機基を表し、
X1及びX2は、互いに独立に、2価の有機基を表し、
*は結合手を表す。
式(54)中、G及びXは、互いに独立に、2価の有機基を表し、
*は結合手を表す。]
Y 2 represents a trivalent organic group,
X 1 and X 2 independently represent a divalent organic group,
* represents a bond.
In formula (54), G and X independently represent a divalent organic group,
* represents a bond. ]
本発明の好適な実施形態では、式(52)及び式(53)において、Y1は式(1)におけるYと同義であり、X1及びX2は、式(1)におけるXと同義である。式(53)におけるY2は式(1)におけるYの結合手のいずれか1つが水素原子に置き換わった基であることが好ましい。Y2としては、式(31)~式(38)で表される基(構造)の結合手のいずれか1つが水素原子に置き換わった基;3価の炭素数1~8の鎖式炭化水素基などが挙げられる。本発明の一実施形態において、ポリイミド系樹脂は、複数種のY1又はY2を含み得、複数種のY1又はY2は、互いに同一であってもよく、異なっていてもよい。
In a preferred embodiment of the present invention, in formulas (52) and (53), Y 1 has the same meaning as Y in formula (1), and X 1 and X 2 have the same meaning as X in formula (1). be. Y 2 in formula (53) is preferably a group in which one of the bonds of Y in formula (1) is replaced with a hydrogen atom. Y 2 is a group in which any one of the bonds (structures) of the groups (structures) represented by formulas (31) to (38) is replaced with a hydrogen atom; a trivalent chain hydrocarbon having 1 to 8 carbon atoms and the like. In one embodiment of the present invention, the polyimide resin may contain multiple types of Y 1 or Y 2 , and the multiple types of Y 1 or Y 2 may be the same or different.
式(54)において、Gは、互いに独立に、2価の有機基であり、好ましくは炭素数1~8の炭化水素基又はフッ素置換された炭素数1~8の炭化水素基で置換されていてもよい、炭素数2~100の2価の有機基であり、より好ましくは炭素数1~8の炭化水素基又はフッ素置換された炭素数1~8の炭化水素基で置換されていてもよい、環状構造を有する炭素数2~100の2価の有機基を表す。環状構造としては、脂環、芳香環、ヘテロ環構造が挙げられる。Gの有機基としては、例えば式(31)~式(38)で表される基の結合手のうち、隣接しない2つが水素原子に置き換わった基及び炭素数6以下の2価の鎖式炭化水素基が挙げられ、好ましくは式(39)~式(51)で表される基の結合手のうち、隣接しない2つが水素原子に置き換わった基などが挙げられる。
式(54)中のXは式(1)におけるXと同義であり、ポリイミド系樹脂が式(1)で表される構成単位と式(54)で表される構成単位とを含む場合、各構成単位におけるXは同一であってもよく、異なっていてもよい。本発明の一実施形態において、ポリイミド系樹脂は、複数種のX又はGを含み得、複数種のX又はGは、互いに同一であってもよく、異なっていてもよい。 In formula (54), each G is independently a divalent organic group, preferably substituted with a hydrocarbon group having 1 to 8 carbon atoms or a fluorine-substituted hydrocarbon group having 1 to 8 carbon atoms. may be substituted with a divalent organic group having 2 to 100 carbon atoms, more preferably a hydrocarbon group having 1 to 8 carbon atoms or a fluorine-substituted hydrocarbon group having 1 to 8 carbon atoms. It represents a divalent organic group having 2 to 100 carbon atoms and having a cyclic structure. Cyclic structures include alicyclic, aromatic and heterocyclic structures. Examples of the organic group for G include, for example, a group in which two non-adjacent bonds among the bonds of the groups represented by formulas (31) to (38) are replaced with hydrogen atoms, and a divalent carbon chain having 6 or less carbon atoms. Examples thereof include hydrogen groups, and preferably groups in which two non-adjacent bonds of the groups represented by formulas (39) to (51) are replaced with hydrogen atoms.
X in formula (54) is synonymous with X in formula (1), and when the polyimide resin contains a structural unit represented by formula (1) and a structural unit represented by formula (54), each X in the structural units may be the same or different. In one embodiment of the present invention, the polyimide resin may contain multiple types of X or G, and the multiple types of X or G may be the same or different.
式(54)中のXは式(1)におけるXと同義であり、ポリイミド系樹脂が式(1)で表される構成単位と式(54)で表される構成単位とを含む場合、各構成単位におけるXは同一であってもよく、異なっていてもよい。本発明の一実施形態において、ポリイミド系樹脂は、複数種のX又はGを含み得、複数種のX又はGは、互いに同一であってもよく、異なっていてもよい。 In formula (54), each G is independently a divalent organic group, preferably substituted with a hydrocarbon group having 1 to 8 carbon atoms or a fluorine-substituted hydrocarbon group having 1 to 8 carbon atoms. may be substituted with a divalent organic group having 2 to 100 carbon atoms, more preferably a hydrocarbon group having 1 to 8 carbon atoms or a fluorine-substituted hydrocarbon group having 1 to 8 carbon atoms. It represents a divalent organic group having 2 to 100 carbon atoms and having a cyclic structure. Cyclic structures include alicyclic, aromatic and heterocyclic structures. Examples of the organic group for G include, for example, a group in which two non-adjacent bonds among the bonds of the groups represented by formulas (31) to (38) are replaced with hydrogen atoms, and a divalent carbon chain having 6 or less carbon atoms. Examples thereof include hydrogen groups, and preferably groups in which two non-adjacent bonds of the groups represented by formulas (39) to (51) are replaced with hydrogen atoms.
X in formula (54) is synonymous with X in formula (1), and when the polyimide resin contains a structural unit represented by formula (1) and a structural unit represented by formula (54), each X in the structural units may be the same or different. In one embodiment of the present invention, the polyimide resin may contain multiple types of X or G, and the multiple types of X or G may be the same or different.
本発明の一実施形態において、ポリイミド系樹脂(A)は、式(1)で表される構成単位、並びに、場合により式(52)で表される構成単位、式(53)で表される構成単位及び式(54)で表される構成単位から選択される少なくとも1つの構成単位からなる。また、組成物及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい観点から、上記ポリイミド系樹脂(A)において、式(1)で表される構成単位の割合は、ポリイミド系樹脂に含まれる全構成単位、例えば式(1)で表される構成単位、並びに、場合により式(52)で表される構成単位、式(53)で表される構成単位及び式(54)で表される構成単位から選択される少なくとも1つの構成単位の総モル量に基づいて、好ましくは80モル%以上、より好ましくは90モル%以上、さらに好ましくは95モル%以上である。なお、ポリイミド系樹脂(A)において、式(1)で表される構成単位の割合の上限は100モル%以下である。なお、上記割合は、例えば、1H-NMRを用いて測定することができ、又は原料の仕込み比から算出することもできる。また、本発明におけるポリイミド系樹脂(A)は、組成物及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい観点から、好ましくはポリイミド樹脂である。
In one embodiment of the present invention, the polyimide resin (A) is a structural unit represented by formula (1), and optionally a structural unit represented by formula (52), represented by formula (53) It consists of at least one structural unit selected from structural units and structural units represented by formula (54). In addition, from the viewpoint of easily improving the dispersibility of the polymer (B) in the composition and the film and easily improving the hygroscopic resistance and heat resistance of the resulting film, the polyimide resin (A) has the formula (1) The ratio of the structural units represented by all the structural units contained in the polyimide resin, for example, the structural unit represented by formula (1), and optionally the structural unit represented by formula (52), the formula (53) Based on the total molar amount of at least one structural unit selected from structural units represented by and structural units represented by formula (54), preferably 80 mol% or more, more preferably 90 mol% or more, and further Preferably, it is 95 mol % or more. In addition, in the polyimide-based resin (A), the upper limit of the proportion of the structural unit represented by formula (1) is 100 mol % or less. The above ratio can be measured, for example, using 1 H-NMR, or can be calculated from the charging ratio of raw materials. Further, the polyimide resin (A) in the present invention is preferably a polyimide from the viewpoint of easily improving the dispersibility of the polymer (B) in the composition and the film and easily improving the moisture absorption resistance and heat resistance of the resulting film. Resin.
本発明の一実施形態において、本発明におけるポリイミド系樹脂(A)は、例えば上記の含ハロゲン原子置換基等によって導入することができる、ハロゲン原子、好ましくはフッ素原子を含有していてもよい。ポリイミド系樹脂(A)がハロゲン原子、好ましくはフッ素原子を含有する場合、組成物及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすいことに加え、光学特性を向上しやすい。ポリイミド系樹脂(A)にフッ素原子を含有させるために好ましい含フッ素置換基としては、例えばフルオロ基及びトリフルオロメチル基が挙げられる。
In one embodiment of the present invention, the polyimide-based resin (A) in the present invention may contain halogen atoms, preferably fluorine atoms, which can be introduced by, for example, the above halogen-containing atom substituents. When the polyimide resin (A) contains a halogen atom, preferably a fluorine atom, it is easy to increase the dispersibility of the polymer (B) in the composition and the film, and the resulting film tends to be improved in hygroscopic resistance and heat resistance. In addition, it is easy to improve the optical characteristics. Preferred fluorine-containing substituents for allowing the polyimide resin (A) to contain fluorine atoms include, for example, a fluoro group and a trifluoromethyl group.
ポリイミド系樹脂(A)がハロゲン原子を含有する場合、ポリイミド系樹脂(A)におけるハロゲン原子の含有量は、ポリイミド系樹脂(A)の質量を基準として、好ましくは0.1~40質量%、より好ましくは1~35質量%、さらに好ましくは5~30質量%である。ハロゲン原子の含有量が上記の下限以上であると、組成物及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。ハロゲン原子の含有量が上記の上限以下であると、フィルムのCTEを低減でき、また合成がしやすくなる。
When the polyimide resin (A) contains halogen atoms, the content of the halogen atoms in the polyimide resin (A) is preferably 0.1 to 40% by mass, based on the mass of the polyimide resin (A), More preferably 1 to 35 mass %, still more preferably 5 to 30 mass %. When the halogen atom content is at least the above lower limit, the dispersibility of the polymer (B) in the composition and film is likely to be enhanced, and the hygroscopic resistance and heat resistance of the resulting film are likely to be enhanced. When the halogen atom content is equal to or less than the above upper limit, the CTE of the film can be reduced, and synthesis is facilitated.
ポリイミド系樹脂(A)のイミド化率は、好ましくは90%以上、より好ましくは93%以上、さらに好ましくは95%以上であり、通常100%以下である。フィルムの誘電特性、光学特性、耐吸湿性及び耐熱性を向上しやすい観点から、イミド化率が上記の下限以上であることが好ましい。イミド化率は、ポリイミド系樹脂(A)中のテトラカルボン酸化合物に由来する構成単位のモル量の2倍の値に対する、ポリイミド系樹脂(A)中のイミド結合のモル量の割合を示す。なお、ポリイミド系樹脂(A)がトリカルボン酸化合物を含む場合には、ポリイミド系樹脂(A)中のテトラカルボン酸化合物に由来する構成単位のモル量の2倍の値と、トリカルボン酸化合物に由来する構成単位のモル量との合計に対する、ポリイミド系樹脂(A)中のイミド結合のモル量の割合を示す。また、イミド化率は、IR法、NMR法などにより求めることができる。
The imidization rate of the polyimide resin (A) is preferably 90% or more, more preferably 93% or more, still more preferably 95% or more, and usually 100% or less. From the viewpoint of easily improving the dielectric properties, optical properties, moisture absorption resistance, and heat resistance of the film, the imidization rate is preferably at least the above lower limit. The imidization rate indicates the ratio of the molar amount of imide bonds in the polyimide resin (A) to twice the molar amount of the structural units derived from the tetracarboxylic acid compound in the polyimide resin (A). Incidentally, when the polyimide resin (A) contains a tricarboxylic acid compound, a value twice the molar amount of the structural unit derived from the tetracarboxylic acid compound in the polyimide resin (A), and derived from the tricarboxylic acid compound It shows the ratio of the molar amount of the imide bond in the polyimide resin (A) to the total of the molar amount of the constituent units. Also, the imidization rate can be determined by IR method, NMR method, or the like.
本発明におけるポリイミド系樹脂(A)は、上記の通り、ポリイミド系樹脂をイミド化する前の前駆体を包含する。ポリイミド系樹脂(A)がポリアミック酸の場合、ポリアミック酸は式(1’):
[式(1’)中、Y及びXはそれぞれ、式(1)におけるY及びXを表す]
で表される構成単位を含む。 The polyimide resin (A) in the present invention includes a precursor before imidization of the polyimide resin, as described above. When the polyimide resin (A) is a polyamic acid, the polyamic acid has the formula (1′):
[In formula (1′), Y and X respectively represent Y and X in formula (1)]
Including the structural unit represented by.
[式(1’)中、Y及びXはそれぞれ、式(1)におけるY及びXを表す]
で表される構成単位を含む。 The polyimide resin (A) in the present invention includes a precursor before imidization of the polyimide resin, as described above. When the polyimide resin (A) is a polyamic acid, the polyamic acid has the formula (1′):
[In formula (1′), Y and X respectively represent Y and X in formula (1)]
Including the structural unit represented by.
ポリイミド系樹脂(A)のTgは、好ましくは100℃以上、より好ましくは150℃以上、さらに好ましくは200℃以上、さらにより好ましくは220℃、特に好ましくは300℃以上、特により好ましくは350℃以上であり、好ましくは550℃以下である。ポリイミド系樹脂(A)のTgが上記の下限以上であると、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。ポリイミド系樹脂(A)のTgが上記の上限以下であると、機械的特性を高めやすい。ポリイミド系樹脂(A)のTgは、例えば動的粘弾性測定(以下、DMA測定と略すことがある)を行うことで求められ、実施例に記載の方法により測定できる。
Tg of the polyimide resin (A) is preferably 100°C or higher, more preferably 150°C or higher, still more preferably 200°C or higher, still more preferably 220°C, particularly preferably 300°C or higher, and particularly preferably 350°C. above, preferably 550° C. or below. When the Tg of the polyimide resin (A) is at least the above lower limit, it is easy to improve the hygroscopic resistance and heat resistance of the resulting film. When the Tg of the polyimide resin (A) is equal to or less than the above upper limit, the mechanical properties are likely to be improved. The Tg of the polyimide resin (A) can be obtained, for example, by performing dynamic viscoelasticity measurement (hereinafter sometimes abbreviated as DMA measurement), and can be measured by the method described in Examples.
ポリイミド系樹脂(A)のMwは、ポリスチレン換算で、好ましくは50,000以上、より好ましくは100,000以上、より好ましくは150,000以上、さらに好ましくは200,000以上、さらにより好ましくは250,000以上、特に好ましくは300,000以上であり、好ましくは1,000,000以下、より好ましくは800,000以下、さらに好ましくは700,000以下、さらにより好ましくは500,000以下、とりわけ好ましくは450,000以下である。ポリイミド系樹脂(A)のMwが上記の下限以上であると、得られるフィルムの耐吸湿性、耐熱性及び機械的特性を向上しやすい。ポリイミド系樹脂(A)のMwが上記の上限以下であると成形性を高めやすい。なお、ポリイミド系樹脂(A)のMwは、例えばGPC測定を行い、標準ポリスチレン換算によって求めることができ、例えば実施例に記載の方法により求められる。
Mw of the polyimide resin (A) is preferably 50,000 or more, more preferably 100,000 or more, more preferably 150,000 or more, still more preferably 200,000 or more, still more preferably 250 in terms of polystyrene. ,000 or more, particularly preferably 300,000 or more, preferably 1,000,000 or less, more preferably 800,000 or less, even more preferably 700,000 or less, even more preferably 500,000 or less, particularly preferably is less than or equal to 450,000. When the Mw of the polyimide resin (A) is at least the above lower limit, it is easy to improve the hygroscopic resistance, heat resistance and mechanical properties of the resulting film. When the Mw of the polyimide resin (A) is equal to or less than the above upper limit, the moldability is likely to be improved. The Mw of the polyimide resin (A) can be obtained, for example, by GPC measurement and standard polystyrene conversion, for example, by the method described in Examples.
本発明の一実施形態において、本発明の組成物に含まれるポリイミド系樹脂(A)の含有量は、ポリイミド系樹脂(A)とポリマー(B)との合計質量に対して、好ましくは50質量%以上、より好ましくは60質量%以上、さらに好ましくは65質量%以上であり、好ましくは99質量%以下、より好ましくは95質量%以下、さらに好ましくは93質量%以下、さらにより好ましくは90質量%以下、特に好ましくは80質量%以下である。ポリイミド系樹脂(A)の含有量が上記下限以上であると、膜形成が容易となるため、フィルム製造の観点から有利である。ポリイミド系樹脂(A)の含有量が上記上限以下であると、組成物中のポリマー(B)の分散性が向上しやすいため、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the content of the polyimide resin (A) contained in the composition of the present invention is preferably 50 mass with respect to the total mass of the polyimide resin (A) and the polymer (B). % or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 93% by mass or less, and even more preferably 90% by mass % or less, particularly preferably 80 mass % or less. When the content of the polyimide resin (A) is at least the above lower limit, film formation is facilitated, which is advantageous from the viewpoint of film production. When the content of the polyimide-based resin (A) is equal to or less than the above upper limit, the dispersibility of the polymer (B) in the composition is likely to be improved, and thus the hygroscopic resistance and heat resistance of the resulting film are likely to be improved.
<ポリイミド系樹脂(A)の製造方法>
ポリイミド系樹脂(A)の製造方法は特に限定されないが、例えば、ジアミン化合物とテトラカルボン酸化合物とを反応させてポリアミック酸を得る工程、及び該ポリアミック酸をイミド化する工程を含む方法により製造できる。また、ポリイミド系樹脂(A)がポリアミック酸である場合、ポリアミック酸を得る工程を実施すればよい。なお、テトラカルボン酸化合物の他に、ジカルボン酸化合物、トリカルボン酸化合物を反応させてもよい。 <Method for producing polyimide resin (A)>
The method for producing the polyimide resin (A) is not particularly limited, but for example, it can be produced by a method including a step of reacting a diamine compound and a tetracarboxylic acid compound to obtain a polyamic acid, and a step of imidizing the polyamic acid. . Moreover, when the polyimide-based resin (A) is polyamic acid, a step of obtaining polyamic acid may be carried out. In addition to the tetracarboxylic acid compound, a dicarboxylic acid compound and a tricarboxylic acid compound may be reacted.
ポリイミド系樹脂(A)の製造方法は特に限定されないが、例えば、ジアミン化合物とテトラカルボン酸化合物とを反応させてポリアミック酸を得る工程、及び該ポリアミック酸をイミド化する工程を含む方法により製造できる。また、ポリイミド系樹脂(A)がポリアミック酸である場合、ポリアミック酸を得る工程を実施すればよい。なお、テトラカルボン酸化合物の他に、ジカルボン酸化合物、トリカルボン酸化合物を反応させてもよい。 <Method for producing polyimide resin (A)>
The method for producing the polyimide resin (A) is not particularly limited, but for example, it can be produced by a method including a step of reacting a diamine compound and a tetracarboxylic acid compound to obtain a polyamic acid, and a step of imidizing the polyamic acid. . Moreover, when the polyimide-based resin (A) is polyamic acid, a step of obtaining polyamic acid may be carried out. In addition to the tetracarboxylic acid compound, a dicarboxylic acid compound and a tricarboxylic acid compound may be reacted.
ポリイミド系樹脂(A)の合成に用いられるテトラカルボン酸化合物としては、芳香族テトラカルボン酸二無水物等の芳香族テトラカルボン酸化合物;及び脂肪族テトラカルボン酸二無水物等の脂肪族テトラカルボン酸化合物等が挙げられる。テトラカルボン酸化合物は、単独で用いてもよいし、2種以上を組合せて用いてもよい。テトラカルボン酸化合物は、二無水物の他、酸クロリド化合物等のテトラカルボン酸化合物類縁体であってもよい。
The tetracarboxylic acid compound used in the synthesis of the polyimide resin (A) includes aromatic tetracarboxylic acid compounds such as aromatic tetracarboxylic dianhydride; and aliphatic tetracarboxylic acid compounds such as aliphatic tetracarboxylic dianhydride. acid compounds and the like. A tetracarboxylic acid compound may be used independently and may be used in combination of 2 or more type. The tetracarboxylic acid compound may be a dianhydride or a tetracarboxylic acid compound analog such as an acid chloride compound.
テトラカルボン酸化合物の具体例としては、無水ピロメリット酸(以下、PMDAと略すことがある)、4,4’-(4,4’-イソプロピリデンジフェノキシ)ジフタル酸無水物(以下、BPADAと略すことがある)、1,4,5,8-ナフタレンテトラカルボン酸二無水物、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(以下、BPDAと略すことがある)、4,4’-(ヘキサフルオロイソプロピリデン)ジフタル酸二無水物(以下、6FDAと略すことがある)、4,4’-オキシジフタル酸無水物(以下、ODPAと略すことがある)、2,2’,3,3’-、2,3,3’,4’-又は3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物、2,3’,3,4’-ビフェニルテトラカルボン酸二無水物、2,2’,3,3’-ビフェニルテトラカルボン酸二無水物、2,3’,3,4’-ジフェニルエーテルテトラカルボン酸二無水物、ビス(2,3-ジカルボキシフェニル)エーテル二無水物、3,3”,4,4”-、2,3,3”,4”-又は2,2”,3,3”-p-テルフェニルテトラカルボン酸二無水物、2,2-ビス(2,3-又は3,4-ジカルボキシフェニル)-プロパン二無水物、ビス(2,3-又は3.4-ジカルボキシフェニル)メタン二無水物、1,1-ビス(2,3-又は3,4-ジカルボキシフェニル)エタン二無水物、1,2,7,8-、1,2,6,7-又は1,2,9,10-フェナンスレン-テトラカルボン酸二無水物、2,2-ビス(3,4-ジカルボキシフェニル)テトラフルオロプロパン二無水物、1,2,4,5-シクロヘキサンテトラカルボン酸二無水物(以下、HPMDAと略すことがある)、2,3,5,6-シクロヘキサンテトラカルボン酸二無水物、2,3,6,7-ナフタレンテトラカルボン酸二無水物、1,2,5,6-ナフタレンテトラカルボン酸二無水物、シクロペンタン-1,2,3,4-テトラカルボン酸二無水物、4,4’-ビス(2,3-ジカルボキシフェノキシ)ジフェニルメタン二無水物、1,2,3,4-シクロブタンテトラカルボン酸二無水物(以下、CBDAと略すことがある)、ノルボルナン-2-スピロ-α’-スピロ-2”-ノルボルナン-5,5’,6,6’-テトラカルボン酸無水物、p-フェニレンビス(トリメリテート無水物)(TAHQと略すことがある)、3,3’,4,4’-ジフェニルスルホンテトラカルボン酸二無水物、2,3,6,7-アントラセンテトラカルボン酸二無水物、4,8-ジメチル-1,2,3,5,6,7-ヘキサヒドロナフタレン-1,2,5,6-テトラカルボン酸二無水物、2,6-又は2,7-ジクロロナフタレン-1,4,5,8-テトラカルボン酸二無水物、2,3,6,7-(又は1,4,5,8-)テトラクロロナフタレン-1,4,5,8-(又は2,3,6,7-)テトラカルボン酸二無水物、2,3,8,9-、3,4,9,10-、4,5,10,11-又は5,6,11,12-ペリレン-テトラカルボン酸二無水物、ピラジン-2,3,5,6-テトラカルボン酸二無水物、ピロリジン-2,3,4,5-テトラカルボン酸二無水物、チオフェン-2,3,4,5-テトラカルボン酸二無水物、ビス(2,3-又は3,4-ジカルボキシフェニル)スルホン二無水物などが挙げられる。これらの中でも、得られるフィルムの耐吸湿性、耐熱性、誘電特性及び機械的特性を向上しやすい観点から、PMDA、BPDA、6FDA、BPADA、ODPA、HPMDA、CBDA、TAHQが好ましい。これらのテトラカルボン酸化合物は単独又は二種以上組合せて使用できる。
Specific examples of tetracarboxylic acid compounds include pyromellitic anhydride (hereinafter sometimes abbreviated as PMDA), 4,4'-(4,4'-isopropylidenediphenoxy) diphthalic anhydride (hereinafter abbreviated as BPADA). 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride (hereinafter sometimes abbreviated as BPDA), 4,4'-(Hexafluoroisopropylidene)diphthalic dianhydride (hereinafter sometimes abbreviated as 6FDA), 4,4'-oxydiphthalic anhydride (hereinafter sometimes abbreviated as ODPA), 2,2 ',3,3'-, 2,3,3',4'- or 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic acid acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3',3,4'-diphenylethertetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl ) ether dianhydride, 3,3″,4,4″-, 2,3,3″,4″- or 2,2″,3,3″-p-terphenyltetracarboxylic dianhydride, 2 , 2-bis (2,3- or 3,4-dicarboxyphenyl)-propane dianhydride, bis (2,3- or 3.4-dicarboxyphenyl) methane dianhydride, 1,1-bis ( 2,3- or 3,4-dicarboxyphenyl)ethane dianhydride, 1,2,7,8-, 1,2,6,7- or 1,2,9,10-phenanthrene-tetracarboxylic acid di anhydride, 2,2-bis(3,4-dicarboxyphenyl)tetrafluoropropane dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride (hereinafter sometimes abbreviated as HPMDA), 2,3,5,6-cyclohexanetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, cyclopentane -1,2,3,4-tetracarboxylic dianhydride, 4,4′-bis(2,3-dicarboxyphenoxy)diphenylmethane dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter sometimes abbreviated as CBDA), norbornane-2-spiro-α'-spiro-2″-norbornane-5,5′,6,6′-tetracarboxylic anhydride, p-phenylene bis(trimellitate anhydride) (sometimes abbreviated as TAHQ), 3,3′,4 ,4'-diphenylsulfonetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene -1,2,5,6-tetracarboxylic dianhydride, 2,6- or 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7 - (or 1,4,5,8-) tetrachloronaphthalene-1,4,5,8- (or 2,3,6,7-) tetracarboxylic dianhydride, 2,3,8,9- , 3,4,9,10-, 4,5,10,11- or 5,6,11,12-perylene-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic acid dianhydride, anhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, bis(2,3- or 3,4-dicarboxy phenyl) sulfone dianhydride and the like. Among these, PMDA, BPDA, 6FDA, BPADA, ODPA, HPMDA, CBDA, and TAHQ are preferred from the viewpoint of easily improving the moisture absorption resistance, heat resistance, dielectric properties, and mechanical properties of the resulting film. These tetracarboxylic acid compounds can be used alone or in combination of two or more.
ポリイミド系樹脂(A)の合成に用いられるジアミン化合物としては、例えば、脂肪族ジアミン、芳香族ジアミン及びこれらの混合物が挙げられる。なお、本実施形態において「芳香族ジアミン」とは、芳香環を有するジアミンを表し、その構造の一部に脂肪族基又はその他の置換基を含んでいてもよい。この芳香環は単環でも縮合環でもよく、ベンゼン環、ナフタレン環、アントラセン環及びフルオレン環等が例示されるが、これらに限定されるわけではない。これらの中でも、好ましくはベンゼン環である。また「脂肪族ジアミン」とは、脂肪族基を有するジアミンを表し、その構造の一部にその他の置換基を含んでいてもよいが、芳香環は有しない。
Diamine compounds used for synthesizing the polyimide resin (A) include, for example, aliphatic diamines, aromatic diamines, and mixtures thereof. In addition, in this embodiment, the “aromatic diamine” represents a diamine having an aromatic ring, and may contain an aliphatic group or other substituents in a part of its structure. This aromatic ring may be a single ring or a condensed ring, and examples include, but are not limited to, benzene ring, naphthalene ring, anthracene ring, and fluorene ring. Among these, a benzene ring is preferred. The term "aliphatic diamine" refers to a diamine having an aliphatic group, which may contain other substituents in part of its structure, but does not have an aromatic ring.
ジアミン化合物の具体例としては、1,4-ジアミノシクロヘキサン、4,4’-ジアミノ-2,2’-ジメチルビフェニル(以下、m-TBと記載することがある)、4,4’-ジアミノ-3,3’-ジメチルビフェニル、2,2’-ビス(トリフルオロメチル)-4,4’-ジアミノジフェニル(以下、TFMBと記載することがある)、4,4’-ジアミノジフェニルエーテル、1,3-ビス(3-アミノフェノキシ)ベンゼン(以下、1,3-APBと略すことがある)、1,4-ビス(4-アミノフェノキシ)ベンゼン(以下、1,4-APBと略すことがある)、1,3-ビス(4-アミノフェノキシ)ベンゼン、2,2’-ビス[4-(4-アミノフェノキシ)フェニル]プロパン(以下、BAPPと記載することがある)、2,2’-ジメチル-4,4’-ジアミノビフェニル、3,3’-ジヒドロキシ-4,4’-ジアミノビフェニル、2,2-ビス-[4-(3-アミノフェノキシ)フェニル]プロパン、ビス[4-(4-アミノフェノキシ)]ビフェニル、ビス[4-(3-アミノフェノキシ)ビフェニル、ビス[1-(4-アミノフェノキシ)]ビフェニル、ビス[1-(3-アミノフェノキシ)]ビフェニル、ビス[4-(4-アミノフェノキシ)フェニル]メタン、ビス[4-(3-アミノフェノキシ)フェニル]メタン、ビス[4-(4-アミノフェノキシ)フェニル]エーテル、ビス[4-(3-アミノフェノキシ)フェニル]エーテル、ビス[4-(4-アミノフェノキシ)]ベンゾフェノン、ビス[4-(3-アミノフェノキシ)]ベンゾフェノン、2,2-ビス-[4-(4-アミノフェノキシ)フェニル]ヘキサフルオロプロパン、2,2-ビス-[4-(3-アミノフェノキシ)フェニル]ヘキサフルオロプロパン、4,4’-メチレンジ-o-トルイジン、4,4’-メチレンジ-2,6-キシリジン、4,4’-メチレン-2,6-ジエチルアニリン、4,4’-メチレンジアニリン、3,3’-メチレンジアニリン、4,4’-ジアミノジフェニルプロパン、3,3’-ジアミノジフェニルプロパン、4,4’-ジアミノジフェニルエタン、3,3’-ジアミノジフェニルエタン、4,4’-ジアミノジフェニルメタン、3,3’-ジアミノジフェニルメタン、3,3-ジアミノジフェニルエーテル、3,4’-ジアミノジフェニルエーテル、ベンジジン、3,3’-ジアミノビフェニル、3,3’-ジメトキシベンジジン、4,4”-ジアミノ-p-テルフェニル、3,3”-ジアミノ-p-テルフェニル、m-フェニレンジアミン、p-フェニレンジアミン(p-PDAと略すことがある)、レゾルシノール-ビス(3-アミノフェニル)エーテル、4,4’-[1,4-フェニレンビス(1-メチルエチリデン)]ビスアニリン、4,4’-[1,3-フェニレンビス(1-メチルエチリデン)]ビスアニリン、ビス(p-アミノシクロヘキシル)メタン、ビス(p-β-アミノ-tert-ブチルフェニル)エーテル、ビス(p-β-メチル-δ-アミノペンチル)ベンゼン、p-ビス(2-メチル-4-アミノペンチル)ベンゼン、p-ビス(1,1-ジメチル-5-アミノペンチル)ベンゼン、1,5-ジアミノナフタレン、2,6-ジアミノナフタレン、2,4-ビス(β-アミノ-tert-ブチル)トルエン、2,4-ジアミノトルエン、m-キシレン-2,5-ジアミン、p-キシレン-2,5-ジアミン、m-キシリレンジアミン、p-キシリレンジアミン、ピペラジン、4,4’-ジアミノ-2,2’-ビス(トリフルオロメチル)ビシクロヘキサン、4,4’-ジアミノジシクロヘキシルメタン、4,4”-ジアミノ-p-ターフェニル、ビス(4-アミノフェニル)テレフタレート、1,4-ビス(4-アミノフェノキシ)-2,5-ジ-tert-ブチルベンゼン、4,4’-(1,3-フェニレンジイソプロピリデン)ビスアニリン、1,4-ビス[2-(4-アミノフェニル)-2-プロピル]ベンゼン、2,4-ジアミノ-3,5-ジエチルトルエン、2,6-ジアミノ-3,5-ジエチルトルエン、4,4’-ビス(3-アミノフェノキシ)ビフェニル、4,4’-(ヘキサフルオロプロピリデン)ジアニリン、1,2-ジアミノエタン、1,3-ジアミノプロパン、1,4-ジアミノブタン、1,5-ジアミノペンタン、1,6-ジアミノヘキンサン、1,2-ジアミノプロパン、1,2-ジアミノブタン、1,3-ジアミノブタン、2-メチル-1,2-ジアミノプロパン、2-メチル-1,3-ジアミノプロパン、1,3-ビス(アミノメチル)シクロヘキサン、1,4-ビス(アミノメチル)シクロヘキサン、ノルボルナンジアミン、2’-メトキシ-4,4’-ジアミノベンズアニリド、4,4’-ジアミノベンズアニリド、ビス[4-(4-アミノフェノキシ)フェニル]スルホン、ビス[4-(3-アミノフェノキシ)フェニル]スルホン、9,9-ビス[4-(4-アミノフェノキシ)フェニル]フルオレン、9,9-ビス[4-(3-アミノフェノキシ)フェニル]フルオレン、4,4’-ジアミノジフェニルスルフィド、3,3’-ジアミノジフェニルスルフィド、4,4’-ジアミノジフェニルスルホン、3,3’-ジアミノジフェニルスルホン、2,5-ジアミノ-1,3,4-オキサジアゾール、ビス[4,4’-(4-アミノフェノキシ)]ベンズアニリド、ビス[4,4’-(3-アミノフェノキシ)]ベンズアニリド、2,6-ジアミノピリジン、2,5-ジアミノピリジンなどが挙げられる。これらの中でも、ポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい観点から、1,4-ジアミノシクロヘキサン、4,4’-ジアミノジフェニルエーテル、TFMB、4,4’-メチレンジアニリン、3,3’-メチレンジアニリン、p-PDA、BAPP、4,4’-ジアミノジシクロヘキシルメタン、4,4’-ジアミノ-2,2’-ビス(トリフルオロメチル)ビシクロヘキサン、m-TB、4,4”-ジアミノ-p-ターフェニル、ビス(4-アミノフェニル)テレフタレート、1,4-ビス(4-アミノフェノキシ)-2,5-ジ-tert-ブチルベンゼン、1,3-APB、1,4-APB、レゾルシノール-ビス(3-アミノフェニル)エーテル、4,4’-(1,3-フェニレンジイソプロピリデン)ビスアニリン、1,4-ビス[2-(4-アミノフェニル)-2-プロピル]ベンゼン、2,4-ジアミノ-3,5-ジエチルトルエン、2,6-ジアミノ-3,5-ジエチルトルエン、4,4’-ビス(3-アミノフェノキシ)ビフェニル、4,4’-(ヘキサフルオロプロピリデン)ジアニリンなどが好ましい。ジアミン化合物は単独又は二種以上組合せて使用できる。
Specific examples of diamine compounds include 1,4-diaminocyclohexane, 4,4'-diamino-2,2'-dimethylbiphenyl (hereinafter sometimes referred to as m-TB), 4,4'-diamino- 3,3'-dimethylbiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl (hereinafter sometimes referred to as TFMB), 4,4'-diaminodiphenyl ether, 1,3 -bis(3-aminophenoxy)benzene (hereinafter sometimes abbreviated as 1,3-APB), 1,4-bis(4-aminophenoxy)benzene (hereinafter sometimes abbreviated as 1,4-APB) , 1,3-bis(4-aminophenoxy)benzene, 2,2′-bis[4-(4-aminophenoxy)phenyl]propane (hereinafter sometimes referred to as BAPP), 2,2′-dimethyl -4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 2,2-bis-[4-(3-aminophenoxy)phenyl]propane, bis[4-(4- aminophenoxy)]biphenyl, bis[4-(3-aminophenoxy)biphenyl, bis[1-(4-aminophenoxy)]biphenyl, bis[1-(3-aminophenoxy)]biphenyl, bis[4-(4 -aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)]benzophenone, bis[4-(3-aminophenoxy)]benzophenone, 2,2-bis-[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2 -bis-[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-2,6-xylidine, 4,4'-methylene-2 ,6-diethylaniline, 4,4'-methylenedianiline, 3,3'-methylenedianiline, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylethane , 3,3′-diaminodiphenylethane, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,3-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, benzidine, 3,3′- Diaminobiphenyl, 3,3′-dimethoxybenzidine, 4,4″-diamino-p-terphenyl, 3,3″-diamino-p-terphenyl, m-phenylenediamine, p-phenylenediamine (abbreviated as p-PDA) ), resorcinol-bis(3-aminophenyl) ether, 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline, 4,4′-[1,3-phenylenebis( 1-methylethylidene)]bisaniline, bis(p-aminocyclohexyl)methane, bis(p-β-amino-tert-butylphenyl)ether, bis(p-β-methyl-δ-aminopentyl)benzene, p-bis (2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-bis(β -amino-tert-butyl)toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, m-xylylenediamine, p-xylylenediamine, piperazine, 4,4′-diamino-2,2′-bis(trifluoromethyl)bicyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4″-diamino-p-terphenyl, bis(4-aminophenyl)terephthalate , 1,4-bis(4-aminophenoxy)-2,5-di-tert-butylbenzene, 4,4′-(1,3-phenylenediisopropylidene)bisaniline, 1,4-bis[2-( 4-aminophenyl)-2-propyl]benzene, 2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene, 4,4'-bis(3-aminophenoxy) Biphenyl, 4,4'-(hexafluoropropylidene)dianiline, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane , 1,2-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 2-methyl-1,2-diaminopropane, 2-methyl-1,3-diaminopropane, 1,3-bis( aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, norbornanediamine, 2'-methoxy-4,4'-diaminobenzanilide, 4,4'-diaminobenzanilide, bis[4- (4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene, 9,9-bis[4- (3-aminophenoxy)phenyl]fluorene, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,5- Diamino-1,3,4-oxadiazole, bis[4,4'-(4-aminophenoxy)]benzanilide, bis[4,4'-(3-aminophenoxy)]benzanilide, 2,6-diaminopyridine , 2,5-diaminopyridine and the like. Among these, 1,4-diaminocyclohexane, 4,4'-diaminodiphenyl ether, TFMB, and 4 are preferred from the viewpoint of easily increasing the dispersibility of the polymer (B) and easily improving the moisture absorption resistance and heat resistance of the resulting film. , 4′-methylenedianiline, 3,3′-methylenedianiline, p-PDA, BAPP, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-2,2′-bis(trifluoromethyl) Bicyclohexane, m-TB, 4,4″-diamino-p-terphenyl, bis(4-aminophenyl)terephthalate, 1,4-bis(4-aminophenoxy)-2,5-di-tert-butylbenzene , 1,3-APB, 1,4-APB, resorcinol-bis(3-aminophenyl)ether, 4,4′-(1,3-phenylenediisopropylidene)bisaniline, 1,4-bis[2-( 4-aminophenyl)-2-propyl]benzene, 2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene, 4,4'-bis(3-aminophenoxy) Preferred are biphenyl, 4,4'-(hexafluoropropylidene)dianiline, etc. The diamine compounds can be used singly or in combination of two or more.
なお、上記ポリイミド系樹脂(A)は、フィルムの各種物性を損なわない範囲で、上記の樹脂合成に用いられるテトラカルボン酸化合物に加えて、他のテトラカルボン酸、ジカルボン酸及びトリカルボン酸並びにそれらの無水物及び誘導体をさらに反応させたものであってもよい。
Incidentally, the polyimide resin (A), in addition to the tetracarboxylic acid compound used in the resin synthesis, other tetracarboxylic acids, dicarboxylic acids and tricarboxylic acids and their Anhydrides and derivatives may be further reacted.
他のテトラカルボン酸としては、上記テトラカルボン酸化合物の無水物の水付加体が挙げられる。
Other tetracarboxylic acids include water adducts of the above tetracarboxylic acid compound anhydrides.
ジカルボン酸化合物としては、芳香族ジカルボン酸、脂肪族ジカルボン酸及びそれらの類縁の酸クロリド化合物、酸無水物等が挙げられ、単独又は2種以上を組合せて用いてもよい。具体例としては、テレフタル酸;イソフタル酸;ナフタレンジカルボン酸;4,4’-ビフェニルジカルボン酸;3,3’-ビフェニルジカルボン酸;炭素数8以下である鎖式炭化水素、のジカルボン酸化合物及び2つの安息香酸が単結合、-O-、-CH2-、-C(CH3)2-、-C(CF3)2-、-SO2-又はフェニレン基で連結された化合物並びに、それらの酸クロリド化合物が挙げられる。
Examples of dicarboxylic acid compounds include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, their analogous acid chloride compounds, acid anhydrides, and the like, which may be used alone or in combination of two or more. Specific examples include terephthalic acid; isophthalic acid; naphthalenedicarboxylic acid; 4,4′-biphenyldicarboxylic acid; 3,3′-biphenyldicarboxylic acid; compounds in which two benzoic acids are linked by a single bond, —O—, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —SO 2 — or a phenylene group, and their acid chloride compounds.
トリカルボン酸化合物としては、芳香族トリカルボン酸、脂肪族トリカルボン酸及びそれらの類縁の酸クロリド化合物、酸無水物等が挙げられ、単独又は2種以上を組合せて用いてもよい。具体例としては、1,2,4-ベンゼントリカルボン酸の無水物;2,3,6-ナフタレントリカルボン酸-2,3-無水物;フタル酸無水物と安息香酸とが単結合、-O-、-CH2-、-C(CH3)2-、-C(CF3)2-、-SO2-又はフェニレン基で連結された化合物が挙げられる。
Examples of tricarboxylic acid compounds include aromatic tricarboxylic acids, aliphatic tricarboxylic acids, their analogous acid chloride compounds, acid anhydrides, and the like, which may be used alone or in combination of two or more. Specific examples include anhydride of 1,2,4-benzenetricarboxylic acid; 2,3,6-naphthalenetricarboxylic acid-2,3-anhydride; a single bond between phthalic anhydride and benzoic acid; , —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —SO 2 — or compounds linked by a phenylene group.
ポリイミド系樹脂(A)の製造において、ジアミン化合物、テトラカルボン酸化合物、ジカルボン酸化合物及びトリカルボン酸化合物の使用量は、所望とする樹脂の各構成単位の比率に応じて適宜選択できる。
本発明の好適な実施形態においては、ジアミン化合物の使用量は、テトラカルボン酸化合物1molに対して、好ましくは0.94mol以上、より好ましくは0.96mol以上、さらに好ましくは0.98mol以上、特に好ましくは0.99mol以上であり、好ましくは1.20mol以下、より好ましくは1.10mol以下、さらに好ましくは1.05mol以下、特に好ましくは1.02mol以下である。テトラカルボン酸化合物に対するジアミン化合物の使用量が上記の範囲であると、組成物及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。 In the production of the polyimide resin (A), the amounts of the diamine compound, the tetracarboxylic acid compound, the dicarboxylic acid compound and the tricarboxylic acid compound to be used can be appropriately selected according to the desired ratio of each structural unit of the resin.
In a preferred embodiment of the present invention, the amount of the diamine compound used is preferably 0.94 mol or more, more preferably 0.96 mol or more, still more preferably 0.98 mol or more, and particularly It is preferably 0.99 mol or more, preferably 1.20 mol or less, more preferably 1.10 mol or less, still more preferably 1.05 mol or less, and particularly preferably 1.02 mol or less. When the amount of the diamine compound used relative to the tetracarboxylic acid compound is within the above range, the dispersibility of the polymer (B) in the composition and the film is easily improved, and the moisture absorption resistance and heat resistance of the resulting film are easily improved.
本発明の好適な実施形態においては、ジアミン化合物の使用量は、テトラカルボン酸化合物1molに対して、好ましくは0.94mol以上、より好ましくは0.96mol以上、さらに好ましくは0.98mol以上、特に好ましくは0.99mol以上であり、好ましくは1.20mol以下、より好ましくは1.10mol以下、さらに好ましくは1.05mol以下、特に好ましくは1.02mol以下である。テトラカルボン酸化合物に対するジアミン化合物の使用量が上記の範囲であると、組成物及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。 In the production of the polyimide resin (A), the amounts of the diamine compound, the tetracarboxylic acid compound, the dicarboxylic acid compound and the tricarboxylic acid compound to be used can be appropriately selected according to the desired ratio of each structural unit of the resin.
In a preferred embodiment of the present invention, the amount of the diamine compound used is preferably 0.94 mol or more, more preferably 0.96 mol or more, still more preferably 0.98 mol or more, and particularly It is preferably 0.99 mol or more, preferably 1.20 mol or less, more preferably 1.10 mol or less, still more preferably 1.05 mol or less, and particularly preferably 1.02 mol or less. When the amount of the diamine compound used relative to the tetracarboxylic acid compound is within the above range, the dispersibility of the polymer (B) in the composition and the film is easily improved, and the moisture absorption resistance and heat resistance of the resulting film are easily improved.
ジアミン化合物とテトラカルボン酸化合物との反応温度は、特に限定されず、例えば5~200℃であってもよく、反応時間も特に限定されず、例えば0.5~72時間程度であってもよい。本発明の好適な実施形態においては、反応温度は、好ましくは5~50℃、より好ましくは10~40℃であり、反応時間は、好ましくは3~24時間である。このような反応温度及び反応時間であると、組成物及びフィルム中のポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
The reaction temperature of the diamine compound and the tetracarboxylic acid compound is not particularly limited, and may be, for example, 5 to 200° C., and the reaction time is also not particularly limited, and may be, for example, about 0.5 to 72 hours. . In a preferred embodiment of the present invention, the reaction temperature is preferably 5-50° C., more preferably 10-40° C., and the reaction time is preferably 3-24 hours. With such a reaction temperature and reaction time, it is easy to improve the dispersibility of the polymer (B) in the composition and the film, and it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
ジアミン化合物とテトラカルボン酸化合物との反応は、溶媒中で行うことが好ましい。溶媒としては、反応に影響を与えない限り特に限定されないが、例えば、水、メタノール、エタノール、エチレングリコール、イソプロピルアルコール、プロピレングリコール、エチレングリコールメチルエーテル、エチレングリコールブチルエーテル、1-メトキシ-2-プロパノール、2-ブトキシエタノール、プロピレングリコールモノメチルエーテル等のアルコール系溶媒;フェノール、クレゾール等のフェノール系溶媒;酢酸エチル、酢酸ブチル、エチレングリコールメチルエーテルアセテート、γ-ブチロラクトン(以下、GBLと記載することがある)、γ-バレロラクトン、プロピレングリコールメチルエーテルアセテート、乳酸エチル等のエステル系溶媒;アセトン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、2-ヘプタノン、メチルイソブチルケトン等のケトン系溶媒;ペンタン、ヘキサン、ヘプタン等の脂肪族炭化水素溶媒;エチルシクロヘキサン等の脂環式炭化水素溶媒;トルエン、キシレン等の芳香族炭化水素溶媒;アセトニトリル等のニトリル系溶媒;テトラヒドロフラン及びジメトキシエタン等のエーテル系溶媒;クロロホルム及びクロロベンゼン等の塩素含有溶媒;N,N-ジメチルアセトアミド(以下、DMAcと記載することがある)、N,N-ジメチルホルムアミド(以下、DMFと記載することがある)等のアミド系溶媒;ジメチルスルホン、ジメチルスルホキシド、スルホラン等の含硫黄系溶媒;エチレンカーボネート、プロピレンカーボネート等のカーボネート系溶媒;N-メチルピロリドン等のピロリドン系溶媒;及びそれらの組合せなどが挙げられる。これらの中でも、溶解性の観点から、フェノール系溶媒、アミド系溶媒、ピロリドン系溶媒を好適に使用できる。
The reaction between the diamine compound and the tetracarboxylic acid compound is preferably carried out in a solvent. The solvent is not particularly limited as long as it does not affect the reaction, but examples include water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, Alcohol solvents such as 2-butoxyethanol and propylene glycol monomethyl ether; Phenolic solvents such as phenol and cresol; Ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone (hereinafter sometimes referred to as GBL) , γ-valerolactone, propylene glycol methyl ether acetate, ethyl lactate and other ester solvents; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone and other ketone solvents; pentane, hexane, heptane and other Aliphatic hydrocarbon solvents; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; Chlorine-containing solvent; amide solvents such as N,N-dimethylacetamide (hereinafter sometimes referred to as DMAc) and N,N-dimethylformamide (hereinafter sometimes referred to as DMF); dimethylsulfone, dimethylsulfoxide , sulfolane; carbonate solvents such as ethylene carbonate and propylene carbonate; pyrrolidone solvents such as N-methylpyrrolidone; and combinations thereof. Among these, phenol-based solvents, amide-based solvents, and pyrrolidone-based solvents can be preferably used from the viewpoint of solubility.
ジアミン化合物とテトラカルボン酸化合物との反応は、必要に応じて、窒素雰囲気、アルゴン雰囲気等の不活性雰囲気又は減圧の条件下において行ってもよく、例えば、窒素雰囲気又はアルゴン雰囲気等の不活性雰囲気下、厳密に制御された脱水溶媒中で撹拌しながら行うことが好ましい。
The reaction between the diamine compound and the tetracarboxylic acid compound may be carried out under an inert atmosphere such as a nitrogen atmosphere or an argon atmosphere or under reduced pressure conditions, for example, an inert atmosphere such as a nitrogen atmosphere or an argon atmosphere. It is preferable to carry out with stirring in a strictly controlled dehydrated solvent.
イミド化工程では、イミド化触媒を用いてイミド化しても、加熱によりイミド化しても、これらを組合せてもよい。イミド化工程で使用するイミド化触媒としては、例えばトリプロピルアミン、ジブチルプロピルアミン、エチルジブチルアミン等の脂肪族アミン;N-エチルピペリジン、N-プロピルピペリジン、N-ブチルピロリジン、N-ブチルピペリジン、及びN-プロピルヘキサヒドロアゼピン等の脂環式アミン(単環式);アザビシクロ[2.2.1]ヘプタン、アザビシクロ[3.2.1]オクタン、アザビシクロ[2.2.2]オクタン、及びアザビシクロ[3.2.2]ノナン等の脂環式アミン(多環式);並びにピリジン、2-メチルピリジン(2-ピコリン)、3-メチルピリジン(3-ピコリン)、4-メチルピリジン(4-ピコリン)、2-エチルピリジン、3-エチルピリジン、4-エチルピリジン、2,4-ジメチルピリジン、2,4,6-トリメチルピリジン、3,4-シクロペンテノピリジン、5,6,7,8-テトラヒドロイソキノリン、及びイソキノリン等の芳香族アミンが挙げられる。また、イミド化反応を促進しやすい観点から、イミド化触媒とともに、酸無水物を用いることが好ましい。酸無水物は、イミド化反応に用いられる慣用の酸無水物等が挙げられ、その具体例としては、無水酢酸、無水プロピオン酸、無水酪酸等の脂肪族酸無水物、フタル酸等の芳香族酸無水物などが挙げられる。加熱によるイミド化工程は、ポリアミック酸が溶解した溶媒中で行ってもよく、後述のようにフィルム化した状態で行ってもよい。
In the imidization step, imidization may be performed using an imidization catalyst, imidization by heating, or a combination thereof. Examples of the imidization catalyst used in the imidization step include aliphatic amines such as tripropylamine, dibutylpropylamine and ethyldibutylamine; N-ethylpiperidine, N-propylpiperidine, N-butylpyrrolidine, N-butylpiperidine, and alicyclic amines (monocyclic) such as N-propylhexahydroazepine; azabicyclo[2.2.1]heptane, azabicyclo[3.2.1]octane, azabicyclo[2.2.2]octane, and Alicyclic amines (polycyclic) such as azabicyclo[3.2.2]nonane; and pyridine, 2-methylpyridine (2-picoline), 3-methylpyridine (3-picoline), 4-methylpyridine (4 -picoline), 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2,4-dimethylpyridine, 2,4,6-trimethylpyridine, 3,4-cyclopentenopyridine, 5,6,7, Aromatic amines such as 8-tetrahydroisoquinoline and isoquinoline are included. Moreover, from the viewpoint of facilitating the imidization reaction, it is preferable to use an acid anhydride together with the imidization catalyst. Acid anhydrides include conventional acid anhydrides used in imidization reactions, and specific examples thereof include aliphatic acid anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride, and aromatic acid anhydrides such as phthalic acid. and acid anhydrides. The imidization step by heating may be performed in a solvent in which the polyamic acid is dissolved, or may be performed in a film state as described later.
本発明の一実施形態では、イミド化する場合、反応温度は、通常20~250℃であり、反応時間は好ましくは0.5~24時間、より好ましくは1~12時間である。
In one embodiment of the present invention, when imidating, the reaction temperature is usually 20 to 250°C, and the reaction time is preferably 0.5 to 24 hours, more preferably 1 to 12 hours.
ポリイミド系樹脂(A)は、慣用の方法、例えば、濾過、濃縮、抽出、晶析、再結晶、カラムクロマトグラフィーなどの分離手段や、これらを組合せた分離手段により分離精製して単離してもよく、好ましい態様では、樹脂を含む反応液に、多量のメタノール等のアルコールを加え、樹脂を析出させ、濃縮、濾過、乾燥等を行うことにより単離することができる。
The polyimide resin (A) can be separated and purified by a conventional method such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. In a preferred embodiment, the resin can be isolated by adding a large amount of alcohol such as methanol to the reaction solution containing the resin to precipitate the resin, followed by concentration, filtration, drying, and the like.
<組成物>
本発明の組成物は、ポリイミド系樹脂(A)、ポリマー(B)及びフェノール系酸化防止剤を含み、フェノール系酸化防止剤が置換基Pを含み、フェノール系酸化防止剤中の置換基Pを水素原子に置換した構造Sが置換基を有していてもよい芳香環を有する。そのため、耐吸湿性に優れ、フィルムの吸湿による誘電特性の悪化を有効に抑制できる。また、耐熱性にも優れ、フィルムが高温環境下に置かれても、ポリマー(B)の酸化による劣化を有効に抑制できる。したがって、本発明の組成物から形成されるフィルムは、優れた耐吸湿性と優れた耐熱性とを両立できる。これは、上記の通り、特定のフェノール系酸化防止剤が、耐湿性等を低下させ得る製膜時のポリマー(B)の酸化を有効に抑制できるからだと考えられる。また、耐吸湿性等の低下は、表面に付着している付着物(例えば界面活性剤などの分散剤や保護材)の変質によっても生じ得るが、特定のフェノール系酸化防止剤により該付着物の変質も抑制できると考えられる。 <Composition>
The composition of the present invention contains a polyimide resin (A), a polymer (B) and a phenolic antioxidant, the phenolic antioxidant contains a substituent P, and the substituent P in the phenolic antioxidant is The structure S in which the hydrogen atom is substituted has an aromatic ring which may have a substituent. Therefore, it is excellent in moisture absorption resistance, and can effectively suppress deterioration of dielectric properties due to moisture absorption of the film. In addition, it is excellent in heat resistance, and even if the film is placed in a high-temperature environment, deterioration due to oxidation of the polymer (B) can be effectively suppressed. Therefore, the film formed from the composition of the present invention can have both excellent moisture absorption resistance and excellent heat resistance. This is presumably because, as described above, the specific phenolic antioxidant can effectively suppress the oxidation of the polymer (B) during film formation, which can reduce moisture resistance and the like. In addition, deterioration of moisture absorption resistance etc. can also occur due to deterioration of deposits adhering to the surface (for example, dispersants such as surfactants and protective materials). It is thought that the alteration of the
本発明の組成物は、ポリイミド系樹脂(A)、ポリマー(B)及びフェノール系酸化防止剤を含み、フェノール系酸化防止剤が置換基Pを含み、フェノール系酸化防止剤中の置換基Pを水素原子に置換した構造Sが置換基を有していてもよい芳香環を有する。そのため、耐吸湿性に優れ、フィルムの吸湿による誘電特性の悪化を有効に抑制できる。また、耐熱性にも優れ、フィルムが高温環境下に置かれても、ポリマー(B)の酸化による劣化を有効に抑制できる。したがって、本発明の組成物から形成されるフィルムは、優れた耐吸湿性と優れた耐熱性とを両立できる。これは、上記の通り、特定のフェノール系酸化防止剤が、耐湿性等を低下させ得る製膜時のポリマー(B)の酸化を有効に抑制できるからだと考えられる。また、耐吸湿性等の低下は、表面に付着している付着物(例えば界面活性剤などの分散剤や保護材)の変質によっても生じ得るが、特定のフェノール系酸化防止剤により該付着物の変質も抑制できると考えられる。 <Composition>
The composition of the present invention contains a polyimide resin (A), a polymer (B) and a phenolic antioxidant, the phenolic antioxidant contains a substituent P, and the substituent P in the phenolic antioxidant is The structure S in which the hydrogen atom is substituted has an aromatic ring which may have a substituent. Therefore, it is excellent in moisture absorption resistance, and can effectively suppress deterioration of dielectric properties due to moisture absorption of the film. In addition, it is excellent in heat resistance, and even if the film is placed in a high-temperature environment, deterioration due to oxidation of the polymer (B) can be effectively suppressed. Therefore, the film formed from the composition of the present invention can have both excellent moisture absorption resistance and excellent heat resistance. This is presumably because, as described above, the specific phenolic antioxidant can effectively suppress the oxidation of the polymer (B) during film formation, which can reduce moisture resistance and the like. In addition, deterioration of moisture absorption resistance etc. can also occur due to deterioration of deposits adhering to the surface (for example, dispersants such as surfactants and protective materials). It is thought that the alteration of the
本発明の一実施形態において、ポリマー(B)とフェノール系酸化防止剤とのHSP値間距離は、好ましくは2.1以上、より好ましくは2.3以上、さらに好ましくは2.5以上、さらにより好ましくは3.0以上、特に好ましくは3.2以上である。前記HSP値間距離が上記下限以上であると、フェノール系酸化防止剤とポリマー(B)との親和性が高すぎず、フェノール系酸化防止剤がポリマー(B)を均一に覆いやすいため、ポリマー(B)の酸化を抑制しやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。フェノール系酸化防止剤とポリマー(B)とのHSP値間距離は好ましくは16.0以下、より好ましくは12.0以下、さらに好ましくは9.0以下、さらにより好ましくは6.0以下、なおさらに好ましくは5.5以下、特に好ましくは5.0以下、特により好ましくは4.5以下、特にさらに好ましくは4.0以下である。前記HSP値間距離が上記上限以下であると、フェノール系酸化防止剤がポリマー(B)に寄りやすく又は吸着しやすく、ポリマー(B)の周りを覆いやすいため、ポリマー(B)の酸化を抑制しやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the distance between the HSP values of the polymer (B) and the phenolic antioxidant is preferably 2.1 or more, more preferably 2.3 or more, still more preferably 2.5 or more, and More preferably 3.0 or more, particularly preferably 3.2 or more. When the distance between the HSP values is at least the above lower limit, the affinity between the phenolic antioxidant and the polymer (B) is not too high, and the phenolic antioxidant tends to uniformly cover the polymer (B). It is easy to suppress the oxidation of (B), and it is easy to improve the hygroscopic resistance and heat resistance of the resulting film. The distance between the HSP values of the phenolic antioxidant and the polymer (B) is preferably 16.0 or less, more preferably 12.0 or less, even more preferably 9.0 or less, still more preferably 6.0 or less, and even more preferably 6.0 or less. is preferably 5.5 or less, particularly preferably 5.0 or less, even more preferably 4.5 or less, and even more preferably 4.0 or less. When the distance between the HSP values is equal to or less than the above upper limit, the phenolic antioxidant tends to approach or adsorb to the polymer (B), and tends to cover the polymer (B), thereby suppressing oxidation of the polymer (B). It is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
本発明の一実施形態において、ポリマー(B)と構造SとのHSP値間距離は、好ましくは1.5以上、より好ましくは2.0以上、さらに好ましくは2.4以上、さらにより好ましくは2.6以上である。前記HSP値間距離が上記下限以上であると、フェノール系酸化防止剤とポリマー(B)との親和性が高すぎず、フェノール系酸化防止剤がポリマー(B)を均一に覆いやすいため、ポリマー(B)の酸化を抑制しやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。構造Sとポリマー(B)とのHSP値間距離は、好ましくは15.5以下、より好ましくは12.0以下、さらに好ましくは10.0以下、さらにより好ましくは7.5以下、なおさらに好ましくは5.0以下、特に好ましくは4.0以下、特により好ましくは3.5以下、特にさらに好ましくは3.0以下である。前記HSP値間距離が上記上限以下であると、フェノール系酸化防止剤がポリマー(B)に寄りやすく又は吸着しやすく、ポリマー(B)の周りを覆いやすいため、ポリマー(B)の酸化を抑制しやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the distance between HSP values between polymer (B) and structure S is preferably 1.5 or more, more preferably 2.0 or more, still more preferably 2.4 or more, still more preferably 2.6 or more. When the distance between the HSP values is at least the above lower limit, the affinity between the phenolic antioxidant and the polymer (B) is not too high, and the phenolic antioxidant tends to uniformly cover the polymer (B). It is easy to suppress the oxidation of (B), and it is easy to improve the hygroscopic resistance and heat resistance of the resulting film. The distance between the HSP values of structure S and polymer (B) is preferably 15.5 or less, more preferably 12.0 or less, still more preferably 10.0 or less, even more preferably 7.5 or less, even more preferably is 5.0 or less, particularly preferably 4.0 or less, particularly more preferably 3.5 or less, and even more preferably 3.0 or less. When the distance between the HSP values is equal to or less than the above upper limit, the phenolic antioxidant tends to approach or adsorb to the polymer (B), and tends to cover the polymer (B), thereby suppressing oxidation of the polymer (B). It is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
本発明の一実施形態において、構造Sとポリマー(B)とのHSP値間距離(以下、HSP値間距離(1)ともいう)は、フェノール系酸化防止剤とポリマー(B)とのHSP値間距離(以下、HSP値間距離(2)ともいう)より小さいことが好ましい。HSP値間距離(1)がHSP値間距離(2)よりも小さいと、ポリマー(B)が酸化しにくいため、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。これは、以下の理由のためであると考えられる。HSP値間距離(1)がHSP値間距離(2)よりも小さいことは、フェノール系酸化防止剤の構造Sの部分が特にポリマー(B)と親和性が高いことを意味しており、酸化防止剤の構造Sの部分が接するようにポリマー(B)に吸着しやすいため、ポリマー(B)の周りにフェノール系酸化防止剤の前記置換基Pが均一に存在しやすくなり、結果、ポリマー(B)の酸化で発生した不安定なラジカルが前記置換基Pでトラップされやすくなる。前記ラジカルのトラップにより生成した置換基Pのラジカルは、さらにポリマー(B)のラジカルをトラップすることができ、ポリマー(B)を不活化させることができる。例えば、前記Rp及びRqがいずれも嵩高い置換基の場合は、置換基Pがラジカル化した後、置換基Pのヒドロキシル基に対してパラ位でポリマー(B)のラジカルをトラップし、ポリマー(B)を不活化させやすい。よって、ポリマー(B)と構造Sとが近くに存在していると、ポリマー(B)の不活性化に寄与する置換基Pのヒドロキシル基のパラ位がポリマー(B)の近くに存在しやすく、置換基Pラジカルがポリマー(B)を不活性化しやすいため、フェノール系酸化防止剤による酸化防止機能が発現しやすい。また、フェノール系酸化防止剤の前記置換基Pのヒドロキシル基が適度にポリマー(B)と離れるため、トラップしたラジカルがポリマー(B)に移ることを防止しやすい。
In one embodiment of the present invention, the distance between the HSP values between the structure S and the polymer (B) (hereinafter also referred to as the distance between the HSP values (1)) is the HSP value between the phenolic antioxidant and the polymer (B) It is preferably smaller than the inter-HSP value distance (hereinafter also referred to as inter-HSP value distance (2)). When the distance between HSP values (1) is smaller than the distance between HSP values (2), the polymer (B) is less likely to be oxidized, and the resulting film tends to have improved moisture absorption resistance and heat resistance. It is believed that this is for the following reasons. The fact that the HSP value distance (1) is smaller than the HSP value distance (2) means that the portion of the structure S of the phenolic antioxidant has a particularly high affinity with the polymer (B), and oxidation Since the portion of the structure S of the inhibitor is easily adsorbed to the polymer (B) so that it is in contact with the polymer (B), the substituent P of the phenolic antioxidant tends to be uniformly present around the polymer (B), and as a result, the polymer ( The unstable radicals generated by the oxidation in B) are likely to be trapped by the substituent P. The radical of the substituent P generated by trapping the radical can further trap the radical of the polymer (B) and inactivate the polymer (B). For example, when both R p and R q are bulky substituents, after the substituent P is radicalized, the radical of the polymer (B) is trapped at the para position with respect to the hydroxyl group of the substituent P, It is easy to inactivate the polymer (B). Therefore, when the polymer (B) and the structure S are present close to each other, the para position of the hydroxyl group of the substituent P, which contributes to deactivation of the polymer (B), tends to be close to the polymer (B). , the substituent P radical tends to inactivate the polymer (B), so that the antioxidant function of the phenolic antioxidant tends to be exhibited. In addition, since the hydroxyl group of the substituent P of the phenolic antioxidant is moderately separated from the polymer (B), it is easy to prevent the trapped radicals from moving to the polymer (B).
本発明の一実施形態において、HSP値間距離(1)がHSP値間距離(2)よりも小さい場合、HSP値間距離(1)とHSP値間距離(2)との差の絶対値は、フェノール系酸化防止剤がポリマー(B)を覆いやすいためポリマー(B)の酸化を抑制しやすく、フィルムの耐吸湿性及び耐熱性を向上しやすい観点から、好ましくは0.1以上、より好ましくは0.2以上、さらに好ましくは0.3以上、さらにより好ましくは0.4以上、特により好ましくは0.5以上である。また、HSP値間距離(1)とHSP値間距離(2)との差の絶対値は、フェノール系酸化防止剤がポリマー(B)に対して均一に吸着しやすく、またフェノール系酸化防止剤の前記置換基Pがポリマー(B)との間に適度な空間を維持しやすい観点から、好ましくは4.0以下、より好ましくは3.0以下、さらに好ましくは2.0以下、さらにより好ましくは1.5以下、特に好ましくは1.0以下である。
In one embodiment of the present invention, when the distance between HSP values (1) is smaller than the distance between HSP values (2), the absolute value of the difference between the distance between HSP values (1) and the distance between HSP values (2) is , From the viewpoint of easily suppressing oxidation of the polymer (B) because the phenolic antioxidant easily covers the polymer (B) and easily improving the moisture absorption resistance and heat resistance of the film, it is preferably 0.1 or more, more preferably is 0.2 or more, more preferably 0.3 or more, even more preferably 0.4 or more, and particularly preferably 0.5 or more. Further, the absolute value of the difference between the distance between HSP values (1) and the distance between HSP values (2) is such that the phenolic antioxidant easily adsorbs uniformly to the polymer (B), and the phenolic antioxidant Preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.0 or less, and even more preferably is 1.5 or less, particularly preferably 1.0 or less.
本発明の一実施形態において、フェノール系酸化防止剤とポリイミド系樹脂(A)とのHSP値間距離は、フェノール系酸化防止剤がポリマー(B)を覆いやすいためポリマー(B)の酸化を抑制しやすく、フィルムの耐吸湿性及び耐熱性を向上しやすい観点から、好ましくは5.0以上、より好ましくは8.0以上、さらに好ましくは8.5以上、さらにより好ましくは9.5以上、特に好ましくは10.0以上、特により好ましくは11.0以上である。また、フェノール系酸化防止剤とポリイミド系樹脂(A)とのHSP値間距離は、組成物中やフィルム中でのフェノール系酸化防止剤の凝集を防ぎやすい観点から、好ましくは16.0以下、より好ましくは15.0以下、さらに好ましくは13.0以下、さらにより好ましくは12.5以下である。
In one embodiment of the present invention, the distance between the HSP values of the phenolic antioxidant and the polyimide resin (A) suppresses the oxidation of the polymer (B) because the phenolic antioxidant easily covers the polymer (B). from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the film, preferably 5.0 or more, more preferably 8.0 or more, still more preferably 8.5 or more, still more preferably 9.5 or more, It is particularly preferably 10.0 or more, and particularly more preferably 11.0 or more. Further, the distance between the HSP values of the phenolic antioxidant and the polyimide resin (A) is preferably 16.0 or less, from the viewpoint of easily preventing aggregation of the phenolic antioxidant in the composition or film. It is more preferably 15.0 or less, still more preferably 13.0 or less, and even more preferably 12.5 or less.
本発明の一実施形態において、構造Sとポリイミド系樹脂(A)とのHSP値間距離は、好ましくは5.0以上、より好ましくは7.0以上、さらに好ましくは8.0以上、さらにより好ましくは9.0以上、特に好ましくは10.0以上であり、好ましくは15.0以下、より好ましくは14.0以下、さらに好ましくは13.0以下、さらにより好ましくは12.0以下である。前記HSP値間距離が上記上限以下又は上記下限以上であると、ポリマー(B)の酸化を抑制しやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the distance between the HSP values of the structure S and the polyimide resin (A) is preferably 5.0 or more, more preferably 7.0 or more, still more preferably 8.0 or more, and still more Preferably 9.0 or more, particularly preferably 10.0 or more, preferably 15.0 or less, more preferably 14.0 or less, still more preferably 13.0 or less, still more preferably 12.0 or less . When the distance between HSP values is equal to or less than the upper limit or equal to or more than the lower limit, it is easy to suppress oxidation of the polymer (B), and it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
本発明の一実施形態において、ポリイミド系樹脂(A)とポリマー(B)とのHSP値間距離は、好ましくは6.0以上、より好ましくは6.5以上、さらに好ましくは7.0以上、さらにより好ましくは8.0以上である。ポリイミド系樹脂(A)とポリマー(B)とのHSP値間距離が上記下限以上であると、ポリマー(B)とポリイミド系樹脂(A)との間に界面ができやすいことから、フェノール系酸化防止剤がポリマー(B)の周りを覆うように吸着しやすく、ポリマー(B)の酸化を防止しやすい。またポリイミド系樹脂(A)とポリマー(B)とのHSP値間距離は、樹脂とポリマー間の親和性の観点から、好ましくは30.0以下、より好ましくは25.0以下、さらに好ましくは20.0以下、さらにより好ましくは15.0以下である。
In one embodiment of the present invention, the distance between the HSP values of the polyimide resin (A) and the polymer (B) is preferably 6.0 or more, more preferably 6.5 or more, still more preferably 7.0 or more, Even more preferably, it is 8.0 or more. If the distance between the HSP values of the polyimide resin (A) and the polymer (B) is at least the above lower limit, an interface is likely to form between the polymer (B) and the polyimide resin (A), so phenolic oxidation The inhibitor is easily adsorbed so as to cover the polymer (B), and the polymer (B) is easily prevented from being oxidized. Further, the distance between the HSP values of the polyimide resin (A) and the polymer (B) is preferably 30.0 or less, more preferably 25.0 or less, still more preferably 20, from the viewpoint of affinity between the resin and the polymer. .0 or less, and even more preferably 15.0 or less.
本発明の組成物は、さらに溶媒を含有していてもよい。本発明の組成物が溶媒を含有する場合、フェノール系酸化防止剤と溶媒とのHSP値間距離が12.0以上であることが好ましい。フェノール系酸化防止剤と溶媒とのHSP値間距離が12.0以上であると、本発明の組成物に含まれるポリマー(B)は製膜時においても酸化しにくく、本発明の組成物は耐吸湿性に優れたフィルムを形成しやすい。これは、フェノール系酸化防止剤と溶媒とのHSP値間距離が12.0以上であると、フェノール系酸化防止剤が溶媒に溶解及び分散しにくいため、相対的にポリマー(B)との親和性が高くなって、フェノール系酸化防止剤がポリマー(B)に寄りやすくなり、フェノール系酸化防止剤がポリマー(B)の周りを覆うことで、フェノール系酸化防止剤によるポリマー(B)の酸化防止効果が高まるためであると考えられる。さらに、ポリマー(B)の周囲を覆う形態でフィルム化されるため、耐熱機能を発現しやすく、得られるフィルムが高温環境下に曝されても、ポリマー(B)の酸化を抑制しやすい。
The composition of the present invention may further contain a solvent. When the composition of the present invention contains a solvent, the distance between the HSP values of the phenolic antioxidant and the solvent is preferably 12.0 or more. When the distance between the HSP values of the phenolic antioxidant and the solvent is 12.0 or more, the polymer (B) contained in the composition of the present invention is hardly oxidized even during film formation, and the composition of the present invention is Easy to form a film with excellent moisture absorption resistance. This is because when the distance between the HSP values between the phenolic antioxidant and the solvent is 12.0 or more, the phenolic antioxidant is difficult to dissolve and disperse in the solvent, so the affinity with the polymer (B) is relatively high. The phenolic antioxidant becomes more likely to approach the polymer (B), and the phenolic antioxidant covers the polymer (B), so that the phenolic antioxidant can oxidize the polymer (B). It is considered that this is because the preventive effect increases. Furthermore, since the polymer (B) is formed into a film so as to cover the surroundings thereof, the polymer (B) is likely to exhibit a heat resistance function, and even when the resulting film is exposed to a high temperature environment, oxidation of the polymer (B) is likely to be suppressed.
本発明の組成物において、フェノール系酸化防止剤と溶媒とのHSP値間距離は、好ましくは12.5以上、より好ましくは13.0以上、さらに好ましくは14.0以上、さらにより好ましくは16.0以上、特に好ましくは16.5以上、特により好ましくは17.0以上である。前記HSP値間距離が上記下限以上であると、フェノール系酸化防止剤がポリマー(B)の周りを覆いやすいため、また、フェノール系酸化防止剤がポリマー(B)の周囲を覆う形態でフィルム化されやすいため、ポリマー(B)の酸化を抑制しやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。また、フェノール系酸化防止剤と溶媒とのHSP値間距離の上限は、好ましくは30以下、より好ましくは25以下、さらに好ましくは20以下である。前記HSP値間距離が上記上限以下であると、フェノール系酸化防止剤が溶媒に分散しやすいため、ポリマー(B)の酸化を抑制しやすい。
In the composition of the present invention, the distance between the HSP values of the phenolic antioxidant and the solvent is preferably 12.5 or more, more preferably 13.0 or more, still more preferably 14.0 or more, still more preferably 16 0.0 or more, particularly preferably 16.5 or more, and particularly more preferably 17.0 or more. When the distance between the HSP values is at least the above lower limit, the phenolic antioxidant tends to surround the polymer (B), and the phenolic antioxidant surrounds the polymer (B) to form a film. Therefore, oxidation of the polymer (B) is easily suppressed, and the hygroscopic resistance and heat resistance of the obtained film are easily improved. Also, the upper limit of the distance between the HSP values of the phenolic antioxidant and the solvent is preferably 30 or less, more preferably 25 or less, still more preferably 20 or less. When the distance between the HSP values is equal to or less than the above upper limit, the phenolic antioxidant tends to disperse in the solvent, so that oxidation of the polymer (B) can be easily suppressed.
HSPはハンセン溶解度パラメータ(δ)であり、(δD,δP,δH)の3次元のパラメータで定義され、式(X):
δ2=(δD)2+(δP)2+(δH)2 ・・・(X)
[式(X)中、δDはLоndоn分散力項を示し、δPは分子分極項(双極子間力項)を示し、δHは水素結合項を表す]
により表される。HSPに係る詳細は、「PROPERTIES OF POLYMERS」(著者:D.W.VANKREVELEN、発行所:ELSEVIER SCIENTFIC PUBLISHING COMPANY、1989年発行、第5版)に記載されている。ハンセン溶解度パラメータのδD,δP、及びδHは、ハンセン溶解球法に従って、ハンセン溶解度パラメータを提案したハンセン博士のグループによって開発されたプログラムであるHSPiP(Hansen Sоlubility Parameters in Practice)を用いて計算することができ、例えば実施例に記載のVer.4.1.07等を用いることができる。以下にハンセン溶解球法の詳細を説明する。対象となる成分をHSP値が既知の溶媒に溶解させ、当該成分の特定の溶媒に対する溶解性を評価する。溶解性の評価は、それぞれ対象とする成分が溶媒に溶解したか否かを目視で判定して行う。これを複数の溶媒について行う。この溶媒の種類は、δtが幅広く異なる溶媒を用いることが好ましく、より具体的には、好ましくは10種以上、より好ましくは15種以上、さらに好ましくは18種以上である。次に、得られた溶解性の評価結果をHSPiPに入力することで得られたHansen球の中心座標(δd,δp,δh)を対象とする成分のHSPとする。また、HSPは上記の方法の他、例えばHSPiPのデータベースの数値や文献値を用いてもよく、HSPiPを使用して構造式から求めてもよい。なお、本明細書において、ハンセン溶解度パラメータの値をHSP値と称し、該HSP値は、25℃における値を表す。ポリイミド樹脂(A)のHSP値、ポリマー(B)のHSP値、及び溶媒のHSP値は、それぞれ、上記のいずれかの方法により求めてもよく、例えば実施例に記載の方法により求められる。 HSP is the Hansen Solubility Parameter (δ), defined by the three-dimensional parameters (δD, δP, δH) and represented by the formula (X):
δ 2 = (δD) 2 + (δP) 2 + (δH) 2 (X)
[In formula (X), δD represents a London dispersion force term, δP represents a molecular polarization term (dipole force term), and δH represents a hydrogen bond term]
is represented by Details of HSP are described in "PROPERTIES OF POLYMERS" (Author: D.W. VANKREVELEN, Publisher: ELSEVIER SCIENTFIC PUBLISHING COMPANY, 1989, 5th edition). The Hansen Solubility Parameters δD, δP, and δH can be calculated using HSPiP (Hansen Solubility Parameters in Practice), a program developed by Dr. Hansen's group who proposed the Hansen Solubility Parameters, according to the Hansen Solubility Sphere Method. For example, Ver. 4.1.07 and the like can be used. Details of the Hansen melting ball method are described below. A component of interest is dissolved in a solvent with a known HSP value, and the solubility of the component in a specific solvent is evaluated. Solubility evaluation is performed by visually judging whether or not each target component is dissolved in the solvent. This is done for multiple solvents. As for the types of solvents, it is preferable to use solvents having a wide range of different δt. Next, the center coordinates (δd, δp, δh) of the Hansen sphere obtained by inputting the obtained solubility evaluation results into HSPiP are used as the HSP of the target component. In addition to the above method, the HSP may be obtained by using, for example, numerical values in the HSPiP database or literature values, or may be determined from the structural formula using HSPiP. In this specification, the value of the Hansen solubility parameter is referred to as the HSP value, and the HSP value represents the value at 25°C. The HSP value of the polyimide resin (A), the HSP value of the polymer (B), and the HSP value of the solvent may each be determined by any of the methods described above, for example, by the methods described in the Examples.
δ2=(δD)2+(δP)2+(δH)2 ・・・(X)
[式(X)中、δDはLоndоn分散力項を示し、δPは分子分極項(双極子間力項)を示し、δHは水素結合項を表す]
により表される。HSPに係る詳細は、「PROPERTIES OF POLYMERS」(著者:D.W.VANKREVELEN、発行所:ELSEVIER SCIENTFIC PUBLISHING COMPANY、1989年発行、第5版)に記載されている。ハンセン溶解度パラメータのδD,δP、及びδHは、ハンセン溶解球法に従って、ハンセン溶解度パラメータを提案したハンセン博士のグループによって開発されたプログラムであるHSPiP(Hansen Sоlubility Parameters in Practice)を用いて計算することができ、例えば実施例に記載のVer.4.1.07等を用いることができる。以下にハンセン溶解球法の詳細を説明する。対象となる成分をHSP値が既知の溶媒に溶解させ、当該成分の特定の溶媒に対する溶解性を評価する。溶解性の評価は、それぞれ対象とする成分が溶媒に溶解したか否かを目視で判定して行う。これを複数の溶媒について行う。この溶媒の種類は、δtが幅広く異なる溶媒を用いることが好ましく、より具体的には、好ましくは10種以上、より好ましくは15種以上、さらに好ましくは18種以上である。次に、得られた溶解性の評価結果をHSPiPに入力することで得られたHansen球の中心座標(δd,δp,δh)を対象とする成分のHSPとする。また、HSPは上記の方法の他、例えばHSPiPのデータベースの数値や文献値を用いてもよく、HSPiPを使用して構造式から求めてもよい。なお、本明細書において、ハンセン溶解度パラメータの値をHSP値と称し、該HSP値は、25℃における値を表す。ポリイミド樹脂(A)のHSP値、ポリマー(B)のHSP値、及び溶媒のHSP値は、それぞれ、上記のいずれかの方法により求めてもよく、例えば実施例に記載の方法により求められる。 HSP is the Hansen Solubility Parameter (δ), defined by the three-dimensional parameters (δD, δP, δH) and represented by the formula (X):
δ 2 = (δD) 2 + (δP) 2 + (δH) 2 (X)
[In formula (X), δD represents a London dispersion force term, δP represents a molecular polarization term (dipole force term), and δH represents a hydrogen bond term]
is represented by Details of HSP are described in "PROPERTIES OF POLYMERS" (Author: D.W. VANKREVELEN, Publisher: ELSEVIER SCIENTFIC PUBLISHING COMPANY, 1989, 5th edition). The Hansen Solubility Parameters δD, δP, and δH can be calculated using HSPiP (Hansen Solubility Parameters in Practice), a program developed by Dr. Hansen's group who proposed the Hansen Solubility Parameters, according to the Hansen Solubility Sphere Method. For example, Ver. 4.1.07 and the like can be used. Details of the Hansen melting ball method are described below. A component of interest is dissolved in a solvent with a known HSP value, and the solubility of the component in a specific solvent is evaluated. Solubility evaluation is performed by visually judging whether or not each target component is dissolved in the solvent. This is done for multiple solvents. As for the types of solvents, it is preferable to use solvents having a wide range of different δt. Next, the center coordinates (δd, δp, δh) of the Hansen sphere obtained by inputting the obtained solubility evaluation results into HSPiP are used as the HSP of the target component. In addition to the above method, the HSP may be obtained by using, for example, numerical values in the HSPiP database or literature values, or may be determined from the structural formula using HSPiP. In this specification, the value of the Hansen solubility parameter is referred to as the HSP value, and the HSP value represents the value at 25°C. The HSP value of the polyimide resin (A), the HSP value of the polymer (B), and the HSP value of the solvent may each be determined by any of the methods described above, for example, by the methods described in the Examples.
二つの物質のハンセン溶解度パラメータ(以下、HSPと略すことがある)の距離をHSP値間距離という。HSP間距離(Ra)は、両物質の親和性を表す指標であって、その値が小さい程、両物質の親和性が高いことを示す。逆に、Raの値が大きい程、両物質の親和性が低いこと、すなわち、相溶しがたいことを示す。
HSP値間距離は、二つの物質A及びBのそれぞれのハンセン溶解度パラメータδA及びδBを、
δA=(δDA,δPA,δHA)
δB=(δDB,δPB,δHB)
と仮定すれば、HSP間距離(Ra)は、式(Y):
Ra=[4×(δDA-δDB)2+(δPA-δPB)2+(δHA-δHB)2]0.5 ・・・(Y)
により計算することができる。
なお、本明細書において、HSP値及びHSP値間距離は上記に定義した通りであり、上記方法に従って求めることができる。 The distance between the Hansen solubility parameters (hereinafter sometimes abbreviated as HSP) of two substances is called the distance between HSP values. The inter-HSP distance (Ra) is an index representing the affinity between both substances, and the smaller the value, the higher the affinity between the two substances. Conversely, the larger the Ra value, the lower the affinity between the two substances, that is, the less compatible they are.
The distance between HSP values is the Hansen solubility parameters δA and δB of the two substances A and B, respectively,
δA = (δDA, δPA, δHA)
δB=(δDB, δPB, δHB)
Assuming that the distance between HSPs (Ra) is given by the formula (Y):
Ra=[4×(δDA−δDB) 2 +(δPA−δPB) 2 +(δHA−δHB) 2 ] 0.5 (Y)
can be calculated by
In this specification, the HSP value and the distance between HSP values are as defined above, and can be obtained according to the above method.
HSP値間距離は、二つの物質A及びBのそれぞれのハンセン溶解度パラメータδA及びδBを、
δA=(δDA,δPA,δHA)
δB=(δDB,δPB,δHB)
と仮定すれば、HSP間距離(Ra)は、式(Y):
Ra=[4×(δDA-δDB)2+(δPA-δPB)2+(δHA-δHB)2]0.5 ・・・(Y)
により計算することができる。
なお、本明細書において、HSP値及びHSP値間距離は上記に定義した通りであり、上記方法に従って求めることができる。 The distance between the Hansen solubility parameters (hereinafter sometimes abbreviated as HSP) of two substances is called the distance between HSP values. The inter-HSP distance (Ra) is an index representing the affinity between both substances, and the smaller the value, the higher the affinity between the two substances. Conversely, the larger the Ra value, the lower the affinity between the two substances, that is, the less compatible they are.
The distance between HSP values is the Hansen solubility parameters δA and δB of the two substances A and B, respectively,
δA = (δDA, δPA, δHA)
δB=(δDB, δPB, δHB)
Assuming that the distance between HSPs (Ra) is given by the formula (Y):
Ra=[4×(δDA−δDB) 2 +(δPA−δPB) 2 +(δHA−δHB) 2 ] 0.5 (Y)
can be calculated by
In this specification, the HSP value and the distance between HSP values are as defined above, and can be obtained according to the above method.
本発明の一実施形態において、フェノール系酸化防止剤は、構造Sと溶媒とのHSP値間距離が10.0以上であることが好ましく、より好ましくは12.3以上、さらに好ましくは12.5以上、さらにより好ましくは12.7以上、特に好ましくは13.0以上、特により好ましくは13.5以上、特にさらにより好ましくは14.0以上、極めて好ましくは15.0以上、極めてより好ましくは16.0以上、極めてさらに好ましくは17.0以上である。前記HSP値間距離が上記下限以上であると、フェノール系酸化防止剤が溶媒に溶解及び分散しにくく、ポリマー(B)の周りを覆いやすいため、ポリマー(B)の酸化を抑制して、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。また、構造Sと溶媒とのHSP値間距離の上限は、好ましくは30.0以下、より好ましくは25.0以下、さらに好ましくは20.0以下である。前記HSP値間距離が上記上限以下であると、フェノール系酸化防止剤が組成物中で凝集することを防ぎ、ポリマー(B)の周りを覆いやすいため、ポリマー(B)の酸化を抑制しやすい。
In one embodiment of the present invention, the phenolic antioxidant preferably has a distance between the HSP values of the structure S and the solvent of 10.0 or more, more preferably 12.3 or more, and even more preferably 12.5. 12.7 or more, particularly preferably 13.0 or more, particularly more preferably 13.5 or more, even more preferably 14.0 or more, extremely preferably 15.0 or more, extremely more preferably 16.0 or higher, and very preferably 17.0 or higher. When the distance between the HSP values is at least the above lower limit, the phenolic antioxidant is difficult to dissolve and disperse in the solvent and easily covers the polymer (B). It is easy to improve the moisture absorption resistance and heat resistance of the resulting film. Also, the upper limit of the distance between the HSP values of Structure S and the solvent is preferably 30.0 or less, more preferably 25.0 or less, and even more preferably 20.0 or less. When the distance between the HSP values is equal to or less than the above upper limit, the phenolic antioxidant is prevented from aggregating in the composition, and the surroundings of the polymer (B) are easily covered, so oxidation of the polymer (B) is easily suppressed. .
フェノール系酸化防止剤とのHSP値間距離が12.0以上である溶媒(以下、「第1溶媒」と記載することがある)は、特に限定されず、例えばN,N-ジメチルアセトアミド(以下、DMAcと記載することがある)、N-N-ジメチルホルムアミド(以下、DMFと記載することがある)等のアミド系溶媒;γ-ブチロラクトン(以下、GBLと記載することがある)、γ-バレロラクトン等のラクトン系溶媒;ジメチルスルホン、ジメチルスルホキシド、スルホラン等の含硫黄系溶媒;エチレンカーボネート、プロピレンカーボネート等のカーボネート系溶媒;N-メチルピロリドン等のピロリドン系溶媒;及びそれらの組合せが挙げられる。これらの中でも、アミド系溶媒又はラクトン系溶媒又はピロリドン系溶媒が好ましい。このような溶媒であると、相対的にフェノール系酸化防止剤とポリマー(B)との親和性が高まって、フェノール系酸化防止剤がポリマー(B)に吸着しやすく、また、ポリマー(B)の凝集を抑制しやすく、ポリマー(B)の分散性を高めやすいので、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。組成物におけるポリマー(B)の分散性が高まると、得られるフィルムにおけるポリマー(B)の分散性が高まるため、フィルムの耐吸湿性、表面平滑性、誘電特性及び機械的特性を高めやすく、フィルムの物性、例えばフィルムの熱伝導率のバラツキや線膨張係数(以下、CTEと称する)、フィルムの表面荒れを低減しやすい。本明細書において、機械的特性とは、屈曲耐性及び弾性率を含む機械的な特性を意味し、機械的特性が高まる又は向上するとは、例えば、屈曲耐性及び/又は弾性率が高くなることを示す。溶媒は単独又は二種以上を組合せて使用できる。
A solvent having an HSP value distance of 12.0 or more with a phenolic antioxidant (hereinafter sometimes referred to as a "first solvent") is not particularly limited, and for example, N,N-dimethylacetamide (hereinafter , sometimes referred to as DMAc), amide solvents such as NN-dimethylformamide (hereinafter sometimes referred to as DMF); γ-butyrolactone (hereinafter sometimes referred to as GBL), γ- lactone solvents such as valerolactone; sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide and sulfolane; carbonate solvents such as ethylene carbonate and propylene carbonate; pyrrolidone solvents such as N-methylpyrrolidone; . Among these, amide-based solvents, lactone-based solvents, and pyrrolidone-based solvents are preferred. With such a solvent, the affinity between the phenolic antioxidant and the polymer (B) is relatively increased, the phenolic antioxidant is easily adsorbed to the polymer (B), and the polymer (B) Aggregation of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily improved, so that the moisture absorption resistance and heat resistance of the obtained film can be easily improved. When the dispersibility of the polymer (B) in the composition increases, the dispersibility of the polymer (B) in the resulting film increases, so the moisture absorption resistance, surface smoothness, dielectric properties and mechanical properties of the film tend to increase, and the film physical properties, such as variation in thermal conductivity of the film, coefficient of linear expansion (hereinafter referred to as CTE), and surface roughness of the film. As used herein, mechanical properties refer to mechanical properties including bending resistance and elastic modulus, and increasing or improving mechanical properties means, for example, increasing bending resistance and/or elastic modulus. show. A solvent can be used individually or in combination of 2 or more types.
本発明の一実施形態において、第1溶媒とポリマー(B)とのHSP値間距離は、好ましくは8.0以上、より好ましくは8.5以上、さらにより好ましくは9.0以上、特に好ましくは10.0以上、特により好ましくは11.0以上である。該HSP値間距離が上記の下限以上であると、相対的にフェノール系酸化防止剤とポリマー(B)との親和性が高まってフェノール系酸化防止剤がポリマー(B)に吸着しやすく、また、ポリマー(B)が粒子状の場合、ポリマー(B)の分散性を高めやすい。また、第1溶媒とポリマー(B)とのHSP値間距離の上限は、好ましくは30.0以下、より好ましくは25.0以下、さらに好ましくは20.0以下である。該第1溶媒とポリマー(B)とのHSP値間距離が上記の上限以下であると、ポリマー(B)の凝集を抑制しやすく、ポリマー(B)の分散性を高めやすい。また、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the distance between the HSP values of the first solvent and the polymer (B) is preferably 8.0 or more, more preferably 8.5 or more, even more preferably 9.0 or more, and particularly preferably is 10.0 or more, and more preferably 11.0 or more. When the distance between the HSP values is at least the above lower limit, the affinity between the phenolic antioxidant and the polymer (B) is relatively increased, and the phenolic antioxidant is easily adsorbed to the polymer (B), and , when the polymer (B) is particulate, the dispersibility of the polymer (B) is likely to be enhanced. Also, the upper limit of the distance between the HSP values between the first solvent and the polymer (B) is preferably 30.0 or less, more preferably 25.0 or less, still more preferably 20.0 or less. When the distance between the HSP values of the first solvent and the polymer (B) is equal to or less than the above upper limit, aggregation of the polymer (B) is likely to be suppressed, and dispersibility of the polymer (B) is likely to be enhanced. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
本発明の一実施形態において、第1溶媒は、ポリマー(B)が溶解しない溶媒であることが好ましい。このような溶媒であると、界面ができやすいことからフェノール系酸化防止剤がポリマー(B)に吸着しやすく、またポリマー(B)の凝集を抑制しやすく、ポリマー(B)の分散性を高めやすい。また、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。ここで、本明細書では、「溶解する」か「溶解しない」かの評価は、実施例における<溶解性の評価>に記載の方法に従って行うことができる。
In one embodiment of the present invention, the first solvent is preferably a solvent in which the polymer (B) does not dissolve. With such a solvent, an interface is easily formed, so the phenolic antioxidant is easily adsorbed to the polymer (B), and aggregation of the polymer (B) is easily suppressed, and the dispersibility of the polymer (B) is improved. Cheap. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. Here, in the present specification, the evaluation of whether "dissolves" or "does not dissolve" can be performed according to the method described in <Evaluation of Solubility> in Examples.
本発明の一実施形態において、第1溶媒とポリマー(B)とのHSP値間距離が、ポリマー(B)の相互作用半径よりも大きいことが好ましい。このような関係であると、ポリマー(B)が第1溶媒に溶解されにくいため、ポリマー(B)の凝集を抑制しやすく、ポリマー(B)の分散性を高めやすい。また、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。なお、本明細書において、相互作用半径とは、ある特定のポリマーを溶解し得る複数の溶媒、すなわち良溶媒のハンセン溶解度パラメータを3次元のHSP空間にプロットすると、各良溶媒のプロットは互いに似たところ、言い換えると、近い位置、すなわち座標に球状に集まる傾向があり、その球、すなわちハンセンの溶解球の半径を指す。相互作用半径が大きい溶質は多くの溶媒に溶けやすく、相互作用半径が小さい溶質は少数の溶媒に溶けやすく、多数の溶媒に溶け難いといえる。未知の特定のポリマーに対しては、各種の溶媒が良溶媒であるか、貧溶媒であるかを、溶解性試験を行って調べ、その結果をHSPiPに入力することにより、当該ポリマーの相互作用半径が算出される。本明細書において、「相互作用半径」は上記に定義した通りであり、上記方法に従って求めることができる。
In one embodiment of the present invention, the distance between the HSP values of the first solvent and polymer (B) is preferably larger than the interaction radius of polymer (B). With such a relationship, the polymer (B) is less likely to be dissolved in the first solvent, so aggregation of the polymer (B) is easily suppressed and the dispersibility of the polymer (B) is easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. In this specification, the interaction radius means a plurality of solvents capable of dissolving a specific polymer, that is, when the Hansen solubility parameters of good solvents are plotted in a three-dimensional HSP space, the plots of each good solvent are similar to each other. Where, in other words, they tend to cluster spherically at close positions, ie coordinates, and refer to the radius of that sphere, the Hansen melting sphere. A solute with a large interaction radius is soluble in many solvents, a solute with a small interaction radius is soluble in a small number of solvents, and is difficult to dissolve in a large number of solvents. For a specific unknown polymer, a solubility test is conducted to determine whether various solvents are good solvents or poor solvents. A radius is calculated. As used herein, the "interaction radius" is as defined above and can be determined according to the above method.
本発明の一実施形態において、第1溶媒とポリイミド系樹脂(A)とのHSP値間距離は、好ましくは11.0以下、より好ましくは10.0以下、さらに好ましくは9.5以下、さらにより好ましくは9.0以下、特に好ましくは8.5以下であり、好ましくは0.01以上、より好ましくは0.1以上、さらに好ましくは1.0以上、さらにより好ましくは3.0以上、特に好ましくは5.0以上である。該HSP値間距離が上記の上限以下であると、第1溶媒とポリイミド系樹脂(A)との親和性が向上し得るため、ポリマー(B)の分散性を高めやすく、また、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the distance between the HSP values of the first solvent and the polyimide resin (A) is preferably 11.0 or less, more preferably 10.0 or less, still more preferably 9.5 or less, and more preferably 9.0 or less, particularly preferably 8.5 or less, preferably 0.01 or more, more preferably 0.1 or more, still more preferably 1.0 or more, still more preferably 3.0 or more, Especially preferably, it is 5.0 or more. When the distance between the HSP values is the above upper limit or less, the affinity between the first solvent and the polyimide resin (A) can be improved, so that the dispersibility of the polymer (B) can be easily increased, and the resulting film It is easy to improve the moisture absorption resistance and heat resistance of
本発明の一実施形態において、第1溶媒は、ポリイミド系樹脂(A)が溶解する溶媒であることが好ましい。このような溶媒であると、得られる組成物及びフィルム中にポリマー(B)が分散しやすい。また、該フィルムは海島構造を形成しやすい。
In one embodiment of the present invention, the first solvent is preferably a solvent in which the polyimide resin (A) dissolves. Such a solvent facilitates dispersion of the polymer (B) in the resulting composition and film. In addition, the film tends to form a sea-island structure.
本発明の一実施形態において、第1溶媒とポリイミド系樹脂(A)とのHSP値間距離は、ポリイミド系樹脂(A)の相互作用半径よりも小さいことが好ましい。このような関係であると、ポリイミド系樹脂(A)が第1溶媒に溶解されやすいため、ポリマー(B)の凝集を抑制しやすく、ポリマー(B)の分散性を高めやすい。
In one embodiment of the present invention, the distance between the HSP values of the first solvent and the polyimide resin (A) is preferably smaller than the interaction radius of the polyimide resin (A). With such a relationship, the polyimide resin (A) is easily dissolved in the first solvent, so aggregation of the polymer (B) is easily suppressed and dispersibility of the polymer (B) is easily improved.
本発明の一実施形態において、第1溶媒の含有量は、本発明の組成物の質量に対して、好ましくは50質量%以上、より好ましくは60質量%以上、さらに好ましくは70質量%以上、さらにより好ましくは80質量%以上、特に好ましくは90質量%以上であり、好ましくは99質量%以下、より好ましくは97質量%以下、さらに好ましくは95質量%以下である。第1溶媒の含有量が上記の範囲であると、界面ができやすいことからフェノール系酸化防止剤がポリマー(B)に吸着しやすく、またポリマー(B)の凝集を抑制しやすい。
In one embodiment of the present invention, the content of the first solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more, relative to the mass of the composition of the present invention. Even more preferably 80% by mass or more, particularly preferably 90% by mass or more, preferably 99% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less. When the content of the first solvent is within the above range, an interface is easily formed, so the phenolic antioxidant is easily adsorbed to the polymer (B), and aggregation of the polymer (B) is easily suppressed.
本発明の一実施形態において、本発明の組成物は、フェノール系酸化防止剤とのHSP値間距離が12.0以上である第1溶媒に加えて、第2溶媒を含んでいてもよい。組成物が第1溶媒に加えて、第2溶媒を含むと、粒子径が低減された粒子状のポリマー(B)を含む組成物を調製しやすい。
In one embodiment of the present invention, the composition of the present invention may contain a second solvent in addition to the first solvent whose HSP value distance to the phenolic antioxidant is 12.0 or more. When the composition contains the second solvent in addition to the first solvent, it is easy to prepare a composition containing the particulate polymer (B) with a reduced particle size.
第2溶媒としては、例えばベンゼン、トルエン、ペンタン、ヘキサン、ヘプタン、シクロヘキサン、キシレン等の炭化水素系溶媒;ジクロロメタン、二塩化エチレン等のハロゲン化炭化水素系溶媒;アセトン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、2-ヘプタノン、メチルイソブチルケトン等のケトン系溶媒などが挙げられる。これらの中でも、炭化水素系溶媒及び/又はケトン系溶媒が好ましく、炭化水素系溶媒がより好ましい。第2溶媒が炭化水素系溶媒を含むと、ポリマー(B)の分散性を高めやすい。また、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。第2溶媒は単独又は二種以上を組合せて使用できる。
Examples of the second solvent include hydrocarbon solvents such as benzene, toluene, pentane, hexane, heptane, cyclohexane, and xylene; halogenated hydrocarbon solvents such as dichloromethane and ethylene dichloride; acetone, methyl ethyl ketone, cyclopentanone, and cyclohexanone. , 2-heptanone, and ketone solvents such as methyl isobutyl ketone. Among these, hydrocarbon-based solvents and/or ketone-based solvents are preferable, and hydrocarbon-based solvents are more preferable. When the second solvent contains a hydrocarbon solvent, the dispersibility of the polymer (B) is likely to be enhanced. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. A 2nd solvent can be used individually or in combination of 2 or more types.
本発明の一実施形態において、第2溶媒とフェノール系酸化防止剤とのHSP値間距離は、好ましくは0.5以上、より好ましくは0.8以上、さらに好ましくは1.0以上、さらにより好ましくは1.5以上である。また、第2溶媒とフェノール系酸化防止剤とのHSP値間距離の上限は、通常15以下、好ましくは10以下、より好ましくは8.0以下、さらに好ましくは5.0以下、さらにより好ましくは2.5以下、特に好ましくは2.0以下である。前記HSP値間距離が上記範囲内であると、フェノール系酸化防止剤がポリマー(B)に吸着しやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the distance between the HSP values of the second solvent and the phenolic antioxidant is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 1.0 or more, and even more preferably Preferably it is 1.5 or more. The upper limit of the distance between the HSP values of the second solvent and the phenolic antioxidant is usually 15 or less, preferably 10 or less, more preferably 8.0 or less, even more preferably 5.0 or less, and even more preferably 2.5 or less, particularly preferably 2.0 or less. When the distance between HSP values is within the above range, the phenolic antioxidant is likely to be adsorbed to the polymer (B), and the hygroscopic resistance and heat resistance of the resulting film are likely to be improved.
本発明の一実施形態において、第2溶媒とポリマー(B)とのHSP値間距離が、好ましくは8.0以下、より好ましくは7.0以下、さらに好ましくは6.0以下、さらにより好ましくは5.0以下、特に好ましくは4.0以下、特により好ましくは3.0以下、特にさらに好ましくは2.5以下である。該HSP値間距離が上記の上限以下であると、第2溶媒とポリマー(B)との溶解性が高まるため、ポリマー(B)の分散性を高めやすい。さらに、フェノール系酸化防止剤がポリマー(B)に吸着しやすいことから、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。HSP値間距離の下限は通常0を超える。
In one embodiment of the present invention, the distance between the HSP values of the second solvent and the polymer (B) is preferably 8.0 or less, more preferably 7.0 or less, even more preferably 6.0 or less, even more preferably is 5.0 or less, particularly preferably 4.0 or less, particularly more preferably 3.0 or less, and even more preferably 2.5 or less. When the distance between the HSP values is equal to or less than the above upper limit, the solubility of the polymer (B) in the second solvent is increased, so that the dispersibility of the polymer (B) is likely to be increased. Furthermore, since the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film. The lower limit of the distance between HSP values is usually greater than zero.
本発明の一実施形態において、第2溶媒はポリマー(B)が溶解する溶媒であることが好ましい。このような溶媒であると、ポリマー(B)の分散性を高めやすい。また、フェノール系酸化防止剤がポリマー(B)に吸着しやすいことから、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the second solvent is preferably a solvent in which the polymer (B) dissolves. Such a solvent tends to improve the dispersibility of the polymer (B). In addition, since the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
本発明の一実施形態において、第2溶媒とポリマー(B)とのHSP値間距離が、ポリマー(B)の相互作用半径よりも小さいことが好ましい。このような関係であると、ポリマー(B)が第2溶媒に溶解されやすいため、ポリマー(B)の分散性を高めやすい。また、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the distance between the HSP values of the second solvent and the polymer (B) is preferably smaller than the interaction radius of the polymer (B). Such a relationship facilitates dissolution of the polymer (B) in the second solvent, thereby enhancing the dispersibility of the polymer (B). In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
本発明の一実施形態において、第2溶媒とポリイミド系樹脂(A)とのHSP値間距離は、好ましくは4.0以上、より好ましくは5.0以上、さらに好ましくは6.0以上、さらにより好ましくは7.0以上、特に好ましくは8.0以上、特により好ましくは9.0以上である。該HSP値間距離が上記の下限以上であると、ポリイミド系樹脂(A)が第2溶媒に溶解されにくいため、ポリマー(B)の凝集体の形成を抑制しやすく、ポリマー(B)の分散性を高めやすい。また、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。第2溶媒とポリイミド系樹脂(A)とのHSP値間距離の上限は好ましくは30.0以下、より好ましくは27.0以下、さらに好ましくは25.0以下、さらにより好ましくは23.0以下、特に好ましくは21.0以下である。第2溶媒とポリイミド系樹脂(A)とのHSP値間距離が上記の上限以下であると、ポリマー(B)の凝集を抑制しやすいことから、ポリマー(B)の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the distance between the HSP values of the second solvent and the polyimide resin (A) is preferably 4.0 or more, more preferably 5.0 or more, still more preferably 6.0 or more, and further It is more preferably 7.0 or higher, particularly preferably 8.0 or higher, and particularly preferably 9.0 or higher. When the distance between the HSP values is at least the above lower limit, the polyimide resin (A) is difficult to dissolve in the second solvent, so the formation of aggregates of the polymer (B) is easily suppressed, and the polymer (B) is dispersed. easy to enhance. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. The upper limit of the distance between the HSP values of the second solvent and the polyimide resin (A) is preferably 30.0 or less, more preferably 27.0 or less, still more preferably 25.0 or less, and even more preferably 23.0 or less. , and particularly preferably 21.0 or less. When the distance between the HSP values of the second solvent and the polyimide resin (A) is the above upper limit or less, aggregation of the polymer (B) is easily suppressed, so the dispersibility of the polymer (B) is easily increased, and It is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
本発明の一実施形態において、第2溶媒は、ポリイミド系樹脂(A)が溶解しない溶媒であることが好ましい。このような溶媒であると、ポリマー(B)の分散性を高めやすい。さらに、フェノール系酸化防止剤がポリマー(B)に吸着しやすいことから、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the second solvent is preferably a solvent in which the polyimide resin (A) does not dissolve. Such a solvent tends to enhance the dispersibility of the polymer (B). Furthermore, since the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
本発明の一実施形態において、第2溶媒とポリイミド系樹脂(A)とのHSP値間距離が、ポリイミド系樹脂(A)の相互作用半径よりも大きいことが好ましい。このような関係であると、ポリイミド系樹脂(A)が第2溶媒に溶解されにくいため、ポリマー(B)の凝集体の形成を抑制しやすく、ポリマー(B)の分散性を高めやすい。さらに、フェノール系酸化防止剤がポリマー(B)に吸着しやすいことから、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the distance between the HSP values of the second solvent and the polyimide resin (A) is preferably larger than the interaction radius of the polyimide resin (A). With such a relationship, the polyimide resin (A) is less likely to be dissolved in the second solvent, so the formation of aggregates of the polymer (B) is easily suppressed, and the dispersibility of the polymer (B) is easily enhanced. Furthermore, since the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
本発明の一実施形態において、ポリマー(B)の第2溶媒に対する溶解度は、ポリマー(B)の第1溶媒に対する溶解度よりも大きいことが好ましい。このような関係であると、ポリマー(B)の凝集体の形成を抑制しやすく、ポリマー(B)の分散性を高めやすい。さらに、フェノール系酸化防止剤がポリマー(B)に吸着しやすいことから、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。なお、ポリマー(B)の溶媒に対する溶解度は、以下の方法で測定できる。サンプル瓶にポリマー(B)1000mgと溶媒3mLとを加え、室温下で2時間撹拌する。次いで、固相と液相とを濾過により分別し、固相を減圧下、80℃で2時間乾燥させた後の質量:X(mg)を測定し、下記式により、溶解度Y(mg/mL)を求めることができる。
Y=(1000-X)/3
なお、例えば本明細書の定義で、ポリマー(B)が、第2溶媒に「溶解する」に相当し、第1溶媒に「溶解しない」に相当する場合、明らかに第2溶媒に対する溶解度の方が大きいため、溶解度を測定しなくてもよい。 In one embodiment of the present invention, the solubility of polymer (B) in the second solvent is preferably greater than the solubility of polymer (B) in the first solvent. Such a relationship tends to suppress the formation of aggregates of the polymer (B), and tends to increase the dispersibility of the polymer (B). Furthermore, since the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film. The solubility of the polymer (B) in solvents can be measured by the following method. 1000 mg of polymer (B) and 3 mL of solvent are added to a sample bottle and stirred at room temperature for 2 hours. Next, the solid phase and the liquid phase are separated by filtration, and the solid phase is dried under reduced pressure at 80° C. for 2 hours. Then, the mass: X (mg) is measured, and the solubility Y (mg/mL ) can be obtained.
Y=(1000−X)/3
In addition, for example, in the definition of this specification, when the polymer (B) corresponds to "dissolve" in the second solvent and corresponds to "does not dissolve" in the first solvent, the solubility in the second solvent is clearly is large, it is not necessary to measure the solubility.
Y=(1000-X)/3
なお、例えば本明細書の定義で、ポリマー(B)が、第2溶媒に「溶解する」に相当し、第1溶媒に「溶解しない」に相当する場合、明らかに第2溶媒に対する溶解度の方が大きいため、溶解度を測定しなくてもよい。 In one embodiment of the present invention, the solubility of polymer (B) in the second solvent is preferably greater than the solubility of polymer (B) in the first solvent. Such a relationship tends to suppress the formation of aggregates of the polymer (B), and tends to increase the dispersibility of the polymer (B). Furthermore, since the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film. The solubility of the polymer (B) in solvents can be measured by the following method. 1000 mg of polymer (B) and 3 mL of solvent are added to a sample bottle and stirred at room temperature for 2 hours. Next, the solid phase and the liquid phase are separated by filtration, and the solid phase is dried under reduced pressure at 80° C. for 2 hours. Then, the mass: X (mg) is measured, and the solubility Y (mg/mL ) can be obtained.
Y=(1000−X)/3
In addition, for example, in the definition of this specification, when the polymer (B) corresponds to "dissolve" in the second solvent and corresponds to "does not dissolve" in the first solvent, the solubility in the second solvent is clearly is large, it is not necessary to measure the solubility.
本発明の一実施形態において、本発明の組成物に含まれ得る第2溶媒の含有量は、第1溶媒の含有量100質量部に対して、好ましくは120質量部以下、より好ましくは100質量部以下、さらに好ましくは60質量部以下、さらにより好ましくは45質量部以下、特に好ましくは40質量部以下、特により好ましくは35質量部以下、特にさらに好ましくは30質量部以下、特にさらにより好ましくは30質量部未満、極めて好ましくは25質量部以下であり、好ましくは0.01質量部以上、より好ましくは0.05質量部以上、さらに好ましくは0.1質量部以上である。第2溶媒の含有量が上記の上限以下であると、ポリマー(B)の凝集体の形成を抑制しやすく、ポリマー(B)の分散性を高めやすい。また、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。第2溶媒の含有量が上記の下限以上であると、組成物を調製しやすい。
In one embodiment of the present invention, the content of the second solvent that can be contained in the composition of the present invention is preferably 120 parts by mass or less, more preferably 100 parts by mass with respect to 100 parts by mass of the content of the first solvent. parts or less, more preferably 60 parts by mass or less, even more preferably 45 parts by mass or less, particularly preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, even more preferably 30 parts by mass or less, and even more preferably is less than 30 parts by mass, extremely preferably 25 parts by mass or less, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and still more preferably 0.1 parts by mass or more. When the content of the second solvent is equal to or less than the above upper limit, the formation of aggregates of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily enhanced. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. It is easy to prepare a composition as content of a 2nd solvent is more than said minimum.
本発明の一実施形態において、本発明の組成物は、本発明の効果を損なわない範囲で、第1溶媒と第2溶媒以外の他の溶媒を含んでいてもよい。他の溶媒としては、特に限定されず、慣用の溶媒を使用することができる。
In one embodiment of the present invention, the composition of the present invention may contain a solvent other than the first solvent and the second solvent within a range that does not impair the effects of the present invention. Other solvents are not particularly limited, and commonly used solvents can be used.
本発明の一実施形態において、本発明の組成物に含まれ得る第1溶媒、第2溶媒及び他の溶媒の合計含有量は、該組成物の質量に対して、好ましくは50質量%以上、より好ましくは60質量%以上、さらに好ましくは70質量%以上、さらにより好ましくは80質量%以上、特に好ましくは90質量%以上であり、好ましくは99質量%以下、より好ましくは97質量%以下、さらに好ましくは95質量%以下である。前記合計含有量が上記の範囲であると、ポリマー(B)の凝集体の形成を抑制しやすく、ポリマー(B)の分散性を高めやすい。さらに、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the total content of the first solvent, the second solvent and other solvents that can be contained in the composition of the present invention is preferably 50% by mass or more, based on the mass of the composition. More preferably 60% by mass or more, still more preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, preferably 99% by mass or less, more preferably 97% by mass or less, More preferably, it is 95% by mass or less. When the total content is within the above range, the formation of aggregates of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily improved. Furthermore, it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
本発明の一実施形態において、第1溶媒と第2溶媒との合計質量は、組成物に含まれ得る第1溶媒、第2溶媒及び他の溶媒の合計質量に対して、好ましくは50質量%以上、より好ましくは70質量%以上、さらに好ましくは90質量%以上、さらにより好ましくは95質量%以上であり、好ましくは100質量%以下である。第1溶媒と第2溶媒との合計質量が上記の範囲であると、ポリマー(B)の凝集体の形成を抑制しやすく、ポリマー(B)の分散性を高めやすい。さらに、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the total weight of the first solvent and the second solvent is preferably 50% by weight based on the total weight of the first solvent, the second solvent and other solvents that may be included in the composition. Above, more preferably 70% by mass or more, still more preferably 90% by mass or more, even more preferably 95% by mass or more, and preferably 100% by mass or less. When the total mass of the first solvent and the second solvent is within the above range, the formation of aggregates of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily improved. Furthermore, it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
本発明の一実施形態において、本発明の組成物は、二次酸化防止剤をさらに含むことが好ましい。一次酸化防止剤であるフェノール系酸化防止剤に加えて二次酸化防止剤を含むことにより、ポリマー(B)の酸化を抑制しやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。二次酸化防止剤としては、リン系酸化防止剤及び硫黄系酸化防止剤等が挙げられ、これらの二次酸化防止剤は単独又は二種以上を組合せて使用できる。
In one embodiment of the present invention, the composition of the present invention preferably further contains a secondary antioxidant. By including the secondary antioxidant in addition to the phenolic antioxidant which is the primary antioxidant, it is easy to suppress oxidation of the polymer (B) and improve the hygroscopic resistance and heat resistance of the resulting film. Secondary antioxidants include phosphorus antioxidants, sulfur antioxidants, and the like, and these secondary antioxidants can be used alone or in combination of two or more.
本発明の一実施形態において、リン系酸化防止剤としては、例えばトリス(2,4-ジ-tert-ブチルフェニル)ホスファイト、トリフェニルホスファイト、トリス(ノニルフェニル)ホスファイト、トリラウリルホスファイト、トリオクタデシルホスファイト、ジステアリルペンタエリスリトールジホスファイト、ジイソデシルペンタエリスリトールジホスファイト、ビス(2,4-ジ-tert-ブチルフェニル)ペンタエリスリトールジホスファイト、ビス(2,4-ジ-tert-ブチル-6-メチルフェニル)ペンタエリスリトールジホスファイト、ビス(2,6-ジ-tert-ブチル-4-メチルフェニル)ペンタエリスリトールジホスファイト、ビス(2,4,6-トリ-tert-ブチルフェニル)ペンタエリスリトールジホスファイト、トリステアリルソルビトールトリホスファイト、テトラキス(2,4-ジ-tert-ブチルフェニル)-4,4’-ジフェニレンジホスホナイト、2,2’-メチレンビス(4,6-ジ-tert-ブチルフェニル)2-エチルヘキシルホスファイト、2,2’-エチリデンビス(4,6-ジ-tert-ブチルフェニル)フルオロホスファイト、ビス(2,4-ジ-tert-ブチル-6-メチルフェニル)エチルホスファイト、ビス(2,4-ジ-tert-ブチル-6-メチルフェニル)メチルホスファイト、2-(2,4,6-トリ-tert-ブチルフェニル)-5-エチル-5-ブチル-1,3,2-オキサホスホリナン、2,2’,2”-ニトリロ[トリエチル-トリス(3,3’,5,5’-テトラ-tert-ブチル-1,1’-ビフェニル-2,2’-ジイル)ホスファイト等が挙げられる。これらのリン系酸化防止剤は単独又は二種以上を組合せて使用できる。
In one embodiment of the present invention, phosphorus-based antioxidants include, for example, tris(2,4-di-tert-butylphenyl)phosphite, triphenylphosphite, tris(nonylphenyl)phosphite, trilaurylphosphite. , trioctadecyl phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert- Butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl) ) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4′-diphenylenediphosphonite, 2,2′-methylenebis(4,6-di -tert-butylphenyl)2-ethylhexylphosphite, 2,2′-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, bis(2,4-di-tert-butyl-6-methyl phenyl)ethyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite, 2-(2,4,6-tri-tert-butylphenyl)-5-ethyl-5- Butyl-1,3,2-oxaphosphorinane, 2,2′,2″-nitrilo[triethyl-tris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2 , 2'-diyl) phosphite, etc. These phosphorus-based antioxidants can be used alone or in combination of two or more.
本発明の一実施形態において、硫黄系酸化防止剤としては、例えばジラウリル3,3’-チオジプロピオネート、トリデシル3,3’-チオジプロピオネート、ジミリスチル3,3’-チオジプロピオネート、ジステアリル3,3’-チオジプロピオネート、ラウリルステアリル3,3’-チオジプロピオネート、ネオペンタンテトライルテトラキス(3-ラウリルチオプロピオネート)等が挙げられる。これらの硫黄系酸化防止剤は単独又は二種以上を組合せて使用できる。
In one embodiment of the present invention, sulfur-based antioxidants include, for example, dilauryl 3,3'-thiodipropionate, tridecyl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3,3'-thiodipropionate, neopentanetetrayl tetrakis(3-laurylthiopropionate) and the like. These sulfur antioxidants can be used alone or in combination of two or more.
本発明の一実施形態において、本発明の組成物に含まれ得る二次酸化防止剤の含有量は、ポリマー(B)100質量部に対して、好ましくは0.002質量部以上、より好ましくは0.01質量部以上、さらに好ましくは0.04質量部以上、さらにより好ましくは0.1質量部以上、特に好ましくは1質量部以上である。二次酸化防止剤の含有量が上記下限以上であると、ポリマー(B)の酸化を十分に抑制しやすいため、フィルムの耐吸湿性及び耐熱性を向上しやすい。二次酸化防止剤の含有量は、ポリマー(B)100質量部に対して、好ましくは30質量部以下、より好ましくは20質量部以下、さらに好ましくは10質量部以下、さらにより好ましくは7質量部以下、特に好ましくは5質量部以下である。二次酸化防止剤の含有量が上記上限以下であると、フィルムの誘電特性を高めやすい。
In one embodiment of the present invention, the content of the secondary antioxidant that can be contained in the composition of the present invention is preferably 0.002 parts by mass or more, more preferably 100 parts by mass of the polymer (B) 0.01 parts by mass or more, more preferably 0.04 parts by mass or more, still more preferably 0.1 parts by mass or more, and particularly preferably 1 part by mass or more. When the content of the secondary antioxidant is at least the above lower limit, the oxidation of the polymer (B) can be sufficiently suppressed, and the hygroscopic resistance and heat resistance of the film can be easily improved. The content of the secondary antioxidant is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and still more preferably 7 parts by mass with respect to 100 parts by mass of the polymer (B). parts or less, particularly preferably 5 parts by mass or less. When the content of the secondary antioxidant is equal to or less than the above upper limit, the dielectric properties of the film are likely to be enhanced.
本発明の一実施形態において、本発明の組成物に含まれ得る二次酸化防止剤の含有量は、フェノール系酸化防止剤100質量部に対して、好ましくは5質量部以上、より好ましくは10質量部以上、さらに好ましくは15質量部以上、特に好ましくは20質量部以上、特に好ましくは30質量部以上である。二次酸化防止剤の含有量が上記下限以上であると、ポリマー(B)の酸化を十分に抑制しやすいため、フィルムの耐吸湿性及び耐熱性を向上しやすい。二次酸化防止剤の含有量は、フェノール系酸化防止剤100質量部に対して、好ましくは1000質量部以下、より好ましくは700質量部以下、さらに好ましくは600質量部以下、さらにより好ましくは500質量部以下、特に好ましくは200質量部以下、特により好ましくは150質量部以下、特にさらに好ましくは100質量部以下である。二次酸化防止剤の含有量が上記上限以下であると、フィルムの誘電特性を高めやすい。
In one embodiment of the present invention, the content of the secondary antioxidant that can be contained in the composition of the present invention is preferably 5 parts by mass or more, more preferably 10 parts by mass with respect to 100 parts by mass of the phenolic antioxidant. It is at least 15 parts by mass, more preferably at least 20 parts by mass, particularly preferably at least 30 parts by mass. When the content of the secondary antioxidant is at least the above lower limit, the oxidation of the polymer (B) can be sufficiently suppressed, and the hygroscopic resistance and heat resistance of the film can be easily improved. The content of the secondary antioxidant is preferably 1000 parts by mass or less, more preferably 700 parts by mass or less, still more preferably 600 parts by mass or less, still more preferably 500 parts by mass or less, relative to 100 parts by mass of the phenolic antioxidant. Part by mass or less, particularly preferably 200 parts by mass or less, particularly more preferably 150 parts by mass or less, and even more preferably 100 parts by mass or less. When the content of the secondary antioxidant is equal to or less than the above upper limit, the dielectric properties of the film are likely to be enhanced.
本発明の一実施形態において、本発明の組成物は、本発明の効果を損なわない範囲で、必要に応じて、添加剤を含んでいてもよい。添加剤としては、例えば、難燃剤、架橋剤、界面活性剤、相溶化剤、イミド化触媒、耐候剤、滑剤、抗ブロッキング剤、帯電防止剤、防曇剤、無滴剤、顔料、フィラーなどが挙げられる。添加剤は単独又は二種以上を組合せて使用できる。本発明の一実施形態において、本発明の組成物は、相溶化剤を含んでいなくても、ポリマー(B)の凝集体の形成を有効に抑制し、ポリマー(B)が高い分散性を示すため、高い耐吸湿性及び耐熱性を示すフィルムを形成できる。そのため、本発明における組成物において、相溶化剤の含有量は、ポリイミド系樹脂(A)100質量部に対して、好ましくは5質量部以下、より好ましくは1質量部以下、さらに好ましくは0.1質量部以下、さらにより好ましくは0.1質量部未満、特に好ましくは0.05質量部以下、特により好ましくは0.01質量部以下、特にさらに好ましくは0.001質量部以下であり、特にさらにより好ましくは0質量部であってもよい。また、例えばポリイミド系樹脂(A)がポリアミック酸のようなポリイミド系樹脂前駆体であり、フィルム製造時に熱イミド化が必要な場合には、相溶化剤によるイミド化の阻害や、加熱による相溶化剤の変質によるフィルムの特性悪化を防ぐ観点から、相溶化剤の含有量は、上記範囲の中でも、0.1質量部未満であることが好ましい。該相溶化剤の上記含有量は、ポリイミド系樹脂(A)100質量部に代えて、ポリイミド系樹脂(A)とポリマー(B)との合計100質量部を基準とした含有量としてもよい。
In one embodiment of the present invention, the composition of the present invention may contain additives as necessary within a range that does not impair the effects of the present invention. Examples of additives include flame retardants, cross-linking agents, surfactants, compatibilizers, imidization catalysts, weathering agents, lubricants, anti-blocking agents, antistatic agents, anti-fogging agents, anti-drip agents, pigments, fillers, etc. is mentioned. Additives can be used alone or in combination of two or more. In one embodiment of the present invention, the composition of the present invention effectively suppresses the formation of aggregates of the polymer (B) even without containing a compatibilizer, and the polymer (B) exhibits high dispersibility. Therefore, it is possible to form a film exhibiting high moisture absorption resistance and heat resistance. Therefore, in the composition of the present invention, the content of the compatibilizing agent is preferably 5 parts by mass or less, more preferably 1 part by mass or less, further preferably 0.1 part by mass or less, with respect to 100 parts by mass of the polyimide resin (A). 1 part by mass or less, still more preferably less than 0.1 part by mass, particularly preferably 0.05 part by mass or less, particularly more preferably 0.01 part by mass or less, and even more preferably 0.001 part by mass or less, Even more preferably, it may be 0 parts by mass. Further, for example, when the polyimide resin (A) is a polyimide resin precursor such as polyamic acid and thermal imidization is required during film production, inhibition of imidization by a compatibilizing agent or compatibilization by heating The content of the compatibilizing agent is preferably less than 0.1 parts by mass within the above range from the viewpoint of preventing deterioration of the properties of the film due to deterioration of the agent. The content of the compatibilizer may be based on 100 parts by mass of the polyimide resin (A) and the polymer (B) in place of 100 parts by mass of the polyimide resin (A).
本発明の一実施形態において、組成物に含まれるポリイミド系樹脂(A)及びポリマー(B)の合計質量は、好ましくは1質量%以上、より好ましくは3質量%以上、さらに好ましくは5質量%以上であり、好ましくは50質量%以下、より好ましくは40質量%以下、さらに好ましくは30質量%以下、さらにより好ましくは25質量%以下、特に好ましくは20質量%以下である。組成物に含まれるポリイミド系樹脂(A)及びポリマー(B)の合計質量が上記の範囲であると、ポリマー(B)の凝集体の形成を抑制しやすく、ポリマー(B)の分散性を高めやすい。また、フェノール系酸化防止剤がポリマー(B)に吸着しやすいことから、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the total mass of the polyimide resin (A) and polymer (B) contained in the composition is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass. It is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less. When the total mass of the polyimide resin (A) and the polymer (B) contained in the composition is within the above range, it is easy to suppress the formation of aggregates of the polymer (B), and the dispersibility of the polymer (B) is increased. Cheap. In addition, since the phenol-based antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.
〔組成物の製造方法〕
本発明の組成物の製造方法は、特に限定されず、例えば、ポリイミド系樹脂(A)、ポリマー(B)、フェノール系酸化防止剤、並びに、任意に溶媒、二次酸化防止剤、及び添加剤等を混合することによって調製又は製造してもよいが、ポリマー(B)が粒子状である本発明の好適な一実施形態では、以下の工程:
粒子状ポリマー(B)を含む分散液(以下、粒子状ポリマー(B)分散液ということがある)を調製する工程(I);及び
該粒子状ポリマー(B)分散液にポリイミド系樹脂(A)を添加する工程(II)
を含み、前記工程(I)及び/又は前記工程(II)において、フェノール系酸化防止剤を添加する方法により製造することが好ましい。このような製造方法を用いると、ポリマー(B)の粒子の凝集を抑制し得るため、ポリマー(B)の分散性を向上しやすい。また、耐吸湿性及び耐熱性に優れたフィルムが得られやすい。 [Method for producing composition]
The method for producing the composition of the present invention is not particularly limited, for example, polyimide resin (A), polymer (B), phenolic antioxidant, and optionally solvent, secondary antioxidant, and additives etc., but in one preferred embodiment of the invention in which the polymer (B) is particulate, the following steps:
Step (I) of preparing a dispersion containing particulate polymer (B) (hereinafter sometimes referred to as particulate polymer (B) dispersion); ) Step (II) of adding
and preferably produced by a method of adding a phenolic antioxidant in the step (I) and/or the step (II). When such a production method is used, aggregation of the particles of the polymer (B) can be suppressed, so that the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to obtain a film excellent in moisture absorption resistance and heat resistance.
本発明の組成物の製造方法は、特に限定されず、例えば、ポリイミド系樹脂(A)、ポリマー(B)、フェノール系酸化防止剤、並びに、任意に溶媒、二次酸化防止剤、及び添加剤等を混合することによって調製又は製造してもよいが、ポリマー(B)が粒子状である本発明の好適な一実施形態では、以下の工程:
粒子状ポリマー(B)を含む分散液(以下、粒子状ポリマー(B)分散液ということがある)を調製する工程(I);及び
該粒子状ポリマー(B)分散液にポリイミド系樹脂(A)を添加する工程(II)
を含み、前記工程(I)及び/又は前記工程(II)において、フェノール系酸化防止剤を添加する方法により製造することが好ましい。このような製造方法を用いると、ポリマー(B)の粒子の凝集を抑制し得るため、ポリマー(B)の分散性を向上しやすい。また、耐吸湿性及び耐熱性に優れたフィルムが得られやすい。 [Method for producing composition]
The method for producing the composition of the present invention is not particularly limited, for example, polyimide resin (A), polymer (B), phenolic antioxidant, and optionally solvent, secondary antioxidant, and additives etc., but in one preferred embodiment of the invention in which the polymer (B) is particulate, the following steps:
Step (I) of preparing a dispersion containing particulate polymer (B) (hereinafter sometimes referred to as particulate polymer (B) dispersion); ) Step (II) of adding
and preferably produced by a method of adding a phenolic antioxidant in the step (I) and/or the step (II). When such a production method is used, aggregation of the particles of the polymer (B) can be suppressed, so that the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to obtain a film excellent in moisture absorption resistance and heat resistance.
<工程(I)>
工程(I)は、粒子状ポリマー(B)を含む分散液を調製する工程である。 <Step (I)>
Step (I) is a step of preparing a dispersion containing particulate polymer (B).
工程(I)は、粒子状ポリマー(B)を含む分散液を調製する工程である。 <Step (I)>
Step (I) is a step of preparing a dispersion containing particulate polymer (B).
本発明の一実施形態において、工程(I)は、例えば以下の工程:
ポリマー(B)を第2溶媒に溶解させてポリマー(B)溶液を得る工程(1);及び
該ポリマー(B)溶液を第1溶媒に接触させた後、第2溶媒を留去して、粒子状ポリマー(B)分散液を得る工程(2)
を含む方法により、粒子状ポリマー(B)分散液を調製する工程であることが好ましい。このような工程を含むと、ポリマー(B)の粒子の凝集を抑制し得るため、ポリマー(B)の分散性を向上しやすい。また、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。 In one embodiment of the invention, step (I) comprises, for example, the following steps:
Step (1) of dissolving polymer (B) in a second solvent to obtain a polymer (B) solution; and after contacting the polymer (B) solution with the first solvent, distilling off the second solvent, Step (2) of obtaining a particulate polymer (B) dispersion
It is preferable that the step of preparing a particulate polymer (B) dispersion is performed by a method comprising: When such a step is included, aggregation of the particles of the polymer (B) can be suppressed, so that the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
ポリマー(B)を第2溶媒に溶解させてポリマー(B)溶液を得る工程(1);及び
該ポリマー(B)溶液を第1溶媒に接触させた後、第2溶媒を留去して、粒子状ポリマー(B)分散液を得る工程(2)
を含む方法により、粒子状ポリマー(B)分散液を調製する工程であることが好ましい。このような工程を含むと、ポリマー(B)の粒子の凝集を抑制し得るため、ポリマー(B)の分散性を向上しやすい。また、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。 In one embodiment of the invention, step (I) comprises, for example, the following steps:
Step (1) of dissolving polymer (B) in a second solvent to obtain a polymer (B) solution; and after contacting the polymer (B) solution with the first solvent, distilling off the second solvent, Step (2) of obtaining a particulate polymer (B) dispersion
It is preferable that the step of preparing a particulate polymer (B) dispersion is performed by a method comprising: When such a step is included, aggregation of the particles of the polymer (B) can be suppressed, so that the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
工程(1)は、ポリマー(B)を第2溶媒に溶解させてポリマー(B)溶液を得る工程である。
Step (1) is a step of dissolving polymer (B) in a second solvent to obtain a polymer (B) solution.
工程(1)において、第2溶媒に溶解させるポリマー(B)の形態は特に限定されず、例えば粒子状、繊維状、シート状、ペレット状などであってもよい。
In step (1), the form of the polymer (B) dissolved in the second solvent is not particularly limited, and may be, for example, particulate, fibrous, sheet-like, or pellet-like.
ポリマー(B)溶液は、該溶液の質量に対して、好ましくは0.01~20質量%のポリマー(B)を含む。ポリマー(B)溶液中のポリマー(B)の含有量は、該溶液の質量に対して、好ましくは0.01質量%以上、より好ましくは0.05質量%以上、さらに好ましくは0.1質量%以上、さらにより好ましくは0.5質量%以上であり、好ましくは20質量%以下、より好ましくは10質量%以下、さらに好ましくは5質量%以下である。該溶液中のポリマー(B)の含有量が上記の下限以上であると、組成物を調整しやすい。また該溶液中のポリマー(B)の含有量が上記の上限以下であると、ポリマー(B)の凝集体の形成を抑制しやすく、ポリマー(B)の分散性を高めやすい。また、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
The polymer (B) solution preferably contains 0.01 to 20% by mass of polymer (B) relative to the mass of the solution. The content of the polymer (B) in the polymer (B) solution is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass, relative to the mass of the solution. % or more, more preferably 0.5 mass % or more, preferably 20 mass % or less, more preferably 10 mass % or less, and even more preferably 5 mass % or less. When the content of the polymer (B) in the solution is at least the above lower limit, it is easy to adjust the composition. Moreover, when the content of the polymer (B) in the solution is equal to or less than the above upper limit, the formation of aggregates of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
ポリマー(B)を第2溶媒に溶解させる方法は、特に限定されないが、例えばポリマー(B)に対して第2溶媒を加えてもよいし、第2溶媒に対してポリマー(B)を加えてもよいし、その両方であってもよい。また、ポリマー(B)に対する第2溶媒の溶解度に応じて、加熱等により溶解させてもよい。
The method of dissolving the polymer (B) in the second solvent is not particularly limited. For example, the second solvent may be added to the polymer (B), or the polymer (B) may be added to the second solvent. or both. Also, depending on the solubility of the second solvent in the polymer (B), it may be dissolved by heating or the like.
工程(2)は、ポリマー(B)溶液を第1溶媒に接触させた後、第2溶媒を留去して、粒子状ポリマー(B)を含む分散液を得る工程である。
The step (2) is a step of bringing the polymer (B) solution into contact with the first solvent and then distilling off the second solvent to obtain a dispersion containing the particulate polymer (B).
工程(2)において、ポリマー(B)溶液を第1溶媒と接触させる方法は、特に限定されないが、例えばポリマー(B)溶液と第1溶媒とを混合する方法が挙げられる。具体的には、第1溶媒に対して、ポリマー(B)溶液を添加する方法、ポリマー(B)溶液に対して、第1溶媒を添加する方法が例示できる。このように接触させることにより、第1溶媒と第2溶媒との混合液中に、粒子径が小さい粒子状ポリマー(B)を析出又は分散させることができる。なお、粒子状ポリマー(B)の凝集が生じない範囲であれば、工程(2)中、任意のタイミングで樹脂(A)や他の添加剤を少量添加してもよい。
In step (2), the method of bringing the polymer (B) solution into contact with the first solvent is not particularly limited, but an example thereof includes a method of mixing the polymer (B) solution and the first solvent. Specifically, a method of adding the polymer (B) solution to the first solvent and a method of adding the first solvent to the polymer (B) solution can be exemplified. By such contact, the particulate polymer (B) having a small particle size can be precipitated or dispersed in the mixture of the first solvent and the second solvent. A small amount of the resin (A) and other additives may be added at any timing during the step (2) as long as the particulate polymer (B) does not aggregate.
第1溶媒と接触させるポリマー(B)溶液の使用量は、第1溶媒の使用量1質量部に対して、好ましくは0.01質量部以上、より好ましくは0.1質量部以上、さらに好ましくは0.3質量部以上、特に好ましくは0.7質量部以上であり、好ましくは100質量部以下、より好ましくは10質量部以下、さらに好ましくは3質量部以下、特に好ましくは1.5質量部以下である。第1溶媒と接触させるポリマー(B)溶液の使用量が上記の範囲であると、ポリマー(B)の凝集体の形成を抑制しやすく、また、粒子径が低減されやすいことから分散性を高めやすい。
The amount of the polymer (B) solution to be brought into contact with the first solvent is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 1 part by mass of the first solvent used. is 0.3 parts by mass or more, particularly preferably 0.7 parts by mass or more, preferably 100 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 3 parts by mass or less, particularly preferably 1.5 parts by mass It is below the department. When the amount of the polymer (B) solution to be brought into contact with the first solvent is within the above range, the formation of aggregates of the polymer (B) is easily suppressed, and the particle size is easily reduced, so the dispersibility is enhanced. Cheap.
工程(2)において、ポリマー(B)溶液を第1溶媒と接触させた後、第2溶媒を留去する。第2溶媒の留去により、粒子状ポリマー(B)の分散安定性を高めることができる。また、第2溶媒の留去により、ポリマー(B)がさらに析出してもよい。第2溶媒は少なくとも部分的に留去又は除去すればよく、粒子状ポリマー(B)分散液中に第2溶媒が残存していてもよい。ポリマー(B)の凝集を抑制しやすく、かつ分散液を調製しやすい観点から、粒子状ポリマー(B)分散液中に第2溶媒が部分的に残存又は一部含有していることが好ましい。
In step (2), after the polymer (B) solution is brought into contact with the first solvent, the second solvent is distilled off. By distilling off the second solvent, the dispersion stability of the particulate polymer (B) can be enhanced. Further, the polymer (B) may be further precipitated by distilling off the second solvent. The second solvent may be at least partially distilled or removed, and the second solvent may remain in the particulate polymer (B) dispersion. From the standpoints of facilitating the suppression of aggregation of the polymer (B) and the facilitating preparation of the dispersion, it is preferred that the second solvent partially remain or partly be contained in the dispersion of the particulate polymer (B).
工程(2)において、第2溶媒を留去する方法としては、特に限定されず、エバポレータ等を用いて減圧留去する方法が例示される。留去時の圧力及び温度については、第2溶媒と第1溶媒の沸点等の特性に応じて適宜選択できる。本発明の好適な製造方法では、第2溶媒と第1溶媒の混合液から第2溶媒を留去するため、通常、第2溶媒の沸点は第1溶媒の沸点よりも低い。このようにして、ポリマー(B)の凝集体を含まず、ポリマー(B)が分散した粒子状ポリマー(B)分散液を得ることができる。
In step (2), the method of distilling off the second solvent is not particularly limited, and a method of distilling off under reduced pressure using an evaporator or the like is exemplified. The pressure and temperature during distillation can be appropriately selected according to the characteristics such as the boiling points of the second solvent and the first solvent. In the preferred production method of the present invention, the second solvent is distilled off from the mixture of the second solvent and the first solvent, so the boiling point of the second solvent is usually lower than that of the first solvent. In this way, a particulate polymer (B) dispersion in which the polymer (B) is dispersed without containing aggregates of the polymer (B) can be obtained.
第2溶媒留去後に得られる粒子状ポリマー(B)分散液に含まれる第2溶媒の含有量は、第1溶媒の含有量100質量部に対して、好ましくは120質量部以下、より好ましくは100質量部以下、さらに好ましくは60質量部以下、さらにより好ましくは45質量部以下、特に好ましくは40質量部以下、特により好ましくは35質量部以下、特にさらに好ましくは30質量部以下、特にさらにより好ましくは30質量部未満、最も好ましくは25質量部以下であり、好ましくは0.01質量部以上、より好ましくは0.05質量部以上、さらに好ましくは0.1質量部以上である。第2溶媒の含有量が上記の上限以下であると、ポリマー(B)の凝集体の形成を抑制しやすく、ポリマー(B)の分散性を高めやすい。また、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。また、第2溶媒の含有量が上記の下限以上であると、分散液を調製しやすい。
The content of the second solvent contained in the particulate polymer (B) dispersion obtained after distilling off the second solvent is preferably 120 parts by mass or less, more preferably 120 parts by mass or less with respect to 100 parts by mass of the first solvent. 100 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 45 parts by mass or less, particularly preferably 40 parts by mass or less, particularly preferably 35 parts by mass or less, even more preferably 30 parts by mass or less, particularly More preferably less than 30 parts by mass, most preferably 25 parts by mass or less, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more. When the content of the second solvent is equal to or less than the above upper limit, the formation of aggregates of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. Moreover, when the content of the second solvent is at least the above lower limit, it is easy to prepare a dispersion.
本発明の別の一実施形態において、工程(I)は、例えば以下の工程:
粒子状ポリマー(B)と溶媒とを混合する工程(1’)
を含む方法により、粒子状ポリマー(B)分散液を調製する工程であってもよい。このような工程を含むと、ポリマー(B)の粒子の凝集を抑制し得るため、ポリマー(B)の分散性を高めやすい。また、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。 In another embodiment of the invention, step (I) is, for example, the following steps:
Step (1′) of mixing particulate polymer (B) and solvent
It may be a step of preparing a particulate polymer (B) dispersion by a method comprising When such a step is included, aggregation of the particles of the polymer (B) can be suppressed, so that the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
粒子状ポリマー(B)と溶媒とを混合する工程(1’)
を含む方法により、粒子状ポリマー(B)分散液を調製する工程であってもよい。このような工程を含むと、ポリマー(B)の粒子の凝集を抑制し得るため、ポリマー(B)の分散性を高めやすい。また、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。 In another embodiment of the invention, step (I) is, for example, the following steps:
Step (1′) of mixing particulate polymer (B) and solvent
It may be a step of preparing a particulate polymer (B) dispersion by a method comprising When such a step is included, aggregation of the particles of the polymer (B) can be suppressed, so that the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
工程(1’)は、粒子状ポリマー(B)と溶媒とを混合して、粒子状ポリマー(B)分散液を得る工程である。
The step (1') is a step of mixing the particulate polymer (B) and a solvent to obtain a particulate polymer (B) dispersion.
工程(1’)において使用する粒子状ポリマー(B)は、例えばポリマー(B)を粉砕機によって粉砕することによって得ることができ、必要に応じて、分級機を用いて、粒子状ポリマー(B)の粒子径を所望の範囲内に調整してもよい。また、前記工程(1)及び(2)によって得られた粒子状ポリマー(B)分散液から取り出した粒子状ポリマー(B)を使用してもよい。
The particulate polymer (B) used in step (1′) can be obtained, for example, by pulverizing the polymer (B) with a pulverizer, and if necessary, using a classifier, the particulate polymer (B ) may be adjusted within a desired range. Alternatively, the particulate polymer (B) taken out from the particulate polymer (B) dispersion obtained by the steps (1) and (2) may be used.
工程(1’)において使用する粒子状ポリマー(B)のメジアン径は、好ましくは0.01μm以上、より好ましくは0.03μm以上、さらに好ましくは0.05μm以上であり、好ましくは15μm以下、より好ましくは10μm以下、さらに好ましくは5μm以下、さらにより好ましくは3μm以下である。添加する粒子状ポリマー(B)のメジアン径が上記の下限以上であると、組成物から形成されるフィルムの誘電特性を高めやすく、またフィルムを製造しやすい。粒子状ポリマー(B)のメジアン径が上記の上限以下であると、組成物から形成されるフィルムの耐吸湿性及び耐熱性を向上しやすい。
The median diameter of the particulate polymer (B) used in step (1′) is preferably 0.01 μm or more, more preferably 0.03 μm or more, still more preferably 0.05 μm or more, and preferably 15 μm or less. It is preferably 10 µm or less, more preferably 5 µm or less, and even more preferably 3 µm or less. When the median diameter of the particulate polymer (B) to be added is at least the above lower limit, the dielectric properties of the film formed from the composition are likely to be enhanced, and the film is easily produced. When the median diameter of the particulate polymer (B) is equal to or less than the above upper limit, the hygroscopic resistance and heat resistance of the film formed from the composition are likely to be improved.
本発明の一実施形態において、粒子状ポリマー(B)と混合する溶媒は、フェノール系酸化防止剤が粒子状ポリマー(B)に吸着しやすい観点から、好ましくは第1溶媒を含む溶媒であり、より好ましくは第1溶媒である。
In one embodiment of the present invention, the solvent to be mixed with the particulate polymer (B) is preferably a solvent containing the first solvent, from the viewpoint that the phenolic antioxidant easily adsorbs to the particulate polymer (B), More preferably, it is the first solvent.
本発明の一実施形態において、工程(I)において得られる粒子状ポリマー(B)分散液は、本発明の効果を損なわない範囲で、第1溶媒と第2溶媒以外の他の溶媒を含んでいてもよい。他の溶媒としては、特に限定されず、慣用の溶媒を使用することができる。
In one embodiment of the present invention, the particulate polymer (B) dispersion obtained in step (I) contains a solvent other than the first solvent and the second solvent within a range that does not impair the effects of the present invention. You can Other solvents are not particularly limited, and commonly used solvents can be used.
本発明の一実施形態において、工程(I)において得られる粒子状ポリマー(B)分散液に含まれ得る第1溶媒、第2溶媒及び他の溶媒の合計含有量は、該分散液の質量に対して、好ましくは50質量%以上、より好ましくは70質量%以上、さらに好ましくは90質量%以上、特に好ましくは95質量%以上であり、好ましくは99.99質量%以下、より好ましくは99.9質量%以下、さらに好ましくは99質量%以下、特に好ましくは95質量%以下である。溶媒の前記含有量が上記の範囲であると、ポリマー(B)の凝集を抑制しやすく、ポリマー(B)の分散性を高めやすい。また、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the total content of the first solvent, the second solvent and other solvents that can be contained in the particulate polymer (B) dispersion obtained in step (I) is On the other hand, it is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, particularly preferably 95% by mass or more, preferably 99.99% by mass or less, more preferably 99.9% by mass or more. It is 9% by mass or less, more preferably 99% by mass or less, and particularly preferably 95% by mass or less. When the content of the solvent is within the above range, aggregation of the polymer (B) is likely to be suppressed, and dispersibility of the polymer (B) is likely to be enhanced. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
本発明の一実施形態において、第1溶媒と第2溶媒との合計質量は、工程(I)において得られる粒子状ポリマー(B)分散液に含まれ得る第1溶媒、第2溶媒及び他の溶媒の合計質量に対して、好ましくは50質量%以上、より好ましくは70質量%以上、さらに好ましくは90質量%以上、さらにより好ましくは95質量%以上であり、好ましくは100質量%以下である。第2溶媒と第1溶媒との合計質量が上記の範囲であると、ポリマー(B)の凝集を抑制しやすく、ポリマー(B)の分散性を向上しやすい。また、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the total mass of the first solvent and the second solvent is the first solvent, the second solvent and other The total mass of the solvent is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and preferably 100% by mass or less. . When the total mass of the second solvent and the first solvent is within the above range, aggregation of the polymer (B) is likely to be suppressed, and dispersibility of the polymer (B) is likely to be improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
本発明の一実施形態において、工程(I)において得られる粒子状ポリマー(B)分散液に含まれる粒子状ポリマー(B)の含有量は、該ポリマー(B)分散液の質量に対して、好ましくは0.01質量%以上、より好ましくは0.1質量%以上、さらに好ましくは1質量%以上であり、好ましくは50質量%以下、より好ましくは30質量%以下、さらに好ましくは10質量%以下、特に好ましくは5質量%以下である。粒子状ポリマー(B)の含有量が上記の範囲であると、ポリマー(B)の凝集を抑制しやすく、ポリマー(B)の分散性を高めやすい。また、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the content of the particulate polymer (B) contained in the particulate polymer (B) dispersion obtained in step (I) is, relative to the mass of the polymer (B) dispersion, Preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more, preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 10% by mass Below, it is 5 mass % or less especially preferably. When the content of the particulate polymer (B) is within the above range, aggregation of the polymer (B) is likely to be suppressed, and dispersibility of the polymer (B) is likely to be enhanced. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.
本発明の一実施形態において、後述の工程(II)において、添加するポリイミド系樹脂(A)をワニスの形態で添加する場合、工程(I)において得られる粒子状ポリマー(B)分散液に含まれる粒子状ポリマー(B)の含有量は、該ポリマー(B)分散液の質量に対して、好ましくは1質量%以上、より好ましくは5質量%以上、さらに好ましくは8質量%以上であり、好ましくは50質量%以下、より好ましくは30質量%以下、さらに好ましくは20質量%以下、特に好ましくは15質量%以下である。
In one embodiment of the present invention, when the polyimide resin (A) to be added is added in the form of varnish in step (II) described later, it is contained in the particulate polymer (B) dispersion obtained in step (I). The content of the particulate polymer (B) is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more, relative to the mass of the polymer (B) dispersion, It is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 15% by mass or less.
粒子状ポリマー(B)分散液に含まれる粒子状ポリマー(B)のメジアン径は、本発明の上記組成物中の粒子状ポリマー(B)のメジアン径と同様の範囲から選択できる。分散液中の粒子状ポリマー(B)のメジアン径が上記の下限以上であると、組成物から形成されるフィルムの誘電特性を高めやすく、またフィルムを製造しやすい。分散液中の粒子状ポリマー(B)のメジアン径が上記の上限以下であると、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。なお、粒子状ポリマー(B)分散液に含まれる粒子状ポリマー(B)のメジアン径は、レーザー回析を用いた散乱式粒度分布測定により求めることができ、例えば実施例に記載の方法により求めることができる。
The median diameter of the particulate polymer (B) contained in the particulate polymer (B) dispersion can be selected from the same range as the median diameter of the particulate polymer (B) in the composition of the present invention. When the median diameter of the particulate polymer (B) in the dispersion is at least the above lower limit, the dielectric properties of the film formed from the composition are likely to be enhanced, and the film is easily produced. When the median diameter of the particulate polymer (B) in the dispersion is equal to or less than the above upper limit, it is easy to improve the hygroscopic resistance and heat resistance of the resulting film. The median diameter of the particulate polymer (B) contained in the particulate polymer (B) dispersion can be determined by scattering particle size distribution measurement using laser diffraction, for example, by the method described in Examples. be able to.
<工程(II)>
工程(II)は、粒子状ポリマー(B)分散液にポリイミド系樹脂(A)を添加する工程である。 <Step (II)>
Step (II) is a step of adding the polyimide resin (A) to the particulate polymer (B) dispersion.
工程(II)は、粒子状ポリマー(B)分散液にポリイミド系樹脂(A)を添加する工程である。 <Step (II)>
Step (II) is a step of adding the polyimide resin (A) to the particulate polymer (B) dispersion.
工程(II)において、添加するポリイミド系樹脂(A)は固体、好ましくは粉体の形態であってもよく、ポリイミド系樹脂(A)を所定の溶媒、例えば第1溶媒に溶かしたワニスの形態であってもよい。本発明の一実施形態では、工程(II)において、ポリイミド樹脂又はポリアミック酸を固体、好ましくは粉体の形態又はワニスの形態で添加することができる。ポリイミド系樹脂(A)をワニスの形態で添加する場合、ワニス中のポリイミド系樹脂(A)の添加量は、該ワニスの質量に対して、好ましくは0.1質量%以上、より好ましくは1質量%以上、さらに好ましくは5質量%以上、さらにより好ましくは10質量%以上であり、好ましくは50質量%以下、より好ましくは30質量%以下、さらに好ましくは20質量%以下である。該ワニス中のポリイミド系樹脂(A)の添加量が上記の範囲であると、膜形成が容易となるため、フィルム製造の観点から有利である。
In step (II), the polyimide resin (A) to be added may be in the form of a solid, preferably powder, or in the form of a varnish obtained by dissolving the polyimide resin (A) in a predetermined solvent, such as the first solvent. may be In one embodiment of the present invention, in step (II), the polyimide resin or polyamic acid can be added in solid, preferably powder form or in varnish form. When the polyimide resin (A) is added in the form of a varnish, the amount of the polyimide resin (A) added in the varnish is preferably 0.1% by mass or more, more preferably 1% by mass, based on the mass of the varnish. % by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. When the amount of the polyimide resin (A) added to the varnish is within the above range, film formation is facilitated, which is advantageous from the viewpoint of film production.
工程(II)で添加するポリイミド系樹脂(A)は、ポリイミド系樹脂(A)とポリマー(B)との合計質量に対して、好ましくは50質量%以上、より好ましくは60質量%以上、さらに好ましくは65質量%以上であり、好ましくは95質量%以下、より好ましくは93質量%以下、さらに好ましくは90質量%以下である。添加するポリイミド系樹脂(A)の含有量が上記の下限以上であると、膜形成が容易となるため、フィルム製造の観点から有利である。また、ポリイミド系樹脂(A)の含有量が上記の上限以下であると、得られるフィルムの耐吸湿性及び耐熱性を向上しやすく、またフィルムの誘電特性を高めやすい。
The polyimide resin (A) added in step (II) is preferably 50% by mass or more, more preferably 60% by mass or more, based on the total mass of the polyimide resin (A) and the polymer (B). It is preferably 65% by mass or more, preferably 95% by mass or less, more preferably 93% by mass or less, and even more preferably 90% by mass or less. When the content of the polyimide-based resin (A) to be added is at least the above lower limit, film formation is facilitated, which is advantageous from the viewpoint of film production. Moreover, when the content of the polyimide resin (A) is equal to or less than the above upper limit, it is easy to improve the moisture absorption resistance and heat resistance of the obtained film, and it is easy to improve the dielectric properties of the film.
該粒子状ポリマー(B)分散液にポリイミド系樹脂(A)を添加する方法は、特に限定されず、ポリイミド系樹脂(A)を一度に添加してもよく、ポリイミド系樹脂(A)を複数回にわけて添加してもよい。
The method of adding the polyimide resin (A) to the particulate polymer (B) dispersion is not particularly limited. It may be added in batches.
上記方法において、前記工程(I)及び/又は前記工程(II)においてフェノール系酸化防止剤を添加することにより、本発明の組成物を製造できる。フェノール系酸化防止剤の添加は、工程(I)及び工程(II)のいずれの工程において行ってもよく、工程(I)及び工程(II)の両方の工程で行ってもよい。フェノール系酸化防止剤を添加する方法は特に限定されず、フェノール系酸化防止剤を一度に添加してもよく、フェノール系酸化防止剤を複数回にわけて添加してもよい。
In the above method, the composition of the present invention can be produced by adding a phenolic antioxidant in the step (I) and/or the step (II). Addition of the phenolic antioxidant may be performed in either step (I) or step (II), or may be performed in both step (I) and step (II). The method of adding the phenolic antioxidant is not particularly limited, and the phenolic antioxidant may be added at once or may be added in multiple portions.
本発明の一実施形態において、工程(I)が工程(1)及び工程(2)を含む工程である場合、フェノール系酸化防止剤を分散させやすく、ポリマー(B)に均一に吸着させやすい観点から、フェノール系酸化防止剤の添加は工程(I)において行うことが好ましい。また、本発明の一実施形態において、工程(I)が工程(1’)を含む工程である場合、フェノール系酸化防止剤を分散させやすく、ポリマー(B)に均一に吸着させやすい観点から、フェノール系酸化防止剤の添加は工程(I)において行うことが好ましい。
In one embodiment of the present invention, when the step (I) is a step including the step (1) and the step (2), the phenolic antioxidant is easily dispersed, and the polymer (B) is easily adsorbed uniformly. Therefore, it is preferable to add the phenolic antioxidant in step (I). Further, in one embodiment of the present invention, when the step (I) is a step including the step (1 '), the phenolic antioxidant is easily dispersed and uniformly adsorbed on the polymer (B). Addition of the phenolic antioxidant is preferably carried out in step (I).
工程(I)においてフェノール系酸化防止剤を添加する場合、工程(1)及び工程(2)、並びに工程(1’)のいずれの工程において行ってもよいが、フェノール系酸化防止剤を分散させやすく、ポリマー(B)に均一に吸着させやすい観点から、工程(2)又は工程(1’)、特に工程(1’)において行うことが好ましい。
When adding a phenolic antioxidant in step (I), it may be performed in any of steps (1), (2), and step (1′), but the phenolic antioxidant is dispersed. It is preferable to carry out in step (2) or step (1′), particularly step (1′), from the viewpoint of easy and uniform adsorption on the polymer (B).
工程(II)においてフェノール系酸化防止剤を添加する場合、フェノール系酸化防止剤とポリイミド系樹脂(A)との添加順序は特に制限されず、フェノール系酸化防止剤を添加した後にポリイミド系樹脂(A)を添加してもよく、ポリイミド系樹脂(A)を添加した後にフェノール系酸化防止剤を添加してもよい。本発明の一実施形態では、フェノール系酸化防止剤を分散させやすく、ポリマー(B)に均一に吸着させやすい観点から、粒子状ポリマー(B)分散液にフェノール系酸化防止剤を添加した後に、ポリイミド系樹脂(A)を添加することが好ましい。
When adding a phenolic antioxidant in step (II), the order of addition of the phenolic antioxidant and the polyimide resin (A) is not particularly limited, and the polyimide resin ( A) may be added, or the phenolic antioxidant may be added after adding the polyimide resin (A). In one embodiment of the present invention, from the viewpoint that the phenolic antioxidant is easily dispersed and uniformly adsorbed on the polymer (B), after adding the phenolic antioxidant to the particulate polymer (B) dispersion, It is preferable to add a polyimide resin (A).
工程(I)及び/又は工程(II)で添加するフェノール系酸化防止剤は、粒子状ポリマー(B)分散液又は組成物中のポリマー(B)100質量部に対して、好ましくは0.01質量部以上、より好ましくは0.05質量部以上、さらに好ましくは0.1質量部以上、さらにより好ましくは0.2質量部以上、特に好ましくは1質量部以上、特により好ましくは2質量部以上である。フェノール系酸化防止剤の添加量が上記下限以上であると、フェノール系酸化防止剤によりポリマー(B)を覆いやすく、ポリマー(B)の酸化を十分に抑制しやすいため、フィルムの耐吸湿性及び耐熱性を向上しやすい。フェノール系酸化防止剤の含有量は、ポリマー(B)100質量部に対して、好ましくは30質量部以下、より好ましくは20質量部以下、さらに好ましくは10質量部以下、さらにより好ましくは7質量部以下、特に好ましくは5質量部以下である。フェノール系酸化防止剤の含有量が上記上限以下であると、フィルムの誘電特性を高めやすい。
The phenolic antioxidant added in step (I) and/or step (II) is preferably 0.01 part per 100 parts by mass of the polymer (B) in the particulate polymer (B) dispersion or composition. Part by mass or more, more preferably 0.05 part by mass or more, still more preferably 0.1 part by mass or more, still more preferably 0.2 part by mass or more, particularly preferably 1 part by mass or more, particularly more preferably 2 parts by mass That's it. When the amount of the phenolic antioxidant added is at least the above lower limit, the polymer (B) is easily covered with the phenolic antioxidant, and the oxidation of the polymer (B) is easily suppressed. Easy to improve heat resistance. The content of the phenolic antioxidant is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and still more preferably 7 parts by mass with respect to 100 parts by mass of the polymer (B). parts or less, particularly preferably 5 parts by mass or less. When the content of the phenolic antioxidant is equal to or less than the above upper limit, the dielectric properties of the film are likely to be enhanced.
本発明における上記製造方法は、本発明の効果を損なわない範囲で、工程(I)及び(II)以外の工程を含んでいてもよく、上述のポリイミド系樹脂(A)及びポリマー(B)以外のポリマー、二次酸化防止剤又は添加剤を加えてもよい。添加剤としては、上記に記載の添加剤が挙げられる。
The above production method in the present invention may include steps other than steps (I) and (II) within a range that does not impair the effects of the present invention, other than the above-described polyimide resin (A) and polymer (B) polymers, secondary antioxidants or additives may be added. Additives include those described above.
なお、本発明の好適な実施形態では、ポリマー(B)分散液にポリイミド系樹脂(A)を添加するが、粉体形態のポリマー(B)をポリイミド系樹脂(A)のワニスに添加してもよい。前記工程(II)に示したように、ポリイミド系樹脂(A)のワニスは、ポリイミド系樹脂(A)を所定の溶媒、例えば第1溶媒に溶かしたものであってもよいし、ポリイミド系樹脂(A)の前駆体を合成した際の樹脂溶液、例えばポリアミック酸溶液(少なくともポリアミック酸と合成溶媒を含む溶液)であってもよい。
In a preferred embodiment of the present invention, the polyimide resin (A) is added to the polymer (B) dispersion. good too. As shown in the step (II), the varnish of the polyimide resin (A) may be obtained by dissolving the polyimide resin (A) in a predetermined solvent, for example, the first solvent, or the polyimide resin It may be a resin solution used when synthesizing the precursor of (A), such as a polyamic acid solution (a solution containing at least polyamic acid and a synthesis solvent).
〔フィルム〕
本発明は、ポリイミド系樹脂(A)、ポリマー(B)及びフェノール系酸化防止剤を含み、フェノール系酸化防止剤は式(P):
[式(P)中、Rp、Rq、Rr及びRsは、互いに独立に、水素原子、炭素数1~12のアルキル基又は炭素数5~12のシクロアルキル基を表し、*は結合手を表す]
で表される置換基Pを含み、フェノール系酸化防止剤中の置換基Pを水素原子に置換した構造Sは置換基を有していてもよい芳香環を有するフィルムを包含する。なお、該芳香環は置換基Pとは異なる芳香環である。 〔the film〕
The present invention comprises a polyimide resin (A), a polymer (B) and a phenolic antioxidant, wherein the phenolic antioxidant has the formula (P):
[In the formula (P), R p , R q , R r and R s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms, and * represents a bond]
The structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom includes a film having an aromatic ring which may have a substituent. The aromatic ring is an aromatic ring different from the substituent P.
本発明は、ポリイミド系樹脂(A)、ポリマー(B)及びフェノール系酸化防止剤を含み、フェノール系酸化防止剤は式(P):
で表される置換基Pを含み、フェノール系酸化防止剤中の置換基Pを水素原子に置換した構造Sは置換基を有していてもよい芳香環を有するフィルムを包含する。なお、該芳香環は置換基Pとは異なる芳香環である。 〔the film〕
The present invention comprises a polyimide resin (A), a polymer (B) and a phenolic antioxidant, wherein the phenolic antioxidant has the formula (P):
The structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom includes a film having an aromatic ring which may have a substituent. The aromatic ring is an aromatic ring different from the substituent P.
本発明のフィルムは、耐吸湿性及び耐熱性に優れるため、発明のフィルムをCCLの樹脂層に使用した場合、誘電特性を高めやすく、誘電損失及び伝送損失を抑制しやすい。
Since the film of the present invention has excellent moisture absorption resistance and heat resistance, when the film of the present invention is used for the resin layer of the CCL, it is easy to improve the dielectric properties and suppress the dielectric loss and transmission loss.
本発明の一実施形態において、本発明のフィルムに含まれるポリマー(B)は、粒子状であることが好ましい。ポリマー(B)が粒子状であると、ポリマー(B)の分散性を高めやすく、フィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the polymer (B) contained in the film of the present invention is preferably particulate. When the polymer (B) is in the form of particles, the dispersibility of the polymer (B) is likely to be enhanced, and the hygroscopic resistance and heat resistance of the film are likely to be improved.
本発明の一実施形態において、ポリマー(B)が粒子状である場合、粒子状ポリマー(B)の平均一次粒子径は15μm以下であることが好ましく、より好ましくは10μm以下、さらに好ましくは5μm以下、さらにより好ましくは3μm以下、特に好ましくは1μm以下、特により好ましくは0.8μm以下、特にさらに好ましくは0.5μm以下であり、好ましくは0.01μm以上、より好ましくは0.03μm以上、さらに好ましくは0.05μm以上である。粒子状ポリマー(B)の平均一次粒子径が上記の下限以上であると、フィルムの機械的特性を高めやすい。粒子状ポリマー(B)の平均一次粒子径が上記の上限以下であると、粒子状ポリマー(B)の粒子分散性を高めやすく、フィルムの耐吸湿性及び耐熱性を向上しやすい。なお、粒子状ポリマー(B)の平均一次粒子径は、電子顕微鏡により撮影した画像の画像解析により求めることができる。例えば、走査型透過電子顕微鏡(STEM)を用いてフィルムの断面観察を行い、観察画像から50個以上の粒子の粒子径を測定し、それらの平均値を粒子状シクロオレフィンコポリマーの平均一次粒子径とすることができ、例えば実施例に記載の方法により測定できる。
In one embodiment of the present invention, when the polymer (B) is particulate, the average primary particle size of the particulate polymer (B) is preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. , still more preferably 3 μm or less, particularly preferably 1 μm or less, particularly more preferably 0.8 μm or less, even more preferably 0.5 μm or less, preferably 0.01 μm or more, more preferably 0.03 μm or more, and further It is preferably 0.05 μm or more. When the average primary particle size of the particulate polymer (B) is at least the above lower limit, the mechanical properties of the film are likely to be enhanced. When the average primary particle size of the particulate polymer (B) is equal to or less than the above upper limit, the particle dispersibility of the particulate polymer (B) is likely to be enhanced, and the hygroscopic resistance and heat resistance of the film are likely to be enhanced. The average primary particle size of the particulate polymer (B) can be determined by image analysis of images taken with an electron microscope. For example, the cross section of the film is observed using a scanning transmission electron microscope (STEM), the particle diameters of 50 or more particles are measured from the observed image, and the average value thereof is the average primary particle diameter of the particulate cycloolefin copolymer. and can be measured, for example, by the method described in Examples.
本発明の好適な実施形態では、本発明のフィルムは、ポリイミド系樹脂(A)に対して、ポリマー(B)が分散、好ましくは均一分散した複合フィルムであることが好ましい。例えば、該複合フィルムは海島構造を有し、ポリイミド系樹脂(A)が海、ポリマー(B)が島であることが好ましい。このような複合フィルムは、耐吸湿性及び耐熱性を向上しやすい。
In a preferred embodiment of the present invention, the film of the present invention is preferably a composite film in which the polymer (B) is dispersed, preferably uniformly dispersed, in the polyimide resin (A). For example, the composite film preferably has a sea-island structure, wherein the polyimide resin (A) is the sea and the polymer (B) is the islands. Such a composite film tends to improve moisture absorption resistance and heat resistance.
本発明の好適な実施形態において、本発明のフィルムは、本発明の上記組成物から形成されたものであることが好ましい。このようなフィルムは、好ましくは本発明の組成物から溶媒を除去して形成されるため、本発明のフィルムに含まれる成分、例えばポリイミド系樹脂(A)、ポリマー(B)、フェノール系酸化防止剤及び二次酸化防止剤などに関する記載は、〔組成物〕の項に記載のものと同様である。また、本発明の好適な一実施形態において、本発明のフィルムに溶媒が含まれる場合、溶媒の種類及び本発明のフィルムに含まれる各成分と溶媒とのHSP値間距離に関する記載は、〔組成物〕の項に記載のものと同様である。
In a preferred embodiment of the present invention, the film of the present invention is preferably formed from the composition of the present invention. Since such a film is preferably formed by removing the solvent from the composition of the present invention, components contained in the film of the present invention, such as polyimide resin (A), polymer (B), phenolic antioxidant The descriptions regarding the agent, secondary antioxidant, etc. are the same as those described in the section [Composition]. In a preferred embodiment of the present invention, when the film of the present invention contains a solvent, the type of the solvent and the distance between the HSP values between each component contained in the film of the present invention and the solvent are described in [Composition Item].
本発明の一実施形態において、フィルムに含まれるポリイミド系樹脂(A)及びポリマー(B)の合計質量は、該フィルムの質量に対して、好ましくは40質量%以上、より好ましくは60質量%以上、さらに好ましくは80質量%以上、特に好ましくは90質量%以上であり、好ましくは100質量%以下である。フィルムに含まれるポリイミド系樹脂(A)及びポリマー(B)の合計質量が上記の下限以上であると、ポリマー(B)の分散性を高めやすく、フィルムの耐吸湿性及び耐熱性を向上しやすい。
In one embodiment of the present invention, the total mass of the polyimide resin (A) and polymer (B) contained in the film is preferably 40% by mass or more, more preferably 60% by mass or more, relative to the mass of the film. , more preferably 80% by mass or more, particularly preferably 90% by mass or more, and preferably 100% by mass or less. When the total mass of the polyimide resin (A) and the polymer (B) contained in the film is at least the above lower limit, the dispersibility of the polymer (B) is easily increased, and the hygroscopic resistance and heat resistance of the film are easily improved. .
本発明のフィルムの厚さは、用途に応じて適宜選択でき、好ましくは5μm以上、より好ましくは10μm以上、さらに好ましくは20μm以上であり、好ましくは500μm以下、より好ましくは300μm以下、さらに好ましくは100μm以下、特に好ましくは80μm以下である。フィルムの厚さは、膜厚計等を用いて測定でき、例えば実施例に記載の方法により測定できる。なお、本発明のフィルムが多層フィルムである場合、上記厚さは単層部分の平均厚さを表す。
The thickness of the film of the present invention can be appropriately selected depending on the application, and is preferably 5 µm or more, more preferably 10 µm or more, still more preferably 20 µm or more, preferably 500 µm or less, more preferably 300 µm or less, and still more preferably. 100 μm or less, particularly preferably 80 μm or less. The thickness of the film can be measured using a film thickness meter or the like, for example, by the method described in Examples. When the film of the present invention is a multilayer film, the above thickness represents the average thickness of the single layer portion.
本発明の一実施形態において、フィルムの吸湿率は、好ましくは0.64質量%以下、より好ましくは0.60質量%以下、さらに好ましくは0.57質量%以下、さらにより好ましくは0.54質量%以下、特に好ましくは0.52質量%以下、特により好ましくは0.50質量%以下である。吸湿率が上記上限以下であると、優れた耐吸湿性を発現できる。そのため、本発明のフィルムをCCLの樹脂層に使用した場合、誘電特性を高めやすく、誘電損失及び伝送損失を抑制しやすい。また、本発明のフィルムの吸湿率は、通常0.01質量%以上であってよい。なお、本発明のフィルムの吸湿率は、フィルムを温度23℃及び湿度50%環境に一定時間曝露し、曝露後のフィルムの水分量を水分計により測定することにより求めることができ、例えば実施例に記載の方法により測定できる。
In one embodiment of the present invention, the moisture absorption rate of the film is preferably 0.64% by mass or less, more preferably 0.60% by mass or less, even more preferably 0.57% by mass or less, and even more preferably 0.54% by mass. % by mass or less, particularly preferably 0.52 mass % or less, particularly preferably 0.50 mass % or less. When the moisture absorption rate is equal to or less than the above upper limit, excellent moisture absorption resistance can be exhibited. Therefore, when the film of the present invention is used for the resin layer of CCL, it is easy to improve the dielectric properties and to suppress dielectric loss and transmission loss. Moreover, the moisture absorption rate of the film of the present invention may generally be 0.01% by mass or more. The moisture absorption rate of the film of the present invention can be determined by exposing the film to an environment with a temperature of 23° C. and a humidity of 50% for a certain period of time and measuring the moisture content of the film after the exposure with a moisture meter. It can be measured by the method described in .
本発明の一実施形態では、本発明のフィルムの耐熱性は、耐熱劣化試験前後のポリマー(B)のIRピーク維持率により評価してよい。例えば、ポリマー(B)がシクロオレフィン系ポリマーである場合、IRピークの維持率は、大気中、360℃で5分間アニール処理した際の(すなわち耐熱劣化試験前後の)シクロオレフィン系ポリマーに由来する2500~3500cm-1、好ましくは2900~3000cm-1の範囲におけるピークの維持率であってよい。具体的には、下記式:
IRピーク維持率
=〔(劣化試験後のシクロオレフィン系ポリマーピーク強度)/(劣化試験後のポリイミド系樹脂のピーク強度)〕÷〔(劣化試験前のシクロオレフィン系ポリマーピーク強度)/(劣化試験前のポリイミド系樹脂のピーク強度)〕
[式中、シクロオレフィン系ポリマーピーク強度は、2500~3500cm-1、好ましくは2900~3000cm-1のピークトップ強度であり、ポリイミド系樹脂ピーク強度は、1450~1550cm-1、好ましくは1480~1520cm-1のピークトップ強度を示す]
により算出できる。
シクロオレフィン系ポリマーにおいて、2500~3500cm-1のピークトップ強度は、シクロオレフィン系ポリマーに含まれるC-Hの伸縮振動を示し、ポリイミド系樹脂において、1450~1550cm-1のピークトップ強度は、ベンゼン環のC=C 伸縮振動を示す。ポリマー(B)のIRピーク維持率は、例えば実施例に記載の方法により求めることができる。 In one embodiment of the present invention, the heat resistance of the film of the present invention may be evaluated by the IR peak retention rate of polymer (B) before and after the heat deterioration test. For example, when the polymer (B) is a cycloolefin-based polymer, the retention rate of the IR peak is derived from the cycloolefin-based polymer when annealed at 360° C. for 5 minutes in air (that is, before and after the heat deterioration test). It may be a peak retention rate in the range of 2500 to 3500 cm −1 , preferably 2900 to 3000 cm −1 . Specifically, the following formula:
IR peak retention rate = [(peak intensity of cycloolefin polymer after deterioration test) / (peak intensity of polyimide resin after deterioration test)] ÷ [(peak intensity of cycloolefin polymer before deterioration test) / (degradation test Peak intensity of the previous polyimide resin)]
[In the formula, the cycloolefin polymer peak intensity is 2500 to 3500 cm -1 , preferably 2900 to 3000 cm -1 peak top intensity, and the polyimide resin peak intensity is 1450 to 1550 cm -1 , preferably 1480 to 1520 cm shows a peak top intensity of -1 ]
It can be calculated by
In the cycloolefin-based polymer, the peak top intensity of 2500 to 3500 cm -1 indicates the stretching vibration of C-H contained in the cycloolefin-based polymer, and in the polyimide-based resin, the peak top intensity of 1450 to 1550 cm -1 is benzene. The C=C stretching vibration of the ring is shown. The IR peak retention rate of polymer (B) can be determined, for example, by the method described in Examples.
IRピーク維持率
=〔(劣化試験後のシクロオレフィン系ポリマーピーク強度)/(劣化試験後のポリイミド系樹脂のピーク強度)〕÷〔(劣化試験前のシクロオレフィン系ポリマーピーク強度)/(劣化試験前のポリイミド系樹脂のピーク強度)〕
[式中、シクロオレフィン系ポリマーピーク強度は、2500~3500cm-1、好ましくは2900~3000cm-1のピークトップ強度であり、ポリイミド系樹脂ピーク強度は、1450~1550cm-1、好ましくは1480~1520cm-1のピークトップ強度を示す]
により算出できる。
シクロオレフィン系ポリマーにおいて、2500~3500cm-1のピークトップ強度は、シクロオレフィン系ポリマーに含まれるC-Hの伸縮振動を示し、ポリイミド系樹脂において、1450~1550cm-1のピークトップ強度は、ベンゼン環のC=C 伸縮振動を示す。ポリマー(B)のIRピーク維持率は、例えば実施例に記載の方法により求めることができる。 In one embodiment of the present invention, the heat resistance of the film of the present invention may be evaluated by the IR peak retention rate of polymer (B) before and after the heat deterioration test. For example, when the polymer (B) is a cycloolefin-based polymer, the retention rate of the IR peak is derived from the cycloolefin-based polymer when annealed at 360° C. for 5 minutes in air (that is, before and after the heat deterioration test). It may be a peak retention rate in the range of 2500 to 3500 cm −1 , preferably 2900 to 3000 cm −1 . Specifically, the following formula:
IR peak retention rate = [(peak intensity of cycloolefin polymer after deterioration test) / (peak intensity of polyimide resin after deterioration test)] ÷ [(peak intensity of cycloolefin polymer before deterioration test) / (degradation test Peak intensity of the previous polyimide resin)]
[In the formula, the cycloolefin polymer peak intensity is 2500 to 3500 cm -1 , preferably 2900 to 3000 cm -1 peak top intensity, and the polyimide resin peak intensity is 1450 to 1550 cm -1 , preferably 1480 to 1520 cm shows a peak top intensity of -1 ]
It can be calculated by
In the cycloolefin-based polymer, the peak top intensity of 2500 to 3500 cm -1 indicates the stretching vibration of C-H contained in the cycloolefin-based polymer, and in the polyimide-based resin, the peak top intensity of 1450 to 1550 cm -1 is benzene. The C=C stretching vibration of the ring is shown. The IR peak retention rate of polymer (B) can be determined, for example, by the method described in Examples.
本発明の一実施形態において、ポリマー(B)のIRピーク維持率は、好ましくは50%以上、より好ましくは60%以上、さらに好ましくは70%以上、さらにより好ましくは80%以上、特に好ましくは85%以上、特により好ましくは90%以上である。ポリマー(B)のIRピーク維持率が上記下限以上であると、優れた耐熱性を発現しやすい。IRピーク維持率の上限は特に限定されず、通常100%以下である。
In one embodiment of the present invention, the IR peak retention rate of the polymer (B) is preferably 50% or higher, more preferably 60% or higher, even more preferably 70% or higher, still more preferably 80% or higher, particularly preferably 85% or more, particularly preferably 90% or more. When the IR peak retention rate of the polymer (B) is at least the above lower limit, excellent heat resistance tends to be exhibited. The upper limit of the IR peak retention rate is not particularly limited, and is usually 100% or less.
本発明のフィルムは、単層フィルムであってもよく、本発明のフィルムからなる層を少なくとも1層含む多層フィルムであってもよい。該多層フィルムは他の層(又は他のフィルム)を含むことができる。このような場合にも全ての層を含めて本発明のフィルムと称する。他の層としては、例えば機能層などが挙げられる。該機能層としては、プライマー層、ガスバリア層、粘着層、保護層などが例示できる。機能層は単独又は二種以上組合せて使用できる。
The film of the present invention may be a single layer film or a multilayer film containing at least one layer made of the film of the present invention. The multilayer film can contain other layers (or other films). Even in such a case, the film including all layers is referred to as the film of the present invention. Other layers include, for example, functional layers. Examples of the functional layer include a primer layer, a gas barrier layer, an adhesive layer, and a protective layer. A functional layer can be used individually or in combination of 2 or more types.
本発明のフィルムは、通常工業的に採用されている方法によって、コロナ放電処理、火炎処理、プラズマ処理、オゾン処理等の表面処理が施されていてもよい。
The film of the present invention may be subjected to surface treatment such as corona discharge treatment, flame treatment, plasma treatment, ozone treatment, etc., by a method commonly employed industrially.
本発明の組成物及びフィルムは、上記実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲で種々の変更が可能である。また、上記以外の実施形態の構成や方法等を任意に採用して組合せてもよく、上記の1つの実施形態に係る構成や方法等を上記の他の実施形態に係る構成や方法等に適用してもよい。
The composition and film of the present invention are not limited to the above embodiments, and various modifications are possible without departing from the gist of the present invention. In addition, the configurations, methods, etc. of the embodiments other than the above may be arbitrarily adopted and combined, and the configurations, methods, etc. according to the above one embodiment are applied to the configurations, methods, etc. according to the above other embodiments. You may
本発明の一実施形態にかかるフィルムは、耐吸湿性及び誘電特性に優れる。そのため、高周波帯域用のプリント回路基板やアンテナ基板に対応可能な基板材料などに好適に利用できる。例えばCCLは、樹脂層の両表面に接着剤を介して銅箔が積層された構造を有する。本発明のフィルムを該樹脂層として使用する場合、耐吸湿性に優れ、誘電損失が小さいため、伝送損失を低減することができる。本発明のフィルムを該樹脂層として使用する場合、耐熱性に優れるため、高温環境下に曝されても、優れた誘電特性を維持できる。さらに、本発明のフィルムを該樹脂層として使用する場合、表面平滑性が高く、また物性のバラツキ及びCTEが低減されているため、従来のものと比較し、銅箔と樹脂層との剥がれを有効に抑制できる。さらには、機械的特性、特に屈曲耐性に優れるため、塑性変形に強く、巻き癖が付きにくく、またフレキシブル基板材料にも使用できる。
本発明のフィルムは、その他、自動車部品、電気・電子部品等の工業材料;レンズ、プリズム、光ファイバー、記録媒体等の光学材料等にも好適に用いられる。 A film according to an embodiment of the present invention has excellent moisture absorption resistance and dielectric properties. Therefore, it can be suitably used as a substrate material compatible with printed circuit boards and antenna substrates for high frequency bands. For example, CCL has a structure in which copper foils are laminated on both surfaces of a resin layer via an adhesive. When the film of the present invention is used as the resin layer, transmission loss can be reduced because of its excellent moisture absorption resistance and low dielectric loss. When the film of the present invention is used as the resin layer, it has excellent heat resistance, so that it can maintain excellent dielectric properties even when exposed to a high-temperature environment. Furthermore, when the film of the present invention is used as the resin layer, the surface smoothness is high, and the variation in physical properties and CTE are reduced. can be effectively suppressed. Furthermore, since it has excellent mechanical properties, especially bending resistance, it is resistant to plastic deformation and is less likely to curl, and can be used as a material for flexible substrates.
The film of the present invention is also suitably used for industrial materials such as automobile parts and electric/electronic parts; optical materials such as lenses, prisms, optical fibers, and recording media.
本発明のフィルムは、その他、自動車部品、電気・電子部品等の工業材料;レンズ、プリズム、光ファイバー、記録媒体等の光学材料等にも好適に用いられる。 A film according to an embodiment of the present invention has excellent moisture absorption resistance and dielectric properties. Therefore, it can be suitably used as a substrate material compatible with printed circuit boards and antenna substrates for high frequency bands. For example, CCL has a structure in which copper foils are laminated on both surfaces of a resin layer via an adhesive. When the film of the present invention is used as the resin layer, transmission loss can be reduced because of its excellent moisture absorption resistance and low dielectric loss. When the film of the present invention is used as the resin layer, it has excellent heat resistance, so that it can maintain excellent dielectric properties even when exposed to a high-temperature environment. Furthermore, when the film of the present invention is used as the resin layer, the surface smoothness is high, and the variation in physical properties and CTE are reduced. can be effectively suppressed. Furthermore, since it has excellent mechanical properties, especially bending resistance, it is resistant to plastic deformation and is less likely to curl, and can be used as a material for flexible substrates.
The film of the present invention is also suitably used for industrial materials such as automobile parts and electric/electronic parts; optical materials such as lenses, prisms, optical fibers, and recording media.
〔フィルムの製造方法〕
本発明のフィルムの製造方法は、特に限定されないが、例えば以下の工程:
(a)ポリイミド系樹脂(A)、ポリマー(B)、フェノール系酸化防止剤及び任意に溶媒を含む組成物を調製する組成物調製工程、
(b)組成物を基材に塗布して塗膜を形成する塗布工程、及び
(c)塗布された液(塗膜)を乾燥させて、フィルムを形成するフィルム形成工程
を含む方法によって製造することができる。ポリイミド系樹脂(A)の熱イミド化を行う際には、イミド化反応を完了させる工程が含まれてもよい。 [Film production method]
The method for producing the film of the present invention is not particularly limited, but for example the following steps:
(a) a composition preparation step of preparing a composition comprising a polyimide resin (A), a polymer (B), a phenolic antioxidant and optionally a solvent;
(b) a coating step of applying the composition to a substrate to form a coating film; and (c) a film forming step of drying the applied liquid (coating film) to form a film. be able to. When performing thermal imidization of the polyimide resin (A), a step of completing the imidization reaction may be included.
本発明のフィルムの製造方法は、特に限定されないが、例えば以下の工程:
(a)ポリイミド系樹脂(A)、ポリマー(B)、フェノール系酸化防止剤及び任意に溶媒を含む組成物を調製する組成物調製工程、
(b)組成物を基材に塗布して塗膜を形成する塗布工程、及び
(c)塗布された液(塗膜)を乾燥させて、フィルムを形成するフィルム形成工程
を含む方法によって製造することができる。ポリイミド系樹脂(A)の熱イミド化を行う際には、イミド化反応を完了させる工程が含まれてもよい。 [Film production method]
The method for producing the film of the present invention is not particularly limited, but for example the following steps:
(a) a composition preparation step of preparing a composition comprising a polyimide resin (A), a polymer (B), a phenolic antioxidant and optionally a solvent;
(b) a coating step of applying the composition to a substrate to form a coating film; and (c) a film forming step of drying the applied liquid (coating film) to form a film. be able to. When performing thermal imidization of the polyimide resin (A), a step of completing the imidization reaction may be included.
<組成物調製工程>
組成物調製工程は、例えば、ポリイミド系樹脂(A)、ポリマー(B)、フェノール系酸化防止剤及び任意に溶媒、前記添加剤を混合することにより組成物を調製すればよい。好ましくは本発明の組成物を使用すること、特に本発明の組成物の上記製造方法を用い、これにより得られる組成物を使用することが好ましい。本発明の組成物を用いることで、フィルム中のポリマー(B)の分散性、耐吸湿性及び耐熱性に優れたフィルムを形成できる。 <Composition preparation step>
In the composition preparation step, for example, the composition may be prepared by mixing the polyimide resin (A), the polymer (B), the phenolic antioxidant, optionally the solvent, and the additives. It is preferred to use the composition of the invention, in particular the composition obtained by using the above-described process for producing the composition of the invention. By using the composition of the present invention, a film having excellent dispersibility of the polymer (B) in the film, moisture absorption resistance and heat resistance can be formed.
組成物調製工程は、例えば、ポリイミド系樹脂(A)、ポリマー(B)、フェノール系酸化防止剤及び任意に溶媒、前記添加剤を混合することにより組成物を調製すればよい。好ましくは本発明の組成物を使用すること、特に本発明の組成物の上記製造方法を用い、これにより得られる組成物を使用することが好ましい。本発明の組成物を用いることで、フィルム中のポリマー(B)の分散性、耐吸湿性及び耐熱性に優れたフィルムを形成できる。 <Composition preparation step>
In the composition preparation step, for example, the composition may be prepared by mixing the polyimide resin (A), the polymer (B), the phenolic antioxidant, optionally the solvent, and the additives. It is preferred to use the composition of the invention, in particular the composition obtained by using the above-described process for producing the composition of the invention. By using the composition of the present invention, a film having excellent dispersibility of the polymer (B) in the film, moisture absorption resistance and heat resistance can be formed.
<塗布工程及びフィルム形成工程>
塗布工程は、組成物調製工程で得られた組成物を基材に塗布して塗膜を形成する工程である。 <Coating step and film forming step>
The application step is a step of applying the composition obtained in the composition preparation step to a substrate to form a coating film.
塗布工程は、組成物調製工程で得られた組成物を基材に塗布して塗膜を形成する工程である。 <Coating step and film forming step>
The application step is a step of applying the composition obtained in the composition preparation step to a substrate to form a coating film.
塗布工程において、公知の塗布方法により、基材上に組成物を塗布して塗膜を形成する。公知の塗布方法としては、例えばワイヤーバーコーティング法、リバースコーティング、グラビアコーティング等のロールコーティング法、ダイコート法、カンマコート法、リップコート法、スピンコーティング法、スクリーンコーティング法、ファウンテンコーティング法、ディッピング法、スプレー法、カーテンコート法、スロットコート法、流涎成形法等が挙げられる。
In the coating step, a coating film is formed by coating the composition on the substrate by a known coating method. Known coating methods include, for example, wire bar coating, reverse coating, roll coating such as gravure coating, die coating, comma coating, lip coating, spin coating, screen coating, fountain coating, dipping, A spray method, a curtain coating method, a slot coating method, a casting method, and the like can be mentioned.
基材の例としては、銅板(銅箔含む)、SUS板(SUS箔、SUSベルト含む)、ガラス基板、PETフィルム、PENフィルム、他のポリイミド系樹脂フィルム、ポリアミド系樹脂フィルム等が挙げられる。中でも、耐熱性に優れる観点から、好ましくはSUS板、ガラス基板、PETフィルム、PENフィルム等が挙げられ、フィルムとの密着性及びコストの観点から、より好ましくはSUS板、ガラス基板又はPETフィルム等が挙げられる。
Examples of base materials include copper plates (including copper foil), SUS plates (including SUS foil and SUS belts), glass substrates, PET films, PEN films, other polyimide resin films, and polyamide resin films. Among them, SUS plate, glass substrate, PET film, PEN film, etc. are preferable from the viewpoint of excellent heat resistance, and SUS plate, glass substrate, PET film, etc. are more preferable from the viewpoint of adhesion to the film and cost. is mentioned.
フィルム形成工程において、塗膜を乾燥し、任意に基材から剥離することによって、フィルムを形成することができる。本発明の一実施形態において、基材が銅箔の場合には、塗膜を銅箔から剥離することなくフィルムを形成し、得られた銅箔上にフィルムが積層された積層体を銅張積層板に用いることもできる。剥離する場合、剥離後にさらにフィルムを乾燥する乾燥工程を行ってもよい。ここで、組成物を基材に塗布してフィルムを形成する場合、塗膜の基材側の面はほぼ平坦であるものの、基材側とは反対側の面(以下、エア面ともいう)に表面荒れが発生することで、厚さのバラツキが発生し、フィルムの表面平滑性が損なわれることがあるが、本発明の組成物を使用すると、このような表面荒れの形成を有効に抑制できるため、表面平滑性に優れたフィルムを形成できる。
塗膜の乾燥は、ポリイミド系樹脂(A)の耐熱性などに応じて適宜選択できるが、通常50~450℃、好ましくは55~400℃、より好ましくは70~380℃の温度にて行うことができでき、本発明の別の実施形態では、50~400℃、好ましくは70~360℃の温度にて行うことができる。本発明の好適な実施形態では、段階的に乾燥を行うことが好ましい。段階的に乾燥を行うことにより、組成物を均一に乾燥することができ、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。例えば、50~150℃の比較的低温下で加熱した後、200~450℃、好ましくは200~400℃、より好ましくは200~350℃で加熱してもよい。乾燥又は加熱の時間は、好ましくは5分~10時間、より好ましくは10分~5時間である。このような範囲で段階的に低温から高温に加熱することにより、得られるフィルムの耐吸湿性、耐熱性、熱伝導率又は熱拡散率の均一性、光学特性及びTgを向上しやすい。必要に応じて、窒素やアルゴン中等の不活性雰囲気条件下、真空もしくは減圧条件下、及び/又は通風下において塗膜の乾燥を行ってもよい。
段階的に乾燥を行う場合、段階的な乾燥の間で、基材から塗膜を剥離後、塗膜の乾燥を継続してもよく、全ての乾燥が終了してから基材から塗膜(フィルム)を剥離してもよい。例えば1段階目の乾燥後に基材から塗膜を剥離して2段階目以降の乾燥を行ってもよいし、すべての乾燥段階が終了した後に基材から塗膜(フィルム)を剥離してもよい。なお、1段階目の乾燥は予備乾燥であってよい。 In the film forming process, the coating can be dried and optionally peeled from the substrate to form a film. In one embodiment of the present invention, when the base material is a copper foil, a film is formed without peeling the coating film from the copper foil, and the obtained laminate is a copper-clad laminate in which the film is laminated on the copper foil. It can also be used for laminates. In the case of peeling, a drying process for further drying the film may be performed after peeling. Here, when the composition is applied to a substrate to form a film, the surface of the coating film on the substrate side is almost flat, but the surface opposite to the substrate side (hereinafter also referred to as the air surface). Due to the occurrence of surface roughness in the film, the thickness may vary and the surface smoothness of the film may be impaired. However, the use of the composition of the present invention effectively suppresses the formation of such surface roughness. Therefore, a film having excellent surface smoothness can be formed.
Drying of the coating film can be appropriately selected depending on the heat resistance of the polyimide resin (A), etc., and is usually carried out at a temperature of 50 to 450°C, preferably 55 to 400°C, more preferably 70 to 380°C. can be carried out, and in another embodiment of the invention, it can be carried out at a temperature of 50-400°C, preferably 70-360°C. In a preferred embodiment of the invention, the drying is preferably done in stages. By performing stepwise drying, the composition can be dried uniformly, and the moisture absorption resistance and heat resistance of the resulting film can be easily improved. For example, after heating at a relatively low temperature of 50 to 150°C, it may be heated to 200 to 450°C, preferably 200 to 400°C, more preferably 200 to 350°C. The drying or heating time is preferably 5 minutes to 10 hours, more preferably 10 minutes to 5 hours. Heating from a low temperature to a high temperature stepwise within such a range tends to improve the hygroscopic resistance, heat resistance, uniformity of thermal conductivity or thermal diffusivity, optical properties, and Tg of the resulting film. If necessary, the coating film may be dried under inert atmosphere conditions such as nitrogen or argon, under vacuum or reduced pressure conditions, and/or under ventilation.
When performing stepwise drying, after peeling the coating film from the substrate during stepwise drying, drying of the coating film may be continued, and after all drying is completed, the coating film ( film) may be peeled off. For example, after the first stage of drying, the coating film may be peeled off from the substrate and the second and subsequent drying stages may be performed, or after all the drying stages are completed, the coating film (film) may be peeled off from the substrate. good. Note that the drying in the first stage may be pre-drying.
塗膜の乾燥は、ポリイミド系樹脂(A)の耐熱性などに応じて適宜選択できるが、通常50~450℃、好ましくは55~400℃、より好ましくは70~380℃の温度にて行うことができでき、本発明の別の実施形態では、50~400℃、好ましくは70~360℃の温度にて行うことができる。本発明の好適な実施形態では、段階的に乾燥を行うことが好ましい。段階的に乾燥を行うことにより、組成物を均一に乾燥することができ、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。例えば、50~150℃の比較的低温下で加熱した後、200~450℃、好ましくは200~400℃、より好ましくは200~350℃で加熱してもよい。乾燥又は加熱の時間は、好ましくは5分~10時間、より好ましくは10分~5時間である。このような範囲で段階的に低温から高温に加熱することにより、得られるフィルムの耐吸湿性、耐熱性、熱伝導率又は熱拡散率の均一性、光学特性及びTgを向上しやすい。必要に応じて、窒素やアルゴン中等の不活性雰囲気条件下、真空もしくは減圧条件下、及び/又は通風下において塗膜の乾燥を行ってもよい。
段階的に乾燥を行う場合、段階的な乾燥の間で、基材から塗膜を剥離後、塗膜の乾燥を継続してもよく、全ての乾燥が終了してから基材から塗膜(フィルム)を剥離してもよい。例えば1段階目の乾燥後に基材から塗膜を剥離して2段階目以降の乾燥を行ってもよいし、すべての乾燥段階が終了した後に基材から塗膜(フィルム)を剥離してもよい。なお、1段階目の乾燥は予備乾燥であってよい。 In the film forming process, the coating can be dried and optionally peeled from the substrate to form a film. In one embodiment of the present invention, when the base material is a copper foil, a film is formed without peeling the coating film from the copper foil, and the obtained laminate is a copper-clad laminate in which the film is laminated on the copper foil. It can also be used for laminates. In the case of peeling, a drying process for further drying the film may be performed after peeling. Here, when the composition is applied to a substrate to form a film, the surface of the coating film on the substrate side is almost flat, but the surface opposite to the substrate side (hereinafter also referred to as the air surface). Due to the occurrence of surface roughness in the film, the thickness may vary and the surface smoothness of the film may be impaired. However, the use of the composition of the present invention effectively suppresses the formation of such surface roughness. Therefore, a film having excellent surface smoothness can be formed.
Drying of the coating film can be appropriately selected depending on the heat resistance of the polyimide resin (A), etc., and is usually carried out at a temperature of 50 to 450°C, preferably 55 to 400°C, more preferably 70 to 380°C. can be carried out, and in another embodiment of the invention, it can be carried out at a temperature of 50-400°C, preferably 70-360°C. In a preferred embodiment of the invention, the drying is preferably done in stages. By performing stepwise drying, the composition can be dried uniformly, and the moisture absorption resistance and heat resistance of the resulting film can be easily improved. For example, after heating at a relatively low temperature of 50 to 150°C, it may be heated to 200 to 450°C, preferably 200 to 400°C, more preferably 200 to 350°C. The drying or heating time is preferably 5 minutes to 10 hours, more preferably 10 minutes to 5 hours. Heating from a low temperature to a high temperature stepwise within such a range tends to improve the hygroscopic resistance, heat resistance, uniformity of thermal conductivity or thermal diffusivity, optical properties, and Tg of the resulting film. If necessary, the coating film may be dried under inert atmosphere conditions such as nitrogen or argon, under vacuum or reduced pressure conditions, and/or under ventilation.
When performing stepwise drying, after peeling the coating film from the substrate during stepwise drying, drying of the coating film may be continued, and after all drying is completed, the coating film ( film) may be peeled off. For example, after the first stage of drying, the coating film may be peeled off from the substrate and the second and subsequent drying stages may be performed, or after all the drying stages are completed, the coating film (film) may be peeled off from the substrate. good. Note that the drying in the first stage may be pre-drying.
基材が銅箔である場合、例えば、銅箔を、第二塩化鉄溶液等でエッチング除去することで、基材である銅箔からフィルムを剥離してよい。
When the base material is a copper foil, for example, the film may be peeled off from the copper foil as the base material by etching away the copper foil with a ferric chloride solution or the like.
本発明の一実施形態において、組成物中のポリイミド系樹脂(A)がポリイミド系樹脂前駆体、例えばポリアミック酸であり、フィルム製造時にポリイミド系樹脂を生成する場合、該組成物を基材に塗布後、加熱により熱イミド化することが好ましい。該加熱により、溶媒を除去する乾燥と熱イミド化を同時に行うことができる。乾燥及びイミド化温度は、通常50~450℃の範囲であり、優れた耐吸湿性を有し、かつ平滑なフィルムを得やすい観点からは、段階的に加熱を行うことが好ましい。例えば、50~150℃の比較的低温下で加熱して溶媒を除去した後、300~450℃の範囲の温度まで段階的に加熱してもよい。加熱の時間は、例えば上記範囲と同様の範囲から選択できる。
In one embodiment of the present invention, when the polyimide resin (A) in the composition is a polyimide resin precursor, such as polyamic acid, and the polyimide resin is produced during film production, the composition is applied to the substrate. After that, it is preferable to thermally imidize by heating. By the heating, drying for removing the solvent and thermal imidization can be performed at the same time. The drying and imidization temperature is usually in the range of 50 to 450° C., and from the viewpoint of easily obtaining a smooth film having excellent moisture absorption resistance, it is preferable to carry out heating in stages. For example, after removing the solvent by heating at a relatively low temperature of 50 to 150°C, it may be heated stepwise to a temperature in the range of 300 to 450°C. The heating time can be selected, for example, from the same range as the above range.
本発明のフィルムが多層フィルムである場合には、例えば、共押出加工法、押出ラミネート法、熱ラミネート法、ドライラミネート法等の多層フィルム形成法により製造することができる。
When the film of the present invention is a multilayer film, it can be produced by a multilayer film forming method such as coextrusion processing, extrusion lamination, heat lamination, and dry lamination.
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。まず測定方法について説明する。
The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples. First, the measurement method will be explained.
<ハンセン溶解度パラメータ(HSP)及びHSP値間距離>
フェノール系酸化防止剤、溶媒、シクロオレフィンコポリマー、ポリイミド系樹脂及びフッ素ポリマーのハンセン溶解度パラメータ(HSP)、並びにHSP値間距離は以下のように求めた。 <Hansen solubility parameter (HSP) and distance between HSP values>
The Hansen Solubility Parameters (HSP) of the phenolic antioxidant, solvent, cycloolefin copolymer, polyimide resin and fluoropolymer, and the distance between the HSP values were obtained as follows.
フェノール系酸化防止剤、溶媒、シクロオレフィンコポリマー、ポリイミド系樹脂及びフッ素ポリマーのハンセン溶解度パラメータ(HSP)、並びにHSP値間距離は以下のように求めた。 <Hansen solubility parameter (HSP) and distance between HSP values>
The Hansen Solubility Parameters (HSP) of the phenolic antioxidant, solvent, cycloolefin copolymer, polyimide resin and fluoropolymer, and the distance between the HSP values were obtained as follows.
(フェノール系酸化防止剤及び溶媒のハンセン溶解度パラメータ(HSP))
ハンセン溶解度パラメータを提案したハンセン博士のグループによって開発されたプログラムであるHSPiP(Ver.4.1.07)を用いて、各種HSP値を求めた。
フェノール系酸化防止剤のHSP値は、HSPiPのデータベースの数値を用い、AO-330のδDは17.9MPa0.5、δPは0.1MPa0.5、δHは0.9MPa0.5であり、Sumilizer GA80のδDは18.3MPa0.5、δPは1.6MPa0.5、δHは4.7MPa0.5であった。
フェノール系酸化防止剤の構造SのHSP値は、HSPiPを用い、構造式から算出し、AO-330の構造SのδDは17.4MPa0.5、δPは0.1MPa0.5、δHは1.4MPa0.5であり、Sumilizer GA80の構造SのδDは16.7MPa0.5、δPは5.0MPa0.5、δHは4.5MPa0.5であった。
溶媒のHSP値は、HSPiPのデータベースの数値を用い、GBLのδDは18.0MPa0.5、δPは16.6MPa0.5、δHは7.4MPa0.5であり、DMAcのδDは16.8MPa0.5、δPは11.5MPa0.5、δHは9.4MPa0.5であり、トルエンのδDは18.0MPa0.5、δPは1.4MPa0.5、δHは2.0MPa0.5であり、アセトンのδDは15.5MPa0.5、δPは10.4MPa0.5、δHは7.0MPa0.5であった。 (Hansen Solubility Parameter (HSP) of Phenolic Antioxidants and Solvents)
Various HSP values were determined using HSPiP (Ver.4.1.07), a program developed by Dr. Hansen's group who proposed the Hansen solubility parameters.
For the HSP value of the phenolic antioxidant, the values in the HSPiP database are used, and the δD of AO-330 is 17.9 MPa 0.5 , the δP is 0.1 MPa 0.5 , and the δH is 0.9 MPa 0.5 . , Sumilizer GA80 had a δD of 18.3 MPa 0.5 , a δP of 1.6 MPa 0.5 and a δH of 4.7 MPa 0.5 .
The HSP value of the structure S of the phenolic antioxidant was calculated from the structural formula using HSPiP . Structure S of Sumilizer GA80 had δD of 16.7 MPa 0.5 , δP of 5.0 MPa 0.5 and δH of 4.5 MPa 0.5 .
The HSP value of the solvent is 18.0 MPa 0.5 for GBL, 16.6 MPa 0.5 for δP, 7.4 MPa 0.5 for δH , and 16 for DMAc. 8 MPa 0.5 , δP is 11.5 MPa 0.5 , δH is 9.4 MPa 0.5 and toluene has δD of 18.0 MPa 0.5 , δP of 1.4 MPa 0.5 , δH of 2.0 MPa 0.5 . Acetone had a δD of 15.5 MPa 0.5 , a δP of 10.4 MPa 0.5 and a δH of 7.0 MPa 0.5 .
ハンセン溶解度パラメータを提案したハンセン博士のグループによって開発されたプログラムであるHSPiP(Ver.4.1.07)を用いて、各種HSP値を求めた。
フェノール系酸化防止剤のHSP値は、HSPiPのデータベースの数値を用い、AO-330のδDは17.9MPa0.5、δPは0.1MPa0.5、δHは0.9MPa0.5であり、Sumilizer GA80のδDは18.3MPa0.5、δPは1.6MPa0.5、δHは4.7MPa0.5であった。
フェノール系酸化防止剤の構造SのHSP値は、HSPiPを用い、構造式から算出し、AO-330の構造SのδDは17.4MPa0.5、δPは0.1MPa0.5、δHは1.4MPa0.5であり、Sumilizer GA80の構造SのδDは16.7MPa0.5、δPは5.0MPa0.5、δHは4.5MPa0.5であった。
溶媒のHSP値は、HSPiPのデータベースの数値を用い、GBLのδDは18.0MPa0.5、δPは16.6MPa0.5、δHは7.4MPa0.5であり、DMAcのδDは16.8MPa0.5、δPは11.5MPa0.5、δHは9.4MPa0.5であり、トルエンのδDは18.0MPa0.5、δPは1.4MPa0.5、δHは2.0MPa0.5であり、アセトンのδDは15.5MPa0.5、δPは10.4MPa0.5、δHは7.0MPa0.5であった。 (Hansen Solubility Parameter (HSP) of Phenolic Antioxidants and Solvents)
Various HSP values were determined using HSPiP (Ver.4.1.07), a program developed by Dr. Hansen's group who proposed the Hansen solubility parameters.
For the HSP value of the phenolic antioxidant, the values in the HSPiP database are used, and the δD of AO-330 is 17.9 MPa 0.5 , the δP is 0.1 MPa 0.5 , and the δH is 0.9 MPa 0.5 . , Sumilizer GA80 had a δD of 18.3 MPa 0.5 , a δP of 1.6 MPa 0.5 and a δH of 4.7 MPa 0.5 .
The HSP value of the structure S of the phenolic antioxidant was calculated from the structural formula using HSPiP . Structure S of Sumilizer GA80 had δD of 16.7 MPa 0.5 , δP of 5.0 MPa 0.5 and δH of 4.5 MPa 0.5 .
The HSP value of the solvent is 18.0 MPa 0.5 for GBL, 16.6 MPa 0.5 for δP, 7.4 MPa 0.5 for δH , and 16 for DMAc. 8 MPa 0.5 , δP is 11.5 MPa 0.5 , δH is 9.4 MPa 0.5 and toluene has δD of 18.0 MPa 0.5 , δP of 1.4 MPa 0.5 , δH of 2.0 MPa 0.5 . Acetone had a δD of 15.5 MPa 0.5 , a δP of 10.4 MPa 0.5 and a δH of 7.0 MPa 0.5 .
(シクロオレフィンコポリマーのHSP)
シクロオレフィンコポリマーの各種溶媒への溶解性を評価した。溶解性の評価は、透明の容器に溶解度パラメータが既知の溶媒(HSPiPのデータベースを参照、使用した溶媒:2-(1-シクロへキセニル)シクロヘキサノン、6-tert-ブチル-2,4-キシレノール、塩化メチル、1,4-ジオキサン、1,4-ジクロロベンゼン、クロロホルム、トルエン、1-フェニルオクタン、p-キシレン、スチレン、エタノール、1-ブタノール、N,N-ジメチルホルムアミド、ジメチルスルホキシド、GBL、N-メチルホルムアミド、酢酸)10mLとシクロオレフィンコポリマー0.1gを投入し混合液を調製した。得られた混合液に対して累計6時間超音波処理を施した。超音波処理後の混合液の外観を目視にて観察し、得られた観察結果から下記の評価基準に基づいて、それぞれの樹脂の溶媒への溶解性を評価した。
(評価基準)
2:室温で混合液の外観は白濁、沈殿が発生しているが、50℃に加温して攪拌子で30分攪拌することで混合液の外観が透明になる。
1:室温で混合液の外観は透明である。
0:室温で混合液の外観は白濁、沈殿が発生しており、50℃に加温して攪拌子で30分攪拌しても混合液の外観が透明にならない。 (HSP of cycloolefin copolymer)
The solubility of cycloolefin copolymers in various solvents was evaluated. Solubility evaluation was carried out using solvents with known solubility parameters in a transparent container (see HSPiP database, solvents used: 2-(1-cyclohexenyl)cyclohexanone, 6-tert-butyl-2,4-xylenol, Methyl chloride, 1,4-dioxane, 1,4-dichlorobenzene, chloroform, toluene, 1-phenyloctane, p-xylene, styrene, ethanol, 1-butanol, N,N-dimethylformamide, dimethylsulfoxide, GBL, N -methylformamide, acetic acid) and 0.1 g of a cycloolefin copolymer were added to prepare a mixed solution. The resulting mixture was subjected to ultrasonic treatment for a total of 6 hours. The appearance of the mixed solution after ultrasonic treatment was visually observed, and the solubility of each resin in the solvent was evaluated based on the following evaluation criteria based on the obtained observation results.
(Evaluation criteria)
2: At room temperature, the appearance of the mixed solution is cloudy and precipitation occurs, but when heated to 50° C. and stirred with a stirrer for 30 minutes, the appearance of the mixed solution becomes transparent.
1: Appearance of mixture is transparent at room temperature.
0: At room temperature, the appearance of the mixture is cloudy and precipitation occurs, and even after heating to 50° C. and stirring with a stirrer for 30 minutes, the appearance of the mixture does not become clear.
シクロオレフィンコポリマーの各種溶媒への溶解性を評価した。溶解性の評価は、透明の容器に溶解度パラメータが既知の溶媒(HSPiPのデータベースを参照、使用した溶媒:2-(1-シクロへキセニル)シクロヘキサノン、6-tert-ブチル-2,4-キシレノール、塩化メチル、1,4-ジオキサン、1,4-ジクロロベンゼン、クロロホルム、トルエン、1-フェニルオクタン、p-キシレン、スチレン、エタノール、1-ブタノール、N,N-ジメチルホルムアミド、ジメチルスルホキシド、GBL、N-メチルホルムアミド、酢酸)10mLとシクロオレフィンコポリマー0.1gを投入し混合液を調製した。得られた混合液に対して累計6時間超音波処理を施した。超音波処理後の混合液の外観を目視にて観察し、得られた観察結果から下記の評価基準に基づいて、それぞれの樹脂の溶媒への溶解性を評価した。
(評価基準)
2:室温で混合液の外観は白濁、沈殿が発生しているが、50℃に加温して攪拌子で30分攪拌することで混合液の外観が透明になる。
1:室温で混合液の外観は透明である。
0:室温で混合液の外観は白濁、沈殿が発生しており、50℃に加温して攪拌子で30分攪拌しても混合液の外観が透明にならない。 (HSP of cycloolefin copolymer)
The solubility of cycloolefin copolymers in various solvents was evaluated. Solubility evaluation was carried out using solvents with known solubility parameters in a transparent container (see HSPiP database, solvents used: 2-(1-cyclohexenyl)cyclohexanone, 6-tert-butyl-2,4-xylenol, Methyl chloride, 1,4-dioxane, 1,4-dichlorobenzene, chloroform, toluene, 1-phenyloctane, p-xylene, styrene, ethanol, 1-butanol, N,N-dimethylformamide, dimethylsulfoxide, GBL, N -methylformamide, acetic acid) and 0.1 g of a cycloolefin copolymer were added to prepare a mixed solution. The resulting mixture was subjected to ultrasonic treatment for a total of 6 hours. The appearance of the mixed solution after ultrasonic treatment was visually observed, and the solubility of each resin in the solvent was evaluated based on the following evaluation criteria based on the obtained observation results.
(Evaluation criteria)
2: At room temperature, the appearance of the mixed solution is cloudy and precipitation occurs, but when heated to 50° C. and stirred with a stirrer for 30 minutes, the appearance of the mixed solution becomes transparent.
1: Appearance of mixture is transparent at room temperature.
0: At room temperature, the appearance of the mixture is cloudy and precipitation occurs, and even after heating to 50° C. and stirring with a stirrer for 30 minutes, the appearance of the mixture does not become clear.
得られたシクロオレフィンコポリマーの溶媒への溶解性の評価結果から、HSPiPを用い、上述のハンセン溶解球法によりHSP値を算出した。
From the results of evaluating the solubility of the obtained cycloolefin copolymer in solvents, the HSP value was calculated by the above-mentioned Hansen dissolving sphere method using HSPiP.
(ポリイミド系樹脂のHSP)
ポリイミド系樹脂の各種溶媒への溶解性を評価した。溶解性の評価は、透明の容器に溶解度パラメータが既知の溶媒(HSPiPのデータベースを参照、使用した溶媒アセトン、トルエン、エタノール、テトラヒドロフラン、N,N-ジメチルホルムアミド、ジメチルスルホキシド、ヘキサン、GBL、エチルアセテート、メチルエチルケトン、プロピレングリコールモノメチルエーテル、1-ブタノール、N-メチルホルムアミド、1-メチルナフタレン、ブロモベンゼン、1-メチルイミダゾール、ピラゾール、酢酸)10mLとポリイミド系樹脂 0.1gを投入し混合液を調製した。得られた混合液に対して累計6時間超音波処理を施した。超音波処理後の混合液の外観を目視にて観察し、得られた観察結果から下記の評価基準に基づいて、それぞれの樹脂の溶媒への溶解性を評価した。
(評価基準)
1:混合液の外観は白濁している。
0:混合液の外観は透明である。 (HSP of polyimide resin)
The solubility of the polyimide resin in various solvents was evaluated. Solubility evaluation was carried out using solvents with known solubility parameters in a transparent container (see HSPiP database, solvents used acetone, toluene, ethanol, tetrahydrofuran, N,N-dimethylformamide, dimethylsulfoxide, hexane, GBL, ethyl acetate , methyl ethyl ketone, propylene glycol monomethyl ether, 1-butanol, N-methylformamide, 1-methylnaphthalene, bromobenzene, 1-methylimidazole, pyrazole, acetic acid) and 0.1 g of polyimide resin were added to prepare a mixed solution. . The resulting mixture was subjected to ultrasonic treatment for a total of 6 hours. The appearance of the mixed solution after ultrasonic treatment was visually observed, and the solubility of each resin in the solvent was evaluated based on the following evaluation criteria based on the obtained observation results.
(Evaluation criteria)
1: The appearance of the mixed liquid is cloudy.
0: Appearance of mixed liquid is transparent.
ポリイミド系樹脂の各種溶媒への溶解性を評価した。溶解性の評価は、透明の容器に溶解度パラメータが既知の溶媒(HSPiPのデータベースを参照、使用した溶媒アセトン、トルエン、エタノール、テトラヒドロフラン、N,N-ジメチルホルムアミド、ジメチルスルホキシド、ヘキサン、GBL、エチルアセテート、メチルエチルケトン、プロピレングリコールモノメチルエーテル、1-ブタノール、N-メチルホルムアミド、1-メチルナフタレン、ブロモベンゼン、1-メチルイミダゾール、ピラゾール、酢酸)10mLとポリイミド系樹脂 0.1gを投入し混合液を調製した。得られた混合液に対して累計6時間超音波処理を施した。超音波処理後の混合液の外観を目視にて観察し、得られた観察結果から下記の評価基準に基づいて、それぞれの樹脂の溶媒への溶解性を評価した。
(評価基準)
1:混合液の外観は白濁している。
0:混合液の外観は透明である。 (HSP of polyimide resin)
The solubility of the polyimide resin in various solvents was evaluated. Solubility evaluation was carried out using solvents with known solubility parameters in a transparent container (see HSPiP database, solvents used acetone, toluene, ethanol, tetrahydrofuran, N,N-dimethylformamide, dimethylsulfoxide, hexane, GBL, ethyl acetate , methyl ethyl ketone, propylene glycol monomethyl ether, 1-butanol, N-methylformamide, 1-methylnaphthalene, bromobenzene, 1-methylimidazole, pyrazole, acetic acid) and 0.1 g of polyimide resin were added to prepare a mixed solution. . The resulting mixture was subjected to ultrasonic treatment for a total of 6 hours. The appearance of the mixed solution after ultrasonic treatment was visually observed, and the solubility of each resin in the solvent was evaluated based on the following evaluation criteria based on the obtained observation results.
(Evaluation criteria)
1: The appearance of the mixed liquid is cloudy.
0: Appearance of mixed liquid is transparent.
得られたポリイミド系樹脂の溶媒への溶解性の評価結果から、HSPiPを用い、上述のハンセン溶解球法によりHSP値を算出した。
Using HSPiP, the HSP value was calculated by the above-mentioned Hansen dissolving sphere method from the evaluation results of the solubility of the obtained polyimide resin in the solvent.
(フッ素ポリマー1(THV221AZ)のHSP)
フッ素ポリマー1(以下、THVとも記載する)の各種溶媒への溶解性を評価した。溶解性の評価は、透明の容器に溶解度パラメータが既知の溶媒(HSPiPのデータベースを参照、使用した溶媒:アセトン、テトラヒドロフラン、N,N-ジメチルホルムアミド、ジメチルスルホキシド、GBL、メチルエチルケトン、1-ブタノール、酢酸ブチル、DMAc、メタノール、酢酸ヘキシル、アセト酢酸エチル、2―プロパノール)10mLとフッ素ポリマー 0.1gとを入れて混合液を調製した。得られた混合液に対して累計6時間超音波処理を施した。超音波処理後の混合液の外観を目視にて観察し、得られた観察結果から下記の評価基準に基づいて、それぞれの樹脂の溶媒への溶解性を評価した。
(評価基準)
1:混合液の外観は白濁している。
0:混合液の外観は透明である。 (HSP of fluoropolymer 1 (THV221AZ))
The solubility of fluoropolymer 1 (hereinafter also referred to as THV) in various solvents was evaluated. Solubility evaluation was carried out using solvents with known solubility parameters in a transparent container (see HSPiP database, solvents used: acetone, tetrahydrofuran, N,N-dimethylformamide, dimethylsulfoxide, GBL, methyl ethyl ketone, 1-butanol, acetic acid Butyl, DMAc, methanol, hexyl acetate, ethyl acetoacetate, 2-propanol) (10 mL) and 0.1 g of fluoropolymer were added to prepare a mixed solution. The resulting mixture was subjected to ultrasonic treatment for a total of 6 hours. The appearance of the mixed solution after ultrasonic treatment was visually observed, and the solubility of each resin in the solvent was evaluated based on the following evaluation criteria based on the obtained observation results.
(Evaluation criteria)
1: The appearance of the mixed liquid is cloudy.
0: Appearance of mixed liquid is transparent.
フッ素ポリマー1(以下、THVとも記載する)の各種溶媒への溶解性を評価した。溶解性の評価は、透明の容器に溶解度パラメータが既知の溶媒(HSPiPのデータベースを参照、使用した溶媒:アセトン、テトラヒドロフラン、N,N-ジメチルホルムアミド、ジメチルスルホキシド、GBL、メチルエチルケトン、1-ブタノール、酢酸ブチル、DMAc、メタノール、酢酸ヘキシル、アセト酢酸エチル、2―プロパノール)10mLとフッ素ポリマー 0.1gとを入れて混合液を調製した。得られた混合液に対して累計6時間超音波処理を施した。超音波処理後の混合液の外観を目視にて観察し、得られた観察結果から下記の評価基準に基づいて、それぞれの樹脂の溶媒への溶解性を評価した。
(評価基準)
1:混合液の外観は白濁している。
0:混合液の外観は透明である。 (HSP of fluoropolymer 1 (THV221AZ))
The solubility of fluoropolymer 1 (hereinafter also referred to as THV) in various solvents was evaluated. Solubility evaluation was carried out using solvents with known solubility parameters in a transparent container (see HSPiP database, solvents used: acetone, tetrahydrofuran, N,N-dimethylformamide, dimethylsulfoxide, GBL, methyl ethyl ketone, 1-butanol, acetic acid Butyl, DMAc, methanol, hexyl acetate, ethyl acetoacetate, 2-propanol) (10 mL) and 0.1 g of fluoropolymer were added to prepare a mixed solution. The resulting mixture was subjected to ultrasonic treatment for a total of 6 hours. The appearance of the mixed solution after ultrasonic treatment was visually observed, and the solubility of each resin in the solvent was evaluated based on the following evaluation criteria based on the obtained observation results.
(Evaluation criteria)
1: The appearance of the mixed liquid is cloudy.
0: Appearance of mixed liquid is transparent.
得られたフッ素ポリマーの溶媒への溶解性の評価結果から、HSPiPを用い、上述のハンセン溶解球法によりHSP値を算出した。
From the obtained evaluation results of the solubility of the fluoropolymer in the solvent, the HSP value was calculated by the above-mentioned Hansen dissolving sphere method using HSPiP.
(フッ素ポリマー2(PTFE)のHSP)
PTFEのHSP値は、文献(Marion K. Buckley-Smith, "The Use of Solubility Parameters to Select Membrane Materials for Pervaporation of Organic Mixtures", The University of Waikato, Hamilton, New Zealand, 2006, P52)に記載の数値を使用した。δDは17.1MPa0.5、δPは8.1MPa0.5、δhは1.3MPa0.5とした。 (HSP of fluoropolymer 2 (PTFE))
The HSP value of PTFE is the numerical value described in the literature (Marion K. Buckley-Smith, "The Use of Solubility Parameters to Select Membrane Materials for Pervaporation of Organic Mixtures", The University of Waikato, Hamilton, New Zealand, 2006, P52) It was used. δD was 17.1 MPa 0.5 , δP was 8.1 MPa 0.5 , and δh was 1.3 MPa 0.5 .
PTFEのHSP値は、文献(Marion K. Buckley-Smith, "The Use of Solubility Parameters to Select Membrane Materials for Pervaporation of Organic Mixtures", The University of Waikato, Hamilton, New Zealand, 2006, P52)に記載の数値を使用した。δDは17.1MPa0.5、δPは8.1MPa0.5、δhは1.3MPa0.5とした。 (HSP of fluoropolymer 2 (PTFE))
The HSP value of PTFE is the numerical value described in the literature (Marion K. Buckley-Smith, "The Use of Solubility Parameters to Select Membrane Materials for Pervaporation of Organic Mixtures", The University of Waikato, Hamilton, New Zealand, 2006, P52) It was used. δD was 17.1 MPa 0.5 , δP was 8.1 MPa 0.5 , and δh was 1.3 MPa 0.5 .
(HSP値間距離)
2つの物質のHSP値間距離(Ra)は、式(Y)に従って求めた。 (Distance between HSP values)
The distance (Ra) between the HSP values of the two substances was obtained according to formula (Y).
2つの物質のHSP値間距離(Ra)は、式(Y)に従って求めた。 (Distance between HSP values)
The distance (Ra) between the HSP values of the two substances was obtained according to formula (Y).
<ノルボルネン(NB)含有量>
シクロオレフィンコポリマーにおけるノルボルネン由来の単量体単位の含有量(「NB含有量」ともいう)は、13C-NMRを用いて測定した。13C-NMR測定条件は、以下の通りである。
装置:Bruker社製 AVANCE600、10mmクライオプローブ
測定温度:135℃
測定方法:プロトンデカップリング法
濃度:100mg/mL
積算回数:1024回
パルス幅:45度
パルス繰り返し時間:4秒
化学シフト値基準:テトラメチルシラン
溶媒:1,2-ジクロロベンゼン-d4と1,1,2,2-テトラクロロエタン-d2との体積比85:15の混合溶媒
シクロオレフィンコポリマー中のNB含有量は、1,2-ジクロロベンゼン(127.68ppm)を基準とし、「R.A.Wendt,G.Fink,Macromol.Chem.Phys.,2001,202,3490」に記載の帰属に基づいて算出した。具体的には、13C-NMRを用いて測定されたスペクトルチャートのケミカルシフト値44.0-52.0ppmに観測されるシグナル積分値:IC2,C3(ノルボルネン環の2、3位の炭素原子に由来)、ケミカルシフト値27.0-33.0ppmに観測されるシグナル積分値:IC5,C6+ICE(ノルボルネン環の5、6位の炭素原子と、エチレン部の炭素原子とに由来)より、以下の式から求めた。
NB含有量(mol%)=IC2,C3/(IC5,C6+ICE)×100 <Norbornene (NB) content>
The content of norbornene-derived monomer units (also referred to as “NB content”) in the cycloolefin copolymer was measured using 13 C-NMR. The 13 C-NMR measurement conditions are as follows.
Apparatus: Bruker AVANCE600, 10 mm cryoprobe Measurement temperature: 135°C
Measurement method: proton decoupling method Concentration: 100 mg/mL
Number of times of integration: 1024 times Pulse width: 45 degrees Pulse repetition time: 4 seconds Chemical shift value standard: Tetramethylsilane Solvent: 1,2-dichlorobenzene-d4 and 1,1,2,2 - tetrachloroethane - d2 The NB content in the cycloolefin copolymer is based on 1,2-dichlorobenzene (127.68 ppm) and is calculated according to RA Wendt, G. Fink, Macromol. , 2001, 202, 3490”. Specifically, signal integral values observed at chemical shift values of 44.0 to 52.0 ppm in a spectrum chart measured using 13 C-NMR: I C2,C3 (carbons at positions 2 and 3 of the norbornene ring atom), signal integral value observed at a chemical shift value of 27.0-33.0 ppm: I C5, C6 + I CE (derived from the carbon atoms at the 5 and 6 positions of the norbornene ring and the carbon atoms of the ethylene part ), it was obtained from the following formula.
NB content (mol%) = I C2, C3 / (I C5, C6 + I CE ) x 100
シクロオレフィンコポリマーにおけるノルボルネン由来の単量体単位の含有量(「NB含有量」ともいう)は、13C-NMRを用いて測定した。13C-NMR測定条件は、以下の通りである。
装置:Bruker社製 AVANCE600、10mmクライオプローブ
測定温度:135℃
測定方法:プロトンデカップリング法
濃度:100mg/mL
積算回数:1024回
パルス幅:45度
パルス繰り返し時間:4秒
化学シフト値基準:テトラメチルシラン
溶媒:1,2-ジクロロベンゼン-d4と1,1,2,2-テトラクロロエタン-d2との体積比85:15の混合溶媒
シクロオレフィンコポリマー中のNB含有量は、1,2-ジクロロベンゼン(127.68ppm)を基準とし、「R.A.Wendt,G.Fink,Macromol.Chem.Phys.,2001,202,3490」に記載の帰属に基づいて算出した。具体的には、13C-NMRを用いて測定されたスペクトルチャートのケミカルシフト値44.0-52.0ppmに観測されるシグナル積分値:IC2,C3(ノルボルネン環の2、3位の炭素原子に由来)、ケミカルシフト値27.0-33.0ppmに観測されるシグナル積分値:IC5,C6+ICE(ノルボルネン環の5、6位の炭素原子と、エチレン部の炭素原子とに由来)より、以下の式から求めた。
NB含有量(mol%)=IC2,C3/(IC5,C6+ICE)×100 <Norbornene (NB) content>
The content of norbornene-derived monomer units (also referred to as “NB content”) in the cycloolefin copolymer was measured using 13 C-NMR. The 13 C-NMR measurement conditions are as follows.
Apparatus: Bruker AVANCE600, 10 mm cryoprobe Measurement temperature: 135°C
Measurement method: proton decoupling method Concentration: 100 mg/mL
Number of times of integration: 1024 times Pulse width: 45 degrees Pulse repetition time: 4 seconds Chemical shift value standard: Tetramethylsilane Solvent: 1,2-dichlorobenzene-d4 and 1,1,2,2 - tetrachloroethane - d2 The NB content in the cycloolefin copolymer is based on 1,2-dichlorobenzene (127.68 ppm) and is calculated according to RA Wendt, G. Fink, Macromol. , 2001, 202, 3490”. Specifically, signal integral values observed at chemical shift values of 44.0 to 52.0 ppm in a spectrum chart measured using 13 C-NMR: I C2,C3 (carbons at positions 2 and 3 of the norbornene ring atom), signal integral value observed at a chemical shift value of 27.0-33.0 ppm: I C5, C6 + I CE (derived from the carbon atoms at the 5 and 6 positions of the norbornene ring and the carbon atoms of the ethylene part ), it was obtained from the following formula.
NB content (mol%) = I C2, C3 / (I C5, C6 + I CE ) x 100
<メソ型二連鎖/ラセモ型二連鎖>
シクロオレフィンコポリマーのノルボルネン二連鎖のメソ型二連鎖とラセモ型二連鎖との比(メソ型二連鎖/ラセモ型二連鎖)は、13C-NMRを用いて上記NB含有量の測定と同様の条件にて測定した。
前記ノルボルネン二連鎖のメソ型二連鎖/ラセモ型二連鎖は、1,1,2,2-テトラクロロエタン(74.24ppm)を基準とし、「R.A.Wendt,G.Fink,Macromol.Chem.Phys.,2001,202,3490」及び「特開2008-285656号公報」に記載の帰属に基づいて算出した。具体的には、メソ型二連鎖/ラセモ型二連鎖は、13C-NMRを用いて測定されたスペクトルチャートのケミカルシフト値27.5-28.4ppmに観測されるシグナル積分値:IC5,C6-m(メソ型二連鎖のノルボルネン環の5、6位の炭素原子に由来)、ケミカルシフト値28.4-29.6ppmに観測されるシグナル積分値:IC5,C6-r(ラセモ型二連鎖のノルボルネン環の5、6位の炭素原子に由来)より、以下の式から求めた。
メソ型二連鎖/ラセモ型二連鎖=IC5,C6-m/IC5,C6-r <Meso type double chain/racemo type double chain>
The ratio of the meso-type double chain and the racemo-type double chain of the norbornene double chain of the cycloolefin copolymer (meso-type double chain/racemo-type double chain) is measured using 13 C-NMR under the same conditions as the measurement of the NB content. Measured at
The meso-type double chain/racemo-type double chain of the norbornene double chain is based on 1,1,2,2-tetrachloroethane (74.24 ppm), and is described in RA Wendt, G. Fink, Macromol. Chem. Phys., 2001, 202, 3490” and “JP-A-2008-285656”. Specifically, the meso-type two-chain/racemo-type two chains are observed at chemical shift values of 27.5-28.4 ppm in a spectrum chart measured using 13 C-NMR: signal integral value: IC5 , C6 -m (derived from carbon atoms at positions 5 and 6 of the norbornene ring of the meso-type double chain), signal integral values observed at chemical shift values 28.4-29.6 ppm: I C5, C6 -r (racemo type derived from carbon atoms at positions 5 and 6 of a double-chained norbornene ring), it was obtained from the following formula.
Meso-type bilinkage/racemo-type bilinkage=I C5,C6 −m/I C5,C6 −r
シクロオレフィンコポリマーのノルボルネン二連鎖のメソ型二連鎖とラセモ型二連鎖との比(メソ型二連鎖/ラセモ型二連鎖)は、13C-NMRを用いて上記NB含有量の測定と同様の条件にて測定した。
前記ノルボルネン二連鎖のメソ型二連鎖/ラセモ型二連鎖は、1,1,2,2-テトラクロロエタン(74.24ppm)を基準とし、「R.A.Wendt,G.Fink,Macromol.Chem.Phys.,2001,202,3490」及び「特開2008-285656号公報」に記載の帰属に基づいて算出した。具体的には、メソ型二連鎖/ラセモ型二連鎖は、13C-NMRを用いて測定されたスペクトルチャートのケミカルシフト値27.5-28.4ppmに観測されるシグナル積分値:IC5,C6-m(メソ型二連鎖のノルボルネン環の5、6位の炭素原子に由来)、ケミカルシフト値28.4-29.6ppmに観測されるシグナル積分値:IC5,C6-r(ラセモ型二連鎖のノルボルネン環の5、6位の炭素原子に由来)より、以下の式から求めた。
メソ型二連鎖/ラセモ型二連鎖=IC5,C6-m/IC5,C6-r <Meso type double chain/racemo type double chain>
The ratio of the meso-type double chain and the racemo-type double chain of the norbornene double chain of the cycloolefin copolymer (meso-type double chain/racemo-type double chain) is measured using 13 C-NMR under the same conditions as the measurement of the NB content. Measured at
The meso-type double chain/racemo-type double chain of the norbornene double chain is based on 1,1,2,2-tetrachloroethane (74.24 ppm), and is described in RA Wendt, G. Fink, Macromol. Chem. Phys., 2001, 202, 3490” and “JP-A-2008-285656”. Specifically, the meso-type two-chain/racemo-type two chains are observed at chemical shift values of 27.5-28.4 ppm in a spectrum chart measured using 13 C-NMR: signal integral value: IC5 , C6 -m (derived from carbon atoms at positions 5 and 6 of the norbornene ring of the meso-type double chain), signal integral values observed at chemical shift values 28.4-29.6 ppm: I C5, C6 -r (racemo type derived from carbon atoms at positions 5 and 6 of a double-chained norbornene ring), it was obtained from the following formula.
Meso-type bilinkage/racemo-type bilinkage=I C5,C6 −m/I C5,C6 −r
<屈折率>
シクロオレフィンコポリマーの屈折率は、真空プレス機で厚さ100μmに成形したシート状の試料を用いて、下記条件で測定することにより求めた。
機器:(株)アタゴ製 アッベ屈折計「TYPE-3」
光源波長:589.3nm
中間液:1-ブロモナフタレン
測定温度:23±1℃ <Refractive index>
The refractive index of the cycloolefin copolymer was obtained by measuring under the following conditions using a sheet-like sample molded to a thickness of 100 μm with a vacuum press.
Equipment: Atago Co., Ltd. Abbe refractometer "TYPE-3"
Light source wavelength: 589.3 nm
Intermediate liquid: 1-bromonaphthalene Measurement temperature: 23 ± 1 ° C
シクロオレフィンコポリマーの屈折率は、真空プレス機で厚さ100μmに成形したシート状の試料を用いて、下記条件で測定することにより求めた。
機器:(株)アタゴ製 アッベ屈折計「TYPE-3」
光源波長:589.3nm
中間液:1-ブロモナフタレン
測定温度:23±1℃ <Refractive index>
The refractive index of the cycloolefin copolymer was obtained by measuring under the following conditions using a sheet-like sample molded to a thickness of 100 μm with a vacuum press.
Equipment: Atago Co., Ltd. Abbe refractometer "TYPE-3"
Light source wavelength: 589.3 nm
Intermediate liquid: 1-bromonaphthalene Measurement temperature: 23 ± 1 ° C
<CTE>
シクロオレフィンコポリマーのCTEは、TMAを用いて、下記条件で測定を行い、50℃から100℃におけるCTEを算出した。
装置:(株)日立ハイテクサイエンス製 TMA/SS6200
圧子(プローブ)径:3.5mm 荷重:38.5mN 温度プログラム:20℃から130℃まで5℃/分の速度で昇温
試験片:10mm×10mm×1mmの直方体 <CTE>
The CTE of the cycloolefin copolymer was measured using TMA under the following conditions, and the CTE at 50°C to 100°C was calculated.
Apparatus: TMA/SS6200 manufactured by Hitachi High-Tech Science Co., Ltd.
Indenter (probe) diameter: 3.5 mm Load: 38.5 mN Temperature program: Temperature rise from 20°C to 130°C at a rate of 5°C/min Test piece: 10 mm x 10 mm x 1 mm rectangular parallelepiped
シクロオレフィンコポリマーのCTEは、TMAを用いて、下記条件で測定を行い、50℃から100℃におけるCTEを算出した。
装置:(株)日立ハイテクサイエンス製 TMA/SS6200
圧子(プローブ)径:3.5mm 荷重:38.5mN 温度プログラム:20℃から130℃まで5℃/分の速度で昇温
試験片:10mm×10mm×1mmの直方体 <CTE>
The CTE of the cycloolefin copolymer was measured using TMA under the following conditions, and the CTE at 50°C to 100°C was calculated.
Apparatus: TMA/SS6200 manufactured by Hitachi High-Tech Science Co., Ltd.
Indenter (probe) diameter: 3.5 mm Load: 38.5 mN Temperature program: Temperature rise from 20°C to 130°C at a rate of 5°C/min Test piece: 10 mm x 10 mm x 1 mm rectangular parallelepiped
<ガラス転移温度>
(シクロオレフィンコポリマーのTg)
シクロオレフィンコポリマーのTgは、JIS K 7196に基づき、TMAにより軟化温度を測定することにより求められた。具体的には、シクロオレフィンコポリマーを真空プレス機でシート状に成型した試料(厚さ:1.0mm)を下記条件で測定し、圧子が試料に沈み込む際の変位のオンセットを軟化温度とした。
装置:(株)日立ハイテクサイエンス製、「TMA/SS6200」
圧子径:1mm
荷重:780mN
温度プログラム:20℃から380℃まで5℃/分の速度で昇温 <Glass transition temperature>
(Tg of cycloolefin copolymer)
The Tg of the cycloolefin copolymer was obtained by measuring the softening temperature by TMA based on JIS K 7196. Specifically, a sample (thickness: 1.0 mm) obtained by molding a cycloolefin copolymer into a sheet with a vacuum press was measured under the following conditions, and the softening temperature was defined as the onset of the displacement when the indenter sinks into the sample. did.
Apparatus: "TMA/SS6200" manufactured by Hitachi High-Tech Science Co., Ltd.
Indenter diameter: 1mm
Load: 780mN
Temperature program: Temperature rise from 20°C to 380°C at a rate of 5°C/min
(シクロオレフィンコポリマーのTg)
シクロオレフィンコポリマーのTgは、JIS K 7196に基づき、TMAにより軟化温度を測定することにより求められた。具体的には、シクロオレフィンコポリマーを真空プレス機でシート状に成型した試料(厚さ:1.0mm)を下記条件で測定し、圧子が試料に沈み込む際の変位のオンセットを軟化温度とした。
装置:(株)日立ハイテクサイエンス製、「TMA/SS6200」
圧子径:1mm
荷重:780mN
温度プログラム:20℃から380℃まで5℃/分の速度で昇温 <Glass transition temperature>
(Tg of cycloolefin copolymer)
The Tg of the cycloolefin copolymer was obtained by measuring the softening temperature by TMA based on JIS K 7196. Specifically, a sample (thickness: 1.0 mm) obtained by molding a cycloolefin copolymer into a sheet with a vacuum press was measured under the following conditions, and the softening temperature was defined as the onset of the displacement when the indenter sinks into the sample. did.
Apparatus: "TMA/SS6200" manufactured by Hitachi High-Tech Science Co., Ltd.
Indenter diameter: 1mm
Load: 780mN
Temperature program: Temperature rise from 20°C to 380°C at a rate of 5°C/min
(ポリイミド系樹脂のTg)
ポリイミド系樹脂のTgは、以下の測定により求められた。TA Instrument社製、「DMA Q800」を用い、次のような試料及び条件下で測定して、損失弾性率と保存弾性率の値の比であるtanδ曲線を得た後、tanδ曲線のピークの最頂点からTgを算出した。
試料:長さ5-15mm、幅5mm
実験モード:DMA Multi-Frequency-Strain
実験モード詳細条件:
(1)Clamp:Tension:Film
(2)Amplitude:5μm
(3)Frequncy:10Hz(全温度区間で変動なし)
(4)Preload Force:0.01N
(5)Force Track:125N
温度条件:(1)昇温範囲:常温~400℃、(2)昇温速度:5℃/分
主要収集データ:(1)保存弾性率(Storage modulus、E’)、(2)損失弾性率(Loss modulus、E”)、(3)tanδ(E”/E’) (Tg of polyimide resin)
The Tg of the polyimide resin was determined by the following measurements. Using TA Instrument Co., Ltd., "DMA Q800", measured under the following samples and conditions to obtain a tan δ curve, which is the ratio of the values of loss modulus and storage modulus, and then the peak of the tan δ curve. Tg was calculated from the highest peak.
Sample: length 5-15 mm, width 5 mm
Experimental mode: DMA Multi-Frequency-Strain
Experiment mode detailed conditions:
(1) Clamp: Tension: Film
(2) Amplitude: 5 μm
(3) Frequency: 10 Hz (no change in all temperature intervals)
(4) Preload Force: 0.01N
(5) Force Track: 125N
Temperature conditions: (1) Range of temperature rise: Normal temperature to 400°C, (2) Rate of temperature rise: 5°C/min Main data collected: (1) Storage modulus (E'), (2) Loss modulus (Loss modulus, E″), (3) tan δ (E″/E′)
ポリイミド系樹脂のTgは、以下の測定により求められた。TA Instrument社製、「DMA Q800」を用い、次のような試料及び条件下で測定して、損失弾性率と保存弾性率の値の比であるtanδ曲線を得た後、tanδ曲線のピークの最頂点からTgを算出した。
試料:長さ5-15mm、幅5mm
実験モード:DMA Multi-Frequency-Strain
実験モード詳細条件:
(1)Clamp:Tension:Film
(2)Amplitude:5μm
(3)Frequncy:10Hz(全温度区間で変動なし)
(4)Preload Force:0.01N
(5)Force Track:125N
温度条件:(1)昇温範囲:常温~400℃、(2)昇温速度:5℃/分
主要収集データ:(1)保存弾性率(Storage modulus、E’)、(2)損失弾性率(Loss modulus、E”)、(3)tanδ(E”/E’) (Tg of polyimide resin)
The Tg of the polyimide resin was determined by the following measurements. Using TA Instrument Co., Ltd., "DMA Q800", measured under the following samples and conditions to obtain a tan δ curve, which is the ratio of the values of loss modulus and storage modulus, and then the peak of the tan δ curve. Tg was calculated from the highest peak.
Sample: length 5-15 mm, width 5 mm
Experimental mode: DMA Multi-Frequency-Strain
Experiment mode detailed conditions:
(1) Clamp: Tension: Film
(2) Amplitude: 5 μm
(3) Frequency: 10 Hz (no change in all temperature intervals)
(4) Preload Force: 0.01N
(5) Force Track: 125N
Temperature conditions: (1) Range of temperature rise: Normal temperature to 400°C, (2) Rate of temperature rise: 5°C/min Main data collected: (1) Storage modulus (E'), (2) Loss modulus (Loss modulus, E″), (3) tan δ (E″/E′)
<シクロオレフィンコポリマーのMw及びMn>
シクロオレフィンコポリマーのポリスチレン換算のMw及びMnは、GPCを用いて測定した。GPC測定は下記条件で行い、ISO16014-1の記載に基づき、クロマトグラム上のベースラインを規定してピークを指定した。 <Mw and Mn of cycloolefin copolymer>
The polystyrene equivalent Mw and Mn of the cycloolefin copolymer were measured using GPC. GPC measurement was performed under the following conditions, and peaks were designated by defining a baseline on the chromatogram based on the description of ISO16014-1.
シクロオレフィンコポリマーのポリスチレン換算のMw及びMnは、GPCを用いて測定した。GPC測定は下記条件で行い、ISO16014-1の記載に基づき、クロマトグラム上のベースラインを規定してピークを指定した。 <Mw and Mn of cycloolefin copolymer>
The polystyrene equivalent Mw and Mn of the cycloolefin copolymer were measured using GPC. GPC measurement was performed under the following conditions, and peaks were designated by defining a baseline on the chromatogram based on the description of ISO16014-1.
(GPC装置及びソフトウェア)
装置:HLC-8121GPC/HT(東ソー(株)製)
測定ソフト:GPC-8020 modelII データ収集 Version 4.32(東ソー(株)製)
解析ソフト:GPC-8020 modelII データ解析 Version 4.32(東ソー(株)製) (GPC device and software)
Apparatus: HLC-8121GPC/HT (manufactured by Tosoh Corporation)
Measurement software: GPC-8020 model II data collection Version 4.32 (manufactured by Tosoh Corporation)
Analysis software: GPC-8020 modelII data analysis Version 4.32 (manufactured by Tosoh Corporation)
装置:HLC-8121GPC/HT(東ソー(株)製)
測定ソフト:GPC-8020 modelII データ収集 Version 4.32(東ソー(株)製)
解析ソフト:GPC-8020 modelII データ解析 Version 4.32(東ソー(株)製) (GPC device and software)
Apparatus: HLC-8121GPC/HT (manufactured by Tosoh Corporation)
Measurement software: GPC-8020 model II data collection Version 4.32 (manufactured by Tosoh Corporation)
Analysis software: GPC-8020 modelII data analysis Version 4.32 (manufactured by Tosoh Corporation)
(測定条件)
GPCカラム:TSKgel GMH6-HT 内径7.8mm×長さ300mm(東ソー(株)製) 3本連結
移動相:オルトジクロロベンゼン(富士フイルム和光純薬(株)製、特級)にBHTを0.1g/100mLの濃度で添加して使用した。
流速:1mL/分
カラムオーブン温度:140℃
オートサンプラー温度:140℃
システムオーブン温度:40℃
検出:示差屈折率検出器(RID)
RIDセル温度:140℃
試料溶液注入量:300μL
GPCカラム校正用標準物質:東ソー(株)製標準ポリスチレンを下記表1のような組合せで量り取り、組合せごとに、前記移動相 5mLを加え、室温で2時間溶解させて調製した。 (Measurement condition)
GPC column: TSKgel GMH6-HT inner diameter 7.8 mm × length 300 mm (manufactured by Tosoh Corporation) 3 columns connected Mobile phase: ortho-dichlorobenzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade) with 0.1 g of BHT /100 mL was added for use.
Flow rate: 1 mL/min Column oven temperature: 140°C
Autosampler temperature: 140°C
System oven temperature: 40°C
Detection: Refractive Index Detector (RID)
RID cell temperature: 140°C
Sample solution injection volume: 300 μL
Standard materials for GPC column calibration: Standard polystyrene manufactured by Tosoh Corporation was weighed out in combinations as shown in Table 1 below, and 5 mL of the mobile phase was added to each combination and dissolved at room temperature for 2 hours to prepare.
GPCカラム:TSKgel GMH6-HT 内径7.8mm×長さ300mm(東ソー(株)製) 3本連結
移動相:オルトジクロロベンゼン(富士フイルム和光純薬(株)製、特級)にBHTを0.1g/100mLの濃度で添加して使用した。
流速:1mL/分
カラムオーブン温度:140℃
オートサンプラー温度:140℃
システムオーブン温度:40℃
検出:示差屈折率検出器(RID)
RIDセル温度:140℃
試料溶液注入量:300μL
GPCカラム校正用標準物質:東ソー(株)製標準ポリスチレンを下記表1のような組合せで量り取り、組合せごとに、前記移動相 5mLを加え、室温で2時間溶解させて調製した。 (Measurement condition)
GPC column: TSKgel GMH6-HT inner diameter 7.8 mm × length 300 mm (manufactured by Tosoh Corporation) 3 columns connected Mobile phase: ortho-dichlorobenzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade) with 0.1 g of BHT /100 mL was added for use.
Flow rate: 1 mL/min Column oven temperature: 140°C
Autosampler temperature: 140°C
System oven temperature: 40°C
Detection: Refractive Index Detector (RID)
RID cell temperature: 140°C
Sample solution injection volume: 300 μL
Standard materials for GPC column calibration: Standard polystyrene manufactured by Tosoh Corporation was weighed out in combinations as shown in Table 1 below, and 5 mL of the mobile phase was added to each combination and dissolved at room temperature for 2 hours to prepare.
(試料溶液調製条件)
溶媒:オルトジクロロベンゼン(富士フイルム和光純薬(株)製、特級)に、BHT[ジブチルヒドロキシトルエン]を0.1g/100mLの濃度で添加して使用した。
試料溶液濃度:1mg/mL
溶解用自動振とう器:DF-8020(東ソー(株)製)
溶解条件:5mgの試料を1,000meshのSUS製の金網袋に封入し、試料を封入した金網袋を試験管に入れ、さらに前記移動相と同組成のオルトジクロロベンゼン 5mLを加え、試験管にアルミホイルで蓋をし、試験管をDF-8020にセットし、60往復/分の撹拌速度で140℃にて120分間撹拌した。攪拌後の溶液を試料として、GPC測定を行った。 (Sample solution preparation conditions)
Solvent: BHT [dibutylhydroxytoluene] was added to ortho-dichlorobenzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade) at a concentration of 0.1 g/100 mL.
Sample solution concentration: 1 mg/mL
Automatic shaker for dissolution: DF-8020 (manufactured by Tosoh Corporation)
Dissolution conditions: 5 mg of sample is enclosed in a 1,000 mesh SUS wire mesh bag, the wire mesh bag containing the sample is placed in a test tube, 5 mL of orthodichlorobenzene having the same composition as the mobile phase is added, and the test tube is The test tube was covered with aluminum foil, set in DF-8020, and stirred at 140° C. for 120 minutes at a stirring rate of 60 reciprocations/minute. GPC measurement was performed using the stirred solution as a sample.
溶媒:オルトジクロロベンゼン(富士フイルム和光純薬(株)製、特級)に、BHT[ジブチルヒドロキシトルエン]を0.1g/100mLの濃度で添加して使用した。
試料溶液濃度:1mg/mL
溶解用自動振とう器:DF-8020(東ソー(株)製)
溶解条件:5mgの試料を1,000meshのSUS製の金網袋に封入し、試料を封入した金網袋を試験管に入れ、さらに前記移動相と同組成のオルトジクロロベンゼン 5mLを加え、試験管にアルミホイルで蓋をし、試験管をDF-8020にセットし、60往復/分の撹拌速度で140℃にて120分間撹拌した。攪拌後の溶液を試料として、GPC測定を行った。 (Sample solution preparation conditions)
Solvent: BHT [dibutylhydroxytoluene] was added to ortho-dichlorobenzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade) at a concentration of 0.1 g/100 mL.
Sample solution concentration: 1 mg/mL
Automatic shaker for dissolution: DF-8020 (manufactured by Tosoh Corporation)
Dissolution conditions: 5 mg of sample is enclosed in a 1,000 mesh SUS wire mesh bag, the wire mesh bag containing the sample is placed in a test tube, 5 mL of orthodichlorobenzene having the same composition as the mobile phase is added, and the test tube is The test tube was covered with aluminum foil, set in DF-8020, and stirred at 140° C. for 120 minutes at a stirring rate of 60 reciprocations/minute. GPC measurement was performed using the stirred solution as a sample.
<ポリイミド樹脂及びポリアミック酸のMw>
ポリイミド樹脂及びポリアミック酸のポリスチレン換算のMwは、GPCを用いて測定した。GPC測定は下記条件で行った。
GPC測定
(1)前処理方法
サンプルにDMF溶離液(10mmol/L臭化リチウム添加DMF溶液)を濃度2mg/mLとなるように加え、80℃にて30分間攪拌しながら加熱し、冷却後、0.45μmメンブランフィルターろ過したものを測定溶液とした。
(2)測定条件
カラム:TSKgel SuperAWM-H×2+SuperAW2500×1(内径6.0mm×長さ150mm、3本連結)
溶離液:DMF(10mmol/Lの臭化リチウム添加)
流量:1.0mL/分
検出器:RI検出器
カラム温度:40℃
注入量:100μL
分子量標準:標準ポリスチレン <Mw of polyimide resin and polyamic acid>
The polystyrene equivalent Mw of the polyimide resin and polyamic acid was measured using GPC. GPC measurement was performed under the following conditions.
GPC measurement (1) Pretreatment method A DMF eluent (10 mmol/L lithium bromide-added DMF solution) was added to the sample to a concentration of 2 mg/mL, heated at 80°C for 30 minutes with stirring, and cooled. A measurement solution was obtained by filtration through a 0.45 μm membrane filter.
(2) Measurement conditions Column: TSKgel SuperAWM-H × 2 + SuperAW2500 × 1 (inner diameter 6.0 mm × length 150 mm, three connected)
Eluent: DMF (10 mmol/L lithium bromide added)
Flow rate: 1.0 mL/min Detector: RI detector Column temperature: 40°C
Injection volume: 100 μL
Molecular weight standard: standard polystyrene
ポリイミド樹脂及びポリアミック酸のポリスチレン換算のMwは、GPCを用いて測定した。GPC測定は下記条件で行った。
GPC測定
(1)前処理方法
サンプルにDMF溶離液(10mmol/L臭化リチウム添加DMF溶液)を濃度2mg/mLとなるように加え、80℃にて30分間攪拌しながら加熱し、冷却後、0.45μmメンブランフィルターろ過したものを測定溶液とした。
(2)測定条件
カラム:TSKgel SuperAWM-H×2+SuperAW2500×1(内径6.0mm×長さ150mm、3本連結)
溶離液:DMF(10mmol/Lの臭化リチウム添加)
流量:1.0mL/分
検出器:RI検出器
カラム温度:40℃
注入量:100μL
分子量標準:標準ポリスチレン <Mw of polyimide resin and polyamic acid>
The polystyrene equivalent Mw of the polyimide resin and polyamic acid was measured using GPC. GPC measurement was performed under the following conditions.
GPC measurement (1) Pretreatment method A DMF eluent (10 mmol/L lithium bromide-added DMF solution) was added to the sample to a concentration of 2 mg/mL, heated at 80°C for 30 minutes with stirring, and cooled. A measurement solution was obtained by filtration through a 0.45 μm membrane filter.
(2) Measurement conditions Column: TSKgel SuperAWM-H × 2 + SuperAW2500 × 1 (inner diameter 6.0 mm × length 150 mm, three connected)
Eluent: DMF (10 mmol/L lithium bromide added)
Flow rate: 1.0 mL/min Detector: RI detector Column temperature: 40°C
Injection volume: 100 μL
Molecular weight standard: standard polystyrene
<溶解性の評価>
実施例及び比較例で使用した溶媒に、シクロオレフィンコポリマー、ポリイミド樹脂及びポリアミック酸が溶解するか否かの評価は以下のように行った。
まず、30mLのガラス製スクリュー管に溶媒9.9gを量り取り、さらにマグネチックスターラーを入れて撹拌する。そこにポリマー、樹脂又はポリアミック酸を0.1g加え、24℃で24時間攪拌する。24時間撹拌後、目視で固体が確認できない、かつ溶液が透明の場合は「溶解する」と評価した。一方、目視で固体を確認できる、又は、溶液が不透明の場合は「溶解しない」と評価した。 <Evaluation of solubility>
Evaluation as to whether or not the cycloolefin copolymer, the polyimide resin and the polyamic acid are dissolved in the solvents used in the examples and comparative examples was performed as follows.
First, 9.9 g of the solvent is weighed into a 30 mL glass screw tube, and stirred with a magnetic stirrer. 0.1 g of polymer, resin or polyamic acid is added thereto and stirred at 24° C. for 24 hours. After stirring for 24 hours, when solids could not be visually confirmed and the solution was transparent, it was evaluated as "dissolved". On the other hand, when a solid was visually confirmed or the solution was opaque, it was evaluated as "not dissolved".
実施例及び比較例で使用した溶媒に、シクロオレフィンコポリマー、ポリイミド樹脂及びポリアミック酸が溶解するか否かの評価は以下のように行った。
まず、30mLのガラス製スクリュー管に溶媒9.9gを量り取り、さらにマグネチックスターラーを入れて撹拌する。そこにポリマー、樹脂又はポリアミック酸を0.1g加え、24℃で24時間攪拌する。24時間撹拌後、目視で固体が確認できない、かつ溶液が透明の場合は「溶解する」と評価した。一方、目視で固体を確認できる、又は、溶液が不透明の場合は「溶解しない」と評価した。 <Evaluation of solubility>
Evaluation as to whether or not the cycloolefin copolymer, the polyimide resin and the polyamic acid are dissolved in the solvents used in the examples and comparative examples was performed as follows.
First, 9.9 g of the solvent is weighed into a 30 mL glass screw tube, and stirred with a magnetic stirrer. 0.1 g of polymer, resin or polyamic acid is added thereto and stirred at 24° C. for 24 hours. After stirring for 24 hours, when solids could not be visually confirmed and the solution was transparent, it was evaluated as "dissolved". On the other hand, when a solid was visually confirmed or the solution was opaque, it was evaluated as "not dissolved".
<分散液及び組成物中の粒子状シクロオレフィンコポリマー及び粒子状フッ素ポリマーの粒子径>
(製造例1、3で得られたシクロオレフィンコポリマー溶液を使用して得られた粒子状シクロオレフィンコポリマー分散液中の粒子状シクロオレフィンコポリマーの粒子径、及び粒子状フッ素ポリマー分散液中の粒子状フッ素ポリマーの粒子径)
実施例1、3、5、9、10、12及び比較例1、3で得られた粒子状シクロオレフィンコポリマーの分散液中の粒子状シクロオレフィンコポリマーのメジアン径、及び実施例7、8で得られた粒子状フッ素ポリマー分散液中の粒子状フッ素ポリマーのメジアン径を、レーザー回折を用いた散乱式粒度分布測定により求めた。
具体的には、容量3.5mLのガラス製セルに、実施例1、3、5、9、10、12及び比較例1、3で得られた粒子状シクロオレフィンコポリマー分散液、又は実施例7、8で得られた粒子状フッ素ポリマー分散液を入れ、さらにGBL又はDMAcを添加して(分散液と同溶媒を用いて)1000倍希釈し、粒子状シクロオレフィンコポリマー又は粒子状フッ素ポリマーを含有する分散液試料を得た。得られた各分散液試料をレーザー回析/散乱式粒度分布測定装置(Malvern Panalytical社製、型式:NanоZS、屈折率:1.70-0.20i)を用いて測定し、粒子状シクロオレフィンコポリマーのメジアン径、及び粒子状フッ素ポリマーのメジアン径をそれぞれ求めた。
なお、上記の通り、実施例1、3、5、7~9、10、12及び比較例1、3では粒子状シクロオレフィンコポリマー又は粒子状フッ素ポリマーの粒子径に影響しない範囲の量でポリイミド樹脂又はポリアミック酸、及び酸化防止剤を分散液に添加して組成物を形成したため、分散液中の粒子状シクロオレフィンコポリマーのメジアン径及び分散液中の粒子状フッ素ポリマーのメジアン径を、それぞれ、組成物中の粒子状シクロオレフィンコポリマーのメジアン径及び組成物中の粒子状フッ素ポリマーのメジアン径とした。 <Particle size of particulate cycloolefin copolymer and particulate fluoropolymer in dispersion and composition>
(The particle size of the particulate cycloolefin copolymer in the particulate cycloolefin copolymer dispersion obtained using the cycloolefin copolymer solutions obtained in Production Examples 1 and 3, and the particle size in the particulate fluoropolymer dispersion Particle size of fluoropolymer)
The median diameter of the particulate cycloolefin copolymers in the dispersions of the particulate cycloolefin copolymers obtained in Examples 1, 3, 5, 9, 10, 12 and Comparative Examples 1 and 3, and the median sizes obtained in Examples 7 and 8 The median diameter of the particulate fluoropolymer in the obtained particulate fluoropolymer dispersion was determined by scattering particle size distribution measurement using laser diffraction.
Specifically, the particulate cycloolefin copolymer dispersion obtained in Examples 1, 3, 5, 9, 10, 12 and Comparative Examples 1 and 3, or Example 7 was placed in a glass cell having a capacity of 3.5 mL. , add the particulate fluoropolymer dispersion obtained in 8, further add GBL or DMAc (using the same solvent as the dispersion) to dilute 1000 times, and contain particulate cycloolefin copolymer or particulate fluoropolymer A dispersion sample was obtained. Each dispersion sample obtained was measured using a laser diffraction/scattering particle size distribution analyzer (manufactured by Malvern Panalytical, model: NanoZS, refractive index: 1.70-0.20i), and the particulate cycloolefin copolymer and the median diameter of the particulate fluoropolymer were determined.
As described above, in Examples 1, 3, 5, 7 to 9, 10, 12 and Comparative Examples 1 and 3, the polyimide resin was used in an amount within a range not affecting the particle size of the particulate cycloolefin copolymer or the particulate fluoropolymer. Alternatively, since the polyamic acid and the antioxidant were added to the dispersion to form the composition, the median size of the particulate cycloolefin copolymer in the dispersion and the median size of the particulate fluoropolymer in the dispersion, respectively, The median diameter of the particulate cycloolefin copolymer in the product and the median diameter of the particulate fluoropolymer in the composition were used.
(製造例1、3で得られたシクロオレフィンコポリマー溶液を使用して得られた粒子状シクロオレフィンコポリマー分散液中の粒子状シクロオレフィンコポリマーの粒子径、及び粒子状フッ素ポリマー分散液中の粒子状フッ素ポリマーの粒子径)
実施例1、3、5、9、10、12及び比較例1、3で得られた粒子状シクロオレフィンコポリマーの分散液中の粒子状シクロオレフィンコポリマーのメジアン径、及び実施例7、8で得られた粒子状フッ素ポリマー分散液中の粒子状フッ素ポリマーのメジアン径を、レーザー回折を用いた散乱式粒度分布測定により求めた。
具体的には、容量3.5mLのガラス製セルに、実施例1、3、5、9、10、12及び比較例1、3で得られた粒子状シクロオレフィンコポリマー分散液、又は実施例7、8で得られた粒子状フッ素ポリマー分散液を入れ、さらにGBL又はDMAcを添加して(分散液と同溶媒を用いて)1000倍希釈し、粒子状シクロオレフィンコポリマー又は粒子状フッ素ポリマーを含有する分散液試料を得た。得られた各分散液試料をレーザー回析/散乱式粒度分布測定装置(Malvern Panalytical社製、型式:NanоZS、屈折率:1.70-0.20i)を用いて測定し、粒子状シクロオレフィンコポリマーのメジアン径、及び粒子状フッ素ポリマーのメジアン径をそれぞれ求めた。
なお、上記の通り、実施例1、3、5、7~9、10、12及び比較例1、3では粒子状シクロオレフィンコポリマー又は粒子状フッ素ポリマーの粒子径に影響しない範囲の量でポリイミド樹脂又はポリアミック酸、及び酸化防止剤を分散液に添加して組成物を形成したため、分散液中の粒子状シクロオレフィンコポリマーのメジアン径及び分散液中の粒子状フッ素ポリマーのメジアン径を、それぞれ、組成物中の粒子状シクロオレフィンコポリマーのメジアン径及び組成物中の粒子状フッ素ポリマーのメジアン径とした。 <Particle size of particulate cycloolefin copolymer and particulate fluoropolymer in dispersion and composition>
(The particle size of the particulate cycloolefin copolymer in the particulate cycloolefin copolymer dispersion obtained using the cycloolefin copolymer solutions obtained in Production Examples 1 and 3, and the particle size in the particulate fluoropolymer dispersion Particle size of fluoropolymer)
The median diameter of the particulate cycloolefin copolymers in the dispersions of the particulate cycloolefin copolymers obtained in Examples 1, 3, 5, 9, 10, 12 and Comparative Examples 1 and 3, and the median sizes obtained in Examples 7 and 8 The median diameter of the particulate fluoropolymer in the obtained particulate fluoropolymer dispersion was determined by scattering particle size distribution measurement using laser diffraction.
Specifically, the particulate cycloolefin copolymer dispersion obtained in Examples 1, 3, 5, 9, 10, 12 and Comparative Examples 1 and 3, or Example 7 was placed in a glass cell having a capacity of 3.5 mL. , add the particulate fluoropolymer dispersion obtained in 8, further add GBL or DMAc (using the same solvent as the dispersion) to dilute 1000 times, and contain particulate cycloolefin copolymer or particulate fluoropolymer A dispersion sample was obtained. Each dispersion sample obtained was measured using a laser diffraction/scattering particle size distribution analyzer (manufactured by Malvern Panalytical, model: NanoZS, refractive index: 1.70-0.20i), and the particulate cycloolefin copolymer and the median diameter of the particulate fluoropolymer were determined.
As described above, in Examples 1, 3, 5, 7 to 9, 10, 12 and Comparative Examples 1 and 3, the polyimide resin was used in an amount within a range not affecting the particle size of the particulate cycloolefin copolymer or the particulate fluoropolymer. Alternatively, since the polyamic acid and the antioxidant were added to the dispersion to form the composition, the median size of the particulate cycloolefin copolymer in the dispersion and the median size of the particulate fluoropolymer in the dispersion, respectively, The median diameter of the particulate cycloolefin copolymer in the product and the median diameter of the particulate fluoropolymer in the composition were used.
(製造例2、4で得られたシクロオレフィンコポリマー破砕粉を使用して得られた粒子状シクロオレフィンコポリマー分散液中の粒子状シクロオレフィンコポリマーの粒子径)
実施例2、4、6、11及び比較例2、4で得られた粒子状シクロオレフィンコポリマー分散液中の粒子状シクロオレフィンコポリマーのメジアン径を、レーザー回析を用いた散乱式粒度分布測定により求めた。
具体的には、製造例2及び4で得られた粒子状シクロオレフィンコポリマーをイソプロパノール中に分散させ、粒子状シクロオレフィンコポリマーを含有する分散液試料を得た。得られた各分散液試料をレーザー回折/散乱式粒度分布測定装置(日機装(株)製、型式:MT3300EX II)を用いて測定し、粒子状シクロオレフィンコポリマーのメジアン径をそれぞれ求めた。
なお、上記の通り、実施例2、4、6、11及び比較例2、4では粒子状シクロオレフィンコポリマーの粒子径に影響しない範囲の量でポリアミック酸を分散液に添加して組成物を形成した。また、粒子状シクロオレフィンコポリマーはイソプロパノール、DMAc及びGBLには溶解しない。そのため、上記分散液試料中の粒子状シクロオレフィンコポリマーのメジアン径を、それぞれ、組成物中の粒子状シクロオレフィンコポリマーのメジアン径とした。 (Particle size of particulate cycloolefin copolymer in particulate cycloolefin copolymer dispersion obtained using crushed cycloolefin copolymer powder obtained in Production Examples 2 and 4)
The median diameter of the particulate cycloolefin copolymer in the particulate cycloolefin copolymer dispersions obtained in Examples 2, 4, 6, 11 and Comparative Examples 2 and 4 was measured by scattering particle size distribution measurement using laser diffraction. asked.
Specifically, the particulate cycloolefin copolymer obtained in Production Examples 2 and 4 was dispersed in isopropanol to obtain a dispersion liquid sample containing the particulate cycloolefin copolymer. Each dispersion sample obtained was measured using a laser diffraction/scattering particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., model: MT3300EX II) to determine the median diameter of each particulate cycloolefin copolymer.
As described above, in Examples 2, 4, 6, and 11 and Comparative Examples 2 and 4, polyamic acid was added to the dispersion in an amount within a range not affecting the particle size of the particulate cycloolefin copolymer to form the composition. did. Also, particulate cycloolefin copolymers are not soluble in isopropanol, DMAc and GBL. Therefore, the median diameter of the particulate cycloolefin copolymer in the dispersion sample was used as the median diameter of the particulate cycloolefin copolymer in the composition.
実施例2、4、6、11及び比較例2、4で得られた粒子状シクロオレフィンコポリマー分散液中の粒子状シクロオレフィンコポリマーのメジアン径を、レーザー回析を用いた散乱式粒度分布測定により求めた。
具体的には、製造例2及び4で得られた粒子状シクロオレフィンコポリマーをイソプロパノール中に分散させ、粒子状シクロオレフィンコポリマーを含有する分散液試料を得た。得られた各分散液試料をレーザー回折/散乱式粒度分布測定装置(日機装(株)製、型式:MT3300EX II)を用いて測定し、粒子状シクロオレフィンコポリマーのメジアン径をそれぞれ求めた。
なお、上記の通り、実施例2、4、6、11及び比較例2、4では粒子状シクロオレフィンコポリマーの粒子径に影響しない範囲の量でポリアミック酸を分散液に添加して組成物を形成した。また、粒子状シクロオレフィンコポリマーはイソプロパノール、DMAc及びGBLには溶解しない。そのため、上記分散液試料中の粒子状シクロオレフィンコポリマーのメジアン径を、それぞれ、組成物中の粒子状シクロオレフィンコポリマーのメジアン径とした。 (Particle size of particulate cycloolefin copolymer in particulate cycloolefin copolymer dispersion obtained using crushed cycloolefin copolymer powder obtained in Production Examples 2 and 4)
The median diameter of the particulate cycloolefin copolymer in the particulate cycloolefin copolymer dispersions obtained in Examples 2, 4, 6, 11 and Comparative Examples 2 and 4 was measured by scattering particle size distribution measurement using laser diffraction. asked.
Specifically, the particulate cycloolefin copolymer obtained in Production Examples 2 and 4 was dispersed in isopropanol to obtain a dispersion liquid sample containing the particulate cycloolefin copolymer. Each dispersion sample obtained was measured using a laser diffraction/scattering particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., model: MT3300EX II) to determine the median diameter of each particulate cycloolefin copolymer.
As described above, in Examples 2, 4, 6, and 11 and Comparative Examples 2 and 4, polyamic acid was added to the dispersion in an amount within a range not affecting the particle size of the particulate cycloolefin copolymer to form the composition. did. Also, particulate cycloolefin copolymers are not soluble in isopropanol, DMAc and GBL. Therefore, the median diameter of the particulate cycloolefin copolymer in the dispersion sample was used as the median diameter of the particulate cycloolefin copolymer in the composition.
<粒子状シクロオレフィンコポリマー分散液中の溶媒含有量>
実施例及び比較例で得られた粒子状シクロオレフィンコポリマー分散液中の溶媒含有量は、ガスクロマトグラフィーにより測定した。具体的には下記条件で測定を行い、一点検量により粒子状シクロオレフィンコポリマー分散液中の溶媒含有量を算出した。
装置:Agilent 7890Bガスクロマトグラフ(アジレント・テクノロジー(株)製)
カラム:DB-5(アジレント・テクノロジー(株)製)
キャリアガス:ヘリウム
注入口温度:200℃
検出器温度:250℃
内部標準液:ベンジルアルコール
溶媒:クロロホルム <Solvent Content in Particulate Cycloolefin Copolymer Dispersion>
The solvent content in the particulate cycloolefin copolymer dispersions obtained in Examples and Comparative Examples was measured by gas chromatography. Specifically, the measurement was performed under the following conditions, and the solvent content in the particulate cycloolefin copolymer dispersion was calculated by one-point calibration.
Apparatus: Agilent 7890B gas chromatograph (manufactured by Agilent Technologies Inc.)
Column: DB-5 (manufactured by Agilent Technologies Inc.)
Carrier gas: Helium Inlet temperature: 200°C
Detector temperature: 250°C
Internal standard solution: benzyl alcohol Solvent: chloroform
実施例及び比較例で得られた粒子状シクロオレフィンコポリマー分散液中の溶媒含有量は、ガスクロマトグラフィーにより測定した。具体的には下記条件で測定を行い、一点検量により粒子状シクロオレフィンコポリマー分散液中の溶媒含有量を算出した。
装置:Agilent 7890Bガスクロマトグラフ(アジレント・テクノロジー(株)製)
カラム:DB-5(アジレント・テクノロジー(株)製)
キャリアガス:ヘリウム
注入口温度:200℃
検出器温度:250℃
内部標準液:ベンジルアルコール
溶媒:クロロホルム <Solvent Content in Particulate Cycloolefin Copolymer Dispersion>
The solvent content in the particulate cycloolefin copolymer dispersions obtained in Examples and Comparative Examples was measured by gas chromatography. Specifically, the measurement was performed under the following conditions, and the solvent content in the particulate cycloolefin copolymer dispersion was calculated by one-point calibration.
Apparatus: Agilent 7890B gas chromatograph (manufactured by Agilent Technologies Inc.)
Column: DB-5 (manufactured by Agilent Technologies Inc.)
Carrier gas: Helium Inlet temperature: 200°C
Detector temperature: 250°C
Internal standard solution: benzyl alcohol Solvent: chloroform
<複合フィルムの厚さ>
実施例及び比較例で得られた複合フィルムの厚さは、デジマチックインジケータ((株)ミツトヨ製、「ID-C112XBS」)を使用し、フィルムの任意の5点以上の厚さを測定し、それらの平均値を複合フィルムの厚さとした。 <Thickness of composite film>
The thickness of the composite films obtained in Examples and Comparative Examples was measured using a digimatic indicator (manufactured by Mitutoyo Co., Ltd., "ID-C112XBS"), and measuring the thickness at five or more arbitrary points of the film. Their average value was taken as the thickness of the composite film.
実施例及び比較例で得られた複合フィルムの厚さは、デジマチックインジケータ((株)ミツトヨ製、「ID-C112XBS」)を使用し、フィルムの任意の5点以上の厚さを測定し、それらの平均値を複合フィルムの厚さとした。 <Thickness of composite film>
The thickness of the composite films obtained in Examples and Comparative Examples was measured using a digimatic indicator (manufactured by Mitutoyo Co., Ltd., "ID-C112XBS"), and measuring the thickness at five or more arbitrary points of the film. Their average value was taken as the thickness of the composite film.
<フィルム中の粒子状シクロオレフィンコポリマー及び粒子状フッ素ポリマーの平均一次粒子径>
実施例及び比較例で得られた複合フィルムについて、走査型透過電子顕微鏡(STEM)を用いて複合フィルムの断面観察を行った。観察画像から50個以上の粒子の粒子径を測定し、それらの平均値を粒子状シクロオレフィンコポリマー及び粒子状フッ素ポリマーの平均一次粒子径とした。
STEM観察測定条件
装置名:日本FEI(株)製 HeLiоsG4UX(剥片作成装置)
(株)日立ハイテク製 S―5500(STEM観察用)
加速電圧:30kv
倍率:20000倍 <Average Primary Particle Size of Particulate Cycloolefin Copolymer and Particulate Fluoropolymer in Film>
Cross-sectional observation of the composite films obtained in Examples and Comparative Examples was performed using a scanning transmission electron microscope (STEM). The particle diameters of 50 or more particles were measured from the observation image, and the average value thereof was taken as the average primary particle diameter of the particulate cycloolefin copolymer and the particulate fluoropolymer.
STEM observation and measurement conditions Apparatus name: HeLiоs G4UX manufactured by Japan FEI Co., Ltd. (flake preparation apparatus)
Hitachi High-Tech Co., Ltd. S-5500 (for STEM observation)
Accelerating voltage: 30kv
Magnification: 20000 times
実施例及び比較例で得られた複合フィルムについて、走査型透過電子顕微鏡(STEM)を用いて複合フィルムの断面観察を行った。観察画像から50個以上の粒子の粒子径を測定し、それらの平均値を粒子状シクロオレフィンコポリマー及び粒子状フッ素ポリマーの平均一次粒子径とした。
STEM観察測定条件
装置名:日本FEI(株)製 HeLiоsG4UX(剥片作成装置)
(株)日立ハイテク製 S―5500(STEM観察用)
加速電圧:30kv
倍率:20000倍 <Average Primary Particle Size of Particulate Cycloolefin Copolymer and Particulate Fluoropolymer in Film>
Cross-sectional observation of the composite films obtained in Examples and Comparative Examples was performed using a scanning transmission electron microscope (STEM). The particle diameters of 50 or more particles were measured from the observation image, and the average value thereof was taken as the average primary particle diameter of the particulate cycloolefin copolymer and the particulate fluoropolymer.
STEM observation and measurement conditions Apparatus name: HeLiоs G4UX manufactured by Japan FEI Co., Ltd. (flake preparation apparatus)
Hitachi High-Tech Co., Ltd. S-5500 (for STEM observation)
Accelerating voltage: 30kv
Magnification: 20000 times
<複合フィルムの吸湿率>
実施例1、2、5~9及び比較例1、2で得られた複合フィルムの吸湿率は、カールフィッシャー水分計(気化式)により測定した。具体的には、水分気化装置用バイアル瓶内に、20mm×20mmの大きさに切り出したフィルムを入れ、温度23℃及び湿度50%(以下、「23℃50%」ともいう)環境に24時間以上曝露した。その後、同環境でバイアル瓶を密封し、下記に示す条件によりフィルム中の水分量を測定した。
・カールフィッシャー装置:Metrohm社製 915 KF Ti-Touch
・滴定試薬:Honeywell社製 HYDRANAL(登録商標)-Coulomat AG
・滴定前コンディショニング:ドリフト値10μg/分以下で安定
・滴定条件:発生電流400mV、待機時間300秒、滴定終点50mV
・水分気化装置:Metrohm社製860 KFサーモプレップ
・フィルム加熱条件:150℃、乾燥空気50mL/分で搬送。
・ブランク測定:空のバイアル瓶を23℃50%環境にて密封し、上記と同条件で測定。
実施例及び比較例で得られた複合フィルムの吸湿率(%)は、下記式より算出した。
吸湿率=[(フィルム中の水分量)-(ブランク測定の水分量)]÷(23℃50%環境で24時間以上曝露した後のフィルム質量)×100 <Moisture absorption rate of composite film>
The moisture absorption of the composite films obtained in Examples 1, 2, 5 to 9 and Comparative Examples 1 and 2 was measured with a Karl Fischer moisture meter (evaporation type). Specifically, a film cut into a size of 20 mm × 20 mm is put in a vial bottle for a moisture vaporizer, and the temperature is 23 ° C. and the humidity is 50% (hereinafter also referred to as “23 ° C. 50%”) for 24 hours. more exposed. After that, the vial was sealed in the same environment, and the water content in the film was measured under the conditions shown below.
・ Karl Fischer device: 915 KF Ti-Touch manufactured by Metrohm
・ Titration reagent: HYDRANAL (registered trademark)-Coulomat AG manufactured by Honeywell
・Conditioning before titration: stable at a drift value of 10 μg/min or less ・Titration conditions: generation current 400 mV, standby time 300 seconds, titration end point 50 mV
Moisture vaporizer: 860 KF thermoprep manufactured by Metrohm Film heating conditions: 150°C, conveyed at 50 mL/min of dry air.
-Blank measurement: An empty vial bottle was sealed in an environment of 23°C and 50%, and measured under the same conditions as above.
The moisture absorption (%) of the composite films obtained in Examples and Comparative Examples was calculated from the following formula.
Moisture absorption rate = [(moisture content in film) - (moisture content in blank measurement)] ÷ (film mass after exposure for 24 hours or more at 23 ° C. 50% environment) × 100
実施例1、2、5~9及び比較例1、2で得られた複合フィルムの吸湿率は、カールフィッシャー水分計(気化式)により測定した。具体的には、水分気化装置用バイアル瓶内に、20mm×20mmの大きさに切り出したフィルムを入れ、温度23℃及び湿度50%(以下、「23℃50%」ともいう)環境に24時間以上曝露した。その後、同環境でバイアル瓶を密封し、下記に示す条件によりフィルム中の水分量を測定した。
・カールフィッシャー装置:Metrohm社製 915 KF Ti-Touch
・滴定試薬:Honeywell社製 HYDRANAL(登録商標)-Coulomat AG
・滴定前コンディショニング:ドリフト値10μg/分以下で安定
・滴定条件:発生電流400mV、待機時間300秒、滴定終点50mV
・水分気化装置:Metrohm社製860 KFサーモプレップ
・フィルム加熱条件:150℃、乾燥空気50mL/分で搬送。
・ブランク測定:空のバイアル瓶を23℃50%環境にて密封し、上記と同条件で測定。
実施例及び比較例で得られた複合フィルムの吸湿率(%)は、下記式より算出した。
吸湿率=[(フィルム中の水分量)-(ブランク測定の水分量)]÷(23℃50%環境で24時間以上曝露した後のフィルム質量)×100 <Moisture absorption rate of composite film>
The moisture absorption of the composite films obtained in Examples 1, 2, 5 to 9 and Comparative Examples 1 and 2 was measured with a Karl Fischer moisture meter (evaporation type). Specifically, a film cut into a size of 20 mm × 20 mm is put in a vial bottle for a moisture vaporizer, and the temperature is 23 ° C. and the humidity is 50% (hereinafter also referred to as “23 ° C. 50%”) for 24 hours. more exposed. After that, the vial was sealed in the same environment, and the water content in the film was measured under the conditions shown below.
・ Karl Fischer device: 915 KF Ti-Touch manufactured by Metrohm
・ Titration reagent: HYDRANAL (registered trademark)-Coulomat AG manufactured by Honeywell
・Conditioning before titration: stable at a drift value of 10 μg/min or less ・Titration conditions: generation current 400 mV, standby time 300 seconds, titration end point 50 mV
Moisture vaporizer: 860 KF thermoprep manufactured by Metrohm Film heating conditions: 150°C, conveyed at 50 mL/min of dry air.
-Blank measurement: An empty vial bottle was sealed in an environment of 23°C and 50%, and measured under the same conditions as above.
The moisture absorption (%) of the composite films obtained in Examples and Comparative Examples was calculated from the following formula.
Moisture absorption rate = [(moisture content in film) - (moisture content in blank measurement)] ÷ (film mass after exposure for 24 hours or more at 23 ° C. 50% environment) × 100
<複合フィルムの耐熱性評価>
実施例3、4、10~12及び比較例3、4で得られた複合フィルムの耐熱性は、下記に示す耐熱劣化試験と、耐熱劣化試験前後のシクロオレフィンコポリマーの一回反射「ATR FT-IR」の変化率から評価した。
・耐熱劣化試験:複合フィルムを大気下で360℃5分維持
・装置:VARIAN社製 VARIAN 670 -IR
・ATRユニット:Specac社製 シルバーゲートATRエボリューション(ゲルマニウムフラットプレート)
・測定面:複合フィルムをガラス基板から剥離した際のガラス基板側の面
・測定条件:積算回数32回、波数分解能4cm-1、スキャンスピード5kHz
・IRピーク維持率算出:下記式より算出した。
IRピーク維持率(%)
=〔(劣化試験後のシクロオレフィンコポリマーピーク強度)/(劣化試験後のポリイミド系樹脂のピーク強度)〕÷〔(劣化試験前のシクロオレフィンコポリマーピーク強度)/(劣化試験前のポリイミド系樹脂のピーク強度)〕×100
・シクロオレフィンコポリマーピーク強度:2900~3000cm-1のピークトップ強度(C-H 伸縮振動)
・ポリイミド系樹脂ピーク強度:1480~1520cm-1のピークトップ強度(ベンゼン環のC=C 伸縮振動) <Heat resistance evaluation of composite film>
The heat resistance of the composite films obtained in Examples 3, 4, 10 to 12 and Comparative Examples 3 and 4 was evaluated by the heat deterioration test shown below and the single reflection "ATR FT- It was evaluated from the rate of change of IR.
・Heat deterioration test: Maintain the composite film at 360 ° C. for 5 minutes in the atmosphere ・Apparatus: VARIAN 670-IR manufactured by VARIAN Co., Ltd.
・ATR unit: Specac silver gate ATR evolution (germanium flat plate)
・Measurement surface: The surface on the glass substrate side when the composite film was peeled from the glass substrate ・Measurement conditions: 32 integration times, wave number resolution 4 cm −1 , scan speed 5 kHz
Calculation of IR peak retention rate: Calculated from the following formula.
IR peak maintenance rate (%)
= [(Peak intensity of cycloolefin copolymer after deterioration test) / (Peak intensity of polyimide resin after deterioration test)] ÷ [(Peak intensity of cycloolefin copolymer before deterioration test) / (Peak intensity of polyimide resin before deterioration test) peak intensity)] × 100
・ Cycloolefin copolymer peak intensity: 2900-3000 cm -1 peak top intensity (CH stretching vibration)
・ Polyimide resin peak intensity: 1480 to 1520 cm -1 peak top intensity (C=C stretching vibration of benzene ring)
実施例3、4、10~12及び比較例3、4で得られた複合フィルムの耐熱性は、下記に示す耐熱劣化試験と、耐熱劣化試験前後のシクロオレフィンコポリマーの一回反射「ATR FT-IR」の変化率から評価した。
・耐熱劣化試験:複合フィルムを大気下で360℃5分維持
・装置:VARIAN社製 VARIAN 670 -IR
・ATRユニット:Specac社製 シルバーゲートATRエボリューション(ゲルマニウムフラットプレート)
・測定面:複合フィルムをガラス基板から剥離した際のガラス基板側の面
・測定条件:積算回数32回、波数分解能4cm-1、スキャンスピード5kHz
・IRピーク維持率算出:下記式より算出した。
IRピーク維持率(%)
=〔(劣化試験後のシクロオレフィンコポリマーピーク強度)/(劣化試験後のポリイミド系樹脂のピーク強度)〕÷〔(劣化試験前のシクロオレフィンコポリマーピーク強度)/(劣化試験前のポリイミド系樹脂のピーク強度)〕×100
・シクロオレフィンコポリマーピーク強度:2900~3000cm-1のピークトップ強度(C-H 伸縮振動)
・ポリイミド系樹脂ピーク強度:1480~1520cm-1のピークトップ強度(ベンゼン環のC=C 伸縮振動) <Heat resistance evaluation of composite film>
The heat resistance of the composite films obtained in Examples 3, 4, 10 to 12 and Comparative Examples 3 and 4 was evaluated by the heat deterioration test shown below and the single reflection "ATR FT- It was evaluated from the rate of change of IR.
・Heat deterioration test: Maintain the composite film at 360 ° C. for 5 minutes in the atmosphere ・Apparatus: VARIAN 670-IR manufactured by VARIAN Co., Ltd.
・ATR unit: Specac silver gate ATR evolution (germanium flat plate)
・Measurement surface: The surface on the glass substrate side when the composite film was peeled from the glass substrate ・Measurement conditions: 32 integration times, wave number resolution 4 cm −1 , scan speed 5 kHz
Calculation of IR peak retention rate: Calculated from the following formula.
IR peak maintenance rate (%)
= [(Peak intensity of cycloolefin copolymer after deterioration test) / (Peak intensity of polyimide resin after deterioration test)] ÷ [(Peak intensity of cycloolefin copolymer before deterioration test) / (Peak intensity of polyimide resin before deterioration test) peak intensity)] × 100
・ Cycloolefin copolymer peak intensity: 2900-3000 cm -1 peak top intensity (CH stretching vibration)
・ Polyimide resin peak intensity: 1480 to 1520 cm -1 peak top intensity (C=C stretching vibration of benzene ring)
<試薬の詳細>
シクロオレフィンコポリマーの合成には、住友化学(株)製のトルエン、富士フィルム和光純薬(株)製のスチレン、荒川化学工業(株)製の2-ノルボルネン(以下「NB」という)、東ソー・ファインケム(株)製のトリイソブチルアルミニウム(以下「TIBA」という)、AGC(株)製のN,N-ジメチルアニリニウムテトラキス(ペンタフルオロフェニル)ボレート(以下「AB」という)を用いた。 <Details of reagents>
For the synthesis of the cycloolefin copolymer, toluene manufactured by Sumitomo Chemical Co., Ltd., styrene manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 2-norbornene manufactured by Arakawa Chemical Industries, Ltd. (hereinafter referred to as "NB"), Tosoh Co., Ltd. Triisobutylaluminum (hereinafter referred to as "TIBA") manufactured by Finechem Co., Ltd. and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (hereinafter referred to as "AB") manufactured by AGC Corporation were used.
シクロオレフィンコポリマーの合成には、住友化学(株)製のトルエン、富士フィルム和光純薬(株)製のスチレン、荒川化学工業(株)製の2-ノルボルネン(以下「NB」という)、東ソー・ファインケム(株)製のトリイソブチルアルミニウム(以下「TIBA」という)、AGC(株)製のN,N-ジメチルアニリニウムテトラキス(ペンタフルオロフェニル)ボレート(以下「AB」という)を用いた。 <Details of reagents>
For the synthesis of the cycloolefin copolymer, toluene manufactured by Sumitomo Chemical Co., Ltd., styrene manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 2-norbornene manufactured by Arakawa Chemical Industries, Ltd. (hereinafter referred to as "NB"), Tosoh Co., Ltd. Triisobutylaluminum (hereinafter referred to as "TIBA") manufactured by Finechem Co., Ltd. and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (hereinafter referred to as "AB") manufactured by AGC Corporation were used.
トルエンは、モレキュラーシーブス13X(ユニオン昭和(株)製)と活性アルミナ(住友化学(株)製「NKHD-24」)とを用いて脱水し、次いで、窒素ガスを吹き込んで溶存酸素を除去したものを使用した。
Toluene is dehydrated using molecular sieves 13X (manufactured by Union Showa Co., Ltd.) and activated alumina ("NKHD-24" manufactured by Sumitomo Chemical Co., Ltd.), and then nitrogen gas is blown to remove dissolved oxygen. It was used.
NBは、トルエンに溶解させた後、モレキュラーシーブス13X(ユニオン昭和(株)製)と活性アルミナ(住友化学(株)製「NKHD-24」)とを用いて脱水し、次いで、窒素ガスを吹き込んで溶存酸素を除去したものを使用した(以下、「NB溶液」という)。なお、NB溶液中のNB濃度は、ガスクロマトグラフィーを用いて測定した。
NB is dissolved in toluene, dehydrated using molecular sieves 13X (manufactured by Union Showa Co., Ltd.) and activated alumina ("NKHD-24" manufactured by Sumitomo Chemical Co., Ltd.), and then nitrogen gas is blown. (hereinafter referred to as "NB solution"). The NB concentration in the NB solution was measured using gas chromatography.
イソプロピリデン(シクロペンタジエニル)(3-tert-ブチル-5-メチル-2-フェノキシ)チタンジクロリド(以下「錯体」という)は、特開平9-183809号公報に記載の方法に従って合成したものを使用した。
Isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride (hereinafter referred to as "complex") was synthesized according to the method described in JP-A-9-183809. used.
[シクロオレフィンコポリマーの製造]
<合成例1>
内部を減圧乾燥したオートクレーブに、NB溶液 1,500mL(NB濃度:3.00mol/L)を加え、60℃に昇温した。系内を攪拌しながら、水素分圧:5kPa、エチレン分圧:100kPaで加圧した後、TIBAのヘキサン溶液 3.0mL(濃度:1.0mol/L)と、ABを0.16gと、錯体のトルエン溶液 7.0mL(濃度:10mmol/L)とを加え、エチレンとNBとの重合を開始した。重合中は系内の温度を60℃に保ち、また、エチレンを連続的に供給して系内の圧力を開始時の値に保った。重合開始から3時間経過後、水 5.0mLを加えて重合を停止し、オートクレーブ内の溶液を抜き出した。抜き出された溶液に、トルエン 1,500gと、硫酸マグネシウム 100gとを加えて攪拌し、次いで、水 100mLを加えて攪拌し、固体を濾過により除去した。得られた液体をアセトンに滴下し、析出した粉末を濾過により単離した。単離された粉末を更にアセトンで洗浄し、減圧下、120℃で2時間乾燥して、シクロオレフィンコポリマーを216g得た。得られたシクロオレフィンコポリマーにおいて、NB含有量は82.5mol%であり、Tgは297℃であり、Mwは343,000であり、Mw/Mnは1.79であり、CTEは47.0ppm/Kであった。該シクロオレフィンコポリマーのδDは17.4MPa0.5であり、δPは1.6MPa0.5であり,δHは3.8MPa0.5であり、メソ型二連鎖/ラセモ型二連鎖は0.11であり、屈折率は1.54であった。合成例1の合成条件を表2に示す。 [Production of cycloolefin copolymer]
<Synthesis Example 1>
1,500 mL of NB solution (NB concentration: 3.00 mol/L) was added to the autoclave whose inside was dried under reduced pressure, and the temperature was raised to 60°C. While stirring the inside of the system, hydrogen partial pressure: 5 kPa, ethylene partial pressure: 100 kPa. 7.0 mL of a toluene solution (concentration: 10 mmol/L) was added to initiate polymerization of ethylene and NB. During the polymerization, the temperature in the system was kept at 60° C., and ethylene was continuously supplied to keep the pressure in the system at the initial value. After 3 hours from the initiation of polymerization, 5.0 mL of water was added to terminate the polymerization, and the solution in the autoclave was extracted. To the extracted solution, 1,500 g of toluene and 100 g of magnesium sulfate were added and stirred, then 100 mL of water was added and stirred, and solids were removed by filtration. The resulting liquid was added dropwise to acetone, and the precipitated powder was isolated by filtration. The isolated powder was further washed with acetone and dried under reduced pressure at 120° C. for 2 hours to obtain 216 g of cycloolefin copolymer. In the resulting cycloolefin copolymer, the NB content is 82.5 mol%, the Tg is 297°C, the Mw is 343,000, the Mw/Mn is 1.79 and the CTE is 47.0 ppm/ was K. The cycloolefin copolymer had a δD of 17.4 MPa 0.5 , a δP of 1.6 MPa 0.5 , a δH of 3.8 MPa 0.5 and a meso/racemo bilink of 0.5 . 11 and the refractive index was 1.54. Table 2 shows the synthesis conditions of Synthesis Example 1.
<合成例1>
内部を減圧乾燥したオートクレーブに、NB溶液 1,500mL(NB濃度:3.00mol/L)を加え、60℃に昇温した。系内を攪拌しながら、水素分圧:5kPa、エチレン分圧:100kPaで加圧した後、TIBAのヘキサン溶液 3.0mL(濃度:1.0mol/L)と、ABを0.16gと、錯体のトルエン溶液 7.0mL(濃度:10mmol/L)とを加え、エチレンとNBとの重合を開始した。重合中は系内の温度を60℃に保ち、また、エチレンを連続的に供給して系内の圧力を開始時の値に保った。重合開始から3時間経過後、水 5.0mLを加えて重合を停止し、オートクレーブ内の溶液を抜き出した。抜き出された溶液に、トルエン 1,500gと、硫酸マグネシウム 100gとを加えて攪拌し、次いで、水 100mLを加えて攪拌し、固体を濾過により除去した。得られた液体をアセトンに滴下し、析出した粉末を濾過により単離した。単離された粉末を更にアセトンで洗浄し、減圧下、120℃で2時間乾燥して、シクロオレフィンコポリマーを216g得た。得られたシクロオレフィンコポリマーにおいて、NB含有量は82.5mol%であり、Tgは297℃であり、Mwは343,000であり、Mw/Mnは1.79であり、CTEは47.0ppm/Kであった。該シクロオレフィンコポリマーのδDは17.4MPa0.5であり、δPは1.6MPa0.5であり,δHは3.8MPa0.5であり、メソ型二連鎖/ラセモ型二連鎖は0.11であり、屈折率は1.54であった。合成例1の合成条件を表2に示す。 [Production of cycloolefin copolymer]
<Synthesis Example 1>
1,500 mL of NB solution (NB concentration: 3.00 mol/L) was added to the autoclave whose inside was dried under reduced pressure, and the temperature was raised to 60°C. While stirring the inside of the system, hydrogen partial pressure: 5 kPa, ethylene partial pressure: 100 kPa. 7.0 mL of a toluene solution (concentration: 10 mmol/L) was added to initiate polymerization of ethylene and NB. During the polymerization, the temperature in the system was kept at 60° C., and ethylene was continuously supplied to keep the pressure in the system at the initial value. After 3 hours from the initiation of polymerization, 5.0 mL of water was added to terminate the polymerization, and the solution in the autoclave was extracted. To the extracted solution, 1,500 g of toluene and 100 g of magnesium sulfate were added and stirred, then 100 mL of water was added and stirred, and solids were removed by filtration. The resulting liquid was added dropwise to acetone, and the precipitated powder was isolated by filtration. The isolated powder was further washed with acetone and dried under reduced pressure at 120° C. for 2 hours to obtain 216 g of cycloolefin copolymer. In the resulting cycloolefin copolymer, the NB content is 82.5 mol%, the Tg is 297°C, the Mw is 343,000, the Mw/Mn is 1.79 and the CTE is 47.0 ppm/ was K. The cycloolefin copolymer had a δD of 17.4 MPa 0.5 , a δP of 1.6 MPa 0.5 , a δH of 3.8 MPa 0.5 and a meso/racemo bilink of 0.5 . 11 and the refractive index was 1.54. Table 2 shows the synthesis conditions of Synthesis Example 1.
<合成例2>
内部を減圧乾燥したオートクレーブに、NB溶液 1,427mL(NB濃度:3.00mol/L)、スチレン 55.2mLを加え、80℃に昇温した。系内を攪拌しながら、TIBAのヘキサン溶液 3.0mL(濃度:1.0mol/L)、AB 0.32g及び、錯体のトルエン溶液 15.0mL(濃度:10mmol/L)を加え、NBとスチレンの重合を開始した。重合中は系内の温度を80℃に保った。重合開始から2時間経過後、水 3.0mLを加えて重合を停止し、オートクレーブ内の溶液を抜き出した。抜き出された溶液に、得られた液体を大過剰量のアセトンに滴下し、析出した粉末を濾過により単離した。単離された粉末を更にアセトンで洗浄し、減圧下、150℃で2時間乾燥して、198.3gのシクロオレフィンコポリマーを得た。得られたシクロオレフィンコポリマーにおいて、NB含有量は96.3mol%であり、Mwは79,000であり、Mw/Mnは1.83であり、Tgは300℃超であった。また、該シクロオレフィンコポリマーのδDは17.4MPa0.5であり、δPは1.6MPa0.5であり,δHは3.8MPa0.5であった。合成例2の合成条件を表3に示す。 <Synthesis Example 2>
1,427 mL of NB solution (NB concentration: 3.00 mol/L) and 55.2 mL of styrene were added to an autoclave whose inside was dried under reduced pressure, and the temperature was raised to 80°C. While stirring the system, 3.0 mL of hexane solution of TIBA (concentration: 1.0 mol / L), 0.32 g of AB, and 15.0 mL of toluene solution of complex (concentration: 10 mmol / L) were added, and NB and styrene were added. started to polymerize. The temperature in the system was kept at 80°C during the polymerization. Two hours after the initiation of polymerization, 3.0 mL of water was added to terminate the polymerization, and the solution in the autoclave was extracted. The resulting liquid was added dropwise to a large excess amount of acetone to the extracted solution, and the precipitated powder was isolated by filtration. The isolated powder was further washed with acetone and dried under vacuum at 150° C. for 2 hours to yield 198.3 g of cycloolefin copolymer. In the resulting cycloolefin copolymer, the NB content was 96.3 mol%, Mw was 79,000, Mw/Mn was 1.83 and Tg was greater than 300°C. The cycloolefin copolymer had a δD of 17.4 MPa 0.5, a δP of 1.6 MPa 0.5 and a δH of 3.8 MPa 0.5 . Table 3 shows the synthesis conditions of Synthesis Example 2.
内部を減圧乾燥したオートクレーブに、NB溶液 1,427mL(NB濃度:3.00mol/L)、スチレン 55.2mLを加え、80℃に昇温した。系内を攪拌しながら、TIBAのヘキサン溶液 3.0mL(濃度:1.0mol/L)、AB 0.32g及び、錯体のトルエン溶液 15.0mL(濃度:10mmol/L)を加え、NBとスチレンの重合を開始した。重合中は系内の温度を80℃に保った。重合開始から2時間経過後、水 3.0mLを加えて重合を停止し、オートクレーブ内の溶液を抜き出した。抜き出された溶液に、得られた液体を大過剰量のアセトンに滴下し、析出した粉末を濾過により単離した。単離された粉末を更にアセトンで洗浄し、減圧下、150℃で2時間乾燥して、198.3gのシクロオレフィンコポリマーを得た。得られたシクロオレフィンコポリマーにおいて、NB含有量は96.3mol%であり、Mwは79,000であり、Mw/Mnは1.83であり、Tgは300℃超であった。また、該シクロオレフィンコポリマーのδDは17.4MPa0.5であり、δPは1.6MPa0.5であり,δHは3.8MPa0.5であった。合成例2の合成条件を表3に示す。 <Synthesis Example 2>
1,427 mL of NB solution (NB concentration: 3.00 mol/L) and 55.2 mL of styrene were added to an autoclave whose inside was dried under reduced pressure, and the temperature was raised to 80°C. While stirring the system, 3.0 mL of hexane solution of TIBA (concentration: 1.0 mol / L), 0.32 g of AB, and 15.0 mL of toluene solution of complex (concentration: 10 mmol / L) were added, and NB and styrene were added. started to polymerize. The temperature in the system was kept at 80°C during the polymerization. Two hours after the initiation of polymerization, 3.0 mL of water was added to terminate the polymerization, and the solution in the autoclave was extracted. The resulting liquid was added dropwise to a large excess amount of acetone to the extracted solution, and the precipitated powder was isolated by filtration. The isolated powder was further washed with acetone and dried under vacuum at 150° C. for 2 hours to yield 198.3 g of cycloolefin copolymer. In the resulting cycloolefin copolymer, the NB content was 96.3 mol%, Mw was 79,000, Mw/Mn was 1.83 and Tg was greater than 300°C. The cycloolefin copolymer had a δD of 17.4 MPa 0.5, a δP of 1.6 MPa 0.5 and a δH of 3.8 MPa 0.5 . Table 3 shows the synthesis conditions of Synthesis Example 2.
<製造例1:シクロオレフィンコポリマー溶液1の製造>
合成例1で得たシクロオレフィンコポリマーをトルエンに2質量%の濃度で溶解して、シクロオレフィンコポリマー溶液1を得た。 <Production Example 1: Production of cycloolefin copolymer solution 1>
A cycloolefin copolymer solution 1 was obtained by dissolving the cycloolefin copolymer obtained in Synthesis Example 1 in toluene at a concentration of 2% by mass.
合成例1で得たシクロオレフィンコポリマーをトルエンに2質量%の濃度で溶解して、シクロオレフィンコポリマー溶液1を得た。 <Production Example 1: Production of cycloolefin copolymer solution 1>
A cycloolefin copolymer solution 1 was obtained by dissolving the cycloolefin copolymer obtained in Synthesis Example 1 in toluene at a concentration of 2% by mass.
<製造例2:シクロオレフィンコポリマー破砕粉1の製造>
合成例1で得たシクロオレフィンコポリマーを、(株)喜多村製のカウンタージェットミルで粉砕し、フィルターにより分級することによって、メジアン径が2.6μmの粒子であるシクロオレフィンコポリマー破砕粉1を得た。 <Production Example 2: Production of crushed cycloolefin copolymer powder 1>
The cycloolefin copolymer obtained in Synthesis Example 1 was pulverized with a counter jet mill manufactured by Kitamura Co., Ltd. and classified by a filter to obtain crushed cycloolefin copolymer powder 1 having a median diameter of 2.6 μm. .
合成例1で得たシクロオレフィンコポリマーを、(株)喜多村製のカウンタージェットミルで粉砕し、フィルターにより分級することによって、メジアン径が2.6μmの粒子であるシクロオレフィンコポリマー破砕粉1を得た。 <Production Example 2: Production of crushed cycloolefin copolymer powder 1>
The cycloolefin copolymer obtained in Synthesis Example 1 was pulverized with a counter jet mill manufactured by Kitamura Co., Ltd. and classified by a filter to obtain crushed cycloolefin copolymer powder 1 having a median diameter of 2.6 μm. .
<製造例3:シクロオレフィンコポリマー溶液2の製造>
合成例2で得たシクロオレフィンコポリマーをトルエンに2質量%の濃度で溶解して、シクロオレフィンコポリマー溶液2を得た。 <Production Example 3: Production of cycloolefin copolymer solution 2>
A cycloolefin copolymer solution 2 was obtained by dissolving the cycloolefin copolymer obtained in Synthesis Example 2 in toluene at a concentration of 2% by mass.
合成例2で得たシクロオレフィンコポリマーをトルエンに2質量%の濃度で溶解して、シクロオレフィンコポリマー溶液2を得た。 <Production Example 3: Production of cycloolefin copolymer solution 2>
A cycloolefin copolymer solution 2 was obtained by dissolving the cycloolefin copolymer obtained in Synthesis Example 2 in toluene at a concentration of 2% by mass.
<製造例4:シクロオレフィンコポリマー破砕粉2の製造>
合成例2で得たシクロオレフィンコポリマーを、(株)喜多村社製のカウンタージェットミルで粉砕し、フィルターにより分級することによって、メジアン径が2.7μmの粒子であるシクロオレフィンコポリマー破砕粉2を得た。 <Production Example 4: Production of crushed cycloolefin copolymer powder 2>
The cycloolefin copolymer obtained in Synthesis Example 2 was pulverized with a counter jet mill manufactured by Kitamura Co., Ltd. and classified by a filter to obtain crushed cycloolefin copolymer powder 2 having a median diameter of 2.7 μm. rice field.
合成例2で得たシクロオレフィンコポリマーを、(株)喜多村社製のカウンタージェットミルで粉砕し、フィルターにより分級することによって、メジアン径が2.7μmの粒子であるシクロオレフィンコポリマー破砕粉2を得た。 <Production Example 4: Production of crushed cycloolefin copolymer powder 2>
The cycloolefin copolymer obtained in Synthesis Example 2 was pulverized with a counter jet mill manufactured by Kitamura Co., Ltd. and classified by a filter to obtain crushed cycloolefin copolymer powder 2 having a median diameter of 2.7 μm. rice field.
[ポリイミド樹脂の合成]
セパラブルフラスコにシリカゲル管、攪拌装置及び温度計を取り付けた反応器と、オイルバスとを準備した。乾燥窒素を用いてこのフラスコ内を窒素雰囲気にした後、6FDA 75.52gと、TFMB 54.44gとを投入した。これを400rpmで攪拌しながらDMAc 519.84gを加え、フラスコの内容物が均一な溶液になるまで攪拌を続けた。続いて、オイルバスを用いて容器内温度が20~30℃の範囲になるように調整しながらさらに20時間攪拌を続け、反応させてポリアミック酸を生成させた。30分後、撹拌速度を100rpmに変更した。20時間攪拌後、反応系温度を室温に戻し、DMAc 649.8gを加えてポリマー濃度が10質量%となるように調整した。さらに、ピリジン 32.27g、無水酢酸 41.65gを加え、室温で10時間攪拌してイミド化を行った。反応容器からポリイミドワニスを取り出した。得られたポリイミドワニスをメタノール中に滴下して再沈殿を行い、得られた粉体を加熱乾燥して溶媒を除去し、固形分としてポリイミド樹脂を得た。得られたポリイミド樹脂のδDは18.1MPa0.5であり、δPは8.3MPa0.5であり、δHは9.3MPa0.5であった。また、該ポリイミド樹脂のMwは334,300であり、Tgは361℃であった。なお、該ポリイミド樹脂と、製造例1で得られたシクロオレフィンコポリマーとのHSP値間距離は8.8であった。 [Synthesis of polyimide resin]
A reactor comprising a separable flask equipped with a silica gel tube, a stirrer and a thermometer, and an oil bath were prepared. After the flask was filled with dry nitrogen to create a nitrogen atmosphere, 75.52 g of 6FDA and 54.44 g of TFMB were added. While this was stirred at 400 rpm, 519.84 g of DMAc was added and stirring was continued until the contents of the flask became a homogeneous solution. Subsequently, stirring was continued for an additional 20 hours while adjusting the temperature in the container to be in the range of 20 to 30° C. using an oil bath, and the mixture was reacted to produce polyamic acid. After 30 minutes, the stirring speed was changed to 100 rpm. After stirring for 20 hours, the temperature of the reaction system was returned to room temperature, and 649.8 g of DMAc was added to adjust the polymer concentration to 10% by mass. Further, 32.27 g of pyridine and 41.65 g of acetic anhydride were added, and imidization was carried out by stirring at room temperature for 10 hours. The polyimide varnish was removed from the reaction vessel. The resulting polyimide varnish was dropped into methanol for reprecipitation, and the resulting powder was dried by heating to remove the solvent to obtain a polyimide resin as a solid content. The resulting polyimide resin had a δD of 18.1 MPa 0.5, a δP of 8.3 MPa 0.5 , and a δH of 9.3 MPa 0.5 . The polyimide resin had an Mw of 334,300 and a Tg of 361°C. The distance between the HSP values of the polyimide resin and the cycloolefin copolymer obtained in Production Example 1 was 8.8.
セパラブルフラスコにシリカゲル管、攪拌装置及び温度計を取り付けた反応器と、オイルバスとを準備した。乾燥窒素を用いてこのフラスコ内を窒素雰囲気にした後、6FDA 75.52gと、TFMB 54.44gとを投入した。これを400rpmで攪拌しながらDMAc 519.84gを加え、フラスコの内容物が均一な溶液になるまで攪拌を続けた。続いて、オイルバスを用いて容器内温度が20~30℃の範囲になるように調整しながらさらに20時間攪拌を続け、反応させてポリアミック酸を生成させた。30分後、撹拌速度を100rpmに変更した。20時間攪拌後、反応系温度を室温に戻し、DMAc 649.8gを加えてポリマー濃度が10質量%となるように調整した。さらに、ピリジン 32.27g、無水酢酸 41.65gを加え、室温で10時間攪拌してイミド化を行った。反応容器からポリイミドワニスを取り出した。得られたポリイミドワニスをメタノール中に滴下して再沈殿を行い、得られた粉体を加熱乾燥して溶媒を除去し、固形分としてポリイミド樹脂を得た。得られたポリイミド樹脂のδDは18.1MPa0.5であり、δPは8.3MPa0.5であり、δHは9.3MPa0.5であった。また、該ポリイミド樹脂のMwは334,300であり、Tgは361℃であった。なお、該ポリイミド樹脂と、製造例1で得られたシクロオレフィンコポリマーとのHSP値間距離は8.8であった。 [Synthesis of polyimide resin]
A reactor comprising a separable flask equipped with a silica gel tube, a stirrer and a thermometer, and an oil bath were prepared. After the flask was filled with dry nitrogen to create a nitrogen atmosphere, 75.52 g of 6FDA and 54.44 g of TFMB were added. While this was stirred at 400 rpm, 519.84 g of DMAc was added and stirring was continued until the contents of the flask became a homogeneous solution. Subsequently, stirring was continued for an additional 20 hours while adjusting the temperature in the container to be in the range of 20 to 30° C. using an oil bath, and the mixture was reacted to produce polyamic acid. After 30 minutes, the stirring speed was changed to 100 rpm. After stirring for 20 hours, the temperature of the reaction system was returned to room temperature, and 649.8 g of DMAc was added to adjust the polymer concentration to 10% by mass. Further, 32.27 g of pyridine and 41.65 g of acetic anhydride were added, and imidization was carried out by stirring at room temperature for 10 hours. The polyimide varnish was removed from the reaction vessel. The resulting polyimide varnish was dropped into methanol for reprecipitation, and the resulting powder was dried by heating to remove the solvent to obtain a polyimide resin as a solid content. The resulting polyimide resin had a δD of 18.1 MPa 0.5, a δP of 8.3 MPa 0.5 , and a δH of 9.3 MPa 0.5 . The polyimide resin had an Mw of 334,300 and a Tg of 361°C. The distance between the HSP values of the polyimide resin and the cycloolefin copolymer obtained in Production Example 1 was 8.8.
[ポリアミック酸の合成]
セパラブルフラスコにシリカゲル管、攪拌装置及び温度計を取り付けた反応器を準備した。乾燥窒素を用いてこのフラスコ内を窒素雰囲気にした後、DMAc 399.20g、p-PDA 16.00g(0.148mol)を加えた後、室温で攪拌して、DMAcにp-PDAを溶解させた。これに、400rpmで攪拌しながら、BPDA 21.2869g(0.0724mol)とTAHQ 33.1603g(0.0724mol)とを加えた。その後、室温下で3時間撹拌することによりポリアミック酸溶液を得た。 [Synthesis of polyamic acid]
A reactor was prepared by attaching a silica gel tube, a stirrer and a thermometer to a separable flask. After creating a nitrogen atmosphere in the flask using dry nitrogen, 399.20 g of DMAc and 16.00 g (0.148 mol) of p-PDA were added, followed by stirring at room temperature to dissolve p-PDA in DMAc. rice field. To this was added 21.2869 g (0.0724 mol) of BPDA and 33.1603 g (0.0724 mol) of TAHQ while stirring at 400 rpm. After that, the mixture was stirred at room temperature for 3 hours to obtain a polyamic acid solution.
セパラブルフラスコにシリカゲル管、攪拌装置及び温度計を取り付けた反応器を準備した。乾燥窒素を用いてこのフラスコ内を窒素雰囲気にした後、DMAc 399.20g、p-PDA 16.00g(0.148mol)を加えた後、室温で攪拌して、DMAcにp-PDAを溶解させた。これに、400rpmで攪拌しながら、BPDA 21.2869g(0.0724mol)とTAHQ 33.1603g(0.0724mol)とを加えた。その後、室温下で3時間撹拌することによりポリアミック酸溶液を得た。 [Synthesis of polyamic acid]
A reactor was prepared by attaching a silica gel tube, a stirrer and a thermometer to a separable flask. After creating a nitrogen atmosphere in the flask using dry nitrogen, 399.20 g of DMAc and 16.00 g (0.148 mol) of p-PDA were added, followed by stirring at room temperature to dissolve p-PDA in DMAc. rice field. To this was added 21.2869 g (0.0724 mol) of BPDA and 33.1603 g (0.0724 mol) of TAHQ while stirring at 400 rpm. After that, the mixture was stirred at room temperature for 3 hours to obtain a polyamic acid solution.
〔実施例1〕
製造例1で得られたシクロオレフィンコポリマー溶液1 100.0gとGBL 98.0gを混合し、トルエン含有量がGBL 100質量部に対して7質量部となるように、50hPa、80℃で減圧留去してトルエンを留去し、粒子状シクロオレフィンコポリマー分散液を得た。上記方法にて測定した分散液及び組成物中の粒子状シクロオレフィンコポリマーのメジアン径は0.14μmであった。
得られた分散液 51.3g(シクロオレフィンコポリマー1.9質量%)に、(株)ADEKA製アデカスタブAO-330;(1,3,5-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシフェニルメチル)-2,4,6-トリメチルベンゼン) 0.0487gを添加して攪拌した後、上記で得られたポリイミド樹脂を2.0g添加して、ポリイミド-シクロオレフィンコポリマー混合液として、組成物を得た。AO-330の含有量は、シクロオレフィンコポリマー 100質量部に対して、5.0質量部である。得られた組成物において、1mmを超えるシクロオレフィンコポリマーの凝集体は確認されなかった。
得られた組成物をガラス基板上において流涎成形し、線速0.4m/分で塗膜を成形した。70℃で60分、塗膜を加熱させ、ガラス基板からフィルムを剥離した後、金枠でフィルムを固定し更に大気下、360℃で15分間加熱することにより、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂及び粒子状シクロオレフィンコポリマーの合計質量に対して、32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は0.16μmであった。
実施例1で使用したシクロオレフィンコポリマーとポリイミド樹脂とのHSP値間距離は8.8であり、該シクロオレフィンコポリマーとトルエンとのHSP値間距離は2.2であり、ポリイミド樹脂とトルエンとのHSP値間距離は10.0であり、該シクロオレフィンコポリマーとGBLとのHSP値間距離は15.5であり、ポリイミド樹脂とGBLとのHSP値間距離は8.5であり、AO-330とGBLとのHSP値間距離は17.7であり、AO-330の構造SとGBLとのHSP値間距離は17.6であり、AO-330とシクロオレフィンコポリマーとのHSP値間距離は3.4であり、AO-330の構造SとシクロオレフィンコポリマーとのHSP値間距離は2.8であった。また、AO-330とポリイミド樹脂とのHSP値間距離は11.7であり、AO-330の構造Sとポリイミド樹脂とのHSP値間距離は11.5であり、AO-330とトルエンとのHSP値間距離は1.7であった。
上記溶解性の評価方法により、実施例1で使用したシクロオレフィンコポリマーはトルエンに溶解し、GBLに溶解しなかった。またポリイミド樹脂は、GBLに溶解し、トルエンに溶解しなかった。 [Example 1]
100.0 g of the cycloolefin copolymer solution 1 obtained in Production Example 1 and 98.0 g of GBL were mixed and distilled under reduced pressure at 50 hPa and 80° C. so that the toluene content was 7 parts by mass with respect to 100 parts by mass of GBL. toluene was distilled off to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the dispersion and composition measured by the above method was 0.14 µm.
To 51.3 g of the resulting dispersion (1.9% by mass of the cycloolefin copolymer), Adekastab AO-330 manufactured by ADEKA Corporation; (1,3,5-tris(3,5-di-tert-butyl-4 -Hydroxyphenylmethyl)-2,4,6-trimethylbenzene) 0.0487 g was added and stirred, and then 2.0 g of the polyimide resin obtained above was added to obtain a polyimide-cycloolefin copolymer mixture, A composition was obtained. The content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer. No cycloolefin copolymer aggregates larger than 1 mm were observed in the resulting composition.
The resulting composition was cast on a glass substrate to form a coating film at a line speed of 0.4 m/min. After heating the coating film at 70 ° C. for 60 minutes and peeling the film from the glass substrate, the film was fixed with a metal frame and further heated at 360 ° C. for 15 minutes in the atmosphere to obtain a polyimide-cycloolefin having a thickness of 50 μm. A copolymer composite film was obtained. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.16 µm.
The distance between the HSP values between the cycloolefin copolymer and the polyimide resin used in Example 1 is 8.8, the distance between the HSP values between the cycloolefin copolymer and toluene is 2.2, and the distance between the polyimide resin and toluene is 8.8. The distance between HSP values is 10.0, the distance between HSP values between the cycloolefin copolymer and GBL is 15.5, the distance between HSP values between polyimide resin and GBL is 8.5, and AO-330 The distance between HSP values between and GBL is 17.7, the distance between HSP values between structure S of AO-330 and GBL is 17.6, and the distance between HSP values between AO-330 and cycloolefin copolymer is 3.4, and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8. Further, the distance between the HSP values between AO-330 and the polyimide resin is 11.7, the distance between the HSP values between the structure S of AO-330 and the polyimide resin is 11.5, and the distance between AO-330 and toluene The distance between HSP values was 1.7.
According to the above solubility evaluation method, the cycloolefin copolymer used in Example 1 dissolved in toluene but did not dissolve in GBL. Also, the polyimide resin dissolved in GBL but did not dissolve in toluene.
製造例1で得られたシクロオレフィンコポリマー溶液1 100.0gとGBL 98.0gを混合し、トルエン含有量がGBL 100質量部に対して7質量部となるように、50hPa、80℃で減圧留去してトルエンを留去し、粒子状シクロオレフィンコポリマー分散液を得た。上記方法にて測定した分散液及び組成物中の粒子状シクロオレフィンコポリマーのメジアン径は0.14μmであった。
得られた分散液 51.3g(シクロオレフィンコポリマー1.9質量%)に、(株)ADEKA製アデカスタブAO-330;(1,3,5-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシフェニルメチル)-2,4,6-トリメチルベンゼン) 0.0487gを添加して攪拌した後、上記で得られたポリイミド樹脂を2.0g添加して、ポリイミド-シクロオレフィンコポリマー混合液として、組成物を得た。AO-330の含有量は、シクロオレフィンコポリマー 100質量部に対して、5.0質量部である。得られた組成物において、1mmを超えるシクロオレフィンコポリマーの凝集体は確認されなかった。
得られた組成物をガラス基板上において流涎成形し、線速0.4m/分で塗膜を成形した。70℃で60分、塗膜を加熱させ、ガラス基板からフィルムを剥離した後、金枠でフィルムを固定し更に大気下、360℃で15分間加熱することにより、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂及び粒子状シクロオレフィンコポリマーの合計質量に対して、32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は0.16μmであった。
実施例1で使用したシクロオレフィンコポリマーとポリイミド樹脂とのHSP値間距離は8.8であり、該シクロオレフィンコポリマーとトルエンとのHSP値間距離は2.2であり、ポリイミド樹脂とトルエンとのHSP値間距離は10.0であり、該シクロオレフィンコポリマーとGBLとのHSP値間距離は15.5であり、ポリイミド樹脂とGBLとのHSP値間距離は8.5であり、AO-330とGBLとのHSP値間距離は17.7であり、AO-330の構造SとGBLとのHSP値間距離は17.6であり、AO-330とシクロオレフィンコポリマーとのHSP値間距離は3.4であり、AO-330の構造SとシクロオレフィンコポリマーとのHSP値間距離は2.8であった。また、AO-330とポリイミド樹脂とのHSP値間距離は11.7であり、AO-330の構造Sとポリイミド樹脂とのHSP値間距離は11.5であり、AO-330とトルエンとのHSP値間距離は1.7であった。
上記溶解性の評価方法により、実施例1で使用したシクロオレフィンコポリマーはトルエンに溶解し、GBLに溶解しなかった。またポリイミド樹脂は、GBLに溶解し、トルエンに溶解しなかった。 [Example 1]
100.0 g of the cycloolefin copolymer solution 1 obtained in Production Example 1 and 98.0 g of GBL were mixed and distilled under reduced pressure at 50 hPa and 80° C. so that the toluene content was 7 parts by mass with respect to 100 parts by mass of GBL. toluene was distilled off to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the dispersion and composition measured by the above method was 0.14 µm.
To 51.3 g of the resulting dispersion (1.9% by mass of the cycloolefin copolymer), Adekastab AO-330 manufactured by ADEKA Corporation; (1,3,5-tris(3,5-di-tert-butyl-4 -Hydroxyphenylmethyl)-2,4,6-trimethylbenzene) 0.0487 g was added and stirred, and then 2.0 g of the polyimide resin obtained above was added to obtain a polyimide-cycloolefin copolymer mixture, A composition was obtained. The content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer. No cycloolefin copolymer aggregates larger than 1 mm were observed in the resulting composition.
The resulting composition was cast on a glass substrate to form a coating film at a line speed of 0.4 m/min. After heating the coating film at 70 ° C. for 60 minutes and peeling the film from the glass substrate, the film was fixed with a metal frame and further heated at 360 ° C. for 15 minutes in the atmosphere to obtain a polyimide-cycloolefin having a thickness of 50 μm. A copolymer composite film was obtained. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.16 µm.
The distance between the HSP values between the cycloolefin copolymer and the polyimide resin used in Example 1 is 8.8, the distance between the HSP values between the cycloolefin copolymer and toluene is 2.2, and the distance between the polyimide resin and toluene is 8.8. The distance between HSP values is 10.0, the distance between HSP values between the cycloolefin copolymer and GBL is 15.5, the distance between HSP values between polyimide resin and GBL is 8.5, and AO-330 The distance between HSP values between and GBL is 17.7, the distance between HSP values between structure S of AO-330 and GBL is 17.6, and the distance between HSP values between AO-330 and cycloolefin copolymer is 3.4, and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8. Further, the distance between the HSP values between AO-330 and the polyimide resin is 11.7, the distance between the HSP values between the structure S of AO-330 and the polyimide resin is 11.5, and the distance between AO-330 and toluene The distance between HSP values was 1.7.
According to the above solubility evaluation method, the cycloolefin copolymer used in Example 1 dissolved in toluene but did not dissolve in GBL. Also, the polyimide resin dissolved in GBL but did not dissolve in toluene.
〔実施例2〕
シクロオレフィンコポリマー破砕粉1 7.31g、DMAc 52.03g、AO-330 0.365gを混合し、撹拌することで分散液を得た。得られた分散液にポリアミック酸溶液 100g(ポリアミック酸 15質量%)を添加して、ポリアミック酸-シクロオレフィンコポリマー混合溶液としての組成物を得た。AO-330の含有量は、シクロオレフィンコポリマー 100質量部に対して、5.0質量部である。
得られた組成物をガラス基板上において流涎成形により、線速0.4m/分で塗膜を作製した。50℃で80分、塗膜を加熱させ、ガラス基板からポリアミック酸-シクロオレフィンコポリマー複合フィルムを剥離した後、金枠でフィルムを固定し更に大気下、360℃で15分間加熱することにより、ポリアミック酸はイミド化され、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られたフィルムにおいて、粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂と粒子状シクロオレフィンコポリマーとの合計質量に対して32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は2.7μmであった。
実施例2で使用したシクロオレフィンコポリマーとポリアミック酸とのHSP値間距離は6.0以上であり、シクロオレフィンコポリマーとDMAcとのHSP値間距離は11.4であり、AO-330とDMAcとのHSP値間距離は14.4であり、AO-330の構造SとDMAcとのHSP値間距離は14.0であり、AO-330とシクロオレフィンコポリマーとのHSP値間距離は3.4であり、AO-330の構造SとシクロオレフィンコポリマーとのHSP値間距離は2.8であった。また、実施例2で使用したシクロオレフィンコポリマーと、ポリアミック酸をイミド化して得られたポリイミド樹脂とのHSP値間距離は6.0以上であった。
上記溶解性の評価方法により、実施例2で使用したポリアミック酸は、DMAcに溶解し、トルエンに溶解しなかった。 [Example 2]
7.31 g of crushed cycloolefin copolymer powder 1, 52.03 g of DMAc and 0.365 g of AO-330 were mixed and stirred to obtain a dispersion. 100 g of polyamic acid solution (15% by mass of polyamic acid) was added to the resulting dispersion to obtain a composition as a polyamic acid-cycloolefin copolymer mixed solution. The content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer.
The resulting composition was cast on a glass substrate to form a coating film at a line speed of 0.4 m/min. After heating the coating film at 50° C. for 80 minutes and peeling the polyamic acid-cycloolefin copolymer composite film from the glass substrate, the film was fixed with a metal frame and further heated at 360° C. for 15 minutes in the atmosphere to obtain a polyamic film. The acid was imidized to obtain a 50 μm thick polyimide-cycloolefin copolymer composite film. In the obtained film, the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 μm.
The distance between the HSP values between the cycloolefin copolymer and the polyamic acid used in Example 2 is 6.0 or more, the distance between the HSP values between the cycloolefin copolymer and DMAc is 11.4, and AO-330 and DMAc The distance between HSP values of AO-330 is 14.4, the distance between HSP values between Structure S of AO-330 and DMAc is 14.0, and the distance between HSP values between AO-330 and cycloolefin copolymer is 3.4. and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8. Further, the distance between the HSP values of the cycloolefin copolymer used in Example 2 and the polyimide resin obtained by imidating the polyamic acid was 6.0 or more.
According to the above solubility evaluation method, the polyamic acid used in Example 2 dissolved in DMAc but did not dissolve in toluene.
シクロオレフィンコポリマー破砕粉1 7.31g、DMAc 52.03g、AO-330 0.365gを混合し、撹拌することで分散液を得た。得られた分散液にポリアミック酸溶液 100g(ポリアミック酸 15質量%)を添加して、ポリアミック酸-シクロオレフィンコポリマー混合溶液としての組成物を得た。AO-330の含有量は、シクロオレフィンコポリマー 100質量部に対して、5.0質量部である。
得られた組成物をガラス基板上において流涎成形により、線速0.4m/分で塗膜を作製した。50℃で80分、塗膜を加熱させ、ガラス基板からポリアミック酸-シクロオレフィンコポリマー複合フィルムを剥離した後、金枠でフィルムを固定し更に大気下、360℃で15分間加熱することにより、ポリアミック酸はイミド化され、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られたフィルムにおいて、粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂と粒子状シクロオレフィンコポリマーとの合計質量に対して32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は2.7μmであった。
実施例2で使用したシクロオレフィンコポリマーとポリアミック酸とのHSP値間距離は6.0以上であり、シクロオレフィンコポリマーとDMAcとのHSP値間距離は11.4であり、AO-330とDMAcとのHSP値間距離は14.4であり、AO-330の構造SとDMAcとのHSP値間距離は14.0であり、AO-330とシクロオレフィンコポリマーとのHSP値間距離は3.4であり、AO-330の構造SとシクロオレフィンコポリマーとのHSP値間距離は2.8であった。また、実施例2で使用したシクロオレフィンコポリマーと、ポリアミック酸をイミド化して得られたポリイミド樹脂とのHSP値間距離は6.0以上であった。
上記溶解性の評価方法により、実施例2で使用したポリアミック酸は、DMAcに溶解し、トルエンに溶解しなかった。 [Example 2]
7.31 g of crushed cycloolefin copolymer powder 1, 52.03 g of DMAc and 0.365 g of AO-330 were mixed and stirred to obtain a dispersion. 100 g of polyamic acid solution (15% by mass of polyamic acid) was added to the resulting dispersion to obtain a composition as a polyamic acid-cycloolefin copolymer mixed solution. The content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer.
The resulting composition was cast on a glass substrate to form a coating film at a line speed of 0.4 m/min. After heating the coating film at 50° C. for 80 minutes and peeling the polyamic acid-cycloolefin copolymer composite film from the glass substrate, the film was fixed with a metal frame and further heated at 360° C. for 15 minutes in the atmosphere to obtain a polyamic film. The acid was imidized to obtain a 50 μm thick polyimide-cycloolefin copolymer composite film. In the obtained film, the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 μm.
The distance between the HSP values between the cycloolefin copolymer and the polyamic acid used in Example 2 is 6.0 or more, the distance between the HSP values between the cycloolefin copolymer and DMAc is 11.4, and AO-330 and DMAc The distance between HSP values of AO-330 is 14.4, the distance between HSP values between Structure S of AO-330 and DMAc is 14.0, and the distance between HSP values between AO-330 and cycloolefin copolymer is 3.4. and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8. Further, the distance between the HSP values of the cycloolefin copolymer used in Example 2 and the polyimide resin obtained by imidating the polyamic acid was 6.0 or more.
According to the above solubility evaluation method, the polyamic acid used in Example 2 dissolved in DMAc but did not dissolve in toluene.
〔比較例1〕
AO-330に代えて、住友化学(株)製Sumilizer GA80;(ビス[3-[3-(tert-ブチル)-4-ヒドロキシ-5-メチルフェニル]プロパン酸]2,4,8,10-テトラオキサスピロ[5.5]ウンデカン-3,9-ジイルビス(2-メチルプロパン-2,1-ジイル) 0.0487gを添加したこと以外は、実施例1と同様にして、ポリイミド-シクロオレフィンコポリマー混合液としての組成物及び厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。Sumilizer GA80の含有量は、シクロオレフィンコポリマー100質量部に対して、5.0質量部である。得られたフィルムにおいて、粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂と粒子状シクロオレフィンコポリマーとの合計質量に対して32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は0.16μmであった。
比較例1で使用したシクロオレフィンコポリマーとポリイミド樹脂とのHSP値間距離は8.8であり、該シクロオレフィンコポリマーとトルエンとのHSP値間距離は2.2であり、該シクロオレフィンコポリマーとGBLとのHSP値間距離は15.5であり、ポリイミド樹脂とトルエンとのHSP値間距離は10.0であり、ポリイミド樹脂とGBLとのHSP値間距離は8.5であり、Sumilizer GA80とGBLとのHSP値間距離は15.3であり、Sumilizer GA80の構造SとGBLとのHSP値間距離は12.2であり、Sumilizer GA80とシクロオレフィンコポリマーとのHSP値間距離は2.0であり、Sumilizer GA80の構造SとシクロオレフィンコポリマーとのHSP値間距離は3.7であった。また、Sumilizer GA80とポリイミド樹脂とのHSP値間距離は8.1であり、Sumilizer GA80の構造Sとポリイミド樹脂とのHSP値間距離は6.5であり、Sumilizer GA80とトルエンとのHSP値間距離は2.8であった。 [Comparative Example 1]
Sumilizer GA80 manufactured by Sumitomo Chemical Co., Ltd. instead of AO-330; Polyimide-cycloolefin copolymer was prepared in the same manner as in Example 1, except that 0.0487 g of tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methylpropane-2,1-diyl) was added. A composition as a mixed liquid and a polyimide-cycloolefin copolymer composite film having a thickness of 50 μm were obtained, and the content of Sumilizer GA80 was 5.0 parts by weight with respect to 100 parts by weight of the cycloolefin copolymer. In the film, the content of the particulate cycloolefin copolymer was 32.8% by weight based on the total weight of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size was 0.16 µm.
The distance between the HSP values between the cycloolefin copolymer and the polyimide resin used in Comparative Example 1 was 8.8, the distance between the HSP values between the cycloolefin copolymer and toluene was 2.2, and the cycloolefin copolymer and GBL The distance between HSP values is 15.5, the distance between HSP values between polyimide resin and toluene is 10.0, the distance between HSP values between polyimide resin and GBL is 8.5, and Sumilizer GA80 and The distance between HSP values with GBL is 15.3, the distance between HSP values between Structure S of Sumilizer GA80 and GBL is 12.2, and the distance between HSP values between Sumilizer GA80 and cycloolefin copolymer is 2.0. and the distance between the HSP values of Structure S of Sumilizer GA80 and the cycloolefin copolymer was 3.7. Further, the distance between the HSP values between Sumilizer GA80 and the polyimide resin is 8.1, the distance between the HSP values between the structure S of Sumilizer GA80 and the polyimide resin is 6.5, and the distance between the HSP values between Sumilizer GA80 and toluene The distance was 2.8.
AO-330に代えて、住友化学(株)製Sumilizer GA80;(ビス[3-[3-(tert-ブチル)-4-ヒドロキシ-5-メチルフェニル]プロパン酸]2,4,8,10-テトラオキサスピロ[5.5]ウンデカン-3,9-ジイルビス(2-メチルプロパン-2,1-ジイル) 0.0487gを添加したこと以外は、実施例1と同様にして、ポリイミド-シクロオレフィンコポリマー混合液としての組成物及び厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。Sumilizer GA80の含有量は、シクロオレフィンコポリマー100質量部に対して、5.0質量部である。得られたフィルムにおいて、粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂と粒子状シクロオレフィンコポリマーとの合計質量に対して32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は0.16μmであった。
比較例1で使用したシクロオレフィンコポリマーとポリイミド樹脂とのHSP値間距離は8.8であり、該シクロオレフィンコポリマーとトルエンとのHSP値間距離は2.2であり、該シクロオレフィンコポリマーとGBLとのHSP値間距離は15.5であり、ポリイミド樹脂とトルエンとのHSP値間距離は10.0であり、ポリイミド樹脂とGBLとのHSP値間距離は8.5であり、Sumilizer GA80とGBLとのHSP値間距離は15.3であり、Sumilizer GA80の構造SとGBLとのHSP値間距離は12.2であり、Sumilizer GA80とシクロオレフィンコポリマーとのHSP値間距離は2.0であり、Sumilizer GA80の構造SとシクロオレフィンコポリマーとのHSP値間距離は3.7であった。また、Sumilizer GA80とポリイミド樹脂とのHSP値間距離は8.1であり、Sumilizer GA80の構造Sとポリイミド樹脂とのHSP値間距離は6.5であり、Sumilizer GA80とトルエンとのHSP値間距離は2.8であった。 [Comparative Example 1]
Sumilizer GA80 manufactured by Sumitomo Chemical Co., Ltd. instead of AO-330; Polyimide-cycloolefin copolymer was prepared in the same manner as in Example 1, except that 0.0487 g of tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methylpropane-2,1-diyl) was added. A composition as a mixed liquid and a polyimide-cycloolefin copolymer composite film having a thickness of 50 μm were obtained, and the content of Sumilizer GA80 was 5.0 parts by weight with respect to 100 parts by weight of the cycloolefin copolymer. In the film, the content of the particulate cycloolefin copolymer was 32.8% by weight based on the total weight of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size was 0.16 µm.
The distance between the HSP values between the cycloolefin copolymer and the polyimide resin used in Comparative Example 1 was 8.8, the distance between the HSP values between the cycloolefin copolymer and toluene was 2.2, and the cycloolefin copolymer and GBL The distance between HSP values is 15.5, the distance between HSP values between polyimide resin and toluene is 10.0, the distance between HSP values between polyimide resin and GBL is 8.5, and Sumilizer GA80 and The distance between HSP values with GBL is 15.3, the distance between HSP values between Structure S of Sumilizer GA80 and GBL is 12.2, and the distance between HSP values between Sumilizer GA80 and cycloolefin copolymer is 2.0. and the distance between the HSP values of Structure S of Sumilizer GA80 and the cycloolefin copolymer was 3.7. Further, the distance between the HSP values between Sumilizer GA80 and the polyimide resin is 8.1, the distance between the HSP values between the structure S of Sumilizer GA80 and the polyimide resin is 6.5, and the distance between the HSP values between Sumilizer GA80 and toluene The distance was 2.8.
〔比較例2〕
AO-330に代えて、住友化学(株)製Sumilizer GA80 0.365gを添加したこと以外は、実施例2と同様にして、ポリアミック酸-シクロオレフィンコポリマー混合液としての組成物及び厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。Sumilizer GA80の含有量は、シクロオレフィンコポリマー100質量部に対して、5.0質量部である。得られたフィルムにおいて、粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂と粒子状シクロオレフィンコポリマーとの合計質量に対して32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は2.7μmであった。
比較例2で使用したシクロオレフィンコポリマーとDMAcとのHSP値間距離は11.4であり、Sumilizer GA80とDMAcとのHSP値間距離は11.4であり、Sumilizer GA80の構造SとDMAcとのHSP値間距離は8.1であり、Sumilizer GA80とシクロオレフィンコポリマーとのHSP値間距離は2.0であり、Sumilizer GA80の構造SとシクロオレフィンコポリマーとのHSP値間距離は3.7であった。 [Comparative Example 2]
A composition as a polyamic acid-cycloolefin copolymer mixture and a thickness of 50 μm were prepared in the same manner as in Example 2, except that 0.365 g of Sumilizer GA80 manufactured by Sumitomo Chemical Co., Ltd. was added instead of AO-330. A polyimide-cycloolefin copolymer composite film was obtained. The content of Sumilizer GA80 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer. In the obtained film, the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 µm.
The distance between the HSP values between the cycloolefin copolymer used in Comparative Example 2 and DMAc was 11.4, the distance between the HSP values between Sumilizer GA80 and DMAc was 11.4, and the distance between Structure S of Sumilizer GA80 and DMAc was 11.4. The HSP value distance is 8.1, the HSP value distance between Sumilizer GA80 and the cycloolefin copolymer is 2.0, and the HSP value distance between Structure S of Sumilizer GA80 and the cycloolefin copolymer is 3.7. there were.
AO-330に代えて、住友化学(株)製Sumilizer GA80 0.365gを添加したこと以外は、実施例2と同様にして、ポリアミック酸-シクロオレフィンコポリマー混合液としての組成物及び厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。Sumilizer GA80の含有量は、シクロオレフィンコポリマー100質量部に対して、5.0質量部である。得られたフィルムにおいて、粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂と粒子状シクロオレフィンコポリマーとの合計質量に対して32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は2.7μmであった。
比較例2で使用したシクロオレフィンコポリマーとDMAcとのHSP値間距離は11.4であり、Sumilizer GA80とDMAcとのHSP値間距離は11.4であり、Sumilizer GA80の構造SとDMAcとのHSP値間距離は8.1であり、Sumilizer GA80とシクロオレフィンコポリマーとのHSP値間距離は2.0であり、Sumilizer GA80の構造SとシクロオレフィンコポリマーとのHSP値間距離は3.7であった。 [Comparative Example 2]
A composition as a polyamic acid-cycloolefin copolymer mixture and a thickness of 50 μm were prepared in the same manner as in Example 2, except that 0.365 g of Sumilizer GA80 manufactured by Sumitomo Chemical Co., Ltd. was added instead of AO-330. A polyimide-cycloolefin copolymer composite film was obtained. The content of Sumilizer GA80 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer. In the obtained film, the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 µm.
The distance between the HSP values between the cycloolefin copolymer used in Comparative Example 2 and DMAc was 11.4, the distance between the HSP values between Sumilizer GA80 and DMAc was 11.4, and the distance between Structure S of Sumilizer GA80 and DMAc was 11.4. The HSP value distance is 8.1, the HSP value distance between Sumilizer GA80 and the cycloolefin copolymer is 2.0, and the HSP value distance between Structure S of Sumilizer GA80 and the cycloolefin copolymer is 3.7. there were.
〔実施例3〕
実施例1と同様にして作製した組成物を、ガラス基板上において流涎成形し、線速0.4m/分で塗膜を成形した。70℃で60分、塗膜を加熱させ、ガラス基板からフィルムを剥離した後、金枠でフィルムを固定し、更に窒素雰囲気下、200℃で60分間加熱することにより、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂及び粒子状シクロオレフィンコポリマーの合計質量に対して、32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は0.16μmであった。 [Example 3]
A composition prepared in the same manner as in Example 1 was cast on a glass substrate to form a coating film at a line speed of 0.4 m/min. After heating the coating film at 70 ° C. for 60 minutes, peeling the film from the glass substrate, fixing the film with a metal frame, and further heating at 200 ° C. for 60 minutes in a nitrogen atmosphere, a 50 μm thick polyimide- A cycloolefin copolymer composite film was obtained. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.16 µm.
実施例1と同様にして作製した組成物を、ガラス基板上において流涎成形し、線速0.4m/分で塗膜を成形した。70℃で60分、塗膜を加熱させ、ガラス基板からフィルムを剥離した後、金枠でフィルムを固定し、更に窒素雰囲気下、200℃で60分間加熱することにより、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂及び粒子状シクロオレフィンコポリマーの合計質量に対して、32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は0.16μmであった。 [Example 3]
A composition prepared in the same manner as in Example 1 was cast on a glass substrate to form a coating film at a line speed of 0.4 m/min. After heating the coating film at 70 ° C. for 60 minutes, peeling the film from the glass substrate, fixing the film with a metal frame, and further heating at 200 ° C. for 60 minutes in a nitrogen atmosphere, a 50 μm thick polyimide- A cycloolefin copolymer composite film was obtained. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.16 µm.
〔実施例4〕
実施例2と同様にして作製した組成物を、ガラス基板上において流涎成形により、線速0.4m/分で塗膜を作製した。50℃で80分、塗膜を加熱させ、ガラス基板からポリアミック酸-シクロオレフィンコポリマー複合フィルムを剥離した後、金枠でフィルムを固定し、更に窒素雰囲気下、360℃まで段階的に昇温し、360℃で5分間加熱することにより、ポリアミック酸はイミド化され、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られたフィルムにおいて、粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂と粒子状シクロオレフィンコポリマーとの合計質量に対して32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は2.7μmであった。 [Example 4]
A coating film was prepared from the composition prepared in the same manner as in Example 2 by casting on a glass substrate at a line speed of 0.4 m/min. The coating film was heated at 50°C for 80 minutes, the polyamic acid-cycloolefin copolymer composite film was peeled off from the glass substrate, the film was fixed with a metal frame, and the temperature was increased stepwise to 360°C in a nitrogen atmosphere. The polyamic acid was imidized by heating at 360° C. for 5 minutes to obtain a polyimide-cycloolefin copolymer composite film having a thickness of 50 μm. In the obtained film, the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 µm.
実施例2と同様にして作製した組成物を、ガラス基板上において流涎成形により、線速0.4m/分で塗膜を作製した。50℃で80分、塗膜を加熱させ、ガラス基板からポリアミック酸-シクロオレフィンコポリマー複合フィルムを剥離した後、金枠でフィルムを固定し、更に窒素雰囲気下、360℃まで段階的に昇温し、360℃で5分間加熱することにより、ポリアミック酸はイミド化され、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られたフィルムにおいて、粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂と粒子状シクロオレフィンコポリマーとの合計質量に対して32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は2.7μmであった。 [Example 4]
A coating film was prepared from the composition prepared in the same manner as in Example 2 by casting on a glass substrate at a line speed of 0.4 m/min. The coating film was heated at 50°C for 80 minutes, the polyamic acid-cycloolefin copolymer composite film was peeled off from the glass substrate, the film was fixed with a metal frame, and the temperature was increased stepwise to 360°C in a nitrogen atmosphere. The polyamic acid was imidized by heating at 360° C. for 5 minutes to obtain a polyimide-cycloolefin copolymer composite film having a thickness of 50 μm. In the obtained film, the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 µm.
〔比較例3〕
比較例1と同様に作製した組成物を用いた以外は、実施例3と同様の方法で、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂及び粒子状シクロオレフィンコポリマーの合計質量に対して、32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は0.16μmであった。 [Comparative Example 3]
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 3, except that the composition prepared in the same manner as in Comparative Example 1 was used. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.16 µm.
比較例1と同様に作製した組成物を用いた以外は、実施例3と同様の方法で、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂及び粒子状シクロオレフィンコポリマーの合計質量に対して、32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は0.16μmであった。 [Comparative Example 3]
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 3, except that the composition prepared in the same manner as in Comparative Example 1 was used. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.16 µm.
〔比較例4〕
比較例2と同様に作製した組成物を用いた以外は、実施例4と同様の方法で、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂及び粒子状シクロオレフィンコポリマーの合計質量に対して、32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は2.7μmであった。 [Comparative Example 4]
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 4 except that the composition prepared in the same manner as in Comparative Example 2 was used. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 μm.
比較例2と同様に作製した組成物を用いた以外は、実施例4と同様の方法で、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂及び粒子状シクロオレフィンコポリマーの合計質量に対して、32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は2.7μmであった。 [Comparative Example 4]
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 4 except that the composition prepared in the same manner as in Comparative Example 2 was used. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 μm.
〔実施例5〕
製造例3で得られたシクロオレフィンコポリマー溶液2 100.0gとDMAc 98.0gを混合し、トルエン含有量がDMAc 100質量部に対して0.6質量部となるように、50hPa、80℃で減圧留去してトルエンを留去し、粒子状シクロオレフィンコポリマー分散液を得た。上記方法にて測定した分散液及び組成物中の粒子状シクロオレフィンコポリマーのメジアン径は0.13μmであった。
得られた分散液 30.0g(シクロオレフィンコポリマー 2.0質量%)に、(株)ADEKA製アデカスタブAO-330;(1,3,5-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシフェニルメチル)-2,4,6-トリメチルベンゼン) 0.03gを添加して攪拌した後、上記で得られたポリアミック酸溶液(ポリアミック酸 15質量%)を8.0g添加して、ポリアミック酸-シクロオレフィンコポリマー混合溶液として、組成物を得た。AO-330の含有量は、シクロオレフィンコポリマー 100質量部に対して、5.0質量部である。得られた組成物において、1mmを超えるシクロオレフィンコポリマーの凝集体は確認されなかった。
上記で得られた組成物を用いた以外は、実施例4と同様にして、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られたフィルムにおいて、粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂と粒子状シクロオレフィンコポリマーとの合計質量に対して33.3質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は0.15μmであった。
実施例5で使用したシクロオレフィンコポリマーとポリアミック酸とのHSP値間距離は6.0以上であり、該シクロオレフィンコポリマーとトルエンとのHSP値間距離は2.2であり、シクロオレフィンコポリマーとDMAcとのHSP値間距離は11.4であり、AO-330とDMAcとのHSP値間距離は14.4であり、AO-330の構造SとDMAcとのHSP値間距離は14.0であり、AO-330とシクロオレフィンコポリマーとのHSP値間距離は3.4であり、AO-330の構造SとシクロオレフィンコポリマーとのHSP値間距離は2.8であった。また、実施例9で使用したシクロオレフィンコポリマーと、ポリアミック酸をイミド化して得られたポリイミド樹脂とのHSP値間距離は6.0以上であった。
上記溶解性の評価方法により、実施例5で使用したシクロオレフィンコポリマーはトルエンに溶解し、DMAcに溶解しなかった。またポリアミック酸は、DMAcに溶解し、トルエンに溶解しなかった。 [Example 5]
100.0 g of the cycloolefin copolymer solution 2 obtained in Production Example 3 and 98.0 g of DMAc were mixed, and the toluene content was 0.6 parts by mass with respect to 100 parts by mass of DMAc at 50 hPa and 80 ° C. Toluene was distilled off under reduced pressure to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the dispersion and composition measured by the above method was 0.13 µm.
To 30.0 g of the obtained dispersion (2.0% by mass of the cycloolefin copolymer), Adekastab AO-330 manufactured by ADEKA Corporation; (1,3,5-tris(3,5-di-tert-butyl-4 -Hydroxyphenylmethyl)-2,4,6-trimethylbenzene) 0.03 g was added and stirred, and then 8.0 g of the polyamic acid solution obtained above (polyamic acid 15% by mass) was added to obtain a polyamic. A composition was obtained as an acid-cycloolefin copolymer mixed solution. The content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer. No cycloolefin copolymer aggregates larger than 1 mm were observed in the resulting composition.
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 4, except that the composition obtained above was used. In the obtained film, the content of the particulate cycloolefin copolymer was 33.3% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.15 μm.
The distance between the HSP values between the cycloolefin copolymer and polyamic acid used in Example 5 is 6.0 or more, the distance between the HSP values between the cycloolefin copolymer and toluene is 2.2, and the cycloolefin copolymer and DMAc The distance between HSP values is 11.4, the distance between HSP values between AO-330 and DMAc is 14.4, and the distance between HSP values between structure S of AO-330 and DMAc is 14.0. , the distance between the HSP values of AO-330 and the cycloolefin copolymer was 3.4, and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8. Further, the distance between the HSP values of the cycloolefin copolymer used in Example 9 and the polyimide resin obtained by imidating the polyamic acid was 6.0 or more.
According to the above solubility evaluation method, the cycloolefin copolymer used in Example 5 dissolved in toluene but did not dissolve in DMAc. Polyamic acid dissolved in DMAc but did not dissolve in toluene.
製造例3で得られたシクロオレフィンコポリマー溶液2 100.0gとDMAc 98.0gを混合し、トルエン含有量がDMAc 100質量部に対して0.6質量部となるように、50hPa、80℃で減圧留去してトルエンを留去し、粒子状シクロオレフィンコポリマー分散液を得た。上記方法にて測定した分散液及び組成物中の粒子状シクロオレフィンコポリマーのメジアン径は0.13μmであった。
得られた分散液 30.0g(シクロオレフィンコポリマー 2.0質量%)に、(株)ADEKA製アデカスタブAO-330;(1,3,5-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシフェニルメチル)-2,4,6-トリメチルベンゼン) 0.03gを添加して攪拌した後、上記で得られたポリアミック酸溶液(ポリアミック酸 15質量%)を8.0g添加して、ポリアミック酸-シクロオレフィンコポリマー混合溶液として、組成物を得た。AO-330の含有量は、シクロオレフィンコポリマー 100質量部に対して、5.0質量部である。得られた組成物において、1mmを超えるシクロオレフィンコポリマーの凝集体は確認されなかった。
上記で得られた組成物を用いた以外は、実施例4と同様にして、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られたフィルムにおいて、粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂と粒子状シクロオレフィンコポリマーとの合計質量に対して33.3質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は0.15μmであった。
実施例5で使用したシクロオレフィンコポリマーとポリアミック酸とのHSP値間距離は6.0以上であり、該シクロオレフィンコポリマーとトルエンとのHSP値間距離は2.2であり、シクロオレフィンコポリマーとDMAcとのHSP値間距離は11.4であり、AO-330とDMAcとのHSP値間距離は14.4であり、AO-330の構造SとDMAcとのHSP値間距離は14.0であり、AO-330とシクロオレフィンコポリマーとのHSP値間距離は3.4であり、AO-330の構造SとシクロオレフィンコポリマーとのHSP値間距離は2.8であった。また、実施例9で使用したシクロオレフィンコポリマーと、ポリアミック酸をイミド化して得られたポリイミド樹脂とのHSP値間距離は6.0以上であった。
上記溶解性の評価方法により、実施例5で使用したシクロオレフィンコポリマーはトルエンに溶解し、DMAcに溶解しなかった。またポリアミック酸は、DMAcに溶解し、トルエンに溶解しなかった。 [Example 5]
100.0 g of the cycloolefin copolymer solution 2 obtained in Production Example 3 and 98.0 g of DMAc were mixed, and the toluene content was 0.6 parts by mass with respect to 100 parts by mass of DMAc at 50 hPa and 80 ° C. Toluene was distilled off under reduced pressure to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the dispersion and composition measured by the above method was 0.13 µm.
To 30.0 g of the obtained dispersion (2.0% by mass of the cycloolefin copolymer), Adekastab AO-330 manufactured by ADEKA Corporation; (1,3,5-tris(3,5-di-tert-butyl-4 -Hydroxyphenylmethyl)-2,4,6-trimethylbenzene) 0.03 g was added and stirred, and then 8.0 g of the polyamic acid solution obtained above (polyamic acid 15% by mass) was added to obtain a polyamic. A composition was obtained as an acid-cycloolefin copolymer mixed solution. The content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer. No cycloolefin copolymer aggregates larger than 1 mm were observed in the resulting composition.
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 4, except that the composition obtained above was used. In the obtained film, the content of the particulate cycloolefin copolymer was 33.3% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.15 μm.
The distance between the HSP values between the cycloolefin copolymer and polyamic acid used in Example 5 is 6.0 or more, the distance between the HSP values between the cycloolefin copolymer and toluene is 2.2, and the cycloolefin copolymer and DMAc The distance between HSP values is 11.4, the distance between HSP values between AO-330 and DMAc is 14.4, and the distance between HSP values between structure S of AO-330 and DMAc is 14.0. , the distance between the HSP values of AO-330 and the cycloolefin copolymer was 3.4, and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8. Further, the distance between the HSP values of the cycloolefin copolymer used in Example 9 and the polyimide resin obtained by imidating the polyamic acid was 6.0 or more.
According to the above solubility evaluation method, the cycloolefin copolymer used in Example 5 dissolved in toluene but did not dissolve in DMAc. Polyamic acid dissolved in DMAc but did not dissolve in toluene.
〔実施例6〕
シクロオレフィンコポリマー破砕粉1に代えて、製造例4で得られたシクロオレフィンコポリマー破砕粉2を添加したこと以外は、実施例2と同様にして、ポリアミック酸-シクロオレフィンコポリマー混合溶液としての組成物及び厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。AO-330の含有量は、シクロオレフィンコポリマー 100質量部に対して、5.0質量部である。得られたフィルムにおいて、粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂と粒子状シクロオレフィンコポリマーとの合計質量に対して32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は2.7μmであった。
実施例6で使用したシクロオレフィンコポリマーとポリアミック酸とのHSP値間距離は6.0以上であり、シクロオレフィンコポリマーとDMAcとのHSP値間距離は11.4であり、AO-330とDMAcとのHSP値間距離は14.4であり、AO-330の構造SとDMAcとのHSP値間距離は14.0であり、AO-330とシクロオレフィンコポリマーとのHSP値間距離は3.4であり、AO-330の構造SとシクロオレフィンコポリマーとのHSP値間距離は2.8であった。また、実施例6で使用したシクロオレフィンコポリマーと、ポリアミック酸をイミド化して得られたポリイミド樹脂とのHSP値間距離は6.0以上であった。
上記溶解性の評価方法により、実施例10で使用したシクロオレフィンコポリマーはトルエンに溶解し、DMAcに溶解しなかった。またポリアミック酸は、DMAcに溶解し、トルエンに溶解しなかった。 [Example 6]
A composition as a polyamic acid-cycloolefin copolymer mixed solution was prepared in the same manner as in Example 2 except that the cycloolefin copolymer crushed powder 2 obtained in Production Example 4 was added instead of the cycloolefin copolymer crushed powder 1. and a polyimide-cycloolefin copolymer composite film with a thickness of 50 μm. The content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer. In the obtained film, the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 μm.
The distance between the HSP values between the cycloolefin copolymer and the polyamic acid used in Example 6 is 6.0 or more, the distance between the HSP values between the cycloolefin copolymer and DMAc is 11.4, and AO-330 and DMAc The distance between HSP values of AO-330 is 14.4, the distance between HSP values between Structure S of AO-330 and DMAc is 14.0, and the distance between HSP values between AO-330 and cycloolefin copolymer is 3.4. and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8. Further, the distance between the HSP values of the cycloolefin copolymer used in Example 6 and the polyimide resin obtained by imidating the polyamic acid was 6.0 or more.
According to the solubility evaluation method described above, the cycloolefin copolymer used in Example 10 dissolved in toluene but did not dissolve in DMAc. Polyamic acid dissolved in DMAc but did not dissolve in toluene.
シクロオレフィンコポリマー破砕粉1に代えて、製造例4で得られたシクロオレフィンコポリマー破砕粉2を添加したこと以外は、実施例2と同様にして、ポリアミック酸-シクロオレフィンコポリマー混合溶液としての組成物及び厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。AO-330の含有量は、シクロオレフィンコポリマー 100質量部に対して、5.0質量部である。得られたフィルムにおいて、粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂と粒子状シクロオレフィンコポリマーとの合計質量に対して32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は2.7μmであった。
実施例6で使用したシクロオレフィンコポリマーとポリアミック酸とのHSP値間距離は6.0以上であり、シクロオレフィンコポリマーとDMAcとのHSP値間距離は11.4であり、AO-330とDMAcとのHSP値間距離は14.4であり、AO-330の構造SとDMAcとのHSP値間距離は14.0であり、AO-330とシクロオレフィンコポリマーとのHSP値間距離は3.4であり、AO-330の構造SとシクロオレフィンコポリマーとのHSP値間距離は2.8であった。また、実施例6で使用したシクロオレフィンコポリマーと、ポリアミック酸をイミド化して得られたポリイミド樹脂とのHSP値間距離は6.0以上であった。
上記溶解性の評価方法により、実施例10で使用したシクロオレフィンコポリマーはトルエンに溶解し、DMAcに溶解しなかった。またポリアミック酸は、DMAcに溶解し、トルエンに溶解しなかった。 [Example 6]
A composition as a polyamic acid-cycloolefin copolymer mixed solution was prepared in the same manner as in Example 2 except that the cycloolefin copolymer crushed powder 2 obtained in Production Example 4 was added instead of the cycloolefin copolymer crushed powder 1. and a polyimide-cycloolefin copolymer composite film with a thickness of 50 μm. The content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer. In the obtained film, the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 μm.
The distance between the HSP values between the cycloolefin copolymer and the polyamic acid used in Example 6 is 6.0 or more, the distance between the HSP values between the cycloolefin copolymer and DMAc is 11.4, and AO-330 and DMAc The distance between HSP values of AO-330 is 14.4, the distance between HSP values between Structure S of AO-330 and DMAc is 14.0, and the distance between HSP values between AO-330 and cycloolefin copolymer is 3.4. and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8. Further, the distance between the HSP values of the cycloolefin copolymer used in Example 6 and the polyimide resin obtained by imidating the polyamic acid was 6.0 or more.
According to the solubility evaluation method described above, the cycloolefin copolymer used in Example 10 dissolved in toluene but did not dissolve in DMAc. Polyamic acid dissolved in DMAc but did not dissolve in toluene.
〔実施例7〕
フッ素ポリマー(3M社製、THV221AZ(テトラフルオロエチレン-ヘキサフルオロプロピレン-フッ化ビニリデン共重合体、テトラフルオロエチレン構成単位のモル比は0.35、Mw ;384,000、融点;120℃)) 2gとアセトン 98gとを混合し、フッ素ポリマー溶液を得た。得られたフッ素ポリマー溶液 100gとGBL 98.0gを混合し、50hPa、40℃で2時間減圧留去してアセトンを留去し、粒子状フッ素ポリマー分散液を得た。得られた分散液のアセトン含有量は、GBL100質量部に対して0.6質量部であった。上記方法にて測定した粒子状フッ素ポリマー分散液中のフッ素ポリマーのメジアン径は0.11μmであった。
得られた分散液 30.0g(粒子状フッ素ポリマー含有量;2.0質量%)に、(株)ADEKA製アデカスタブAO-330;(1,3,5-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシフェニルメチル)-2,4,6-トリメチルベンゼン) 0.03gを添加して攪拌した後、上記で得られたポリイミド樹脂 1.2gを添加することで、ポリイミド-フッ素ポリマー混合溶液として、組成物を得た。AO-330の含有量は、フッ素ポリマー 100質量部に対して、5.0質量部である。得られた組成物において、1mmを超えるフッ素ポリマーの凝集体は確認されなかった。
得られた組成物をガラス基板上において流涎成形し、線速0.4m/分で塗膜を成形した。70℃で60分、塗膜を加熱させ、ガラス基板からフィルムを剥離した後、金枠でフィルムを固定し、更に大気下360℃で15分間加熱することにより、厚さ50μmのポリイミド-フッ素ポリマー複合フィルムを得た。得られた複合フィルム中の粒子状フッ素ポリマーの含有量は、ポリイミド樹脂及び粒子状フッ素ポリマーの合計質量に対して、33.3質量%であった。得られた複合フィルム中の粒子状フッ素ポリマーの平均一次粒子径は0.13μmであった。
実施例7で使用したフッ素ポリマーとポリイミドとのHSP値間距離は11.2であり、該フッ素ポリマーとアセトンとのHSP値間距離は5.2であり、該フッ素ポリマーとGBLとのHSP値間距離は10.3であり、AO-330とアセトンとのHSP値間距離は12.9であり、AO-330とフッ素ポリマーとのHSP値間距離は15.9であり、AO-330の構造Sとフッ素ポリマーとのHSP値間距離は15.3であり、ポリイミド樹脂とアセトンとのHSP値間距離は6.1であり、ポリイミド樹脂とGBLとのHSP値間距離は8.5であった。
上記溶解性の評価方法により、実施例7で使用したフッ素ポリマーは、アセトンに溶解し、GBLに溶解しなかった。実施例7で使用したポリイミドは、GBL、アセトンに溶解した。 [Example 7]
Fluorine polymer (manufactured by 3M, THV221AZ (tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, molar ratio of tetrafluoroethylene structural units: 0.35, Mw: 384,000, melting point: 120° C.)) 2 g and 98 g of acetone were mixed to obtain a fluoropolymer solution. 100 g of the obtained fluoropolymer solution and 98.0 g of GBL were mixed and distilled under reduced pressure at 50 hPa and 40° C. for 2 hours to remove acetone and obtain a particulate fluoropolymer dispersion. The acetone content of the resulting dispersion was 0.6 parts by weight per 100 parts by weight of GBL. The median diameter of the fluoropolymer in the particulate fluoropolymer dispersion measured by the above method was 0.11 μm.
To 30.0 g of the resulting dispersion (particulate fluoropolymer content: 2.0% by mass), Adekastab AO-330 manufactured by ADEKA Corporation; (1,3,5-tris(3,5-di-tert -Butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene) 0.03 g was added and stirred, and then 1.2 g of the polyimide resin obtained above was added to obtain a polyimide-fluoropolymer. A composition was obtained as a mixed solution. The content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the fluoropolymer. No fluoropolymer aggregates larger than 1 mm were observed in the resulting composition.
The resulting composition was cast on a glass substrate to form a coating film at a line speed of 0.4 m/min. After heating the coating film at 70 ° C. for 60 minutes, peeling the film from the glass substrate, fixing the film with a metal frame, and further heating at 360 ° C. for 15 minutes in the atmosphere, a polyimide-fluoropolymer having a thickness of 50 μm. A composite film was obtained. The content of the particulate fluoropolymer in the obtained composite film was 33.3% by mass with respect to the total mass of the polyimide resin and the particulate fluoropolymer. The average primary particle size of the particulate fluoropolymer in the obtained composite film was 0.13 μm.
The HSP value distance between the fluoropolymer and polyimide used in Example 7 was 11.2, the HSP value distance between the fluoropolymer and acetone was 5.2, and the HSP value between the fluoropolymer and GBL. The inter-HSP value distance between AO-330 and acetone is 12.9, and the inter-HSP value distance between AO-330 and fluoropolymer is 15.9. The distance between HSP values between structure S and fluoropolymer is 15.3, the distance between HSP values between polyimide resin and acetone is 6.1, and the distance between HSP values between polyimide resin and GBL is 8.5. there were.
According to the solubility evaluation method described above, the fluoropolymer used in Example 7 dissolved in acetone, but did not dissolve in GBL. The polyimide used in Example 7 was dissolved in GBL and acetone.
フッ素ポリマー(3M社製、THV221AZ(テトラフルオロエチレン-ヘキサフルオロプロピレン-フッ化ビニリデン共重合体、テトラフルオロエチレン構成単位のモル比は0.35、Mw ;384,000、融点;120℃)) 2gとアセトン 98gとを混合し、フッ素ポリマー溶液を得た。得られたフッ素ポリマー溶液 100gとGBL 98.0gを混合し、50hPa、40℃で2時間減圧留去してアセトンを留去し、粒子状フッ素ポリマー分散液を得た。得られた分散液のアセトン含有量は、GBL100質量部に対して0.6質量部であった。上記方法にて測定した粒子状フッ素ポリマー分散液中のフッ素ポリマーのメジアン径は0.11μmであった。
得られた分散液 30.0g(粒子状フッ素ポリマー含有量;2.0質量%)に、(株)ADEKA製アデカスタブAO-330;(1,3,5-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシフェニルメチル)-2,4,6-トリメチルベンゼン) 0.03gを添加して攪拌した後、上記で得られたポリイミド樹脂 1.2gを添加することで、ポリイミド-フッ素ポリマー混合溶液として、組成物を得た。AO-330の含有量は、フッ素ポリマー 100質量部に対して、5.0質量部である。得られた組成物において、1mmを超えるフッ素ポリマーの凝集体は確認されなかった。
得られた組成物をガラス基板上において流涎成形し、線速0.4m/分で塗膜を成形した。70℃で60分、塗膜を加熱させ、ガラス基板からフィルムを剥離した後、金枠でフィルムを固定し、更に大気下360℃で15分間加熱することにより、厚さ50μmのポリイミド-フッ素ポリマー複合フィルムを得た。得られた複合フィルム中の粒子状フッ素ポリマーの含有量は、ポリイミド樹脂及び粒子状フッ素ポリマーの合計質量に対して、33.3質量%であった。得られた複合フィルム中の粒子状フッ素ポリマーの平均一次粒子径は0.13μmであった。
実施例7で使用したフッ素ポリマーとポリイミドとのHSP値間距離は11.2であり、該フッ素ポリマーとアセトンとのHSP値間距離は5.2であり、該フッ素ポリマーとGBLとのHSP値間距離は10.3であり、AO-330とアセトンとのHSP値間距離は12.9であり、AO-330とフッ素ポリマーとのHSP値間距離は15.9であり、AO-330の構造Sとフッ素ポリマーとのHSP値間距離は15.3であり、ポリイミド樹脂とアセトンとのHSP値間距離は6.1であり、ポリイミド樹脂とGBLとのHSP値間距離は8.5であった。
上記溶解性の評価方法により、実施例7で使用したフッ素ポリマーは、アセトンに溶解し、GBLに溶解しなかった。実施例7で使用したポリイミドは、GBL、アセトンに溶解した。 [Example 7]
Fluorine polymer (manufactured by 3M, THV221AZ (tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, molar ratio of tetrafluoroethylene structural units: 0.35, Mw: 384,000, melting point: 120° C.)) 2 g and 98 g of acetone were mixed to obtain a fluoropolymer solution. 100 g of the obtained fluoropolymer solution and 98.0 g of GBL were mixed and distilled under reduced pressure at 50 hPa and 40° C. for 2 hours to remove acetone and obtain a particulate fluoropolymer dispersion. The acetone content of the resulting dispersion was 0.6 parts by weight per 100 parts by weight of GBL. The median diameter of the fluoropolymer in the particulate fluoropolymer dispersion measured by the above method was 0.11 μm.
To 30.0 g of the resulting dispersion (particulate fluoropolymer content: 2.0% by mass), Adekastab AO-330 manufactured by ADEKA Corporation; (1,3,5-tris(3,5-di-tert -Butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene) 0.03 g was added and stirred, and then 1.2 g of the polyimide resin obtained above was added to obtain a polyimide-fluoropolymer. A composition was obtained as a mixed solution. The content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the fluoropolymer. No fluoropolymer aggregates larger than 1 mm were observed in the resulting composition.
The resulting composition was cast on a glass substrate to form a coating film at a line speed of 0.4 m/min. After heating the coating film at 70 ° C. for 60 minutes, peeling the film from the glass substrate, fixing the film with a metal frame, and further heating at 360 ° C. for 15 minutes in the atmosphere, a polyimide-fluoropolymer having a thickness of 50 μm. A composite film was obtained. The content of the particulate fluoropolymer in the obtained composite film was 33.3% by mass with respect to the total mass of the polyimide resin and the particulate fluoropolymer. The average primary particle size of the particulate fluoropolymer in the obtained composite film was 0.13 μm.
The HSP value distance between the fluoropolymer and polyimide used in Example 7 was 11.2, the HSP value distance between the fluoropolymer and acetone was 5.2, and the HSP value between the fluoropolymer and GBL. The inter-HSP value distance between AO-330 and acetone is 12.9, and the inter-HSP value distance between AO-330 and fluoropolymer is 15.9. The distance between HSP values between structure S and fluoropolymer is 15.3, the distance between HSP values between polyimide resin and acetone is 6.1, and the distance between HSP values between polyimide resin and GBL is 8.5. there were.
According to the solubility evaluation method described above, the fluoropolymer used in Example 7 dissolved in acetone, but did not dissolve in GBL. The polyimide used in Example 7 was dissolved in GBL and acetone.
〔実施例8〕
粒子状PTFE(Pоlysciences Inc.製、融点:320℃、Mw:20,000、) 5.69g、DMAc 42.1gを混合し、撹拌することで粒子状PTFE分散液を得た。得られたPTFE分散液に、(株)ADEKA製アデカスタブAO-330;(1,3,5-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシフェニルメチル)-2,4,6-トリメチルベンゼン) 0.2845gを添加して攪拌した後、上記で得られたポリアミック酸溶液 100g(ポリアミック酸 15質量%)を添加して、ポリアミック酸-PTFE混合溶液としての組成物を得た。AO-330の含有量は、フッ素ポリマー 100質量部に対して、5.0質量部である。得られた組成物において、1mmを超えるフッ素ポリマーの凝集体は確認されなかった。
上記で得られた組成物を用いた以外は、実施例4と同様にして、厚さ50μmのポリイミド-PTFE複合フィルムを得た。得られたフィルムにおいて、粒子状PTFEの含有量は、ポリイミド樹脂とPTFEとの合計質量に対して27.5質量%であった。得られた複合フィルム中の粒子状PTFEの平均一次粒子径は3μmであった。
実施例8で使用したPTFEとポリアミック酸とのHSP値間距離は6.0以上であり、PTFEとDMAcとのHSP値間距離は8.8であり、AO-330とPTFEとのHSP値間距離は8.2であり、AO-330の構造SとPTFEとのHSP値間距離は8.0であった。また、実施例8で使用したPTFEと、ポリアミック酸をイミド化して得られたポリイミド樹脂とのHSP値間距離は6.0以上であった。
上記溶解性の評価方法により、実施例8で使用したPTFEはDMAcに溶解しなかった。またポリアミック酸は、DMAcに溶解し、トルエンに溶解しなかった。 [Example 8]
5.69 g of particulate PTFE (manufactured by Polysciences Inc., melting point: 320° C., Mw: 20,000) and 42.1 g of DMAc were mixed and stirred to obtain a particulate PTFE dispersion. Adekastab AO-330 manufactured by ADEKA Corporation; (1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6- After adding 0.2845 g of trimethylbenzene and stirring, 100 g of the polyamic acid solution obtained above (15% by mass of polyamic acid) was added to obtain a composition as a polyamic acid-PTFE mixed solution. The content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the fluoropolymer. No fluoropolymer aggregates larger than 1 mm were observed in the resulting composition.
A polyimide-PTFE composite film having a thickness of 50 μm was obtained in the same manner as in Example 4, except that the composition obtained above was used. In the resulting film, the content of particulate PTFE was 27.5% by mass with respect to the total mass of the polyimide resin and PTFE. The average primary particle size of the particulate PTFE in the obtained composite film was 3 μm.
The distance between the HSP values between PTFE and polyamic acid used in Example 8 is 6.0 or more, the distance between the HSP values between PTFE and DMAc is 8.8, and the distance between the HSP values between AO-330 and PTFE The distance was 8.2, and the distance between the HSP values of Structure S of AO-330 and PTFE was 8.0. Further, the distance between the HSP values of the PTFE used in Example 8 and the polyimide resin obtained by imidizing the polyamic acid was 6.0 or more.
The PTFE used in Example 8 did not dissolve in DMAc by the above solubility evaluation method. Polyamic acid dissolved in DMAc but did not dissolve in toluene.
粒子状PTFE(Pоlysciences Inc.製、融点:320℃、Mw:20,000、) 5.69g、DMAc 42.1gを混合し、撹拌することで粒子状PTFE分散液を得た。得られたPTFE分散液に、(株)ADEKA製アデカスタブAO-330;(1,3,5-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシフェニルメチル)-2,4,6-トリメチルベンゼン) 0.2845gを添加して攪拌した後、上記で得られたポリアミック酸溶液 100g(ポリアミック酸 15質量%)を添加して、ポリアミック酸-PTFE混合溶液としての組成物を得た。AO-330の含有量は、フッ素ポリマー 100質量部に対して、5.0質量部である。得られた組成物において、1mmを超えるフッ素ポリマーの凝集体は確認されなかった。
上記で得られた組成物を用いた以外は、実施例4と同様にして、厚さ50μmのポリイミド-PTFE複合フィルムを得た。得られたフィルムにおいて、粒子状PTFEの含有量は、ポリイミド樹脂とPTFEとの合計質量に対して27.5質量%であった。得られた複合フィルム中の粒子状PTFEの平均一次粒子径は3μmであった。
実施例8で使用したPTFEとポリアミック酸とのHSP値間距離は6.0以上であり、PTFEとDMAcとのHSP値間距離は8.8であり、AO-330とPTFEとのHSP値間距離は8.2であり、AO-330の構造SとPTFEとのHSP値間距離は8.0であった。また、実施例8で使用したPTFEと、ポリアミック酸をイミド化して得られたポリイミド樹脂とのHSP値間距離は6.0以上であった。
上記溶解性の評価方法により、実施例8で使用したPTFEはDMAcに溶解しなかった。またポリアミック酸は、DMAcに溶解し、トルエンに溶解しなかった。 [Example 8]
5.69 g of particulate PTFE (manufactured by Polysciences Inc., melting point: 320° C., Mw: 20,000) and 42.1 g of DMAc were mixed and stirred to obtain a particulate PTFE dispersion. Adekastab AO-330 manufactured by ADEKA Corporation; (1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6- After adding 0.2845 g of trimethylbenzene and stirring, 100 g of the polyamic acid solution obtained above (15% by mass of polyamic acid) was added to obtain a composition as a polyamic acid-PTFE mixed solution. The content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the fluoropolymer. No fluoropolymer aggregates larger than 1 mm were observed in the resulting composition.
A polyimide-PTFE composite film having a thickness of 50 μm was obtained in the same manner as in Example 4, except that the composition obtained above was used. In the resulting film, the content of particulate PTFE was 27.5% by mass with respect to the total mass of the polyimide resin and PTFE. The average primary particle size of the particulate PTFE in the obtained composite film was 3 μm.
The distance between the HSP values between PTFE and polyamic acid used in Example 8 is 6.0 or more, the distance between the HSP values between PTFE and DMAc is 8.8, and the distance between the HSP values between AO-330 and PTFE The distance was 8.2, and the distance between the HSP values of Structure S of AO-330 and PTFE was 8.0. Further, the distance between the HSP values of the PTFE used in Example 8 and the polyimide resin obtained by imidizing the polyamic acid was 6.0 or more.
The PTFE used in Example 8 did not dissolve in DMAc by the above solubility evaluation method. Polyamic acid dissolved in DMAc but did not dissolve in toluene.
〔実施例9〕
製造例1で得られたシクロオレフィンコポリマー溶液1 100.0gとDMAc 98.0gを混合し、トルエン含有量がDMAc 100質量部に対して7質量部となるように、50hPa、80℃で減圧留去してトルエンを留去し、粒子状シクロオレフィンコポリマー分散液を得た。上記方法にて測定した分散液及び組成物中の粒子状シクロオレフィンコポリマーのメジアン径は0.13μmであった。
上記で作製した粒子状シクロオレフィンコポリマー分散液を用いた以外は、実施例1と同様の方法で、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂及び粒子状シクロオレフィンコポリマーの合計質量に対して、32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は0.14μmであった。
実施例9で使用したシクロオレフィンコポリマーとトルエンとのHSP値間距離は2.2であり、該シクロオレフィンコポリマーとDMAcとのHSP値間距離は11.4であり、AO-330とDMAcとのHSP値間距離は14.4であり、AO-330の構造SとDMAcとのHSP値間距離は14.0であった。
上記溶解性の評価方法により、実施例9で使用したシクロオレフィンコポリマーはトルエンに溶解し、DMAcに溶解しなかった。またポリイミド樹脂は、DMAcに溶解し、トルエンに溶解しなかった。 [Example 9]
100.0 g of the cycloolefin copolymer solution 1 obtained in Production Example 1 and 98.0 g of DMAc were mixed and distilled under reduced pressure at 50 hPa and 80° C. so that the toluene content was 7 parts by mass with respect to 100 parts by mass of DMAc. toluene was distilled off to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the dispersion and composition measured by the above method was 0.13 µm.
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 1, except that the particulate cycloolefin copolymer dispersion prepared above was used. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the obtained composite film was 0.14 µm.
The distance between the HSP values between the cycloolefin copolymer used in Example 9 and toluene was 2.2, the distance between the HSP values between the cycloolefin copolymer and DMAc was 11.4, and the distance between AO-330 and DMAc was The inter-HSP value distance was 14.4, and the inter-HSP value distance between structure S of AO-330 and DMAc was 14.0.
According to the solubility evaluation method described above, the cycloolefin copolymer used in Example 9 dissolved in toluene but did not dissolve in DMAc. Also, the polyimide resin dissolved in DMAc but did not dissolve in toluene.
製造例1で得られたシクロオレフィンコポリマー溶液1 100.0gとDMAc 98.0gを混合し、トルエン含有量がDMAc 100質量部に対して7質量部となるように、50hPa、80℃で減圧留去してトルエンを留去し、粒子状シクロオレフィンコポリマー分散液を得た。上記方法にて測定した分散液及び組成物中の粒子状シクロオレフィンコポリマーのメジアン径は0.13μmであった。
上記で作製した粒子状シクロオレフィンコポリマー分散液を用いた以外は、実施例1と同様の方法で、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂及び粒子状シクロオレフィンコポリマーの合計質量に対して、32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は0.14μmであった。
実施例9で使用したシクロオレフィンコポリマーとトルエンとのHSP値間距離は2.2であり、該シクロオレフィンコポリマーとDMAcとのHSP値間距離は11.4であり、AO-330とDMAcとのHSP値間距離は14.4であり、AO-330の構造SとDMAcとのHSP値間距離は14.0であった。
上記溶解性の評価方法により、実施例9で使用したシクロオレフィンコポリマーはトルエンに溶解し、DMAcに溶解しなかった。またポリイミド樹脂は、DMAcに溶解し、トルエンに溶解しなかった。 [Example 9]
100.0 g of the cycloolefin copolymer solution 1 obtained in Production Example 1 and 98.0 g of DMAc were mixed and distilled under reduced pressure at 50 hPa and 80° C. so that the toluene content was 7 parts by mass with respect to 100 parts by mass of DMAc. toluene was distilled off to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the dispersion and composition measured by the above method was 0.13 µm.
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 1, except that the particulate cycloolefin copolymer dispersion prepared above was used. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the obtained composite film was 0.14 µm.
The distance between the HSP values between the cycloolefin copolymer used in Example 9 and toluene was 2.2, the distance between the HSP values between the cycloolefin copolymer and DMAc was 11.4, and the distance between AO-330 and DMAc was The inter-HSP value distance was 14.4, and the inter-HSP value distance between structure S of AO-330 and DMAc was 14.0.
According to the solubility evaluation method described above, the cycloolefin copolymer used in Example 9 dissolved in toluene but did not dissolve in DMAc. Also, the polyimide resin dissolved in DMAc but did not dissolve in toluene.
〔実施例10〕
実施例5と同様に作製した組成物を用いた以外は、実施例4と同様の方法で、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂及び粒子状シクロオレフィンコポリマーの合計質量に対して、33.3質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は0.15μmであった。 [Example 10]
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 4, except that the composition prepared in the same manner as in Example 5 was used. The content of the particulate cycloolefin copolymer in the resulting composite film was 33.3% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.15 μm.
実施例5と同様に作製した組成物を用いた以外は、実施例4と同様の方法で、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂及び粒子状シクロオレフィンコポリマーの合計質量に対して、33.3質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は0.15μmであった。 [Example 10]
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 4, except that the composition prepared in the same manner as in Example 5 was used. The content of the particulate cycloolefin copolymer in the resulting composite film was 33.3% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.15 μm.
〔実施例11〕
実施例6と同様に作製した組成物を用いた以外は、実施例4と同様の方法で、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂及び粒子状シクロオレフィンコポリマーの合計質量に対して、32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は2.7μmであった。 [Example 11]
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 4 except that a composition prepared in the same manner as in Example 6 was used. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 µm.
実施例6と同様に作製した組成物を用いた以外は、実施例4と同様の方法で、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂及び粒子状シクロオレフィンコポリマーの合計質量に対して、32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は2.7μmであった。 [Example 11]
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 4 except that a composition prepared in the same manner as in Example 6 was used. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 µm.
〔実施例12〕
実施例9と同様に作製した組成物を用いた以外は、実施例3と同様の方法で、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂及び粒子状シクロオレフィンコポリマーの合計質量に対して、32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は0.15μmであった。 [Example 12]
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 3 except that a composition prepared in the same manner as in Example 9 was used. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.15 μm.
実施例9と同様に作製した組成物を用いた以外は、実施例3と同様の方法で、厚さ50μmのポリイミド-シクロオレフィンコポリマー複合フィルムを得た。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの含有量は、ポリイミド樹脂及び粒子状シクロオレフィンコポリマーの合計質量に対して、32.8質量%であった。得られた複合フィルム中の粒子状シクロオレフィンコポリマーの平均一次粒子径は0.15μmであった。 [Example 12]
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 3 except that a composition prepared in the same manner as in Example 9 was used. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.15 μm.
実施例1、2、5~9及び比較例1、2で得られたポリイミド-シクロオレフィンコポリマー複合フィルムの吸湿率を上記方法に従い測定した。得られた結果を表43に示す。
実施例3、4、10~12及び比較例3、4で得られたポリイミド-シクロオレフィンコポリマー複合フィルムのIRピーク維持率を上記方法に従い測定した。得られた結果を表54に示す。 The moisture absorption rate of the polyimide-cycloolefin copolymer composite films obtained in Examples 1, 2, 5 to 9 and Comparative Examples 1 and 2 was measured according to the above method. The results obtained are shown in Table 43.
The IR peak retention rate of the polyimide-cycloolefin copolymer composite films obtained in Examples 3, 4, 10 to 12 and Comparative Examples 3 and 4 was measured according to the above method. The results obtained are shown in Table 54.
実施例3、4、10~12及び比較例3、4で得られたポリイミド-シクロオレフィンコポリマー複合フィルムのIRピーク維持率を上記方法に従い測定した。得られた結果を表54に示す。 The moisture absorption rate of the polyimide-cycloolefin copolymer composite films obtained in Examples 1, 2, 5 to 9 and Comparative Examples 1 and 2 was measured according to the above method. The results obtained are shown in Table 43.
The IR peak retention rate of the polyimide-cycloolefin copolymer composite films obtained in Examples 3, 4, 10 to 12 and Comparative Examples 3 and 4 was measured according to the above method. The results obtained are shown in Table 54.
表4に示されるように、実施例1、2、5~9で得られたフィルムは、比較例1及び2と比べ、吸湿率が低く、耐吸水性に優れていた。また、表5に示されるように、実施例3、4、10~12で得られたフィルムは、比較例3及び4と比べ、COCのIRピーク維持率が高く、耐熱性に優れていた。
As shown in Table 4, the films obtained in Examples 1, 2, 5 to 9 had lower moisture absorption rates and superior water absorption resistance than Comparative Examples 1 and 2. In addition, as shown in Table 5, the films obtained in Examples 3, 4, and 10 to 12 had higher COC IR peak retention rates and superior heat resistance than Comparative Examples 3 and 4.
Claims (11)
- ポリイミド系樹脂(A)、ポリマー(B)及びフェノール系酸化防止剤を含み、
フェノール系酸化防止剤は式(P):
で表される置換基Pを含み、フェノール系酸化防止剤中の置換基Pを水素原子に置換した構造Sは、置換基を有していてもよい芳香環を有する、組成物。 Containing a polyimide resin (A), a polymer (B) and a phenolic antioxidant,
The phenolic antioxidant has the formula (P):
wherein the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom has an aromatic ring which may have a substituent. - ポリマー(B)とフェノール系酸化防止剤とのHSP値間距離は16.0以下である、請求項1に記載の組成物。 The composition according to claim 1, wherein the distance between the HSP values of the polymer (B) and the phenolic antioxidant is 16.0 or less.
- 芳香環は、炭素数6~15の単環式芳香族炭化水素環である、請求項1又は2に記載の組成物。 The composition according to claim 1 or 2, wherein the aromatic ring is a monocyclic aromatic hydrocarbon ring having 6 to 15 carbon atoms.
- さらに溶媒を含み、構造Sと溶媒とのHSP値間距離は10.0以上である、請求項1又は2に記載の組成物。 The composition according to claim 1 or 2, further comprising a solvent, wherein the distance between the HSP values of structure S and the solvent is 10.0 or more.
- ポリマー(B)は粒子状である、請求項1又は2に記載の組成物。 The composition according to claim 1 or 2, wherein the polymer (B) is particulate.
- ポリマー(B)は、オレフィン系ポリマー、ポリイミド系ポリマー、フッ素系ポリマー、シリコーン系ポリマー、液晶ポリマー、アラミドポリマー、スチレン系ポリマー及びエーテル系ポリマーからなる群から選択される少なくとも1つのポリマーである、請求項1又は2に記載の組成物。 The polymer (B) is at least one polymer selected from the group consisting of olefin-based polymer, polyimide-based polymer, fluorine-based polymer, silicone-based polymer, liquid crystal polymer, aramid polymer, styrene-based polymer and ether-based polymer. 3. The composition according to Item 1 or 2.
- ポリマー(B)のガラス転移温度は100℃以上である、請求項1又は2に記載の組成物。 The composition according to claim 1 or 2, wherein the polymer (B) has a glass transition temperature of 100°C or higher.
- ポリマー(B)は、シクロオレフィン系ポリマーである、請求項1又は2に記載の組成物。 The composition according to claim 1 or 2, wherein the polymer (B) is a cycloolefin polymer.
- シクロオレフィン系ポリマーは、式(I):
で表されるシクロオレフィン由来の単量体単位(I)を含む、請求項8に記載の組成物。 The cycloolefin-based polymer has the formula (I):
9. The composition according to claim 8, comprising a cycloolefin-derived monomeric unit (I) represented by: - シクロオレフィン系ポリマーにおける前記単量体単位(I)の含有量は、シクロオレフ
ィン系ポリマーを構成する繰り返し単位の合計モル量に対して、60モル%以上である、請求項9に記載の組成物。 10. The composition according to claim 9, wherein the content of the monomer unit (I) in the cycloolefin-based polymer is 60 mol% or more relative to the total molar amount of repeating units constituting the cycloolefin-based polymer. . - ポリイミド系樹脂(A)、ポリマー(B)及びフェノール系酸化防止剤を含み、
フェノール系酸化防止剤は式(P):
で表される置換基Pを含み、フェノール系酸化防止剤中の置換基Pを水素原子に置換した構造Sは、置換基を有していてもよい芳香環を有する、フィルム。 Containing a polyimide resin (A), a polymer (B) and a phenolic antioxidant,
The phenolic antioxidant has the formula (P):
A film wherein the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom has an aromatic ring which may have a substituent.
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JP2006152173A (en) * | 2004-11-30 | 2006-06-15 | Sumitomo Bakelite Co Ltd | Resin composition, resin layer, carrier material with resin layers and circuit board |
JP2009185242A (en) * | 2008-02-08 | 2009-08-20 | Hitachi Chem Co Ltd | Resin composition and film-forming material containing the same |
JP2013127597A (en) * | 2011-11-16 | 2013-06-27 | Jsr Corp | Liquid crystal aligning agent, liquid crystal alignment layer and liquid crystal display element |
JP2017125176A (en) * | 2016-08-31 | 2017-07-20 | 三井化学株式会社 | Low-dielectric resin composition, cured product, dry film, film, prepreg, metal-clad laminate, printed wiring board and electronic apparatus |
WO2020189481A1 (en) * | 2019-03-19 | 2020-09-24 | 富士フイルム株式会社 | Curable resin composition, cured film, multilayer body, method for producing cured film, and semiconductor device |
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JP2006152173A (en) * | 2004-11-30 | 2006-06-15 | Sumitomo Bakelite Co Ltd | Resin composition, resin layer, carrier material with resin layers and circuit board |
JP2009185242A (en) * | 2008-02-08 | 2009-08-20 | Hitachi Chem Co Ltd | Resin composition and film-forming material containing the same |
JP2013127597A (en) * | 2011-11-16 | 2013-06-27 | Jsr Corp | Liquid crystal aligning agent, liquid crystal alignment layer and liquid crystal display element |
JP2017125176A (en) * | 2016-08-31 | 2017-07-20 | 三井化学株式会社 | Low-dielectric resin composition, cured product, dry film, film, prepreg, metal-clad laminate, printed wiring board and electronic apparatus |
WO2020189481A1 (en) * | 2019-03-19 | 2020-09-24 | 富士フイルム株式会社 | Curable resin composition, cured film, multilayer body, method for producing cured film, and semiconductor device |
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