CN113227211A - Polyamide resin, optical film, and flexible display device - Google Patents
Polyamide resin, optical film, and flexible display device Download PDFInfo
- Publication number
- CN113227211A CN113227211A CN201980086116.2A CN201980086116A CN113227211A CN 113227211 A CN113227211 A CN 113227211A CN 201980086116 A CN201980086116 A CN 201980086116A CN 113227211 A CN113227211 A CN 113227211A
- Authority
- CN
- China
- Prior art keywords
- formula
- group
- optical film
- structural unit
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012788 optical film Substances 0.000 title claims abstract description 196
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 142
- 230000009975 flexible effect Effects 0.000 title claims description 38
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 170
- 125000003118 aryl group Chemical group 0.000 claims abstract description 102
- 125000000962 organic group Chemical group 0.000 claims abstract description 100
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 63
- -1 diphenylmethylene, fluorenyl Chemical group 0.000 claims description 138
- 239000000126 substance Substances 0.000 claims description 93
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 66
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 125000005843 halogen group Chemical group 0.000 claims description 35
- 125000001424 substituent group Chemical group 0.000 claims description 15
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 11
- 125000002723 alicyclic group Chemical group 0.000 claims description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 239000010408 film Substances 0.000 description 87
- 150000001875 compounds Chemical class 0.000 description 75
- 239000010410 layer Substances 0.000 description 65
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 63
- 239000000203 mixture Substances 0.000 description 52
- 239000002904 solvent Substances 0.000 description 49
- 239000000853 adhesive Substances 0.000 description 45
- 230000001070 adhesive effect Effects 0.000 description 45
- 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 44
- 229920005989 resin Polymers 0.000 description 41
- 239000011347 resin Substances 0.000 description 41
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 150000002430 hydrocarbons Chemical group 0.000 description 32
- 239000004973 liquid crystal related substance Substances 0.000 description 32
- 238000000576 coating method Methods 0.000 description 29
- 150000003254 radicals Chemical class 0.000 description 28
- 239000011248 coating agent Substances 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000000758 substrate Substances 0.000 description 25
- 239000000463 material Substances 0.000 description 23
- 238000003756 stirring Methods 0.000 description 22
- 238000005452 bending Methods 0.000 description 21
- 239000012790 adhesive layer Substances 0.000 description 19
- 125000003545 alkoxy group Chemical group 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- 239000002966 varnish Substances 0.000 description 19
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 18
- 239000004962 Polyamide-imide Substances 0.000 description 18
- 229920002312 polyamide-imide Polymers 0.000 description 18
- 230000003247 decreasing effect Effects 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 17
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 17
- 230000003287 optical effect Effects 0.000 description 16
- 230000002829 reductive effect Effects 0.000 description 16
- 238000002834 transmittance Methods 0.000 description 16
- 239000003505 polymerization initiator Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000000945 filler Substances 0.000 description 14
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- 125000001153 fluoro group Chemical group F* 0.000 description 12
- 230000006870 function Effects 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- 238000010538 cationic polymerization reaction Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000000049 pigment Substances 0.000 description 11
- 230000001681 protective effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 239000000654 additive Substances 0.000 description 10
- 125000001309 chloro group Chemical group Cl* 0.000 description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 10
- 239000002346 layers by function Substances 0.000 description 10
- 125000002950 monocyclic group Chemical group 0.000 description 10
- 125000003367 polycyclic group Chemical group 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 9
- 150000008064 anhydrides Chemical class 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 9
- 239000000975 dye Substances 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 8
- 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 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 150000004984 aromatic diamines Chemical class 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 7
- 125000003700 epoxy group Chemical group 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 7
- 239000007870 radical polymerization initiator Substances 0.000 description 7
- 238000010526 radical polymerization reaction Methods 0.000 description 7
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 7
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 6
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000003086 colorant Substances 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000010954 inorganic particle Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 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 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 4
- UNIBAJHMJGXVHL-UHFFFAOYSA-N 3-phenylbenzene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C=2C=CC=CC=2)=C1C(O)=O UNIBAJHMJGXVHL-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 4
- DJRGWIOMYBEUFK-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1.CC1=CC=NC=C1 DJRGWIOMYBEUFK-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 239000003125 aqueous solvent Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 4
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 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 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 125000003566 oxetanyl group Chemical group 0.000 description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 description 3
- IWXCYYWDGDDPAC-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)methyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C(C(O)=O)=C1 IWXCYYWDGDDPAC-UHFFFAOYSA-N 0.000 description 3
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 3
- AQVOMFPTJXMAQE-UHFFFAOYSA-N 4-propylphthalic acid Chemical compound CCCC1=CC=C(C(O)=O)C(C(O)=O)=C1 AQVOMFPTJXMAQE-UHFFFAOYSA-N 0.000 description 3
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 125000002015 acyclic group Chemical group 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 150000004292 cyclic ethers Chemical group 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N gamma-methylpyridine Natural products CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 2
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 description 2
- IFZNGUXGNISUPF-UHFFFAOYSA-N 2,5-bis(trifluoromethyl)benzene-1,4-dicarbonyl chloride Chemical compound FC(F)(F)c1cc(C(Cl)=O)c(cc1C(Cl)=O)C(F)(F)F IFZNGUXGNISUPF-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- TURIHPLQSRVWHU-UHFFFAOYSA-N 2-phenylnaphthalene Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=C1 TURIHPLQSRVWHU-UHFFFAOYSA-N 0.000 description 2
- MUGUJRSYUSHCBS-UHFFFAOYSA-N 3-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=CC(N)=C1 MUGUJRSYUSHCBS-UHFFFAOYSA-N 0.000 description 2
- MFEIKQPHQINPRI-UHFFFAOYSA-N 3-Ethylpyridine Chemical compound CCC1=CC=CN=C1 MFEIKQPHQINPRI-UHFFFAOYSA-N 0.000 description 2
- TYKLCAKICHXQNE-UHFFFAOYSA-N 3-[(2,3-dicarboxyphenyl)methyl]phthalic acid Chemical compound OC(=O)C1=CC=CC(CC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O TYKLCAKICHXQNE-UHFFFAOYSA-N 0.000 description 2
- UCPOEBHXOCKECV-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenyl)ethyl]phthalic acid Chemical compound OC(=O)C1=CC=CC(CCC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O UCPOEBHXOCKECV-UHFFFAOYSA-N 0.000 description 2
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 2
- MUBMBUGIVIAHII-UHFFFAOYSA-N 3-propylphthalic acid Chemical compound CCCC1=CC=CC(C(O)=O)=C1C(O)=O MUBMBUGIVIAHII-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- ZWQOXRDNGHWDBS-UHFFFAOYSA-N 4-(2-phenylphenoxy)aniline Chemical group C1=CC(N)=CC=C1OC1=CC=CC=C1C1=CC=CC=C1 ZWQOXRDNGHWDBS-UHFFFAOYSA-N 0.000 description 2
- BQHIADYTQBPQMV-UHFFFAOYSA-N 4-(2-propylphenoxy)phthalic acid Chemical compound CCCC1=CC=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 BQHIADYTQBPQMV-UHFFFAOYSA-N 0.000 description 2
- DDVYLSFEKWFRFS-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1CCC1=CC=C(C(O)=O)C(C(O)=O)=C1 DDVYLSFEKWFRFS-UHFFFAOYSA-N 0.000 description 2
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 2
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 2
- XMQHKFGLFALBAX-UHFFFAOYSA-N 4-[4-carbonochloridoyl-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)benzoyl chloride Chemical compound FC(F)(F)C1=CC(C(Cl)=O)=CC=C1C1=CC=C(C(Cl)=O)C=C1C(F)(F)F XMQHKFGLFALBAX-UHFFFAOYSA-N 0.000 description 2
- LVRNKEBRXQHJIN-UHFFFAOYSA-N 4-ethylphthalic acid Chemical compound CCC1=CC=C(C(O)=O)C(C(O)=O)=C1 LVRNKEBRXQHJIN-UHFFFAOYSA-N 0.000 description 2
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 2
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 2
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical group [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- XNFGDDFDPXGEGL-UHFFFAOYSA-N 1,3-dioxobenzo[f][2]benzofuran-6-carboxylic acid Chemical compound C1=C2C(=O)OC(=O)C2=CC2=CC(C(=O)O)=CC=C21 XNFGDDFDPXGEGL-UHFFFAOYSA-N 0.000 description 1
- JVCBVWTTXCNJBJ-UHFFFAOYSA-N 1-azabicyclo[2.2.1]heptane Chemical compound C1CC2CCN1C2 JVCBVWTTXCNJBJ-UHFFFAOYSA-N 0.000 description 1
- STHHLVCQSLRQNI-UHFFFAOYSA-N 1-azabicyclo[3.2.1]octane Chemical compound C1C2CCN1CCC2 STHHLVCQSLRQNI-UHFFFAOYSA-N 0.000 description 1
- AXWLKJWVMMAXBD-UHFFFAOYSA-N 1-butylpiperidine Chemical compound CCCCN1CCCCC1 AXWLKJWVMMAXBD-UHFFFAOYSA-N 0.000 description 1
- JSHASCFKOSDFHY-UHFFFAOYSA-N 1-butylpyrrolidine Chemical compound CCCCN1CCCC1 JSHASCFKOSDFHY-UHFFFAOYSA-N 0.000 description 1
- IYDMICQAKLQHLA-UHFFFAOYSA-N 1-phenylnaphthalene Chemical compound C1=CC=CC=C1C1=CC=CC2=CC=CC=C12 IYDMICQAKLQHLA-UHFFFAOYSA-N 0.000 description 1
- VTDIWMPYBAVEDY-UHFFFAOYSA-N 1-propylpiperidine Chemical compound CCCN1CCCCC1 VTDIWMPYBAVEDY-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NARFILZKWWKCHH-UHFFFAOYSA-N 2-chloro-4-(9H-fluoren-1-yl)aniline Chemical compound ClC=1C=C(C=CC=1N)C1=CC=CC=2C3=CC=CC=C3CC1=2 NARFILZKWWKCHH-UHFFFAOYSA-N 0.000 description 1
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 description 1
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 description 1
- NMWDYLYNWRFEMR-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1.CC1=CC=CC=N1 NMWDYLYNWRFEMR-UHFFFAOYSA-N 0.000 description 1
- RGBSGRUHELUMOF-UHFFFAOYSA-N 3,4-cyclopentenopyridine Natural products C1=NC=C2CCCC2=C1 RGBSGRUHELUMOF-UHFFFAOYSA-N 0.000 description 1
- KHZYMPDILLAIQY-UHFFFAOYSA-N 3-(3-carboxyphenyl)benzoic acid Chemical compound OC(=O)C1=CC=CC(C=2C=C(C=CC=2)C(O)=O)=C1 KHZYMPDILLAIQY-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- UCFMKTNJZCYBBJ-UHFFFAOYSA-N 3-[1-(2,3-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)C1=CC=CC(C(O)=O)=C1C(O)=O UCFMKTNJZCYBBJ-UHFFFAOYSA-N 0.000 description 1
- NMGBFVPQUCLJGM-UHFFFAOYSA-N 3-ethylphthalic acid Chemical compound CCC1=CC=CC(C(O)=O)=C1C(O)=O NMGBFVPQUCLJGM-UHFFFAOYSA-N 0.000 description 1
- AURDEEIHMPRBLI-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1.CC1=CC=CN=C1 AURDEEIHMPRBLI-UHFFFAOYSA-N 0.000 description 1
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 description 1
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 1
- YCIGYTFKOXGYTA-UHFFFAOYSA-N 4-(3-cyanopropyldiazenyl)butanenitrile Chemical compound N#CCCCN=NCCCC#N YCIGYTFKOXGYTA-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- LCCYEGJIEFWDSA-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)-2-methylaniline Chemical compound C1=C(N)C(C)=CC(C=2C3=C(C4=CC=CC=C4C3)C=CC=2)=C1 LCCYEGJIEFWDSA-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- RXNKCIBVUNMMAD-UHFFFAOYSA-N 4-[9-(4-amino-3-fluorophenyl)fluoren-9-yl]-2-fluoroaniline Chemical compound C1=C(F)C(N)=CC=C1C1(C=2C=C(F)C(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 RXNKCIBVUNMMAD-UHFFFAOYSA-N 0.000 description 1
- VJXRKZJMGVSXPX-UHFFFAOYSA-N 4-ethylpyridine Chemical compound CCC1=CC=NC=C1 VJXRKZJMGVSXPX-UHFFFAOYSA-N 0.000 description 1
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 1
- HTMGQIXFZMZZKD-UHFFFAOYSA-N 5,6,7,8-tetrahydroisoquinoline Chemical compound N1=CC=C2CCCCC2=C1 HTMGQIXFZMZZKD-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- RBUCAPSNRDZVKR-UHFFFAOYSA-N [Fe+]C1C=CC=C1 Chemical class [Fe+]C1C=CC=C1 RBUCAPSNRDZVKR-UHFFFAOYSA-N 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 230000005250 beta ray Effects 0.000 description 1
- XMSVKICKONKVNM-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,4-diamine Chemical compound C1CC2(N)C(N)CC1C2 XMSVKICKONKVNM-UHFFFAOYSA-N 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- BEQNOZDXPONEMR-UHFFFAOYSA-N cadmium;oxotin Chemical compound [Cd].[Sn]=O BEQNOZDXPONEMR-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 125000006001 difluoroethyl group Chemical group 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- HRHKULZDDYWVBE-UHFFFAOYSA-N indium;oxozinc;tin Chemical compound [In].[Sn].[Zn]=O HRHKULZDDYWVBE-UHFFFAOYSA-N 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000983 mordant dye Substances 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- BBDGYADAMYMJNO-UHFFFAOYSA-N n-butyl-n-ethylbutan-1-amine Chemical compound CCCCN(CC)CCCC BBDGYADAMYMJNO-UHFFFAOYSA-N 0.000 description 1
- VEBPYKMCKZTFPJ-UHFFFAOYSA-N n-butyl-n-propylbutan-1-amine Chemical compound CCCCN(CCC)CCCC VEBPYKMCKZTFPJ-UHFFFAOYSA-N 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 125000005246 nonafluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000011242 organic-inorganic particle Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 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
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[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
- 238000000746 purification Methods 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010897 surface acoustic wave method Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- OAXARSVKYJPDPA-UHFFFAOYSA-N tert-butyl 4-prop-2-ynylpiperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(CC#C)CC1 OAXARSVKYJPDPA-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
-
- 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
- C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Theoretical Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- Materials Engineering (AREA)
- Human Computer Interaction (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polyamides (AREA)
Abstract
The present invention provides an optical film having a high elastic modulus and a low coefficient of humidity expansion. An optical film comprising a polyamide resin having a weight average molecular weight of 200,000 to 1,000,000, the polyamide resin having at least a structural unit represented by formula (1) and a structural unit represented by formula (3). In the formula (1), Ar1Represents a 2-valent aromatic group having a fluoroalkyl group having 1 to 12 carbon atoms, X1Represents a 2-valent organic group. In the formula (3), Z1Represents Ar1Or means other than Ar1A 2-valent organic radical of (A), Ar1As defined in the aforementioned formula (1), X2Represents a 2-valent organic group, wherein, in Z1Represents Ar1In the case of (1), X1And X in formula (3)2Are different from each other.
Description
Technical Field
The present invention relates to an optical film containing a polyamide resin, a flexible display device provided with the optical film, and a polyamide resin.
Background
At present, display devices such as liquid crystal display devices and organic EL display devices are widely used not only for televisions but also for various applications such as mobile phones and smartwatches. Conventionally, glass has been used as a front panel of such a display device. However, glass has high transparency and can exhibit high hardness depending on the type, but on the other hand, it is very rigid and easily broken, and therefore, it is difficult to use it as a front panel material for a flexible display device.
Therefore, studies have been made on flexible use of polymer materials as materials replacing glass. A front panel made of a polymer material is expected to be used for various applications because it is easy to exhibit flexibility. As one of polymer materials having flexibility, for example, an optical film using a polyamide resin has been studied (patent documents 1 and 2).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2015-521686
Patent document 2: japanese patent laid-open publication No. 2018-119132
Disclosure of Invention
Problems to be solved by the invention
However, when an optical film using a polyamide resin is used for a flexible display device or the like, defects such as damage and wrinkles may occur in the optical film due to bending or contact with an external factor. The inventors of the present application have made various studies on means for improving the above-described situation, and have found that a defect such as a scratch is less likely to occur in an optical film by increasing the elastic modulus of the optical film. In addition, a flexible display device is a device used under various environments for a long time, and particularly, an optical film to which a load is applied in accordance with a change in temperature, humidity, or the like may expand and contract in a planar direction. Therefore, the optical film is also required to have a low humidity expansion coefficient with respect to changes in temperature and humidity.
Accordingly, an object of the present invention is to provide an optical film having a high elastic modulus and a low coefficient of expansion under humidity.
Means for solving the problems
In order to solve the above problems, the present inventors have made intensive studies focusing on the structure of a monomer constituting a polyamide resin contained in an optical film. As a result, they have found that an optical film comprising a polyamide resin having at least a specific structural unit and a weight average molecular weight in a specific range has both a high elastic modulus and a low coefficient of expansion under humidity, and have completed the present invention.
That is, the present invention includes the following preferred embodiments.
An optical film comprising a polyamide resin having a weight average molecular weight of 200,000 to 1,000,000, the polyamide resin having at least a structural unit represented by formula (1) and a structural unit represented by formula (3).
[ chemical formula 1]
[ formula (1) wherein Ar is1Represents a 2-valent aromatic group having a fluoroalkyl group having 1 to 12 carbon atoms, X1Represents a 2-valent organic group]
[ chemical formula 2]
[ in the formula (3),
Z1represents Ar1Or means other than Ar1A 2-valent organic radical of (A), Ar1As defined in the aforementioned formula (1),
X2represents a 2-valent organic group, wherein, in Z1Represents Ar1In the case of (1), X1And X in formula (3)2Are different from each other]
[ 2] the optical film according to [ 1], wherein Ar in the formula (1)1Wherein the fluoroalkyl group having 1 to 12 carbon atoms is a perfluoroalkyl group having 1 to 12 carbon atoms.
[ 3] the optical film according to the above [ 1] or [ 2], wherein the structural unit represented by the formula (1) contains an aromatic group represented by the formula (4) as Ar1。
[ chemical formula 3]
[ in the formula (4),
R1represents a fluoroalkyl group having 1 to 12 carbon atoms,
n and k independently represent an integer of 1 to 4, wherein when n and/or k represent an integer of 2 to 4, a plurality of R exist1May be the same as, or different from,
denotes a chemical bond
[ 4] the optical film according to the above [ 3], wherein 2 chemical bonds in the formula (4) are in alignment with each other.
[ 5] the optical film according to the above [ 3] or [ 4], wherein k in the formula (4) is 1 or 2.
[ 6] the optical film according to any one of [ 3] to [ 5], wherein R in the formula (4)1Represents a perfluoroalkyl group having 1 to 12 carbon atoms, and n is 1 or 2.
[ 7] the optical film according to any one of [ 1] to [ 6], wherein the structural unit represented by formula (1) and the structural unit represented by formula (3) each contain a 2-valent organic group represented by formula (5) as X1And X2。
[ chemical formula 4]
[ in the formula (5),
Ar2represents a 2-valent aromatic group which may have a substituent,
v represents a single bond, -O-, diphenylmethylene, fluorenyl, a linear, branched or alicyclic 2-valent hydrocarbon group having 1 to 12 carbon atoms, -SO2-、-S-、-CO-、-PO-、-PO2-、-N(Ra) -or-Si (R)b)2-, wherein the hydrogen atoms contained in the hydrocarbon group independently of each other may be substituted by halogen atoms, RaAnd RbIndependently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom,
m represents an integer of 0 to 3,
denotes a chemical bond
[ 8] the optical film according to [ 7], wherein m in the formula (5) is 1.
[ 9] the optical film according to [ 7] or [ 8], wherein the formula (5) is represented by the formula (5 a).
[ chemical formula 5]
[ in the formula (5),
R2represents a fluoroalkyl group having 1 to 12 carbon atoms,
p and q independently represent an integer of 1 to 4, wherein when p and/or q represents an integer of 2 to 4, a plurality of R exist2May be the same as, or different from,
denotes a chemical bond
[ 10] the optical film according to [ 9], wherein the formula (5a) is represented by the formula (5 c).
[ chemical formula 6]
[ in the formula (5c), the symbol "x" represents a chemical bond ]
The optical film according to any one of [ 1] to [ 10] above, wherein the thickness is 10 to 200 μm.
A flexible display device comprising the optical film according to any one of [ 1] to [ 11 ].
The flexible display device according to [ 13] above [ 12], further comprising a touch sensor.
The flexible display device according to any one of the above [ 12] and [ 13], further comprising a polarizing plate.
[ 15] A polyamide resin having a weight average molecular weight of 200,000 to 1,000,000, which comprises at least: an aromatic group represented by formula (1) and containing formula (4) as Ar in formula (1)1And a structural unit represented by formula (3).
[ chemical formula 7]
[ in the formula (1),
Ar1represents a 2-valent aromatic group having a fluoroalkyl group having 1 to 12 carbon atoms,
X1represents a 2-valent organic group]
[ chemical formula 8]
[ in formula (4), R1Represents a fluoroalkyl group having 1 to 12 carbon atoms,
n and k independently represent an integer of 1 to 4, wherein when n and/or k represent an integer of 2 to 4, a plurality of R exist1May be the same as, or different from,
represents a chemical bond ]
[ chemical formula 9]
[ in the formula (3), Z1Represents Ar1Or means other than Ar1A 2-valent organic radical of (A), Ar1As defined in the aforementioned formula (1),
X2represents a 2-valent organic group, wherein, in Z1Represents Ar1In the case of (1), X1And X in formula (3)2Are different from each other]
ADVANTAGEOUS EFFECTS OF INVENTION
The optical film of the present invention has a high elastic modulus and a low coefficient of humidity expansion.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the present invention.
The optical film of the present invention contains a polyamide resin having a weight average molecular weight of 200,000 to 1,000,000, the polyamide resin having at least a structural unit represented by formula (1) and a structural unit represented by formula (3).
[ chemical formula 10]
[ formula (1) wherein Ar is1Represents a 2-valent aromatic group having a fluoroalkyl group having 1 to 12 carbon atoms, X1Represents a 2-valent organic group]
[ chemical formula 11]
[ in the formula (3), Z1To representAr1Or means other than Ar1A 2-valent organic radical of (A), Ar1As defined in the aforementioned formula (1),
X2represents a 2-valent organic group, wherein, in Z1Represents Ar1In the case of (1), X1And X in formula (3)2Are different from each other]
In the formulae (1) and (3), the bond represented by a dotted line represents a chemical bond with an adjacent structural unit. In the present specification, the bond represented by a dotted line in the other chemical structural formulae also represents a chemical bond to an adjacent structural unit or group.
The polyamide resin contained in the optical film of the present invention may have 1 kind of structural unit represented by formula (1), or may have 2 or more kinds of structural units represented by formula (1). Similarly, the polyamide resin may have 1 kind of structural unit represented by formula (3), or may have 2 or more kinds of structural units represented by formula (3). The structural unit represented by the formula (1) and the structural unit represented by the formula (3) are structural units formed by reacting a dicarboxylic acid compound with a diamine compound. In the present specification, the structural unit represented by formula (1) is also referred to as "structural unit (1)", and the structural unit represented by formula (3) is also referred to as "structural unit (3)". When the polyamide resin contained in the optical film of the present invention has 2 or more kinds of structural units represented by formula (1), at least one of the structural units may be represented by formula (1), and at least one of the other structural units may be represented by formula (3).
The polyamide resin having a structural unit represented by the above formula (1) and a structural unit represented by the above formula (3) means that in the polyamide resin,
(a) at least having a structural unit represented by formula (1), and Z1Is not represented by Ar1A 2-valent organic group of (3), in which case X in formula (1)1And X in formula (3)2May be the same or different from each other; alternatively, the first and second electrodes may be,
(b) at least having a structural unit represented by formula (1), and Z1Belong to Ar1The structural unit represented by the formula (3), in this case, X in the formula (1)1And X in formula (3)2Are different from each other.
In the case of the above (a), the structural unit represented by the formula (3) is represented by the formula (3a), and in the case of the above (b), the structural unit represented by the formula (3) is represented by the formula (3 b). In the present specification, the structural unit represented by formula (3a) is also referred to as "structural unit (3 a)", and the structural unit represented by formula (3b) is also referred to as "structural unit (3 b)".
[ chemical formula 12]
[ in the formula (3a), Z2A 2-valent organic group which is not a 2-valent aromatic group having a fluoroalkyl group having 1 to 12 carbon atoms,
X3represents a 2-valent organic group]
[ chemical formula 13]
[ formula (3a) wherein Ar is3Represents a 2-valent aromatic group having a fluoroalkyl group having 1 to 12 carbon atoms,
X4x in the formula (1)1Different 2-valent organic radicals]
The reason why the elastic modulus is improved and the coefficient of expansion due to humidity can be reduced in the optical film of the present invention comprising the polyamide resin having the structural unit (1) and the structural unit (3) and having a weight average molecular weight of 200,000 to 1,000,000 is not clear, but the following may be considered: ar in the above formula (1) in the skeleton of the polyamide resin having a predetermined weight average molecular weight1The polyamide resin is a 2-valent aromatic group having a fluoroalkyl group having 1 to 12 carbon atoms, and thus a specific portion in the skeleton of the polyamide resin has appropriate rigidity. Further, it is considered that the polyamide resin further has a structural unit (3a) and/or a structural unit(3b) And thus have intermolecular repulsive force. As a result, surprisingly, it is considered that both an increase in the elastic modulus and a decrease in the coefficient of humidity expansion of the optical film containing the polyamide resin can be achieved. The coefficient of humidity expansion is an index indicating the degree of expansion and contraction in the plane direction of the optical film in a state in which a load is applied, and it has been confirmed that the coefficient of humidity expansion has a large influence on the molecular structure of the polyamide resin constituting the optical film. Further, it was confirmed that it is difficult to simultaneously realize a high elastic modulus and a low coefficient of wet expansion of the optical film only by simply increasing the structure having a halogen atom. The present invention has found that an optical film having both a high elastic modulus and a low coefficient of wet expansion can be obtained by an optical film comprising a polyamide resin having at least a structural unit (1) containing a 2-valent aromatic group having a fluoroalkyl group having 1 to 12 carbon atoms and a structural unit (3) and having a weight average molecular weight in a predetermined range.
The polyamide resin contained in the optical film of the present invention has a structural unit (1) and a structural unit (3). From the viewpoint of easily improving the elastic modulus of the optical film and easily reducing the coefficient of expansion due to humidity, the proportion of the structural unit (1) is preferably 10 to 99 mol%, more preferably 20 to 95 mol%, further preferably 30 to 90 mol%, and particularly preferably 40 to 85 mol%, based on 100 mol% of the total of the structural unit (1) and the structural unit (3) contained in the polyamide resin. When the ratio of the structural unit (1) is not less than the lower limit, the elastic modulus of the optical film is easily increased, and the coefficient of humidity expansion is easily decreased. When the proportion of the structural unit (1) is not more than the above upper limit, the solubility in a solvent can be easily ensured. The contents of the structural units (1) and (3) may be, for example, those used1H-NMR, or the ratio of the raw materials charged may be calculated.
In a preferred embodiment of the present invention in which the polyamide resin contained in the optical film of the present invention has the structural unit (1) and the structural unit (3a), the proportion of the structural unit (1) is preferably 10 to 99 mol%, more preferably 20 to 95 mol%, further preferably 30 to 90 mol%, and particularly preferably 40 to 85 mol%, when the total of the structural unit (1) and the structural unit (3a) contained in the polyamide resin is 100 mol%, from the viewpoint of easily increasing the elastic modulus of the optical film and easily reducing the coefficient of expansion due to humidity. When the ratio of the structural unit (1) is not less than the lower limit, the elastic modulus of the optical film is easily increased, and the coefficient of humidity expansion is easily decreased. When the proportion of the structural unit (1) is not more than the above upper limit, the solubility in a solvent can be easily ensured.
In a preferred embodiment of the present invention in which the polyamide resin contained in the optical film of the present invention has the structural unit (1) and the structural unit (3b), the proportion of the structural unit (1) is preferably 10 to 99 mol%, more preferably 20 to 95 mol%, further preferably 30 to 90 mol%, and particularly preferably 40 to 85 mol%, when the total of the structural unit (1) and the structural unit (3b) contained in the polyamide resin is 100 mol%, from the viewpoint of easily increasing the elastic modulus of the optical film and easily reducing the coefficient of expansion due to humidity. When the ratio of the structural unit (1) is not less than the lower limit, the elastic modulus of the optical film is easily increased, and the coefficient of humidity expansion is easily decreased. When the proportion of the structural unit (1) is not more than the above upper limit, the solubility in a solvent can be easily ensured. The contents of the structural unit (3a) and the structural unit (3b) may be used, for example1H-NMR, or the ratio of the raw materials charged.
Ar in formula (1)1Represents a 2-valent aromatic group having a fluoroalkyl group having 1 to 12 carbon atoms. In the present specification, the 2-valent aromatic group is a group in which 2 hydrogen atoms of a monocyclic aromatic ring, a condensed polycyclic aromatic ring, or a ring-assembly aromatic ring are replaced with a chemical bond. The 2-valent aromatic group may include an aromatic ring having a ring (a single ring, a condensed multiple ring, or a ring assembly) formed only of carbon atoms, or may include an aromatic heterocyclic ring having a ring formed so as to contain an atom other than carbon atoms. Examples of the atom other than carbon atoms include a nitrogen atom, a sulfur atom and an oxygen atom. Carbon atoms or atoms other than carbon atoms forming aromatic ringsThe total number of the subgroups is not particularly limited, but is preferably 5 to 18, more preferably 5 to 14, and further preferably 5 to 12.
Examples of the monocyclic aromatic ring include benzene, furan, pyrrole, thiophene, pyridine, imidazole, pyrazole, oxazole, thiazole, imidazoline, and the like.
Examples of the fused polycyclic aromatic ring include naphthalene, anthracene, phenanthrene, indole, benzothiazole, benzimidazole, and benzoxazole.
The ring-assembled aromatic ring may have a structure in which 2 or more monocyclic aromatic rings and/or condensed polycyclic aromatic rings are connected by a single bond, and examples thereof include: examples of the monocyclic aromatic ring or the condensed polycyclic aromatic ring include those in which 2 or more of the above-described rings are connected by a single bond, such as biphenyl, terphenyl, quaterphenyl, binaphthyl, 1-phenylnaphthalene, 2-phenylnaphthalene, and bipyridine (bipyridine).
From the viewpoint of easily improving the elastic modulus of the optical film and easily reducing the coefficient of expansion due to humidity, the 2-valent aromatic group having a fluoroalkyl group having 1 to 12 carbon atoms is preferably a group in which 2 hydrogen atoms of an aromatic hydrocarbon ring having a fluoroalkyl group having 1 to 12 carbon atoms are replaced with a chemical bond, more preferably a group in which 2 hydrogen atoms of a benzene, biphenyl, terphenyl or quaterphenyl group having a fluoroalkyl group having 1 to 12 carbon atoms are replaced with a chemical bond, and even more preferably a group in which 2 hydrogen atoms of a benzene or biphenyl group having a fluoroalkyl group having 1 to 12 carbon atoms are replaced with a chemical bond.
Ar in formula (1)1Wherein the fluoroalkyl group having 1 to 12 carbon atoms is a group in which at least 1 hydrogen atom of a linear or branched alkyl group having 1 to 12 carbon atoms is substituted with a fluorine atom. Examples of the linear or branched fluoroalkyl group having 1 to 12 carbon atoms include groups in which at least 1 hydrogen atom in a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a 2-methyl-butyl group, a 3-methylbutyl group, a 2-ethyl-propyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a tert-octyl group, an n-nonyl group, an n-decyl group, and the like is substituted with a fluorine atom. As carbon atomsSpecific examples of the fluoroalkyl group having 1 to 12 atoms include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group and the like. The number of carbon atoms of the fluoroalkyl group is preferably 1 to 6, more preferably 1 to 4, and further preferably 1 or 2.
The fluoroalkyl group having 1 to 12 carbon atoms is preferably a perfluoroalkyl group having 1 to 12 carbon atoms, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, still more preferably a perfluoroalkyl group having 1 to 4 carbon atoms, and particularly preferably a trifluoromethyl group or a pentafluoroethyl group, from the viewpoint of easily improving the elastic modulus of the optical film and easily reducing the coefficient of expansion due to humidity.
Ar in formula (1)1The fluoroalkyl group having at least 1 carbon atom of 1 to 12 may be used, and the number is not particularly limited, but Ar is a group that easily increases the elastic modulus of the optical film and easily decreases the coefficient of expansion under humidity1The number of fluoroalkyl groups having 1 to 12 carbon atoms is preferably 1 to 6, and more preferably 1 to 4. Ar in formula (1)1In the case of a fluoroalkyl group having 2 or more carbon atoms of 1 to 12, they may be the same or different from each other.
Ar in formula (1)1The fluorine-containing polymer may have a substituent other than the fluoroalkyl group having 1 to 12 carbon atoms. Examples of the other substituent include 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.
In a preferred embodiment of the present invention, the structural unit represented by formula (1) contains a 2-valent aromatic group represented by formula (4) as Ar from the viewpoint of easily increasing the elastic modulus of the optical film and easily decreasing the coefficient of expansion under humidity1。
[ chemical formula 14]
[ in the formula (4),
R1independently represent fluorine having 1 to 12 carbon atomsAn alkyl group, a carboxyl group,
n and k independently represent an integer of 1 to 4, wherein when n and/or k represent an integer of 2 to 4, a plurality of R exist1May be the same as, or different from,
denotes a chemical bond
The structural unit (1) contains a 2-valent aromatic group represented by the formula (4) as Ar1In the case where the structural unit (1) may contain 1 or 2 or more aromatic groups represented by the formula (4) as Ar1In addition to the aromatic group represented by the formula (4), another aromatic group having a fluoroalkyl group may be contained instead of the aromatic group represented by the formula (4).
The polyamide resin contained in the optical film of the present invention has at least the structural unit (1) and the structural unit (3) as described above, and the resin usually has a plurality of structural units (1), a plurality of structural units (3), and any other structural unit. In the present specification, the structural unit (1) includes an aromatic group represented by the formula (4) as Ar1In the polyamide resin, Ar in at least a part of the plurality of structural units (1) is Ar in the structural units (1)1Represented by formula (4). The above description is also applicable to other descriptions in the present specification.
As R1Fluoroalkyl group having 1 to 12 carbon atoms in the group (A), and Ar1The above description concerning the fluoroalkyl group having 1 to 12 carbon atoms in (A) is also applicable, and the preferable description is also applicable.
n and k independently represent an integer of 1 to 4. From the viewpoint of optical characteristics, n is preferably an integer of 1 or 2, and more preferably 1. From the viewpoint of the elastic modulus, k is preferably an integer of 1 or 2, and more preferably 1. Here, when n and/or k represents an integer of 2 to 4, a plurality of R exist1May be the same or different from each other, but in view of solubility in a solvent, a plurality of R's are present1Preferably identical to each other. From the viewpoint of easily increasing the elastic modulus of the optical film and easily decreasing the coefficient of expansion due to humidity, it is more preferable that k be 1 and n be 2, or that k be 2 and n be 1.
The 2 chemical bonds in the formula (4) are not particularly limited in position, and may be any of ortho, meta, and para positions, but are preferably in the para position from the viewpoint of easily increasing the elastic modulus of the optical film and easily decreasing the coefficient of expansion due to humidity.
Preferred examples of the 2-valent aromatic group represented by the formula (4) include: r in the formula (4)1Represents a perfluoroalkyl group having 1 to 12 carbon atoms, k is 1 or 2, n is 1 or 2, and/or 2 aromatic groups in which the bonds are para to each other.
The structural unit represented by formula (1) contained in the polyamide resin contained in the optical film of the present invention contains a 2-valent aromatic group represented by formula (4) as Ar1In a preferred embodiment of the present invention, Ar in the formula (1) is 100 mol% of the total of the structural units represented by the formula (1) contained in the polyamide resin, from the viewpoint of easily increasing the elastic modulus of the optical film and easily reducing the coefficient of expansion due to humidity1The proportion of the structural unit which is a 2-valent aromatic group represented by the formula (4) is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, further preferably 90 to 100 mol%, and may be Ar in all the structural units represented by the formula (1)1Is a 2-valent aromatic group represented by the formula (4).
As a preferable example of the 2-valent aromatic group represented by formula (4), an aromatic group represented by formula (4a) in which the chemical bonds in formula (4) are in para-position to each other can be exemplified.
[ chemical formula 15]
[ in the formula (4a), R3~R6Independently represent a hydrogen atom or a fluoroalkyl group having 1 to 12 carbon atoms, wherein R3~R6At least one of them represents a fluoroalkyl group having 1 to 12 carbon atoms, k represents an integer of 1 to 4, and represents a chemical bond]
In the case where k in the formula (4a) is 1, from the viewpoint of easily increasing the elastic modulus of the optical film and easily decreasing the coefficient of expansion due to humidity,R3~R6at least one of them represents a fluoroalkyl group having 1 to 12 carbon atoms, preferably R3~R6At least two of them represent fluoroalkyl groups having 1 to 12 carbon atoms, more preferably at least R3And R5Represents a fluoroalkyl group having 1 to 12 carbon atoms, and more preferably R3And R5Represents a fluoroalkyl group having 1 to 12 carbon atoms and R4And R6Represents a hydrogen atom. From the viewpoint of easily increasing the elastic modulus of the optical film and easily decreasing the coefficient of expansion due to humidity, when k in the formula (4a) is 2, the group on the 1 st benzene ring is R3~R36Taking the group on the 2 nd benzene ring as R3’~R6’When, R is preferred3~R6And R3’~R6’At least two of them represent fluoroalkyl groups having 1 to 12 carbon atoms, and more preferably at least R present at a position close to a single bond linking 2 benzene rings4And R6’Represents a fluoroalkyl group having 1 to 12 carbon atoms, and more preferably R4And R6’Represents a fluoroalkyl group having 1 to 12 carbon atoms and R3、R5、R6And R3’~R5’Represents a hydrogen atom. As fluoroalkyl group having 1 to 12 carbon atoms, with Ar1The above description concerning the fluoroalkyl group having 1 to 12 carbon atoms in (A) is also applicable, and the preferable description is also applicable. From the viewpoint of easily increasing the elastic modulus of the optical film and easily decreasing the coefficient of expansion with respect to humidity, k in the formula (4a) is preferably an integer of 1 or 2. From the viewpoint of easily improving the pencil hardness of the optical film, k in the formula (4a) is preferably 2.
Z in the formula (3)1Represents Ar1In the case of (2) with Ar in the formula (1)1The above description is similarly applied to Z in formula (3)1. And, in addition, with Ar in formula (1)1The same applies to Ar in formula (3b)3。
Z in the formula (3)1Is not Ar1In the case of a 2-valent organic group of (3), Z1Is a 2-valent organic group not belonging to a 2-valent aromatic group having a fluoroalkyl group having 1 to 12 carbon atoms, and may beFor example, do not belong to Ar1The 2-valent organic group having a C4-40 cyclic structure (preferably an alicyclic structure, aromatic ring structure or heterocyclic structure) which has a C1-12 fluoroalkyl group and a 2-valent aromatic group, and which may be substituted with a C1-8 hydrocarbon group or a C1-8 fluorine-substituted hydrocarbon group. Examples of the 2-valent organic group having 4 to 40 carbon atoms and including a cyclic structure include groups in which 2 of chemical bonds of the groups represented by formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), formula (28), and formula (29) that are not adjacent are replaced with a hydrogen atom, and groups having a thiophene ring structure.
[ chemical formula 16]
It is to be noted that, among these groups,
w substituted with a fluorine-substituted hydrocarbon group having 1 to 8 carbon atoms1A group obtained by replacing 2 nonadjacent chemical bonds of the group represented by the formula (26) which is a single bond or the formula (26') which will be described later with hydrogen atoms,
a group obtained by replacing 2 non-adjacent ones of the chemical bonds of the group represented by the formulae (28) and (29) or the formulae (28 ') and (29') described later, which are substituted with a fluorine-substituted hydrocarbon group having 1 to 8 carbon atoms, with hydrogen atoms, and
a group having a thiophene ring structure substituted with a fluorine-substituted hydrocarbon group having 1 to 8 carbon atoms for Ar1The 2-valent aromatic group having a fluoroalkyl group having 1 to 12 carbon atoms as described above, and therefore does not belong to Z in formula (3) in this embodiment1。
In the formulae (20) to (29),
w represents a chemical bond1Represents a single bond, -O-, -CH2-、-CH2-CH2-、-CH(CH3)-、-C(CH3)2-、-C(CF3)2-、-Ar-、-SO2-、-CO-、-O-Ar-O-、-Ar-O-Ar-、-Ar-CH2-Ar-、-Ar-C(CH3)2-Ar-or-Ar-SO2-Ar-. Ar represents an arylene group having 6 to 20 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom, and specific examples thereof include phenylene groups.
About Z as in formula (3)1The cyclic-structure-containing 2-valent organic group having 4 to 40 carbon atoms is more preferably a 2-valent organic group represented by formula (20 '), formula (21'), formula (22 '), formula (23'), formula (24 '), formula (25'), formula (26 '), formula (27'), formula (28 ') and formula (29').
[ chemical formula 17]
In [ formulae (20 ') to (29'), W1And the same as defined in formula (20) to formula (29)]
From the viewpoint of easily improving the film-forming property of the varnish and easily obtaining the uniformity of the optical film, it is preferable that the polyamide resin has Z in formula (3) in addition to the structural unit represented by formula (1)1When the structural unit represented by any one of the above formulae (20 ') to (29'), particularly, Z in formula (3) is contained1In the case of the structural unit represented by the formula (7) described later, the structural unit has a structural unit derived from a carboxylic acid represented by the following formula (d1) in addition to the structural unit.
[ chemical formula 18]
[ in the formula (d1), ReIndependently represent 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, RfRepresents Reor-C (═ O) -, represents a chemical bond]
ReIn (1) as an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms and a carbon atomThe aryl groups having a sub-number of 6 to 12 are each Ar in the formula (5) described later2The alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms or the aryl group having 6 to 12 carbon atoms. Specific examples of the structural unit (d1) include ReAnd RfStructural units each of which is a hydrogen atom (structural units derived from a dicarboxylic acid compound), ReAre all hydrogen atoms and RfA structural unit (a structural unit derived from a tricarboxylic acid compound) representing-C (═ O) -, and the like.
In the structural unit represented by the formula (3), as Z1Preferably, the 2-valent organic group represented by the formula (7a) is contained, and more preferably, the 2-valent organic group represented by the formula (7) is contained.
[ chemical formula 19]
[ in the formula (7a), RgAnd RhIndependently represents 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, A, s is the same as A, s and t in the formula (7), t and u are independently integers of 0 to 4, wherein when s is an integer of 1 to 4 and A is not a single bond, R is an alkyl group having 1 to 6 carbon atomsgAnd RhThe hydrogen atoms contained in (A) may be substituted independently of each other by halogen atoms]
[ chemical formula 20]
[ in the formula (7), R31~R38Independently represents 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,
a independently of each other represents a single bond, -O-, -CH2-、-CH2-CH2-、-CH(CH3)-、-C(CH3)2-、-C(CF3)2-、-SO2-, -S-, -CO-or-N (R)39)-,R39Represents a hydrogen atom, a C1-valent hydrocarbon group which may be substituted with a halogen atom and has 1 to 12 carbon atoms, s is an integer of 0 to 4,
it represents a chemical bond,
wherein when s is an integer of 1 to 4 and A is not a single bond, R31~R38The hydrogen atoms contained in (A) may be substituted independently of each other by halogen atoms]
In the formula (7a), the chemical bond of each benzene ring may be bonded to any of the ortho-position, meta-position or para-position based on-a-, and preferably may be bonded to the meta-position or para-position. R in the formula (7a)gAnd RhIndependently represents 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. T and u in the formula (7a) are preferably 0, but when t and/or u is 1 or more, RgAnd RhPreferably represents an alkyl group having 1 to 6 carbon atoms, and more preferably represents an alkyl group having 1 to 3 carbon atoms. R in the formula (7a)gAnd RhIn the formula (7), examples of the halogen atom, 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 include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms.
T and u in formula (7a) are independently an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
In the formulae (7) and (7a), A represents a single bond, -O-, -CH2-、-CH2-CH2-、-CH(CH3)-、-C(CH3)2-、-C(CF3)2-、-SO2-, -S-, -CO-or-N (R)39) From the viewpoint of the bending resistance of the optical film, the compound preferably represents-O-or-S-, and more preferably represents-O-.
In the formula (7), R31、R32、R33、R34、R35、R36、R37And R38Independently of each other representA hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. As the alkyl group having 1 to 12 carbon atoms, the alkoxy group having 1 to 6 carbon atoms and the aryl group having 6 to 12 carbon atoms, Ar in the formula (5) is mentioned2Wherein the alkyl group having 1 to 12 carbon atoms, the alkoxy group having 1 to 6 carbon atoms or the aryl group having 6 to 12 carbon atoms is exemplified above. From the viewpoint of surface hardness and flexibility of the optical film, R31~R38Independently of each other, the alkyl group preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and still more preferably represents a hydrogen atom. Here, when s is an integer of 1 to 4 and A is not a single bond, R31~R38The hydrogen atoms contained in (a) may be substituted by halogen atoms independently of each other.
R39Represents a hydrogen atom, a C1-valent hydrocarbon group which may be substituted with a halogen atom and has 1 to 12 carbon atoms. Examples of the 1-valent hydrocarbon group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-methyl-butyl, 3-methylbutyl, 2-ethyl-propyl, n-hexyl, n-heptyl, n-octyl, tert-octyl, n-nonyl, and n-decyl groups, which may be substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. In the polyamide resin, Z is the number represented by formula (3)1The compound may contain 1 type of 2-valent organic group represented by formula (7) or formula (7a), or may contain 2 or more types of organic groups represented by formula (7) or formula (7 a).
In the formulae (7) and (7a), s is an integer in the range of 0 to 4, and when s is in this range, the optical film tends to have good bending resistance and good elastic modulus. In the formulae (7) and (7a), s is preferably an integer in the range of 0 to 3, more preferably 0 to 2, and further preferably 0 or 1. When s is within this range, the optical film tends to have improved bending resistance and modulus of elasticity.
In the polyamide resin contained in the optical film of the present invention, the structural unit represented by formula (3) may haveA structural unit represented by the formula (3') as Z1. In this case, the surface hardness and the bending resistance of the optical film are easily improved, and the yellowness (hereinafter, also referred to as YI value) is easily reduced.
[ chemical formula 21]
And Z in formula (3)1Is not Ar1Z in the case of a 2-valent organic group of1The above description is also applicable to Z in the above formula (3a)2。
X in the formula (1)1And X in the formula (3)2The compound represents a 2-valent organic group, preferably a 2-valent organic group having 4 to 40 carbon atoms, and more preferably a 2-valent organic group having 4 to 40 carbon atoms and having a cyclic structure. Examples of the cyclic structure include alicyclic, aromatic ring, and heterocyclic structure. The organic group may have hydrogen atoms substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group, and in this case, the number of carbon atoms in the hydrocarbon group and the fluorine-substituted hydrocarbon group is preferably 1 to 8. In one embodiment of the present invention, in the structural unit (1) and the structural unit (3) included in the polyamide resin, X is the number1And X2The organic group may include 1 kind of organic group, or 2 or more kinds of organic groups. However, Z in the formula (3)1Represents Ar1In the case of (1), X1And X in formula (3)1Are different from each other.
In a preferred embodiment of the present invention, the structural unit represented by formula (1) and the structural unit represented by formula (3) each contain a 2-valent organic group represented by formula (5) as X from the viewpoint of easily increasing the elastic modulus of the optical film and easily reducing the coefficient of expansion due to humidity1And X2。
[ chemical formula 22]
[ formula (5) wherein Ar is2Represents a 2-valent aromatic group which may have a substituent,
v represents a single bond, -O-, diphenylmethylene, fluorenyl, a linear, branched or alicyclic 2-valent hydrocarbon group having 1 to 12 carbon atoms, -SO2-、-S-、-CO-、-PO-、-PO2-、-N(Ra) -or-Si (R)b)2-, wherein the hydrogen atoms contained in the hydrocarbon group independently of each other may be substituted by halogen atoms, RaAnd RbIndependently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom,
m represents an integer of 0 to 3,
denotes a chemical bond
The structural unit (1) and the structural unit (3) each contain a 2-valent organic group represented by the formula (5) as X1And X2In the case where the structural unit (1) and the structural unit (3) each may contain 1 or 2 or more of the 2-valent organic groups represented by the formula (5) as X1And X2. In the structural unit (1) and the structural unit (3), X is1And X2In addition to the 2-valent organic group represented by formula (5), other 2-valent organic groups that do not belong to the 2-valent organic group represented by formula (5) may be contained.
Ar in formula (5)2Represents a 2-valent aromatic group which may have a substituent. The 2-valent aromatic group is a group obtained by substituting 2 hydrogen atoms of a monocyclic aromatic ring, a condensed polycyclic aromatic ring or a ring-fused aromatic ring with Ar1The same exemplifications and preferred descriptions as to the monocyclic aromatic ring, the condensed polycyclic aromatic ring or the ring-fused aromatic ring in (1) apply to Ar2The monocyclic aromatic ring, the condensed polycyclic aromatic ring or the ring-assembly aromatic ring in (1). In the formula (5), when m is 1 or more, Ar is present in plural2May be the same or different from each other.
From the viewpoint of easily improving the elastic modulus of the optical film and easily reducing the coefficient of humidity expansion, the 2-valent aromatic group that may have a substituent is preferably a group in which 2 hydrogen atoms of the aromatic hydrocarbon ring that may have a substituent are replaced with a chemical bond, more preferably a group in which 2 hydrogen atoms of benzene, biphenyl, terphenyl, or quaterphenyl that may have a substituent are replaced with a chemical bond, and even more preferably a group in which 2 hydrogen atoms of benzene or biphenyl that may have a substituent are replaced with a chemical bond.
As Ar2Examples of the substituent in (3) include a halogen group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a group in which a hydrogen atom contained in these groups is substituted with a halogen atom.
The alkyl group having 1 to 12 carbon atoms may be a linear or branched alkyl group having 1 to 12 carbon atoms, and is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. Examples of such a group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-methyl-butyl, 3-methylbutyl, 2-ethyl-propyl, n-hexyl, n-heptyl, n-octyl, tert-octyl, n-nonyl, and n-decyl groups.
Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, a cyclohexyloxy group, and the like.
Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
As Ar2The substituent(s) in (1) is preferably a halogen group or an alkyl group having 1 to 12 carbon atoms in which a hydrogen atom may be substituted with a halogen atom, and more preferably a methyl group, a fluoro group, a chloro group or a trifluoromethyl group.
V in the formula (5) represents a single bond, -O-, diphenylmethylene, fluorenyl, linear, branched or alicyclic 2-valent hydrocarbon group having 1 to 12 carbon atoms, -SO2-、-S-、-CO-、-PO-、-PO2-、-N(Ra) -or-Si (R)b)2-. Here, the hydrogen atoms contained in the hydrocarbon group may be independent of each otherSubstituted by halogen atoms, RaAnd RbIndependently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a 2-methyl-butyl group, a 3-methylbutyl group, a 2-ethyl-propyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a tert-octyl group, an n-nonyl group, an n-decyl group, and the like, and these groups may be substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. From the viewpoint of easily improving the elastic modulus, the coefficient of humidity expansion, and the bending resistance of the optical film, V in formula (5) is preferably a single bond, -O-, or-S-, more preferably a single bond or-O-, and even more preferably a single bond.
In the formula (5), m represents an integer of 0 to 3, and is preferably 0 to 2, more preferably 0 or 1, and even more preferably 1, from the viewpoint of easily increasing the elastic modulus of the optical film and easily decreasing the coefficient of expansion due to humidity.
The structural unit (1) and the structural unit (3) contained in the polyamide resin contained in the optical film of the present invention each contain a 2-valent organic group represented by formula (5) as X1And X2In a preferred embodiment of the present invention, X in the formula (1) is X when the total of the structural unit (1) and the structural unit (3) contained in the polyamide resin is 100 mol%, from the viewpoint of easily increasing the elastic modulus of the optical film and easily reducing the coefficient of expansion due to humidity1Is a structural unit of a 2-valent organic group represented by formula (5) and X in formula (3)2The total proportion of the structural units of the 2-valent organic group represented by the formula (5) is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, and further preferably 90 to 100 mol%, and may be X in all the structural units of the structural unit (1) and the structural unit (3)1And X2Is a 2-valent organic group represented by the formula (5).
In a preferred embodiment of the present invention, from the viewpoint of easily increasing the elastic modulus of the optical film and easily decreasing the coefficient of expansion due to humidity, formula (5) is represented by formula (5 a).
[ chemical formula 23]
[ in the formula (5a), R2Represents a fluoroalkyl group having 1 to 12 carbon atoms,
p and q independently represent an integer of 1 to 4, wherein when p and/or q represents an integer of 2 to 4, a plurality of R exist2May be the same as, or different from,
denotes a chemical bond
In the formula (5a), V represents a single bond and Ar represents Ar in the formula (5)2Represents a fluoroalkyl group (R) having 1 to 12 carbon atoms2) A substituted benzene ring, m represents an integer of 0 to 3. The structural unit (1) and the structural unit (3) each contain a 2-valent organic group represented by the formula (5a) as X1And X2In the case of (1), the structural unit (1) and the structural unit (3) may each contain 1 or 2 or more of the 2-valent organic groups represented by the formula (5a) as X1And X2. In the structural unit (1) and the structural unit (3), X is1And X2In addition to the 2-valent organic group represented by formula (5a), other 2-valent organic groups that do not belong to the 2-valent organic group represented by formula (5a) may be contained.
R in the formula (5a)2Represents a fluoroalkyl group having 1 to 12 carbon atoms as the group, and Ar1The above description concerning the fluoroalkyl group having 1 to 12 carbon atoms in (A) is also applicable, and the preferable description is also applicable.
p and q independently represent an integer of 1 to 4. From the viewpoint of the elastic modulus and the coefficient of humidity expansion of the optical film, p is preferably an integer of 1 or 2, and more preferably 2. From the viewpoint of the elastic modulus and the coefficient of humidity expansion of the optical film, q is preferably an integer of 1 or 2, and more preferably 1. Here, when p and/or q represents an integer of 2 to 4, a plurality of R's are present2May be the same or different from each other, but in view of solubility in a solvent, a plurality of R's are present2Preferably identical to each other.
The 2 chemical bonds in the formula (5a) may be located at any of the ortho, meta, and para positions, but are preferably located at the para position from the viewpoint of easily increasing the elastic modulus of the optical film and easily decreasing the coefficient of moisture expansion.
Preferred examples of the 2-valent aromatic group represented by the formula (5a) include: r in the formula (5a)2An aromatic group having 1 to 12 carbon atoms, p is 2, q is 1 or 2, and/or 2 bonds are para to each other.
The structural unit (1) and the structural unit (3) contained in the polyamide resin contained in the optical film of the present invention each contain a 2-valent organic group represented by formula (5a) as X1And X2In a preferred embodiment of the present invention, X in the formula (1) is X when the total of the structural unit (1) and the structural unit (3) contained in the polyamide resin is 100 mol%, from the viewpoint of easily increasing the elastic modulus of the optical film and easily reducing the coefficient of expansion due to humidity1Is a structural unit of a 2-valent organic group represented by formula (5a) and X in formula (3)2The total proportion of the structural units of the 2-valent organic group represented by the formula (5a) is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, and further preferably 90 to 100 mol%, and may be X in all the structural units of the structural unit (1) and the structural unit (3)1And X2Is a 2-valent organic group represented by the formula (5 a).
In a preferred embodiment of the present invention, from the viewpoint of easily increasing the elastic modulus of the optical film and easily decreasing the coefficient of expansion due to humidity, the formula (5a) is represented by the formula (5 b).
[ chemical formula 24]
[ in the formula (5b), R7~R14Independently represent a hydrogen atom or a fluoroalkyl group having 1 to 12 carbon atoms, wherein R7~R14At least one of them is a fluoroalkyl group having 1 to 12 carbon atoms, and represents a chemical bond]
The formula (5b) corresponds to a formula which is an aromatic group in which the bonds in the formula (5a) are in para position and p is 2. In the formula (5b), R is preferably R from the viewpoint of easily increasing the elastic modulus of the optical film and easily decreasing the coefficient of expansion due to humidity7~R14At least two of them represent fluoroalkyl groups having 1 to 12 carbon atoms, more preferably at least R8And R14Represents a fluoroalkyl group having 1 to 12 carbon atoms, and more preferably R8And R14Represents a fluoroalkyl group having 1 to 12 carbon atoms and R7、R9、R10、R11、R12And R13Represents a hydrogen atom. In the above aspect, the fluoroalkyl group having 1 to 12 carbon atoms is preferably a perfluoroalkyl group having 1 to 12 carbon atoms, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, still more preferably a perfluoroalkyl group having 1 to 4 carbon atoms, yet still more preferably a trifluoromethyl group or a pentafluoroethyl group, and particularly preferably a trifluoromethyl group.
The structural unit (1) and the structural unit (3) contained in the polyamide resin contained in the optical film of the present invention each contain a 2-valent organic group represented by formula (5b) as X1And X2In a preferred embodiment of the present invention, X in the formula (1) is X when the total of the structural unit (1) and the structural unit (3) contained in the polyamide resin is 100 mol%, from the viewpoint of easily increasing the elastic modulus of the optical film and easily reducing the coefficient of expansion due to humidity1Is a structural unit of a 2-valent organic group represented by formula (5b) and X in formula (3)2The total proportion of the structural units of the 2-valent organic group represented by the formula (5b) is preferably 20 to 100 mol%, more preferably 30 to 100 mol%, and further preferably 40 to 100 mol%, and may be X in all the structural units of the structural unit (1) and the structural unit (3)1And X2Is a 2-valent organic group represented by the formula (5 b).
In a preferred embodiment of the present invention, formula (5b) is represented by formula (5 c).
[ chemical formula 25]
[ in the formula (5c), the symbol "x" represents a chemical bond ]
Since formula (5b) is a chemical formula included in formula (5a), formula (5a) may be represented by formula (5 c). The 2-valent organic group represented by the formula (5c) is represented by the formula (5b)9And R11Represents a trifluoromethyl group, and R7、R8、R10、R12、R13And R14A group corresponding to a 2-valent aromatic group which represents a hydrogen atom. The structural unit (1) and the structural unit (3) each contain a 2-valent organic group represented by the formula (5b) or the formula (5c) as X1And X2In the case of (1) and (3), X is the number1And X2The organic compound may contain 1 or 2 or more of the 2-valent organic groups represented by the formula (5b) or the formula (5c), or may contain other 2-valent organic groups other than the 2-valent organic groups represented by the formula (5b) or the formula (5c) in addition to the 2-valent organic groups represented by the formula (5b) or the formula (5 c).
The structural unit (1) and the structural unit (3) contained in the polyamide resin contained in the optical film of the present invention each contain a 2-valent organic group represented by formula (5c) as X1And X2In a preferred embodiment of the present invention, X in the formula (1) is X when the total of the structural unit (1) and the structural unit (2) contained in the polyamide resin is 100 mol%, from the viewpoint of easily increasing the elastic modulus of the optical film and easily reducing the coefficient of expansion due to humidity1Is a structural unit of a 2-valent organic group represented by formula (5c) and X in formula (3)2The total proportion of the structural units of the 2-valent organic group represented by the formula (5c) is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, and further preferably 90 to 100 mol%, and may be X in all the structural units of the structural unit (1) and the structural unit (3)1And X2Is a 2-valent organic group represented by the formula (5 c).
X in the above-described formula (1)1Description of the related Art with respect to X in formula (3a)3And X in the formula (3b)4The same applies. Wherein, X4Is combined ofNot X1A 2-valent organic group of (1). Here, X1When two or more kinds of them are used, one of them may be X1The other is X4。
The polyamide resin contained in the optical film of the present invention may contain a structural unit represented by formula (2) (hereinafter, also referred to as "structural unit (2)") in addition to the structural unit (1) and the structural unit (3).
[ chemical formula 26]
[ in the formula (2), X represents a 2-valent organic group and Y represents a 4-valent organic group ]
In this case, the polyamide resin is also referred to as a polyamideimide resin. In this embodiment, from the viewpoint of easily improving the elastic modulus of the optical film and easily reducing the coefficient of expansion due to humidity, the total proportion of the structural unit (1) and the structural unit (2) is preferably 60 mol% or more, more preferably 70 mol% or more, further preferably 80 mol% or more, further more preferably 85 mol% or more, and particularly preferably 90 mol% or more, when the total of the structural unit (1), the structural unit (2), and the structural unit (3) included in the polyamide resin is defined as 100 mol%. The upper limit of the above proportion of the total of the structural unit (1) and the structural unit (2) may be less than 100 mol%. The content of the structural unit (1), the structural unit (2) or the structural unit (3) may be, for example, the content1H-NMR, or the ratio of the raw materials charged may be calculated.
Y in the structural unit represented by the formula (2) represents a 4-valent organic group, preferably represents a 4-valent organic group having 4 to 40 carbon atoms, and more preferably represents a 4-valent organic group having a cyclic structure and having 4 to 40 carbon atoms. Examples of the cyclic structure include alicyclic, aromatic ring, and heterocyclic structure. The organic group is an organic group in which a hydrogen atom in the organic group may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group, and in this case, the number of carbon atoms in the hydrocarbon group and the fluorine-substituted hydrocarbon group is preferably 1 to 8. In one embodiment of the present invention, the structural unit (2) may have 1 kind of 4-valent organic group or 2 or more kinds of 4-valent organic groups as Y. Examples of Y may include groups represented by formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), formula (28) and formula (29); a group represented by the formulae (20) to (29) wherein a hydrogen atom is substituted with a methyl group, a fluoro group, a chloro group or a trifluoromethyl group; and a chain hydrocarbon group having a valence of 4 and 6 or less carbon atoms.
[ chemical formula 27]
In the formulae (20) to (29), the bond is represented by,
W1represents a single bond, -O-, -CH2-、-CH2-CH2-、-CH(CH3)-、-C(CH3)2-、-C(CF3)2-、-Ar3-、-SO2-、-CO-、-O-Ar3-O-、-Ar3-O-Ar3-、-Ar3-CH2-Ar3-、-Ar3-C(CH3)2-Ar3-or-Ar3-SO2-Ar3-。Ar3The arylene group having 6 to 20 carbon atoms, in which a hydrogen atom may be substituted with a fluorine atom, is exemplified by phenylene. Ar (Ar)3In case of plural, Ar3May be the same or different from each other.
Among the groups represented by formulae (20) to (29), the group represented by formula (26), formula (28), or formula (29) is preferable, and the group represented by formula (26) is more preferable, from the viewpoint of the elastic modulus, surface hardness, and bending resistance of the optical film. In addition, from the viewpoint of easily improving the elastic modulus, surface hardness and bending resistance of the optical film and easily lowering the YI value, W1Independently of one another, are preferably single bonds, -O-, -CH2-、-CH2-CH2-、-CH(CH3)-、-C(CH3)2-or-C (CF)3)2-, more preferably a single bond, -O-, -CH2-、-CH(CH3)-、-C(CH3)2-or-C (CF)3)2-is more preferably a single bond, -C (CH)3)2-or-C (CF)3)2-。
In a preferred embodiment of the present invention, the structural unit represented by formula (2) contains a 4-valent organic group represented by formula (6) as Y.
[ chemical formula 28]
[ in the formula (6), R18~R25Independently represent 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, R18~R25The hydrogen atoms contained in (a) may be substituted independently of each other by halogen atoms,
denotes a chemical bond
When the structural unit (2) contains a 4-valent organic group represented by formula (6) as Y, the elastic modulus of the optical film is easily increased, and the coefficient of humidity expansion is easily decreased. In this case, the solubility of the polyamide resin in the solvent is improved, the viscosity of the varnish containing the resin is easily reduced, and the processability of the optical film is easily improved. In addition, the optical characteristics of the optical film are easily improved.
In the formula (6), R18、R19、R20、R21、R22、R23、R24And R25Independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. As 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, Ar in the formula (5) is mentioned2Wherein the alkyl group having 1 to 12 carbon atoms, the alkoxy group having 1 to 6 carbon atoms or the aryl group having 6 to 12 carbon atoms is exemplified above. R18~R25Independently of each other, preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atomsPreferably represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, wherein R18~R25The hydrogen atoms contained in (a) may be substituted by halogen atoms independently of each other. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R is a group of elements which can easily increase the elastic modulus of the optical film, easily decrease the coefficient of expansion due to humidity, and easily improve the surface hardness, bending resistance and transparency18~R25Independently of each other, a hydrogen atom, a methyl group, a fluoro group, a chloro group or a trifluoromethyl group is more preferable, and R is further more preferable18、R19、R20、R23、R24And R25Is a hydrogen atom, R21And R22Is hydrogen, methyl, fluoro, chloro or trifluoromethyl, particularly preferably R21And R22Is methyl or trifluoromethyl.
In one preferred embodiment of the present invention in which the structural unit (2) contained in the polyamide resin contained in the optical film of the present invention contains a 4-valent organic group represented by formula (6) as Y, the proportion of the structural unit in which Y in formula (2) is the 4-valent organic group represented by formula (6) is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, and even more preferably 90 to 100 mol%, and Y in all the structural units of the structural unit (2) may be the 4-valent organic group represented by formula (6), when the total of the structural units (2) contained in the polyamide resin is 100 mol%, from the viewpoint of easily increasing the elastic modulus of the optical film and easily reducing the coefficient of humidity expansion.
In a preferred embodiment of the present invention, formula (6) is represented by formula (6 a).
[ chemical formula 29]
The formula (6a) corresponds to R in the formula (6)21And R22Is trifluoromethyl and R18、R19、R20、R23、R24And R25Is the chemical formula of hydrogen atom. Structural unit(2) When the 4-valent organic group represented by the formula (6a) is contained as Y, the elastic modulus of the optical film is easily increased, and the coefficient of humidity expansion is easily decreased. In this case, the solubility of the polyamide resin in the solvent is improved, the viscosity of the varnish containing the resin is easily reduced, and the processability of the optical film is easily improved. In addition, the optical characteristics of the optical film are easily improved.
In a preferred embodiment of the present invention in which the structural unit (2) contained in the polyamide resin contained in the optical film of the present invention contains a 4-valent organic group represented by formula (6a) as Y, the proportion of the structural unit in which Y in formula (2) is the 4-valent organic group represented by formula (6a) is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, even more preferably 90 to 100 mol%, and Y in all the structural units of the structural unit (2) may be the 4-valent organic group represented by formula (6a), when the total of the structural units (2) contained in the polyamide resin is 100 mol%, from the viewpoint of easily increasing the elastic modulus of the optical film and easily reducing the coefficient of humidity expansion.
The polyamide resin may contain a structural unit represented by formula (30) and/or a structural unit represented by formula (31) in addition to the structural units represented by formulae (1) and (2).
[ chemical formula 30]
In the formula (30), Y1Is a 4-valent organic group, preferably an organic group in which a hydrogen atom in the organic group may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. As Y1Examples thereof include groups described as Y in the formula (2). In one embodiment of the present invention, the polyamide-based resin may contain a plurality of Y' s1Plural kinds of Y1May be the same or different from each other.
In the formula (31), Y2Is a 3-valent organic group, preferably an organic group in which a hydrogen atom in the organic group may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. As Y2Examples thereof may include a group represented by Y in the formula (2)A group obtained by replacing any one of the chemical bonds of the group with a hydrogen atom, and a chain hydrocarbon group having 3-valent carbon atoms of 6 or less. In one embodiment of the present invention, the polyamide-based resin may contain a plurality of Y' s2Plural kinds of Y2May be the same or different from each other.
In the formulae (30) and (31), X1And X2Independently of one another, are 2-valent organic groups, preferably organic groups in which the hydrogen atoms of the organic groups can be replaced by hydrocarbon groups or fluorine-substituted hydrocarbon groups. As X1And X2Examples of the "X" in the formulae (1) and (2)1And X2The groups described above.
In one embodiment of the present invention, the polyamide resin is formed from a structural unit represented by formula (1), a structural unit represented by formula (2), and, if necessary, a structural unit represented by formula (3), a structural unit represented by formula (30), and/or a structural unit represented by formula (31). In the polyamide resin, the structural unit represented by formula (1) and formula (2) is preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more, based on all the structural units represented by formula (1) and formula (2) and, if included, formula (3), formula (30), and formula (31), from the viewpoint of easily improving the elastic modulus of the optical film, easily reducing the coefficient of moisture expansion, and easily improving the optical characteristics, surface hardness, and bending resistance. In the polyamide resin, the structural units represented by the formulae (1) and (2) are usually 100% or less based on all the structural units represented by the formulae (1) and (2) and, if necessary, the formulae (3), (30) and/or (31). The above ratio can be used, for example1H-NMR, or the ratio of the raw materials charged may be calculated.
In one embodiment of the present invention, the content of the polyamide resin in the optical film is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, preferably 99.5 parts by mass or less, and more preferably 95 parts by mass or less, per 100 parts by mass of the optical film. When the content of the polyamide resin is within the above range, the optical properties and the elastic modulus of the optical film are easily improved, and the coefficient of expansion due to humidity is easily reduced.
The polyamide resin has a weight average molecular weight (Mw) of 200,000 to 1,000,000 in terms of standard polystyrene. When the weight average molecular weight (Mw) of the polyamide resin is less than 200,000, the elastic modulus of the optical film cannot be sufficiently increased or the coefficient of expansion due to humidity cannot be sufficiently reduced. When the weight average molecular weight (Mw) of the polyamide resin exceeds 1,000,000, the solubility of the polyamide resin in a solvent is lowered, and the optical film is not easily processed. The weight average molecular weight (Mw) of the polyamide resin is preferably 220,000 or more, more preferably 250,000 or more, further preferably 270,000 or more, and particularly preferably 300,000 or more in terms of standard polystyrene, from the viewpoint of easily improving the elastic modulus, surface hardness, and bending resistance of the optical film and easily reducing the coefficient of expansion under humidity of the optical film. In addition, the weight average molecular weight of the polyamide resin is preferably 900,000 or less, more preferably 800,000 or less, further preferably 700,000 or less, and particularly preferably 600,000 or less, from the viewpoint of easily improving the solubility of the resin in a solvent and easily improving the stretchability and processability of the optical film. The weight average molecular weight can be determined by GPC measurement and conversion to standard polystyrene, for example, and can be calculated by the method described in examples.
From the viewpoint of easily preventing scratches and the like of the optical film, the elastic modulus of the optical film of the present invention is preferably 4GPa or more, more preferably 4.5GPa or more, further preferably 4.8GPa or more, and usually 100GPa or less. The elastic modulus can be measured using a tensile tester (the distance between chucks is 50mm, and the tensile speed is 10 mm/min), and can be measured, for example, by the method described in examples.
The coefficient of humidity expansion (hereinafter sometimes referred to as CME) of the optical film of the present invention is preferably 23ppm or less, more preferably 22ppm or less, further preferably 21ppm or less, and particularly preferably 20ppm or less, from the viewpoint of easily suppressing the expansion and contraction in the planar direction of the optical film when the temperature and humidity change occurs in a state where a load is applied to the optical film. The smaller the humidity expansion coefficient, the easier it is to suppress the expansion and contraction in the plane direction of the optical film when the temperature and humidity change in a state where a load is applied to the optical film, and the lower limit thereof is not particularly limited and may be 0ppm or more. The CME may be the coefficient of humidity expansion of the film when it is held for 1 hour at 60 ℃ and 90% r.h., and may be measured, for example, by the method described in examples.
The optical film of the present invention has a total light transmittance and/or a light transmittance with respect to light of 300 to 800nm of preferably 80% or more, more preferably 85% or more, further preferably 90% or more, particularly preferably 91% or more, and usually 100% or less. When the total light transmittance is not less than the lower limit, visibility is easily improved when the optical film, particularly, the front panel is incorporated into a display device. The optical film of the present invention generally exhibits a high total light transmittance, and therefore, for example, the light emission intensity of a display element or the like required to obtain a certain luminance can be suppressed as compared with the case of using a film having a low transmittance. Therefore, power consumption can be reduced. For example, when the optical film of the present invention is incorporated into a display device, bright display tends to be obtained even when the amount of light from a backlight is reduced, and this contributes to energy saving. The total light transmittance may be, for example, a value in accordance with JIS K7361-1: 1997. the haze was determined using a haze computer. The total light transmittance may be a total light transmittance within a range of a thickness of an optical film to be described later.
The haze of the optical film of the present invention is preferably 5% or less, more preferably 4% or less, further preferably 3% or less, further more preferably 2.5% or less, particularly preferably 2% or less, particularly preferably 1% or less, particularly preferably 0.5% or less, particularly preferably 0.2% or less, and usually 0.01% or more. When the haze of the optical film is not more than the above upper limit, the visibility is easily improved when the optical film is incorporated into a display device, particularly as a front panel. The haze may be measured according to JIS K7136: 2000. the haze was determined using a haze computer.
The YI value of the optical film of the present invention is preferably 3.5 or less, more preferably 3.0 or less, further preferably 2.5 or less, and usually-5 or more, preferably-2 or more. When the YI value of the optical film is not more than the above upper limit, the transparency becomes good, and when the optical film is applied to a front panel of a display device, high visibility can be contributed. The YI value can be calculated based on the formula of YI × (1.2769X-1.0592Z)/Y by measuring the transmittance to light of 300 to 800nm using an ultraviolet-visible near-infrared spectrophotometer to obtain the tristimulus value (X, Y, Z). In the present specification, the optical film having excellent optical properties means a high light transmittance.
The thickness of the optical film of the present invention is preferably 10 μm or more, more preferably 20 μm or more, further preferably 25 μm or more, particularly preferably 30 μm or more, preferably 200 μm or less, more preferably 100 μm or less, further preferably 80 μm or less, particularly preferably 60 μm or less, and may be a combination of these upper and lower limits. When the thickness of the optical film is within the above range, the elastic modulus of the optical film is more easily increased. The thickness of the optical film can be measured using a micrometer, and can be measured, for example, by the method described in examples.
The optical film of the present invention is preferably bent 150,000 times or more (bend radius R ═ 1mm) in a bending resistance test, more preferably 180,000 times or more, and still more preferably 200,000 times or more. When the number of times of bending is not less than the above lower limit, the sheet has sufficient bending resistance as a front panel material of a flexible display device or the like. The number of bending times in the bending resistance test is represented by: the optical film was repeatedly bent using a bending tester with a bending radius (curvature radius) R of 1mm, and the number of bending cycles until the film broke was repeated (1 round trip was defined as 1 round trip).
The pencil hardness of at least one surface of the optical film of the present invention is preferably H or more, and more preferably 2H or more. When the pencil hardness of at least one surface of the optical film is equal to or higher than the above hardness, damage or the like on the surface of the optical film can be easily prevented. The pencil hardness may be measured in accordance with JIS K5600-5-4: 1999, it can be measured, for example, by the method described in examples.
The present invention provides an optical film comprising the above polyamide resin, and also provides the above polyamide resin suitable for producing the optical film. The polyamide resin may be, for example, a polyamide resin having a weight average molecular weight of 200,000 to 1,000,000, and the polyamide resin has at least: an aromatic group represented by formula (1) and containing formula (4) as Ar in formula (1)1And a structural unit represented by formula (3).
[ chemical formula 31]
[ formula (1) wherein Ar is1Represents a 2-valent aromatic group having a fluoroalkyl group having 1 to 12 carbon atoms,
X1represents a 2-valent organic group]
[ chemical formula 32]
[ in formula (4), R1Represents a fluoroalkyl group having 1 to 12 carbon atoms,
n and k independently represent an integer of 1 to 4, wherein when n and/or k represent an integer of 2 to 4, a plurality of R exist1May be the same as, or different from,
represents a chemical bond ]
[ chemical formula 33]
[ in the formula (3), Z1Represents Ar1Or means other than Ar1A 2-valent organic radical of (A), Ar1As defined in the formula (1),
X2represents a valence of 2An organic radical, wherein in Z1Represents Ar1In the case of (1), X1And X in formula (3)2Are different from each other]
The above description concerning the polyamide resin contained in the optical film of the present invention applies similarly to the examples and preferred embodiments of the kind of each symbol and the ratio of the structural unit in the polyamide resin.
The content of the halogen atom in the polyamide resin is preferably 1 to 60% by mass, more preferably 5 to 55% by mass, and still more preferably 10 to 50% by mass, based on the mass of the polyamide resin. When the content of the halogen atom is not less than the above lower limit, the elastic modulus of the optical film is easily increased, the coefficient of humidity expansion is easily decreased, and the transparency and the visibility are more easily improved. When the content of the halogen atom is not more than the above upper limit, the synthesis of the resin becomes easy.
When the polyamide resin of the present invention is a polyamide-imide resin having the structural unit (2), the imidization ratio of the resin is preferably 90% or more, more preferably 93% or more, further preferably 96% or more, and usually 100% or less. The imidization ratio is preferably not less than the above-described lower limit from the viewpoint of easily improving the optical properties of the optical film. The imidization ratio represents a ratio of a molar amount of imide bonds in the polyamide resin to a value 2 times a molar amount of structural units derived from a tetracarboxylic acid compound in the polyamide resin. When the polyamide resin contains a tricarboxylic acid compound, the molar ratio of the imide bond in the polyamide resin is represented by a value 2 times the molar amount of the structural unit derived from the tetracarboxylic acid compound in the polyamide resin and the total molar amount of the structural unit derived from the tricarboxylic acid compound. The imidization ratio can be determined by an IR method, an NMR method or the like.
< method for producing resin >
The polyamide resin can be produced, for example, from a dicarboxylic acid compound and a diamine compound as main raw materials. Here, the structural units represented by the above formulae (1) and (3) are structural units formed by reacting a dicarboxylic acid compound with a diamine compound. Therefore, the polyamide resin can be produced using a dicarboxylic acid compound and a diamine compound which form the structural units represented by the above formulae (1) and (3).
The structural unit represented by the formula (2) which the polyamide resin of the present invention optionally has is a structural unit formed by reacting a tetracarboxylic acid compound with a diamine compound. Therefore, in this case, the polyamide resin can be produced by further using a tetracarboxylic acid compound and a diamine compound which form the structural unit represented by the above formula (2).
From this viewpoint, the dicarboxylic acid compound preferably contains at least the compound represented by formula (8).
[ chemical formula 34]
[ formula (8) wherein Ar is1As for Ar in formula (1)1As is defined herein, the term "a", "an", "the" or "the" is intended to mean,
Rcand RdIndependently of one another, represents a hydroxyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group or a chlorine atom.]
In a preferred embodiment of the present invention, the dicarboxylic acid compound is RcAnd RdA compound represented by the formula (8) which is a chlorine atom. In addition, a diisocyanate compound may be used instead of the diamine compound.
As the dicarboxylic acid compound that can be used for producing the resin, it is preferable to use an aromatic dicarboxylic acid having a fluoroalkyl group or an acid chloride compound thereof, for example, terephthalic acid having a fluoroalkyl group, 4' -oxybis benzoic acid or an acid chloride compound thereof. In addition to terephthalic acid, 4' -oxybis-benzoic acid or their acid chloride compounds, other dicarboxylic acid compounds may also be used. Examples of the other dicarboxylic acid compound include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and their analogous acid chloride compounds and acid anhydrides, and 2 or more of them may be used in combination. Specific examples thereof include aromatic dicarboxylic acid compounds having a trifluoromethyl group (isophthalic acid; naphthalenedicarboxylic acid; 4,4 '-biphenyldicarboxylic acid; 3, 3' -biphenyldicarboxylic acid), compounds in which 2 benzoic acids having a trifluoromethyl group are linked by a single bond or a phenylene group, and acid chloride compounds thereof. Specific examples thereof include 2,2 '-bis (trifluoromethyl) -4, 4' -biphenyldicarbonyl chloride and 2, 5-bis (trifluoromethyl) terephthaloyl chloride.
As the dicarboxylic acid compound, a compound represented by the formula (8) and other dicarboxylic acid compounds can be used. As the other dicarboxylic acid compound, a dicarboxylic acid compound represented by the formula (7') can be mentioned.
[ chemical formula 35]
[ formula (7') wherein R31~R38Independently represent 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, R31~R38The hydrogen atoms contained in (a) may be substituted independently of each other by halogen atoms,
a represents a single bond, -O-, -CH2-、-CH2-CH2-、-CH(CH3)-、-C(CH3)2-、-C(CF3)2-、-SO2-, -S-, -CO-or-N (R)39)-,
R39Represents a hydrogen atom, a C1-valent hydrocarbon group which may be substituted with a halogen atom and has 1 to 12 carbon atoms,
s is an integer of 0 to 4,
Rcand RdAs for R in formula (8)cAnd RdAs defined in]
In one embodiment of the present invention, the other dicarboxylic acid compound may be a compound represented by formula (7') wherein s is 1 to 4 and A is an oxygen atom.
Examples of the diamine compound that can be used for producing the resin include aliphatic diamines, aromatic diamines, and mixtures thereof. In the present embodiment, the "aromatic diamine" refers to a diamine in which an amino group is directly bonded to an aromatic ring, and may contain an aliphatic group or other substituent in a part of the structure. The aromatic ring may be a monocyclic ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring, but are not limited thereto. Among these, benzene rings are preferred. The "aliphatic diamine" refers to a diamine in which an amino group is directly bonded to an aliphatic group, and may contain an aromatic ring or other substituent in a part of the structure.
Examples of the aliphatic diamine include acyclic aliphatic diamines such as 1, 6-hexamethylenediamine, and cyclic aliphatic diamines such as 1, 3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane, norbornanediamine, and 4, 4' -diaminodicyclohexylmethane. These may be used alone or in combination of 2 or more.
Examples of the aromatic diamine include aromatic diamines having 1 aromatic ring such as p-phenylenediamine, m-phenylenediamine, 2, 4-tolylenediamine, m-xylylenediamine, p-xylylenediamine, 1, 5-diaminonaphthalene and 2, 6-diaminonaphthalene, 4 ' -diaminodiphenylmethane, 4 ' -diaminodiphenylpropane, 4 ' -diaminodiphenyl ether, 3 ' -diaminodiphenyl ether, 4 ' -diaminodiphenyl sulfone, 3 ' -diaminodiphenyl sulfone, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl ] sulfone, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, 1, 5-diaminonaphthalene, 2, 6-diaminonaphthalene, etc., 4 ' -diaminodiphenyl methane, 4 ' -diaminodiphenyl propane, 4 ' -diaminodiphenyl ether, 3,4 ' -diaminodiphenyl ether, 4-diaminodiphenyl sulfone, 3 ' -diaminodiphenyl sulfone, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-amino-phenoxy) benzene, bis (4-phenylene) sulfone, bis (4-phenylene) benzene, bis (4-phenylene) benzene, bis (bis) benzene) sulfone, bis (4-phenylene) benzene, bis (4-phenylene) benzene, bis (p) benzene, bis (4-phenylene) benzene, bis (p-phenylene) benzene, bis (2, bis (p-phenylene) benzene, 2, bis (p-phenylene) benzene, 2, bis (p-phenylene) benzene, bis (p-phenylene) benzene, 2, bis (bis) benzene, 2, bis (p) benzene, 2, bis (p-phenylene) benzene, Bis [4- (3-aminophenoxy) phenyl ] sulfone, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (3-aminophenoxy) phenyl ] propane, 2 ' -dimethylbenzidine, 2 ' -bis (trifluoromethyl) -4,4 ' -diaminobiphenyl (sometimes referred to as TFMB), aromatic diamines having 2 or more aromatic rings, such as 4, 4' -bis (4-aminophenoxy) biphenyl, 9-bis (4-aminophenyl) fluorene, 9-bis (4-amino-3-methylphenyl) fluorene, 9-bis (4-amino-3-chlorophenyl) fluorene, and 9, 9-bis (4-amino-3-fluorophenyl) fluorene. These may be used alone or in combination of 2 or more.
The aromatic diamine is preferably 4,4 ' -diaminodiphenylmethane, 4 ' -diaminodiphenylpropane, 4 ' -diaminodiphenylether, 3 ' -diaminodiphenylether, 4 ' -diaminodiphenylsulfone, 3 ' -diaminodiphenylsulfone, 1, 4-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] sulfone, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (3-aminophenoxy) phenyl ] propane, 2 ' -dimethylbenzidine, 2 ' -bis (trifluoromethyl) -4,4 ' -diaminobiphenyl (TFMB), 4,4 ' -bis (4-aminophenoxy) biphenyl, more preferably 4,4 ' -diaminodiphenylmethane, 4 ' -diaminodiphenylpropane, 4 ' -diaminodiphenyl ether, 4 ' -diaminodiphenylsulfone, 1, 4-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl ] sulfone, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2 ' -dimethylbenzidine, 2 ' -bis (trifluoromethyl) -4,4 ' -diaminobiphenyl (TFMB), 4 ' -bis (4-aminophenoxy) biphenyl. These may be used alone or in combination of 2 or more.
Among the diamine compounds, 1 or more selected from the group consisting of aromatic diamines having a biphenyl structure are preferably used from the viewpoints of high surface hardness, high transparency, high flexibility, high bending resistance, and low coloring of the optical film. More preferably, 1 or more selected from the group consisting of 2,2 '-dimethylbenzidine, 2' -bis (trifluoromethyl) benzidine, 4 '-bis (4-aminophenoxy) biphenyl, and 4, 4' -diaminodiphenyl ether is used, and still more preferably, 2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl (TFMB) is used.
When a tetracarboxylic acid compound is used for producing the resin, examples of the tetracarboxylic acid compound include aromatic tetracarboxylic acid compounds such as aromatic tetracarboxylic dianhydride; and aliphatic tetracarboxylic acid compounds such as aliphatic tetracarboxylic dianhydride. The tetracarboxylic acid compound may be used alone or in combination of 2 or more. The tetracarboxylic acid compound may be a tetracarboxylic acid compound analog such as an acid chloride compound, in addition to the dianhydride.
Specific examples of the aromatic tetracarboxylic dianhydride include non-condensed polycyclic aromatic tetracarboxylic dianhydrides, monocyclic aromatic tetracarboxylic dianhydrides, and condensed polycyclic aromatic tetracarboxylic dianhydrides. Examples of the non-condensed polycyclic aromatic tetracarboxylic acid dianhydride include 4,4 ' -oxydiphthalic anhydride (4,4 ' -oxydiphthalic dianhydride), 3,3 ', 4,4 ' -benzophenonetetracarboxylic acid dianhydride, 2 ', 3,3 ' -benzophenonetetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -biphenyltetracarboxylic acid dianhydride, 2 ', 3,3 ' -biphenyltetracarboxylic acid dianhydride, 3,3 ', 4,4 ' -diphenylsulfonetetracarboxylic acid dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenoxyphenyl) propane dianhydride, 4,4 ' - (hexafluoroisopropylidene) diphthalic anhydride (4,4 ' - (hexafluoroisopropylidene) dicarboxylic anhydride, which is sometimes referred to as 6FDA), 1, 2-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1, 2-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, 4 ' - (p-phenylenedioxy) diphthalic anhydride, 4 ' - (m-phenylenedioxy)) diphthalic anhydride. Examples of the monocyclic aromatic tetracarboxylic acid dianhydride include 1,2,4, 5-benzenetetracarboxylic acid dianhydride, and examples of the condensed polycyclic aromatic tetracarboxylic acid dianhydride include 2,3,6, 7-naphthalenetetracarboxylic acid dianhydride.
Of these, preferred examples include 4,4 '-oxydiphthalic anhydride, 3, 3', 4,4 '-benzophenonetetracarboxylic dianhydride, 2', 3,3 '-benzophenonetetracarboxylic dianhydride, 3, 3', 4,4 '-biphenyltetracarboxylic dianhydride, 2', 3,3 '-biphenyltetracarboxylic dianhydride, 3, 3', 4,4 '-diphenylsulfonetetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenoxyphenyl) propane dianhydride, 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA), 1, 2-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1, 2-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, 4,4 '- (terephthaloxy) bisphthalic anhydride and 4, 4' - (m-phenylenedioxy) bisphthalic anhydride, more preferably 4,4 '-oxydiphthalic anhydride, 3, 3', 4,4 '-biphenyltetracarboxylic dianhydride, 2', 3,3 '-biphenyltetracarboxylic dianhydride, 4, 4' - (hexafluoroisopropylidene) bisphthalic anhydride (6FDA), bis (3, 4-dicarboxyphenyl) methane dianhydride and 4, 4' - (p-phenylenedioxy) diphthalic anhydride. These may be used alone or in combination of 2 or more.
Examples of the aliphatic tetracarboxylic dianhydride include cyclic and acyclic aliphatic tetracarboxylic dianhydrides. The cyclic aliphatic tetracarboxylic dianhydride is a tetracarboxylic dianhydride having an alicyclic hydrocarbon structure, and specific examples thereof include cycloalkanetetracarboxylic dianhydrides such as 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, 1,2,3, 4-cyclobutanetetracarboxylic dianhydride and 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, dicyclohexyl-3, 3 ', 4, 4' -tetracarboxylic dianhydride and positional isomers thereof. These may be used alone or in combination of 2 or more. Specific examples of the acyclic aliphatic tetracarboxylic acid dianhydride include 1,2,3, 4-butanetetracarboxylic acid dianhydride, and 1,2,3, 4-pentanedicarboxylic acid dianhydride, and these can be used alone or in combination of 2 or more. In addition, a cyclic aliphatic tetracarboxylic dianhydride and an acyclic aliphatic tetracarboxylic dianhydride may be used in combination.
Among the tetracarboxylic dianhydrides, from the viewpoint of high surface hardness, high transparency, high flexibility, high bending resistance, and low coloring property of the optical film, 4,4 ' -oxydiphthalic dianhydride, 3,3 ', 4,4 ' -benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 ' -biphenyl tetracarboxylic dianhydride, 2 ', 3,3 ' -biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 ' -diphenylsulfone tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 4,4 ' - (hexafluoroisopropylidene) diphthalic anhydride, and mixtures thereof are preferable, and 3,3 ', 4,4 ' -biphenyl tetracarboxylic dianhydride and 4,4 ' - (hexafluoroisopropylidene) diphthalic anhydride, and mixtures thereof are more preferable, further preferred is 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA).
The polyamide resin may be a product obtained by further reacting tetracarboxylic acid, tricarboxylic acid, and their anhydrides and derivatives in addition to the tetracarboxylic acid compound, within a range that does not impair various physical properties of the optical laminate.
Examples of the tetracarboxylic acid include water adducts of anhydrides of the above tetracarboxylic acid compounds.
Examples of the tricarboxylic acid compound include an aromatic tricarboxylic acid, an aliphatic tricarboxylic acid, and a similar acid chloride compound or acid anhydride thereof, and 2 or more kinds thereof may be used in combination. Specific examples thereof include anhydrides of 1,2, 4-benzenetricarboxylic acid; 2,3, 6-naphthalene tricarboxylic acid-2, 3-anhydride; phthalic anhydride and benzoic acid through single bond, -O-, -CH2-、-C(CH3)2-、-C(CF3)2-、-SO2-or phenylene groups.
In the production of the resin, the amount of the diamine compound and the dicarboxylic acid compound used, and the amount of the tetracarboxylic acid compound used in some cases, may be appropriately selected depending on the ratio of each structural unit of the desired polyamide resin.
In the production of the resin, the reaction temperature of the diamine compound, the dicarboxylic acid compound and, optionally, the tetracarboxylic acid compound is not particularly limited, and is, for example, 5 to 350 ℃, preferably 5 to 200 ℃, and more preferably 5 to 100 ℃. The reaction time is also not particularly limited, and is, for example, about 30 minutes to 10 hours. If necessary, the reaction may be carried out in an inert atmosphere or under reduced pressure. In a preferred embodiment, the reaction is carried out under normal pressure and/or in an inert gas atmosphere while stirring. In addition, the reaction is preferably carried out in a solvent which is inactive to the reaction. The solvent is not particularly limited as long as it does not affect the reaction, and examples thereof include alcohol solvents such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ -butyrolactone, γ -valerolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; 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 solvents such as chloroform and chlorobenzene; amide solvents such as N, N-dimethylacetamide and N, N-dimethylformamide; sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide and sulfolane; carbonate solvents such as ethylene carbonate and propylene carbonate; combinations thereof, and the like. Among these, an amide solvent is preferably used from the viewpoint of solubility.
In the case of producing a polyamide resin (polyamideimide resin) which has a structural unit (2) in addition to the structural unit (1) and the structural unit (3) and has a weight average molecular weight of 200,000 to 1,000,000, the production method is not particularly limited as long as the polyamideimide resin described above can be obtained, and from the viewpoint of easily improving the elastic modulus of an optical film and easily reducing the coefficient of expansion due to humidity, it is preferable to produce a polyamideimide resin by a production method in which a dicarboxylic acid compound is added in portions and a diamine compound, a tetracarboxylic acid compound and a dicarboxylic acid compound are reacted; the polyamide resin is preferably produced by a method comprising a step (I) of reacting a diamine compound with a tetracarboxylic acid compound to produce an intermediate (a), and a step (II) of reacting the intermediate (a) with a dicarboxylic acid compound (preferably a compound represented by formula (8)), wherein the dicarboxylic acid compound is added in portions in the step (II).
The polyamide resin contained in the optical film of the present invention is considered to be due to Ar in the above formula (1)1The aromatic group has a valence of 2 and has a fluoroalkyl group having 1-12 carbon atoms, so that a specific part in the skeleton of the polyamide resin has appropriate rigidity and intermolecular repulsion. When a polyamide resin having such a structure is produced without using a method of adding a dicarboxylic acid compound in a batch manner, it may be difficult to control the weight average molecular weight of the polyamide resin to be within the above range. In addition, the preparation is carried out by using a method of adding in batchesAlthough not clear, it is considered that a resin which is most suitable for increasing the elastic modulus of an optical film and reducing the coefficient of expansion due to humidity can be obtained.
Therefore, the polyamide resin contained in the optical film of the present invention and the polyamide resin of the present invention are preferably resins obtained by a production method in which a dicarboxylic acid compound is added in portions and a diamine compound and a tetracarboxylic acid compound are reacted with each other, and more preferably resins obtained by a production method in which a dicarboxylic acid compound is added in portions and a process (II) in which a diamine compound and a tetracarboxylic acid compound are reacted with each other to form an intermediate (a) and a dicarboxylic acid compound (preferably a compound represented by formula (8)) is added in portions in the process (II). When a polyamideimide resin having at least the structural unit (1), the structural unit (2) and the structural unit (3) and having a weight average molecular weight of 200,000 to 1,000,000 is produced by a production method including a step of adding a dicarboxylic acid compound in a batch manner, the weight average molecular weight of the polyamide resin can be easily adjusted to fall within the above range.
When the polyamideimide resin is produced by the production method including the above-mentioned step (I) and step (II), the reaction temperature of the step (I) of reacting the diamine compound with the tetracarboxylic acid compound to produce the intermediate (a) is not particularly limited, and may be, for example, 5 to 200 ℃, preferably 5 to 100 ℃, more preferably 5 to 50 ℃, and further preferably 5 to room temperature (about 25 ℃). The reaction time may be, for example, 1 minute to 72 hours, preferably 10 minutes to 24 hours. The reaction may be carried out in air or an inert gas atmosphere such as nitrogen or argon while stirring, or may be carried out under normal pressure, increased pressure or reduced pressure. In a preferred embodiment, the stirring is carried out under normal pressure and/or under the inert gas atmosphere.
In the step (I), the diamine compound reacts with the tetracarboxylic acid compound to produce the intermediate (a), i.e., polyamic acid. Therefore, the intermediate (a) has at least a structural unit derived from a diamine compound and a structural unit derived from a tetracarboxylic acid compound.
Next, in the step (II), the intermediate (a) is reacted with a dicarboxylic acid compound, and here, the dicarboxylic acid compound is preferably added in portions. The intermediate (a) is reacted with a dicarboxylic acid compound by adding the dicarboxylic acid compound to the reaction solution obtained in the step (I) in portions. The addition of the dicarboxylic acid compound in portions rather than at once makes it easy to increase the molecular weight of the polyamide resin. In the present specification, the batch addition means: the dicarboxylic acid compound to be added is added in several portions, and more specifically, the dicarboxylic acid to be added is divided into specific amounts and added separately at predetermined intervals (predetermined time). The prescribed interval (prescribed time) also includes a very short interval (or time), and therefore the batch addition also includes continuous addition (or continuous feeding).
In the step (II), the number of times of addition of the dicarboxylic acid compound in portions may be appropriately selected depending on the scale of the reaction, the kind of the raw material, and the like, and is preferably 2 to 20 times, more preferably 3 to 10 times, and still more preferably 3 to 6 times. When the number of times of the batch is within the above range, the molecular weight of the polyamide resin is easily increased.
The dicarboxylic acid compound may be added in an equal amount or in an unequal amount. The time between each addition (sometimes referred to as the addition interval) may be the same or different. In addition, in the case of adding two or more dicarboxylic acid compounds, the term "adding in portions" means adding all the dicarboxylic acid compounds in portions, and the method of adding the dicarboxylic acid compounds in portions is not particularly limited, and for example, the dicarboxylic acid compounds may be added together or in portions, or the dicarboxylic acid compounds may be added in portions, or a combination thereof.
In the step (II), the dicarboxylic acid compound is preferably added in an amount of 1 to 40 mol%, more preferably 2 to 25 mol%, based on the total molar amount of the dicarboxylic acid compound to be added, when the weight average molecular weight of the polyamide resin is preferably 10% or more, more preferably 15% or more, based on the weight average molecular weight of the polyamide resin to be obtained.
The reaction temperature in the step (II) is not particularly limited, and may be, for example, 5 to 200 ℃, preferably 5 to 100 ℃, more preferably 5 to 50 ℃, and still more preferably 5 ℃ to room temperature (about 25 ℃). The reaction may be carried out in air or an inert gas atmosphere such as nitrogen or argon while stirring, or may be carried out under normal pressure, increased pressure or reduced pressure. In a preferred embodiment, the step (II) is performed under normal pressure and/or under the inert gas atmosphere while stirring.
In the step (II), the dicarboxylic acid compound is added in portions, and then the mixture is reacted by stirring for a predetermined time, whereby a polyamideimide precursor can be obtained. The polyamideimide precursor may be isolated, for example, by: the polyamideimide precursor is precipitated by adding a large amount of water or the like to a reaction solution containing the polyamideimide precursor, followed by filtration, concentration, drying, and the like.
In the step (II), the intermediate (a) is reacted with a dicarboxylic acid compound to obtain a polyamideimide precursor. Accordingly, the polyamideimide precursor means a polyamideimide having at least a structural unit derived from a diamine compound, a structural unit derived from a tetracarboxylic acid, and a structural unit derived from a dicarboxylic acid compound before imidization (before ring closure).
In the case of producing a polyamide resin further having the structural unit (2), the method for producing a polyamide resin may further include an imidization step (III) of imidizing the polyamide imide precursor in the presence of an imidization catalyst. By subjecting the polyamideimide precursor obtained in the step (II) to the step (III), a structural unit having a polyamic acid structure in a structural unit of the polyamideimide precursor is partially imidized (ring-closed), and a polyamide resin including a structural unit represented by the formula (1), a structural unit represented by the formula (2), and a structural unit represented by the formula (3) can be obtained. In the imidization step, imidization may be performed in the presence of an imidization catalyst. Examples of the imidization catalyst include aliphatic amines such as tripropylamine, dibutylpropylamine, and ethyldibutylamine; n-ethylpiperidine, N-propylpiperidine, N-butylpyrrolidine, N-butylpiperidine, and N-propylhexahydroazepinoAlicyclic amines (monocyclic); azabicyclo [2.2.1]Heptane, azabicyclo [3.2.1]Octane, azabicyclo [2.2.2]Octane, and azabicyclo [3.2.2]Alicyclic amines (polycyclic) such as nonane; and aromatic amines such as 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, 8-tetrahydroisoquinoline, and isoquinoline. In addition, from the viewpoint of facilitating the imidization reaction, it is preferable to use an acid anhydride together with an imidization catalyst. Examples of the acid anhydride include conventional acid anhydrides usable in the imidization reaction, 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.
The polyamide resin can be separated by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, and column chromatography, or separation and purification means combining these, and in a preferred embodiment, the separation can be performed by: a large amount of alcohol such as methanol is added to a reaction solution containing a polyamide resin to precipitate the resin, and the resin is concentrated, filtered, dried, and the like.
< Filler >
The optical film of the present invention may comprise at least 1 filler. Examples of the filler include organic particles and inorganic particles, and preferably inorganic particles. The inorganic particles include metal oxide particles such as silica, zirconia, alumina, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide, and metal fluoride particles such as magnesium fluoride and sodium fluoride, and among these, silica particles, zirconia particles, and alumina particles are preferable from the viewpoint of easily improving the elastic modulus and/or tear strength of the optical film and easily improving the impact resistance, and silica particles are more preferable. These fillers may be used alone or in combination of 2 or more.
The average primary particle diameter of the filler, preferably the silica particles, is usually 1nm or more, preferably 5nm or more, more preferably 10nm or more, further preferably 15nm or more, particularly preferably 20nm or more, preferably 100nm or less, more preferably 90nm or less, further preferably 80nm or less, further preferably 70nm or less, particularly preferably 60nm or less, particularly preferably 50nm or less, and particularly preferably 40nm or less. When the average primary particle size of the silica particles is within the above range, aggregation of the silica particles is easily suppressed, and the optical properties of the obtained optical film are easily improved. The average primary particle diameter of the filler can be measured by the BET method. The average primary particle size may be measured by image analysis using a transmission electron microscope or a scanning electron microscope.
When the optical film of the present invention contains a filler, preferably silica particles, the content of the filler is usually 0.1 part by mass or more, preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, further preferably 20 parts by mass or more, particularly preferably 30 parts by mass or more, and preferably 60 parts by mass or less, per 100 parts by mass of the optical film. When the content of the filler is not less than the above lower limit, the elastic modulus of the optical film to be obtained is easily increased. When the content of the filler is not more than the upper limit, the optical properties of the optical film are easily improved.
< ultraviolet absorber >
The optical film of the present invention may comprise at least 1 ultraviolet absorber. The ultraviolet absorber can be appropriately selected from those generally used as ultraviolet absorbers in the field of resin materials. The ultraviolet absorber may contain a compound that absorbs light having a wavelength of 400nm or less. Examples of the ultraviolet absorber include at least 1 compound selected from the group consisting of benzophenone-based compounds, salicylate-based compounds, benzotriazole-based compounds, and triazine-based compounds. The ultraviolet absorber may be used alone or in combination of two or more. Since the optical film contains the ultraviolet absorber, deterioration of the resin can be suppressed, and thus, when the optical film of the present invention is applied to a display device or the like, visibility can be improved. In the present specification, the term "related compound" refers to a derivative of a compound to which the "related compound" is attached. For example, the "benzophenone-based compound" refers to a compound having benzophenone as a matrix skeleton and a substituent bonded to benzophenone.
When the optical film of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.01 to 10 parts by mass, more preferably 1 to 8 parts by mass, and still more preferably 2 to 7 parts by mass, relative to the mass of the polyamide resin contained in the optical film. When the content of the ultraviolet absorber is not less than the above lower limit, the ultraviolet absorbability is easily improved. When the content of the ultraviolet absorber is not more than the above upper limit, decomposition of the ultraviolet absorber by heat during production of the substrate can be suppressed, and optical characteristics, for example, haze can be easily improved.
< other additives >
The optical film of the present invention may further contain other additives besides the filler and the ultraviolet absorber. Examples of the other additives include colorants such as antioxidants, mold release agents, stabilizers, bluing agents, flame retardants, pH adjusters, silica dispersants, lubricants, thickeners, and leveling agents. When other additives are contained, the content thereof may be preferably 0.001 to 20 parts by mass, more preferably 0.01 to 15 parts by mass, and still more preferably 0.1 to 10 parts by mass, relative to the mass of the optical film.
(method for producing optical film)
The method for producing the optical film of the present invention is not particularly limited, and for example, a production method including the following steps may be used.
(a) A step of preparing a polyamide resin composition (hereinafter also referred to as "varnish") containing at least the polyamide resin and a solvent (varnish preparation step),
(b) a step of applying a varnish to a support material to form a coating film (coating step), and
(c) a step of drying the applied liquid (coating film) to form an optical film (optical film forming step)
In the varnish preparation step, a polyamide resin is dissolved in a solvent, and if necessary, the above-mentioned additives such as a filler and an ultraviolet absorber are added thereto and stirred and mixed to prepare a varnish. When silica particles are used as the filler, a silica sol obtained by replacing a dispersion of a silica sol containing silica particles with a solvent capable of dissolving the resin, for example, a solvent usable in the preparation of a varnish described below, may be added to the resin.
The solvent used in the preparation of the varnish is not particularly limited as long as the resin can be dissolved. Examples of the solvent include amide solvents such as N, N-dimethylacetamide and N, N-dimethylformamide; lactone solvents such as γ -butyrolactone and γ -valerolactone; sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide and sulfolane; carbonate solvents such as ethylene carbonate and propylene carbonate; and combinations thereof. Among these, amide solvents or lactone solvents are preferable. These solvents may be used alone or in combination of two or more. The varnish may contain water, an alcohol solvent, a ketone solvent, an acyclic ester solvent, an ether solvent, and the like. The solid content concentration of the varnish is preferably 1 to 25 mass%, more preferably 5 to 20 mass%, and still more preferably 5 to 15 mass%.
In the coating step, a varnish is applied to the support material by a known coating method to form a coating film. Examples of known coating methods include roll coating methods such as wire bar coating, reverse coating, and gravure coating, die coating, comma coating, lip coating, spin coating, screen coating, spray coating, dipping, spraying, and casting.
In the film forming step, the coating film is dried and peeled from the support material, whereby an optical film can be formed. After the peeling, a step of drying the optical film may be further provided. The drying of the coating film may be carried out at a temperature of 50 to 350 ℃. If necessary, the coating film may be dried in an inert atmosphere or under reduced pressure.
Examples of the support material include a metal-based SUS plate, and a resin-based PET film, a PEN film, a polyamide-based resin film, a polyimide-based resin film, a cycloolefin-based polymer (COP) film, and an acrylic film. Among them, a PET film, a COP film, and the like are preferable from the viewpoint of excellent smoothness and heat resistance, and a PET film is more preferable from the viewpoint of adhesion to an optical film and cost.
(functional layer)
At least one surface of the optical film of the present invention may have 1 or more functional layers stacked thereon. Examples of the functional layer include an ultraviolet absorbing layer, a hard coat layer, a primer layer, a gas barrier layer, an adhesive layer, a hue adjusting layer, and a refractive index adjusting layer. The functional layers may be used alone or in combination of two or more.
A hard coat layer may be provided on at least one side of the optical film of the present invention. The thickness of the hard coat layer is not particularly limited, and may be, for example, 2 to 100 μm. When the thickness of the hard coat layer is within the above range, sufficient scratch resistance can be secured, and the flex resistance is less likely to be lowered, and the problem of curling due to curing shrinkage is less likely to occur.
The aforementioned hard coat layer may be formed by: curing the hard coating composition including the reactive material capable of forming a cross-linked structure by irradiating active energy rays or imparting thermal energy; preferably by irradiation with active energy rays. The active energy ray is defined as an energy ray that can decompose a compound that generates an active species to generate an active species, and examples thereof include visible light, ultraviolet light, infrared light, X-ray, α -ray, β -ray, γ -ray, and electron beam, and preferable examples thereof include ultraviolet light. The hard coat composition contains at least 1 polymer selected from the group consisting of a radically polymerizable compound and a cationically polymerizable compound.
The radical polymerizable compound is a compound having a radical polymerizable group. The radical polymerizable group of the radical polymerizable compound may be a functional group capable of undergoing a radical polymerization reaction, and examples thereof include a group containing a carbon-carbon unsaturated double bond, specifically, a vinyl group and a (meth) acryloyl group. When the radical polymerizable compound has 2 or more radical polymerizable groups, the radical polymerizable groups may be the same or different from each other. The number of radical polymerizable groups in 1 molecule of the radical polymerizable compound is preferably 2 or more in terms of increasing the hardness of the hard coat layer. The radical polymerizable compound preferably includes a compound having a (meth) acryloyl group in view of high reactivity, specifically, a compound called a polyfunctional acrylate monomer having 2 to 6 (meth) acryloyl groups in 1 molecule, an oligomer called epoxy (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate having several (meth) acryloyl groups in a molecule and having a molecular weight of several hundred to several thousand, and preferably 1 or more selected from the group consisting of epoxy (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate.
The cationically polymerizable compound is a compound having a cationically polymerizable group such as an epoxy group, an oxetane group, or a vinyl ether group. The number of the cationically polymerizable groups contained in 1 molecule of the cationically polymerizable compound is preferably 2 or more, and more preferably 3 or more, from the viewpoint of improving the hardness of the hard coat layer.
Among the above cationically polymerizable compounds, preferred are compounds having at least 1 of an epoxy group and an oxetanyl group as a cationically polymerizable group. A cyclic ether group such as an epoxy group or an oxetane group is preferable in that shrinkage accompanying the polymerization reaction is small. In addition, the compound having an epoxy group in a cyclic ether group has the following advantages: it is easy to obtain compounds having various structures, to exert no adverse effect on the durability of the obtained hard coat layer, and to control the compatibility with the radical polymerizable compound. In addition, the oxetanyl group in the cyclic ether group has the following advantages as compared with the epoxy group: the polymerization degree is easily increased, the forming speed of the network obtained by the cationic polymerizable compound of the obtained hard coat layer is increased, and even in the area mixed with the radical polymerizable compound, the unreacted monomer is not remained in the film, and the independent network is formed; and so on.
Examples of the cationically polymerizable compound having an epoxy group include: polyglycidyl ethers of polyhydric alcohols having an alicyclic ring or alicyclic epoxy resins obtained by epoxidizing compounds containing a cyclohexene ring or cyclopentene ring with an appropriate oxidizing agent such as hydrogen peroxide or a peroxy acid; aliphatic epoxy resins such as polyglycidyl ethers of aliphatic polyols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers and copolymers of glycidyl (meth) acrylate; glycidyl ethers produced by the reaction of bisphenols such as bisphenol a, bisphenol F and hydrogenated bisphenol a, or their derivatives such as alkylene oxide adducts and caprolactone adducts with epichlorohydrin, and glycidyl ether type epoxy resins derived from bisphenols such as Novolac epoxy resins.
The aforementioned hard coating composition may further comprise a polymerization initiator. Examples of the polymerization initiator include a radical polymerization initiator, a cationic polymerization initiator, a radical and cationic polymerization initiator, and they can be appropriately selected and used. These polymerization initiators are decomposed by at least one of irradiation with active energy rays and heating to generate radicals or cations, and radical polymerization and cationic polymerization are performed.
The radical polymerization initiator may be a substance that can release and initiate radical polymerization by at least one of irradiation with active energy rays and heating. Examples of the thermal radical polymerization initiator include organic peroxides such as hydrogen peroxide and perbenzoic acid, and azo compounds such as azobisbutyronitrile.
The active energy ray radical polymerization initiator includes a Type1 radical polymerization initiator which generates radicals by decomposition of molecules and a Type2 radical polymerization initiator which generates radicals by hydrogen abstraction reaction in the coexistence of a tertiary amine, and they can be used alone or in combination.
The cationic polymerization initiator may be a substance which can release a substance for initiating cationic polymerization by at least one of irradiation with active energy rays and heating. As the cationic polymerization initiator, aromatic iodonium salts, aromatic sulfonium salts, cyclopentadienyl iron (II) complexes, and the like can be used. Depending on the difference in structure, they can initiate cationic polymerization by either or both of irradiation with active energy rays or heating.
The polymerization initiator may be preferably contained in an amount of 0.1 to 10% by mass based on 100% by mass of the entire hard coat composition. When the content of the polymerization initiator is within the above range, the curing can be sufficiently advanced, the mechanical properties and the adhesion of the finally obtained coating film can be in a good range, and poor adhesion, a crack phenomenon, and a curl phenomenon due to curing shrinkage tend to be less likely to occur.
The hard coating composition may further include one or more selected from the group consisting of a solvent and an additive. The solvent may be used in a range that does not impair the effects of the present invention, as long as it is a solvent that can dissolve or disperse the polymerizable compound and the polymerization initiator and is known as a solvent for a hard coat composition in the art. The aforementioned additives may further include inorganic particles, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, and the like.
The ultraviolet absorbing layer is a layer having an ultraviolet absorbing function, and is composed of a main material selected from an ultraviolet curable transparent resin, an electron beam curable transparent resin, and a thermosetting transparent resin, and an ultraviolet absorber dispersed in the main material.
The pressure-sensitive adhesive layer is a layer having a pressure-sensitive adhesive function and has a function of bonding the optical film to another member. As a material for forming the adhesive layer, a generally known material can be used. For example, a thermosetting resin composition or a photocurable resin composition can be used. In this case, the resin composition can be cured by converting the polymer into a polymer by supplying energy after the curing.
The Pressure-Sensitive Adhesive layer may be a layer called a Pressure-Sensitive Adhesive (PSA) that is pressed and attached to an object. The pressure-sensitive adhesive may be a capsule adhesive as "a substance having adhesiveness at normal temperature and adhering to an adherend under light pressure" (JIS K6800) or as "an adhesive which contains a specific component in a protective film (microcapsule) and can maintain stability until the film is broken by an appropriate means (pressure, heat, or the like)".
The hue adjustment layer is a layer having a hue adjustment function and is a layer capable of adjusting a laminate including an optical film to a target hue. The hue adjustment layer is, for example, a layer containing a resin and a colorant. Examples of the colorant include inorganic pigments such as titanium oxide, zinc oxide, red iron oxide, titanium oxide-based calcined pigments, ultramarine blue, cobalt aluminate, and carbon black; organic pigments such as azo-based compounds, quinacridone-based compounds, anthraquinone-based compounds, perylene-based compounds, isoindolinone-based compounds, phthalocyanine-based compounds, quinophthalone-based compounds, threne-based compounds, and diketopyrrolopyrrole-based compounds; bulk pigments such as barium sulfate and calcium carbonate; and basic dyes, acid dyes, mordant dyes, and the like.
The refractive index adjustment layer is a layer having a function of adjusting the refractive index, and is, for example, a layer having a refractive index different from that of the optical film and capable of providing a predetermined refractive index to the optical laminate. The refractive index adjusting layer may be, for example, a resin layer containing an appropriately selected resin and, in some cases, a pigment, or may be a thin film of a metal. Examples of the pigment for adjusting the refractive index include silicon oxide, aluminum oxide, antimony oxide, tin oxide, titanium oxide, zirconium oxide, and tantalum oxide. The average primary particle diameter of the pigment may be 0.1 μm or less. By setting the average primary particle diameter of the pigment to 0.1 μm or less, diffuse reflection of light transmitted through the refractive index adjustment layer can be prevented, and deterioration in transparency can be prevented. Examples of the metal usable for the refractive index adjustment layer include metal oxides and metal nitrides such as titanium oxide, tantalum oxide, zirconium oxide, zinc oxide, tin oxide, silicon oxide, indium oxide, titanium oxynitride, titanium nitride, silicon oxynitride, and silicon nitride.
In a preferred embodiment of the present invention, the optical film of the present invention is useful as a front panel of a display device, particularly a front panel of a flexible display device (hereinafter, may be referred to as a window film). The flexible display device includes, for example, a flexible functional layer and an optical film laminated on the flexible functional layer and functioning as a front panel. That is, the front panel of the flexible display device is arranged on the viewing side on the flexible functional layer. The front panel has the function of protecting the flexible functional layer.
Examples of the display device include wearable devices such as televisions, smartphones, mobile phones, car navigation systems, tablet PCs, portable game machines, electronic paper, indicators, bulletin boards, clocks, and smartwatches. As the flexible display device, all display devices having a flexible characteristic can be cited.
[ Flexible display device ]
The present invention also provides a flexible display device comprising the optical film of the present invention. The optical film of the present invention is preferably used as a front panel in a flexible display device, which is sometimes referred to as a window film. The flexible display device is formed of a laminate for flexible display device and an organic EL display panel, and the laminate for flexible display device is disposed on the viewing side of the organic EL display panel and is configured to be bendable. The laminate for a flexible display device may contain a window film, a polarizing plate, preferably a circularly polarizing plate, and a touch sensor, and the lamination order thereof is arbitrary, and preferably the window film, the polarizing plate, and the touch sensor are laminated in this order or the window film, the touch sensor, and the polarizing plate are laminated in this order from the viewing side. The presence of the polarizing plate on the viewing side of the touch sensor is preferable because the pattern of the touch sensor is less likely to be observed and the visibility of the display image is good. The members may be laminated using an adhesive, a bonding agent, or the like. Further, the light-shielding film may include a light-shielding pattern formed on at least one surface of any one of the window, the polarizing plate, and the touch sensor.
[ polarizing plate ]
The flexible display device of the present invention may further include a polarizing plate, preferably a circular polarizing plate. The circularly polarizing plate is a functional layer having a function of transmitting only a right-handed circularly polarized light component or a left-handed circularly polarized light component by laminating a λ/4 phase difference plate on a linearly polarizing plate. For example, can be used for: the external light is converted into right-handed circularly polarized light, the external light which is reflected by the organic EL panel and becomes left-handed circularly polarized light is blocked, only the light-emitting component of the organic EL is transmitted, and therefore the influence of reflected light is inhibited, and the image can be easily viewed. In order to achieve the circularly polarized light function, the absorption axis of the linear polarizer and the slow axis of the λ/4 phase difference plate need to be 45 ° in theory, but in practical applications, 45 ± 10 °. The linear polarizing plate and the λ/4 phase difference plate do not necessarily have to be stacked adjacent to each other, and the relationship between the absorption axis and the slow axis may satisfy the above range. It is preferable to achieve completely circularly polarized light at all wavelengths, but this is not necessarily the case in practical applications, and therefore, the circularly polarizing plate in the present invention also includes an elliptically polarizing plate. It is also preferable to further laminate a λ/4 retardation film on the viewing side of the linear polarizing plate to convert the emitted light into circularly polarized light, thereby improving visibility in a state where the polarized sunglasses are worn.
The linear polarizing plate is a functional layer having the following functions: light vibrating in the direction of the transmission axis is passed through, and polarized light of a vibration component perpendicular to the light is blocked. The linear polarizing plate may be a single linear polarizer or a structure including a linear polarizer and a protective film attached to at least one surface of the linear polarizer. The thickness of the linearly polarizing plate may be 200 μm or less, and preferably 0.5 to 100 μm. When the thickness is within the above range, the flexibility tends not to be lowered easily.
The linear polarizer may be a film-type polarizer manufactured by dyeing and stretching a polyvinyl alcohol (PVA) film. The polarizing performance can be exhibited by adsorbing a dichroic dye such as iodine to a PVA film that has been stretched to be oriented, or by stretching the PVA film in a state of being adsorbed to the dichroic dye to orient the dichroic dye. The film-type polarizer may be produced by steps such as swelling, crosslinking with boric acid, washing with an aqueous solution, and drying. The stretching and dyeing step may be performed as a PVA film alone or in a state of being laminated with another film such as polyethylene terephthalate. The thickness of the PVA film to be used is preferably 10 to 100 μm, and the stretch ratio is preferably 2 to 10 times.
In addition, as another example of the polarizer, a liquid crystal coating type polarizer formed by coating a liquid crystal polarizing composition may be used. The liquid crystal polarizing composition may include a liquid crystal compound and a dichroic dye compound. The liquid crystalline compound is preferably used because it has a property of exhibiting a liquid crystal state, and when it has a high-order alignment state such as a smectic state, it can exhibit high polarizing performance. The liquid crystalline compound preferably has a polymerizable functional group.
The dichroic dye may have liquid crystallinity or may have a polymerizable functional group, and may be aligned with the liquid crystal compound to exhibit dichroism. Any of the compounds in the liquid crystal polarizing composition has a polymerizable functional group.
The liquid crystal polarizing composition may further include an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a crosslinking agent, a silane coupling agent, and the like.
The liquid crystal polarizing layer is produced by applying a liquid crystal polarizing composition to an alignment film to form a liquid crystal polarizing layer.
The liquid crystal polarizing layer can be formed to a thinner thickness than the film type polarizer. The thickness of the liquid crystal polarizing layer may be preferably 0.5 to 10 μm, and more preferably 1 to 5 μm.
The foregoing alignment film can be produced, for example, by: the alignment film-forming composition is applied to a substrate, and alignment properties are imparted by rubbing, polarized light irradiation, or the like. The alignment film forming composition may contain a solvent, a crosslinking agent, an initiator, a dispersant, a leveling agent, a silane coupling agent, and the like in addition to the alignment agent. Examples of the orientation agent include polyvinyl alcohols, polyacrylates, polyamide acids, and polyimides. In the case of applying photo-alignment, an alignment agent containing a cinnamate group (cinnamate group) is preferably used. The weight average molecular weight of the polymer that can be used as the orientation agent may be about 10,000 to 1,000,000. The thickness of the alignment film is preferably 5 to 10,000nm, more preferably 10 to 500nm, from the viewpoint of alignment regulating force. The liquid crystal polarizing layer may be laminated by being peeled off from the substrate and then transferred, or the substrate may be directly laminated. The substrate preferably functions as a protective film, a retardation plate, or a transparent substrate for a window.
The protective film may be a transparent polymer film, and a material and an additive that can be used for the transparent base material may be used. Cellulose-based films, olefin-based films, acrylic films, and polyester films are preferable. The protective film may be a coating type protective film obtained by coating and curing a cationically curable composition such as an epoxy resin or a radically curable composition such as an acrylate. If necessary, a plasticizer, an ultraviolet absorber, an infrared absorber, a pigment, a colorant such as a dye, a fluorescent brightener, a dispersant, a heat stabilizer, a light stabilizer, an antistatic agent, an antioxidant, a lubricant, a solvent, or the like may be included. The thickness of the protective film may be 200 μm or less, preferably 1 to 100 μm. When the thickness of the protective film is within the above range, the flexibility of the protective film is not easily lowered. The protective film may also function as a transparent substrate for the window.
The λ/4 retardation plate is a film that imparts a retardation of λ/4 in a direction perpendicular to the traveling direction of incident light (i.e., in-plane direction of the film). The λ/4 retardation plate may be a stretched retardation plate produced by stretching a polymer film such as a cellulose film, an olefin film, or a polycarbonate film. If necessary, a phase difference adjusting agent, a plasticizer, an ultraviolet absorber, an infrared absorber, a pigment, a colorant such as a dye, a fluorescent brightener, a dispersant, a heat stabilizer, a light stabilizer, an antistatic agent, an antioxidant, a lubricant, a solvent, and the like may be included. The thickness of the stretched retardation film may be 200 μm or less, preferably 1 to 100 μm. When the thickness is within the above range, the flexibility of the film tends not to be easily lowered.
Further, another example of the λ/4 retardation plate may be a liquid crystal coating type retardation plate formed by coating a liquid crystal composition. The liquid crystal composition contains a liquid crystalline compound having a property of exhibiting a liquid crystal state such as a nematic state, a cholesteric state, or a smectic state. Any compound including a liquid crystalline compound in the liquid crystal composition has a polymerizable functional group. The liquid crystal coating type retardation plate may further contain an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a crosslinking agent, a silane coupling agent, and the like. The liquid crystal coated retardation plate can be produced by coating a liquid crystal composition on an alignment film and curing the coating to form a liquid crystal retardation layer, as described in the liquid crystal polarizing layer. The liquid crystal coating type retardation plate can be formed to a smaller thickness than the stretching type retardation plate. The thickness of the liquid crystal polarizing layer may be usually 0.5 to 10 μm, preferably 1 to 5 μm. The liquid crystal coated retardation film may be laminated by being peeled from a substrate and then transferred, or the substrate may be directly laminated. The substrate preferably functions as a protective film, a retardation plate, or a transparent substrate for a window.
In general, the birefringence is large as the wavelength is shorter, and the birefringence is small as the wavelength is longer. In this case, since it is not possible to achieve a retardation of λ/4 in all visible light regions, it is often designed so that an in-plane retardation of λ/4 is 100 to 180nm, preferably 130 to 150nm, in the vicinity of 560nm, which is high in visibility. The use of an inverse dispersion λ/4 phase difference plate using a material having a birefringence wavelength dispersion characteristic opposite to that of the usual one is preferable because it can improve visibility. As such a material, the material described in japanese patent application laid-open No. 2007-232873 and the like is preferably used also in the case of a stretched phase difference plate, and the material described in japanese patent application laid-open No. 2010-30979 is preferably used also in the case of a liquid crystal coated phase difference plate.
As another method, a technique of obtaining a wide-band λ/4 phase difference plate by combining with a λ/2 phase difference plate is also known (japanese patent application laid-open No. h 10-90521). The λ/2 phase difference plate can be manufactured by the same material method as the λ/4 phase difference plate. The combination of the stretching type retardation plate and the liquid crystal coating type retardation plate is arbitrary, and the use of the liquid crystal coating type retardation plate is preferable because the thickness can be reduced.
For the circularly polarizing plate, a method of laminating a positive C plate is also known in order to improve visibility in an oblique direction (japanese patent application laid-open No. 2014-224837). The positive C plate may be a liquid crystal coated retardation plate or a stretched retardation plate. The phase difference in the thickness direction is-200 to-20 nm, preferably-140 to-40 nm.
[ touch sensor ]
The flexible display device of the present invention may further include a touch sensor. The touch sensor may be used as an input mechanism. As the touch sensor, various types such as a resistive film type, a surface acoustic wave type, an infrared ray type, an electromagnetic induction type, and a capacitance type have been proposed, and any type may be used. Among them, the electrostatic capacitance system is preferable. The capacitive touch sensor may be divided into an active region and an inactive region located at a peripheral portion of the active region. The active region is a region corresponding to a display portion on the display panel on which a screen is displayed, and is a region in which a user's touch is sensed, and the inactive region is a region corresponding to a non-display portion on the display device on which a screen is not displayed. The touch sensor may include: a substrate having flexible properties; a sensing pattern formed on the active region of the substrate; and each sensing line formed in the inactive region of the substrate and used for connecting the sensing pattern with an external driving circuit through a pad (pad) portion. As the substrate having the flexible property, the same material as the transparent substrate of the window can be used. The substrate of the touch sensor preferably has a toughness of 2,000 MPa% or more in terms of suppressing cracks in the touch sensor. The toughness may be more preferably 2,000 to 30,000 MPa%. Here, the toughness is defined as the area of the lower part of a Stress (MPa) -strain (%) curve (Stress-strain curve) obtained by a tensile test of a polymer material up to a failure point.
The sensing pattern may include a 1 st pattern formed along a 1 st direction and a 2 nd pattern formed along a 2 nd direction. The 1 st pattern and the 2 nd pattern are arranged in mutually different directions. The 1 st pattern and the 2 nd pattern are formed in the same layer, and in order to sense a touched position, the patterns must be electrically connected. The 1 st pattern is a form in which the unit patterns are connected to each other via a terminal, and the 2 nd pattern is a structure in which the unit patterns are separated from each other into islands, and therefore, in order to electrically connect the 2 nd pattern, a separate bridge electrode is required. The sensing pattern may use a known transparent electrode material. Examples thereof include Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), zinc oxide (ZnO), Indium Zinc Tin Oxide (IZTO), Indium Gallium Zinc Oxide (IGZO), Cadmium Tin Oxide (CTO), PEDOT (poly (3, 4-ethylenedioxythiophene)), Carbon Nanotube (CNT), graphene, and a metal wire, and these may be used alone or in combination of 2 or more. Preferably, ITO can be used. The metal usable for the wire is not particularly limited, and examples thereof include silver, gold, aluminum, copper, iron, nickel, titanium, selenium, chromium, and the like. These may be used alone or in combination of 2 or more.
The bridge electrode may be formed on the insulating layer with an insulating layer interposed therebetween, on the sensing pattern, the bridge electrode may be formed on the substrate, and the insulating layer and the sensing pattern may be formed thereon. The bridge electrode may be formed of the same material as the sensor pattern, or may be formed of a metal such as molybdenum, silver, aluminum, copper, palladium, gold, platinum, zinc, tin, titanium, or an alloy of 2 or more of these metals. The 1 st pattern and the 2 nd pattern must be electrically insulated, and thus, an insulating layer is formed between the sensing pattern and the bridge electrode. The insulating layer may be formed only between the tab of the 1 st pattern and the bridge electrode, or may be formed in a structure of a layer covering the sensing pattern. In the latter case, the 2 nd pattern may be connected to the bridge electrode through a contact hole formed in the insulating layer. In the touch sensor, as means for appropriately compensating for a difference in transmittance between a pattern region where a pattern is formed and a non-pattern region where no pattern is formed (specifically, a difference in transmittance due to a difference in refractive index in these regions), an optical adjustment layer may be further included between the substrate and the electrode, and the optical adjustment layer may include an inorganic insulating substance or an organic insulating substance. The optical adjustment layer can be formed by applying a photocurable composition containing a photocurable organic binder and a solvent onto a substrate. The aforementioned photocurable composition may further comprise inorganic particles. The refractive index of the optical adjustment layer can be increased by the inorganic particles.
The photocurable organic binder may include, for example, a copolymer of monomers such as an acrylate monomer, a styrene monomer, and a carboxylic acid monomer. The photocurable organic binder may be, for example, a copolymer containing mutually different repeating units such as an epoxy group-containing repeating unit, an acrylate repeating unit, and a carboxylic acid repeating unit.
The inorganic particles may include, for example, zirconium dioxide particles, titanium dioxide particles, aluminum oxide particles, and the like. The photocurable composition may further contain various additives such as a photopolymerization initiator, a polymerizable monomer, and a curing assistant.
[ adhesive layer ]
The layers of the laminate for a flexible display device, such as a window film, a polarizing plate, and a touch sensor, and the film members of the layers, such as a linear polarizing plate and a λ/4 retardation plate, may be bonded together with an adhesive. As the adhesive, a commonly used adhesive such as an aqueous adhesive, an organic solvent adhesive, a solventless adhesive, a solid adhesive, a solvent volatile adhesive, a moisture curable adhesive, a heat curable adhesive, an anaerobic curable adhesive, an active energy ray curable adhesive, a curing agent hybrid adhesive, a hot melt adhesive, a pressure sensitive adhesive, and a remoistenable adhesive can be used. Among them, water-based solvent-volatile adhesives, active energy ray-curable adhesives, and adhesives are generally used. The thickness of the adhesive layer can be adjusted as appropriate according to the required adhesive strength, and is, for example, 0.01 to 500. mu.m, preferably 0.1 to 300. mu.m. The adhesive layer may be present in a plurality of layers in the laminate for a flexible display device, and the thickness of each layer and the type of the adhesive used may be the same or different.
As the aqueous solvent volatile adhesive, a polyvinyl alcohol polymer, a water-soluble polymer such as starch, or a water-dispersed polymer such as an ethylene-vinyl acetate emulsion or a styrene-butadiene emulsion can be used as a main polymer. In addition to water and the main agent polymer, a crosslinking agent, a silane compound, an ionic compound, a crosslinking catalyst, an antioxidant, a dye, a pigment, an inorganic filler, an organic solvent, and the like may be added. In the case of bonding with the aqueous solvent volatile adhesive, the aqueous solvent volatile adhesive may be injected between the layers to be bonded, and the layers to be bonded may be bonded and then dried to impart adhesiveness. The thickness of the adhesive layer when the aqueous solvent-based volatile adhesive is used may be 0.01 to 10 μm, preferably 0.1 to 1 μm. When the aqueous solvent-volatile adhesive is used for forming a plurality of layers, the thickness of each layer and the type of the adhesive may be the same or different.
The active energy ray-curable adhesive can be formed by curing an active energy ray-curable composition containing a reactive material capable of forming an adhesive layer by irradiation with an active energy ray. The active energy ray-curable composition may contain at least 1 polymer selected from the group consisting of radical polymerizable compounds and cationic polymerizable compounds, which are similar to the hard coat composition. The radical polymerizable compound may be the same type of radical polymerizable compound as used in the hard coat composition, as used in the hard coat composition. As the radical polymerizable compound that can be used in the adhesive layer, a compound having an acryloyl group is preferable. In order to reduce the viscosity of the adhesive composition, a monofunctional compound is preferably contained.
The cationic polymerizable compound may be the same kind of cationic polymerizable compound as used in the hard coat composition, similarly to the hard coat composition. As the cationically polymerizable compound which can be used in the active energy ray-curable composition, an epoxy compound is particularly preferable. To reduce the viscosity of the adhesive composition, it is also preferable to include a monofunctional compound as a reactive diluent.
In the active energy ray composition, a polymerization initiator may be further contained. The polymerization initiator may be selected from a radical polymerization initiator, a cationic polymerization initiator, a radical and cationic polymerization initiator, and the like. These polymerization initiators are those which can be decomposed by at least one of irradiation with active energy rays and heating to generate radicals or cations, thereby allowing radical polymerization and cationic polymerization to proceed. The initiator described in the description of the hard coating composition, which can initiate at least either of radical polymerization or cationic polymerization by irradiation with active energy rays, may be used.
The active energy ray-curable composition may further contain an ion scavenger, an antioxidant, a chain transfer agent, an adhesion-imparting agent, a thermoplastic resin, a filler, a flow viscosity modifier, a plasticizer, an antifoaming agent, an additive, and a solvent. When the bonding is performed by the active energy ray-curable adhesive, the bonding may be performed by: the active energy ray-curable composition is applied to one or both of the adhesive layers and then bonded thereto, and the adhesive layer or both of the adhesive layers is irradiated with active energy rays through the adhesive layer or both of the adhesive layers to be cured. The thickness of the adhesive layer when the active energy ray-curable adhesive is used may be 0.01 to 20 μm, preferably 0.1 to 10 μm. When the active energy ray-curable adhesive is used for forming a plurality of layers, the thickness of each layer and the type of the adhesive used may be the same or different.
The adhesive may be classified into an acrylic adhesive, a urethane adhesive, a rubber adhesive, a silicone adhesive, and the like according to the base polymer, and may be used. The binder may contain a crosslinking agent, a silane compound, an ionic compound, a crosslinking catalyst, an antioxidant, an adhesion promoter, a plasticizer, a dye, a pigment, an inorganic filler, and the like in addition to the main polymer. The adhesive layer or the adhesive layer can be formed by dissolving and dispersing the components constituting the adhesive in a solvent to obtain an adhesive composition, applying the adhesive composition to a substrate, and then drying the adhesive composition. The adhesive layer may be formed directly or by transferring an adhesive layer separately formed on the substrate. A release film is also preferably used to cover the pressure-sensitive adhesive surface before bonding. The thickness of the adhesive layer when the adhesive is used may be 1 to 500. mu.m, preferably 2 to 300. mu.m. When the above-mentioned adhesive is used for forming a plurality of layers, the thickness of each layer and the kind of the adhesive used may be the same or different.
[ light-shielding pattern ]
The light-shielding pattern may be applied as at least a portion of a bezel (bezel) or a housing of the flexible display device. The wiring disposed at the edge of the flexible display device is hidden by the light-shielding pattern and is not easily viewed, thereby improving visibility of an image. The light-shielding pattern may be in the form of a single layer or a plurality of layers. The color of the light-shielding pattern is not particularly limited, and may have various colors such as black, white, metallic color, and the like. The light-shielding pattern may be formed of a pigment for color, and a polymer such as an acrylic resin, an ester resin, an epoxy resin, polyurethane, or polysiloxane. They may be used alone or in the form of a mixture of 2 or more. The light-shielding pattern can be formed by various methods such as printing, photolithography, and inkjet. The thickness of the light-shielding pattern is usually 1 to 100 μm, preferably 2 to 50 μm. Further, it is preferable to provide a shape such as an inclination in the thickness direction of the light-shielding pattern.
Examples
The present invention will be described in further detail below with reference to examples. In the examples, "%" and "part(s)" refer to% by mass and part(s) by mass unless otherwise specified. First, the evaluation method will be explained.
< determination of elastic modulus >
The elastic modulus of the polyamide films obtained in examples and comparative examples was measured by using "AUTOGRAPH AG-IS" manufactured by Shimadzu corporation. A film having a width of 10mm was produced, and an S-S curve was measured under conditions that the distance between chucks was 50mm and the stretching speed was 10 mm/min, and the elastic modulus was calculated from the slope.
< measurement of light transmittance >
According to JIS K7105: 1981, the total light transmittance Tt of the samples was measured for the optical films obtained in the examples and comparative examples by using a fully automatic direct haze computer HGM-2DP manufactured by Suga Test Instruments co.
< determination of coefficient of humidity expansion (CME) >
The measurement was carried out using "model TMA/SS 6100" manufactured by Hitachi High-Tech Science Corporation. A film having a width of 2mm and a length of 20mm was placed on a chuck (distance between chucks was 10mm) in a nitrogen atmosphere, and held at 60 ℃ under a load of 20mN until saturation at 0% r.h., and then controlled at 60 ℃ under 90% r.h., and the coefficient of humidity expansion of the film when held for 1 hour was measured. The humidity expansion coefficient was calculated by the following equation, where l (mm) is the length of the membrane, Δ l (mm) is the amount of change in the length of the membrane before and after being held for 1 hour under the above-mentioned condition of 90% r.h., and Δ M (%) is the amount of change in humidity.
Coefficient of humidity expansion ═ 1/L (Δ L/Δ M)
< YI value of film >
According to JIS K7373: the YI value (Yellow Index) of the sample was measured by using an ultraviolet-visible near infrared spectrophotometer V-670 manufactured by Nippon spectral Co., Ltd. After background measurement in a state where no sample is present, the sample is set in a sample holder, and transmittance with respect to light of 300 to 800nm is measured to obtain a tristimulus value (X, Y, Z). The YI value was calculated based on the following formula.
YI=100×(1.2769X-1.0592Z)/Y
< haze >
According to JIS K7105: 1981, haze of the optical film was measured using a fully automated direct reading haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd.
< determination of Pencil hardness >
The surface hardness of the polyamideimide films obtained in examples and comparative examples was measured in accordance with JIS K5600-5-4: 1999, pencil hardness of the film surface was used. The presence or absence of damage was evaluated under an environment of 4,000 lux with a load of 100g and a scanning speed of 60 mm/min, and pencil hardness was measured as surface hardness.
< determination of weight average molecular weight >
Gel Permeation Chromatography (GPC) measurement
(1) Pretreatment method
DMF eluent (10mmol/L lithium bromide solution) was added to the sample so that the concentration became 2mg/mL, and the mixture was heated at 80 ℃ for 30 minutes with stirring, cooled, and then filtered through a 0.45 μm membrane filter to obtain a filtrate as a measurement solution.
(2) Measurement conditions
Column: TSKgel α -2500 (7)7.8mm diameter. times.300 mm). times.1, and α -M ((13)7.8mm diameter. times.300 mm). times.2, manufactured by Tosoh Corporation
Eluent: DMF (with addition of 10mmol/L lithium bromide)
Flow rate: 1.0 mL/min
A detector: RI detector
Column temperature: 40 deg.C
Sample introduction amount: 100 μ L
Molecular weight standard: standard polystyrene
< measurement of thickness of optical film >
The thickness of the polyamide resin films obtained in examples and comparative examples was measured using a micrometer ("ID-C112 XBS" manufactured by Mitutoyo Co., Ltd.).
< example 1 >
[ preparation of Polyamide resin (1) ]
2, 2' -bis (trifluoromethyl) benzidine (TFMB) and N, N-dimethylacetamide (DMAc) were charged into a separable flask equipped with a stirring blade under a nitrogen atmosphere so that the solid content of TFMB became 4.90 mass%, and TFMB was dissolved in DMAc with stirring at room temperature. Next, 4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA) was added to the flask so that it became 30.30 mol% with respect to TFMB, and the mixture was stirred at room temperature for 3 hours. Thereafter, after cooling to 10 ℃, 4' -oxybis (benzoyl chloride) (OBBC) was added in an amount of 5.05 mol% based on TFMB, and 2, 5-bis (trifluoromethyl) terephthaloyl chloride (6FTPC) was added in an amount of 27.28 mol% based on TFMB, and after stirring for 10 minutes, OBBC was further added in an amount of 5.05m o l% based on TFMB, and 6FTPC was further added in an amount of 27.28m o l% based on TFMB, and the mixture was stirred for 30 minutes. Subsequently, DMAc was added in an amount equivalent to that of the initially added DMAc, and after stirring for 10 minutes, 6FTPC was added so that it became 6.06 mol% with respect to TFMB, and stirring was carried out for 2 hours. Subsequently, diisopropylethylamine and 4-methylpyridine in an amount of 70.71 mol% based on TFMB, and acetic anhydride in an amount of 212.12 mol% based on TFMB were added to the flask, and the mixture was stirred for 30 minutes, then the internal temperature was increased to 70 ℃, and the mixture was further stirred for 3 hours to obtain a reaction solution.
The obtained reaction solution was cooled to room temperature, put into a large amount of methanol in a linear form, and the precipitated precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Then, the precipitate was dried under reduced pressure at 60 ℃ to obtain a polyamide resin (1).
[ production of Polyamide resin film (1) ]
DMAc was added to the obtained polyamide resin (1) so that the concentration thereof became 10% by mass, thereby producing a polyamide resin varnish (1). The obtained polyamide resin varnish (1) was applied to a smooth surface of a polyester substrate (manufactured by Toyobo Co., Ltd., trade name "A4100") using an applicator so that the thickness of the self-supporting film became 50 μm, and dried at 50 ℃ for 30 minutes and then at 140 ℃ for 15 minutes to obtain a self-supporting film. The self-supporting film was fixed to a metal frame, and further dried at 200 ℃ for 60 minutes to obtain a polyamide resin film (1) having a thickness of 45 μm.
< example 2 >
[ preparation of Polyamide resin (2) ]
TFMB and DMAc were charged into a separable flask equipped with a stirring blade under a nitrogen atmosphere so that the solid content of TFMB became 2.36 mass%, and TFMB was dissolved in DMAc with stirring at room temperature. Then, 6FDA was added to the flask so that it became 30.30 mol% to TFMB, and the mixture was stirred at room temperature for 3 hours. Thereafter, after cooling to 10 ℃, 5.5 mol% of OBBC relative to TFMB, 27.28 mol% of 2,2 '-bis (trifluoromethyl) -4, 4' -biphenyldicarbonyl chloride (6FBPDOC) relative to TFMB were added, and after stirring for 10 minutes, 5.05m o l% of OBBC relative to TFMB, 27.28m o l% of 6FBPDOC relative to TFMB were further added and stirred for 30 minutes. Subsequently, DMAc was added in an amount equivalent to that of the initially added DMAc, and after stirring for 10 minutes, 6FBPDOC was added so as to be 6.06 mol% with respect to TFMB, and stirring was carried out for 2 hours. Subsequently, diisopropylethylamine and 4-methylpyridine in an amount of 70.71 mol% based on TFMB, and acetic anhydride in an amount of 212.12 mol% based on TFMB were added to the flask, and the mixture was stirred for 30 minutes, then the internal temperature was increased to 70 ℃, and the mixture was further stirred for 3 hours to obtain a reaction solution.
The obtained reaction solution was cooled to room temperature, put into a large amount of methanol in a linear form, and the precipitated precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Then, the precipitate was dried under reduced pressure at 60 ℃ to obtain a polyamide resin (2).
[ production of Polyamide resin film (2) ]
DMAc was added to the obtained polyamide resin (2) so that the concentration thereof became 10% by mass, thereby producing a polyamide resin varnish (2). The obtained polyamide resin varnish (2) was applied to a smooth surface of a polyester substrate (manufactured by Toyobo Co., Ltd., trade name "A4100") using an applicator so that the thickness of the self-supporting film became 55 μm, and dried at 50 ℃ for 30 minutes and then at 140 ℃ for 15 minutes to obtain a self-supporting film. The self-supporting film was fixed to a metal frame, and further dried at 200 ℃ for 60 minutes to obtain a polyamide resin film (2) having a thickness of 50 μm.
< comparative example 1 >
[ preparation of Polyamide resin (3) ]
TFMB and DMAc were added to a separable flask equipped with a stirring blade under a nitrogen atmosphere so that the solid content of TFMB became 5.54 mass%, and TFMB was dissolved in DMAc with stirring at room temperature. Then, 6FDA was added to the flask so that it became 30.20 mol% to TFMB, and the mixture was stirred at room temperature for 3 hours. Thereafter, the mixture was cooled to 10 ℃ and then, OBBC at 10.07 mol% based on TFMB and terephthaloyl chloride (TPC) at 54.35 mol% based on TFMB were added thereto, followed by stirring for 30 minutes. Then, DMAc was added in an amount equivalent to that of the initially added DMAc, and after stirring for 10 minutes, TPC was added so as to be 6.04 mol% with respect to TFMB, and stirring was carried out for 2 hours. Subsequently, diisopropylethylamine and 4-methylpyridine, each in an amount of 70.46 mol% based on TFMB, and acetic anhydride in an amount of 211.37 mol% based on TFMB were added to the flask, and the mixture was stirred for 30 minutes, then the internal temperature was increased to 70 ℃, and the mixture was further stirred for 3 hours to obtain a reaction solution.
The obtained reaction solution was cooled to room temperature, put into a large amount of methanol in a linear form, and the precipitated precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Then, the precipitate was dried under reduced pressure at 60 ℃ to obtain a polyamide resin (3).
[ production of Polyamide resin film (3) ]
DMAc was added to the obtained polyamide resin (3) so that the concentration thereof became 10% by mass, thereby producing a polyamide resin varnish (3). The obtained polyamide resin varnish (3) was applied to a smooth surface of a polyester substrate (manufactured by Toyobo Co., Ltd., trade name "A4100") using an applicator so that the thickness of the self-supporting film became 55 μm, and dried at 50 ℃ for 30 minutes and then at 140 ℃ for 15 minutes to obtain a self-supporting film. The self-supporting film was fixed to a metal frame, and further dried at 200 ℃ for 60 minutes to obtain a polyamide resin film (3) having a thickness of 50 μm.
The weight average molecular weights (Mw) of the obtained polyamide resins (1) to (3), and the elastic moduli, CME, light transmittances, YI values, and haze values of the polyamide resin films (1) to (3) were measured by the methods described above. The obtained results are shown in table 1. The pencil hardness of the optical film (1) was 3B, and the pencil hardness of the optical film (2) was 2H.
[ Table 1]
Claims (15)
1. An optical film comprising a polyamide resin having a weight average molecular weight of 200,000 to 1,000,000, the polyamide resin having at least a structural unit represented by formula (1) and a structural unit represented by formula (3),
[ chemical formula 1]
In the formula (1), Ar1Represents a 2-valent aromatic group having a fluoroalkyl group having 1 to 12 carbon atoms,
X1represents a 2-valent organic group;
[ chemical formula 2]
In the formula (3), Z1Represents Ar1Or means other than Ar1The 2-valent organic group of (a),
Ar1as defined in said formula (1),
X2represents a 2-valent organic group, wherein, in Z1Represents Ar1In the case of (1), X1And X in formula (3)2Are different from each other.
2. The optical film according to claim 1, wherein Ar in formula (1)1Wherein the fluoroalkyl group having 1 to 12 carbon atoms is a perfluoroalkyl group having 1 to 12 carbon atoms.
3. The optical film according to claim 1 or 2, wherein the structural unit represented by formula (1) contains an aromatic group represented by formula (4) as Ar1,
[ chemical formula 3]
In the formula (4), R1Represents a fluoroalkyl group having 1 to 12 carbon atoms,
n and k independently represent an integer of 1 to 4, wherein when n and/or k represent an integer of 2 to 4, a plurality of R exist1May be the same as, or different from,
it represents a chemical bond.
4. The optical film according to claim 3, wherein the 2 chemical bonds in formula (4) are located in alignment with each other.
5. The optical film according to claim 3 or 4, wherein k in formula (4) is 1 or 2.
6. The optical film according to any one of claims 3 to 5, wherein R in the formula (4)1Represents a perfluoroalkyl group having 1 to 12 carbon atoms, and n is 1 or 2.
7. The optical film according to any one of claims 1 to 6, wherein the structural unit represented by formula (1) and the structural unit represented by formula (3) each contain a 2-valent organic group represented by formula (5) as X1And X2,
[ chemical formula 4]
In the formula (5), Ar2Represents a 2-valent aromatic group which may have a substituent,
v represents a single bond, -O-, diphenylmethylene, fluorenyl, a linear, branched or alicyclic 2-valent hydrocarbon group having 1 to 12 carbon atoms, -SO2-、-S-、-CO-、-PO-、-PO2-、-N(Ra) -or-Si (R)b)2-, wherein the hydrogen atoms contained in the hydrocarbon group independently of each other may be substituted by halogen atoms, RaAnd RbIndependently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom,
m represents an integer of 0 to 3,
it represents a chemical bond.
8. The optical film according to claim 7, wherein m in formula (5) is 1.
9. The optical film according to claim 7 or 8, wherein formula (5) is represented by formula (5a),
[ chemical formula 5]
In the formula (5), R2Represents a fluoroalkyl group having 1 to 12 carbon atoms,
p and q independently represent an integer of 1 to 4, wherein when p and/or q represents an integer of 2 to 4, a plurality of R exist2May be the same as, or different from,
it represents a chemical bond.
11. The optical film according to any one of claims 1 to 10, which has a thickness of 10 to 200 μm.
12. A flexible display device comprising the optical film according to any one of claims 1 to 11.
13. The flexible display device of claim 12, further provided with a touch sensor.
14. The flexible display device according to claim 12 or 13, further comprising a polarizing plate.
15. A polyamide resin having a weight average molecular weight of 200,000 to 1,000,000, the polyamide resin having at least:
represented by formula (1)And an aromatic group represented by the formula (4) as Ar in the formula (1)1Structural unit of, and
a structural unit represented by formula (3);
[ chemical formula 7]
In the formula (1), Ar1Represents a 2-valent aromatic group having a fluoroalkyl group having 1 to 12 carbon atoms,
X1represents a 2-valent organic group;
[ chemical formula 8]
In the formula (4), R1Represents a fluoroalkyl group having 1 to 12 carbon atoms,
n and k independently represent an integer of 1 to 4, wherein when n and/or k represent an integer of 2 to 4, a plurality of R exist1May be the same as, or different from,
represents a chemical bond;
[ chemical formula 9]
In the formula (3), Z1Represents Ar1Or means other than Ar1The 2-valent organic group of (a),
Ar1as defined in said formula (1),
X2represents a 2-valent organic group, wherein, in Z1Represents Ar1In the case of (1), X1And X in formula (3)2Are different from each other.
Applications Claiming Priority (17)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018-248561 | 2018-12-28 | ||
JP2018-248567 | 2018-12-28 | ||
JP2018248562 | 2018-12-28 | ||
JP2018248567 | 2018-12-28 | ||
JP2018248566 | 2018-12-28 | ||
JP2018248561 | 2018-12-28 | ||
JP2018-248562 | 2018-12-28 | ||
JP2018-248566 | 2018-12-28 | ||
JP2019218267A JP7382810B2 (en) | 2018-12-28 | 2019-12-02 | optical film |
JP2019-218261 | 2019-12-02 | ||
JP2019218261A JP2020109155A (en) | 2018-12-28 | 2019-12-02 | Optical film, flexible display device and polyamide-imide resin |
JP2019218262A JP2020109156A (en) | 2018-12-28 | 2019-12-02 | Optical film, flexible display device and polyamide-imide resin |
JP2019-218262 | 2019-12-02 | ||
JP2019218263A JP2020109157A (en) | 2018-12-28 | 2019-12-02 | Polyamide resin, optical film and flexible display device |
JP2019-218263 | 2019-12-02 | ||
JP2019-218267 | 2019-12-02 | ||
PCT/JP2019/050540 WO2020138044A1 (en) | 2018-12-28 | 2019-12-24 | Polyamide-based resin, optical film, and flexible display device |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113227211A true CN113227211A (en) | 2021-08-06 |
Family
ID=74103578
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201980085962.2A Pending CN113227208A (en) | 2018-12-28 | 2019-12-24 | Optical film, flexible display device, and polyamide-imide resin |
CN201980086116.2A Pending CN113227211A (en) | 2018-12-28 | 2019-12-24 | Polyamide resin, optical film, and flexible display device |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201980085962.2A Pending CN113227208A (en) | 2018-12-28 | 2019-12-24 | Optical film, flexible display device, and polyamide-imide resin |
Country Status (3)
Country | Link |
---|---|
KR (2) | KR20210110646A (en) |
CN (2) | CN113227208A (en) |
TW (2) | TW202037637A (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH024224A (en) * | 1988-06-21 | 1990-01-09 | Hitachi Chem Co Ltd | Production of liquid crystal display element and liquid crystal display element |
CN1184123A (en) * | 1996-08-29 | 1998-06-10 | 三井东压化学株式会社 | Organic optical component |
JPH1152152A (en) * | 1997-08-07 | 1999-02-26 | Nippon Telegr & Teleph Corp <Ntt> | High polymer optical waveguide |
JP2001139684A (en) * | 1999-08-30 | 2001-05-22 | Sumitomo Bakelite Co Ltd | Interlaminar insulating film for multilevel interconnection and resin to be used therefor and its production method |
WO2018135432A1 (en) * | 2017-01-20 | 2018-07-26 | 住友化学株式会社 | Film, resin composition, and production method for polyamide-imide resin |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5580950A (en) * | 1993-04-21 | 1996-12-03 | The University Of Akron | Negative birefringent rigid rod polymer films |
JP4024579B2 (en) * | 2002-01-22 | 2007-12-19 | 住友ベークライト株式会社 | Plastic optical waveguide material and optical waveguide |
JP2006265385A (en) * | 2005-03-24 | 2006-10-05 | Fuji Photo Film Co Ltd | Polybenzazole, film obtained using the same, and image display device |
EP2864400A4 (en) | 2012-06-25 | 2016-02-24 | Kolon Inc | Polyamide-imide copolymer film and method of preparing polyamide-imide copolymer |
JP7084710B2 (en) | 2017-01-20 | 2022-06-15 | 住友化学株式会社 | Polyamide-imide resin and an optical member containing the polyamide-imide resin. |
-
2019
- 2019-12-24 CN CN201980085962.2A patent/CN113227208A/en active Pending
- 2019-12-24 TW TW108147349A patent/TW202037637A/en unknown
- 2019-12-24 CN CN201980086116.2A patent/CN113227211A/en active Pending
- 2019-12-24 KR KR1020217023793A patent/KR20210110646A/en not_active Application Discontinuation
- 2019-12-24 TW TW108147367A patent/TW202037643A/en unknown
- 2019-12-24 KR KR1020217023784A patent/KR20210110644A/en not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH024224A (en) * | 1988-06-21 | 1990-01-09 | Hitachi Chem Co Ltd | Production of liquid crystal display element and liquid crystal display element |
CN1184123A (en) * | 1996-08-29 | 1998-06-10 | 三井东压化学株式会社 | Organic optical component |
JPH1152152A (en) * | 1997-08-07 | 1999-02-26 | Nippon Telegr & Teleph Corp <Ntt> | High polymer optical waveguide |
JP2001139684A (en) * | 1999-08-30 | 2001-05-22 | Sumitomo Bakelite Co Ltd | Interlaminar insulating film for multilevel interconnection and resin to be used therefor and its production method |
WO2018135432A1 (en) * | 2017-01-20 | 2018-07-26 | 住友化学株式会社 | Film, resin composition, and production method for polyamide-imide resin |
Also Published As
Publication number | Publication date |
---|---|
KR20210110644A (en) | 2021-09-08 |
TW202037643A (en) | 2020-10-16 |
CN113227208A (en) | 2021-08-06 |
KR20210110646A (en) | 2021-09-08 |
TW202037637A (en) | 2020-10-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109765642B (en) | Optical laminate | |
CN111161634B (en) | Optical film | |
CN114599708A (en) | Polyamide-imide resin | |
CN113811562A (en) | Varnish, optical film, and method for producing optical film | |
CN113227209A (en) | Polyamide-imide resin, optical film, and flexible display device | |
CN111378129A (en) | Polyamide-imide resin, polyamide-imide resin varnish, optical film, and flexible display device | |
JP2020109155A (en) | Optical film, flexible display device and polyamide-imide resin | |
CN113272361A (en) | Method for producing polyimide resin | |
CN111333885A (en) | Optical film, flexible display device, and resin composition | |
CN111378130A (en) | Optical film | |
WO2020138046A1 (en) | Optical film | |
CN111499893A (en) | Optical film, flexible display device, and resin composition | |
CN113227211A (en) | Polyamide resin, optical film, and flexible display device | |
CN113227222A (en) | Optical film, flexible display device, and polyamide-imide resin | |
WO2020138041A1 (en) | Optical film, flexible display device, and polyamide-imide resin | |
CN115197457A (en) | Optical laminate and flexible display device | |
CN114555676A (en) | Polyimide resin | |
JP2020109157A (en) | Polyamide resin, optical film and flexible display device | |
CN115206186A (en) | Optical film | |
CN113227212A (en) | Optical film | |
CN114556165A (en) | Optical film | |
CN114599739A (en) | Optical film and flexible display device | |
CN113227205A (en) | Polyimide resin and method for producing same | |
CN110922753A (en) | Composition for forming optical film | |
CN112778522A (en) | Polyamide-imide resin, optical film, and flexible display device |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210806 |
|
WD01 | Invention patent application deemed withdrawn after publication |