WO2022108046A1 - 폴리이미드 수지 필름, 이를 이용한 플렉서블 디스플레이 장치용 기판, 및 플렉서블 디스플레이 장치 - Google Patents
폴리이미드 수지 필름, 이를 이용한 플렉서블 디스플레이 장치용 기판, 및 플렉서블 디스플레이 장치 Download PDFInfo
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- WO2022108046A1 WO2022108046A1 PCT/KR2021/010878 KR2021010878W WO2022108046A1 WO 2022108046 A1 WO2022108046 A1 WO 2022108046A1 KR 2021010878 W KR2021010878 W KR 2021010878W WO 2022108046 A1 WO2022108046 A1 WO 2022108046A1
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- WIPO (PCT)
- Prior art keywords
- formula
- polyimide resin
- functional group
- resin film
- repeating unit
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 190
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 120
- 239000000758 substrate Substances 0.000 title claims abstract description 42
- 230000009975 flexible effect Effects 0.000 title claims abstract description 32
- 125000000524 functional group Chemical group 0.000 claims description 100
- 239000004642 Polyimide Substances 0.000 claims description 47
- 125000003118 aryl group Chemical group 0.000 claims description 39
- 239000000126 substance Substances 0.000 claims description 39
- -1 aromatic tetracarboxylic acids Chemical class 0.000 claims description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 22
- 238000002834 transmittance Methods 0.000 claims description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 18
- 239000011737 fluorine Substances 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 230000009477 glass transition Effects 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 150000004984 aromatic diamines Chemical class 0.000 claims description 8
- 125000000962 organic group Chemical group 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000005567 fluorenylene group Chemical group 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 abstract description 14
- 239000010408 film Substances 0.000 description 77
- 230000000052 comparative effect Effects 0.000 description 19
- 125000001424 substituent group Chemical group 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 239000002243 precursor Substances 0.000 description 11
- 229920005575 poly(amic acid) Polymers 0.000 description 10
- 239000004033 plastic Substances 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 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 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000011342 resin composition Substances 0.000 description 8
- 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 7
- 239000011521 glass Substances 0.000 description 7
- FMACFWAQBPYRFO-UHFFFAOYSA-N 5-[9-(1,3-dioxo-2-benzofuran-5-yl)fluoren-9-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 FMACFWAQBPYRFO-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 125000001188 haloalkyl group Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 150000008064 anhydrides Chemical group 0.000 description 4
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
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- 230000001681 protective effect Effects 0.000 description 3
- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 229920001709 polysilazane Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- AETVBWZVKDOWHH-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(1-ethylazetidin-3-yl)oxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OC1CN(C1)CC AETVBWZVKDOWHH-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- HCDJVEYJSSTYSW-UHFFFAOYSA-N 2-propan-2-yloxyethyl acetate Chemical compound CC(C)OCCOC(C)=O HCDJVEYJSSTYSW-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- QMAQLCVJIYANPZ-UHFFFAOYSA-N 2-propoxyethyl acetate Chemical compound CCCOCCOC(C)=O QMAQLCVJIYANPZ-UHFFFAOYSA-N 0.000 description 1
- LVYXPOCADCXMLP-UHFFFAOYSA-N 3-butoxy-n,n-dimethylpropanamide Chemical compound CCCCOCCC(=O)N(C)C LVYXPOCADCXMLP-UHFFFAOYSA-N 0.000 description 1
- PVKDNXFNSSLPRN-UHFFFAOYSA-N 3-ethoxy-n,n-dimethylpropanamide Chemical compound CCOCCC(=O)N(C)C PVKDNXFNSSLPRN-UHFFFAOYSA-N 0.000 description 1
- LBVMWHCOFMFPEG-UHFFFAOYSA-N 3-methoxy-n,n-dimethylpropanamide Chemical compound COCCC(=O)N(C)C LBVMWHCOFMFPEG-UHFFFAOYSA-N 0.000 description 1
- RHLVCLIPMVJYKS-UHFFFAOYSA-N 3-octanone Chemical compound CCCCCC(=O)CC RHLVCLIPMVJYKS-UHFFFAOYSA-N 0.000 description 1
- MVODMCPZFNNNBR-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(C1=C(C=CC(=C1)N)C1=C(C=C(N)C=C1)C(F)(F)F)(F)F.FC(C1=C(C=CC(=C1)N)C1=C(C=C(N)C=C1)C(F)(F)F)(F)F MVODMCPZFNNNBR-UHFFFAOYSA-N 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006001 Methyl nonyl ketone Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- KMPQYAYAQWNLME-UHFFFAOYSA-N Undecanal Natural products CCCCCCCCCCC=O KMPQYAYAQWNLME-UHFFFAOYSA-N 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005332 alkyl sulfoxy group Chemical group 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
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- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 235000013336 milk Nutrition 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 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 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- KYWIYKKSMDLRDC-UHFFFAOYSA-N undecan-2-one Chemical compound CCCCCCCCCC(C)=O KYWIYKKSMDLRDC-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5397—Phosphine oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
- H10K77/111—Flexible substrates
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133305—Flexible substrates, e.g. plastics, organic film
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/311—Flexible OLED
Definitions
- the present invention relates to a polyimide resin film capable of implementing excellent optical properties and high heat resistance, a substrate for a flexible display device using the same, and a flexible display device.
- the display device market is rapidly changing mainly for flat panel displays (FPDs) that have a large area and can be thin and lightweight.
- Such flat panel displays include a liquid crystal display (LCD), an organic light emitting display (OLED), or an electrophoretic display (EPD).
- LCD liquid crystal display
- OLED organic light emitting display
- EPD electrophoretic display
- a TFT device is manufactured by forming a multilayer inorganic film such as a buffer layer, an active layer, and a gate insulator on a cured polyimide.
- the plastic substrate As a plastic substrate is applied to a flexible type display, a problem such as a restored afterimage appears.
- the plastic substrate has a problem in that heat resistance, thermal conductivity, and electrical insulation are inferior compared to the glass substrate.
- Polyimide resin is easy to synthesize, can be manufactured into a thin film, and has the advantage of being applicable to high-temperature processes.
- polyimide resin is widely applied as an integration material for semiconductor materials.
- many studies are being conducted to apply the polyimide resin to a flexible plastic display board that requires light and flexible properties.
- the present invention relates to a polyimide resin film capable of implementing excellent optical properties and high heat resistance.
- Another object of the present invention is to provide a substrate for a flexible display device using the polyimide resin film, and a flexible display device.
- a polyimide resin including a repeating unit derived from a reaction product between three or more types of aromatic tetracarboxylic acids or derivatives thereof having different structures and an aromatic diamine is included, and wavelengths of 450 nm and 550 nm are provided.
- a polyimide resin film having a transmittance of 70% or more, a coefficient of thermal expansion of -10 ppm/°C or more and 30 ppm/°C or less in a temperature range of 100°C or more and 400°C or less, and a glass transition temperature of 400°C or more do.
- a substrate for a flexible display device comprising the polyimide resin film.
- a flexible display device including the polyimide resin film is also provided.
- first element may be referred to as a second element, and similarly, a second element may be referred to as a first element.
- the (co)polymer is meant to include both polymers or copolymers, the polymer means a homopolymer consisting of a single repeating unit, and the copolymer means a composite polymer containing two or more kinds of repeating units.
- substituted means that other functional groups are bonded instead of hydrogen atoms in the compound, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, the position where the substituent is substituted, is not limited, and when two or more substituted , two or more substituents may be the same as or different from each other.
- substituted or unsubstituted refers to deuterium; halogen group; cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amide group; primary amino group; carboxyl group; sulfonic acid group; sulfonamide group; a phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; alkoxysilylalkyl group; an arylphosphine group; Or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the
- a substituent in which two or more substituents are connected may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.
- aromatic is a characteristic that satisfies the Huckels Rule, and a case in which all of the following three conditions are satisfied according to the Huckels Rule may be defined as aromatic.
- the alkyl group is a monovalent functional group derived from an alkane, and may be straight-chain or branched, and the number of carbon atoms in the straight-chain alkyl group is not particularly limited, but is preferably 1 to 20. In addition, the number of carbon atoms of the branched chain alkyl group is 3 to 20.
- alkyl group examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-non
- the haloalkyl group refers to a functional group in which a halogen group is substituted with the aforementioned alkyl group, and examples of the halogen group include fluorine, chlorine, bromine or iodine.
- the haloalkyl group may be substituted or unsubstituted, and when substituted, examples of the substituent are as described above.
- a multivalent functional group is a residue in a form in which a plurality of hydrogen atoms bonded to an arbitrary compound are removed, and may include, for example, a divalent functional group, a trivalent functional group, and a tetravalent functional group.
- the tetravalent functional group derived from cyclobutane refers to a residue in which 4 hydrogen atoms bonded to cyclobutane are removed.
- the electron withdrawing group may include at least one selected from the group consisting of a haloalkyl group, a halogen group, a cyano group, a nitro group, a sulfonic acid group, a carbonyl group and a sulfonyl group, preferably
- it may be a haloalkyl group such as a trifluoromethyl group (-CF 3 ).
- a direct bond or a single bond means that no atom or group of atoms is present at the corresponding position, and thus is connected by a bonding line. Specifically, it means a case in which a separate atom does not exist in the portion represented by L 1 and L 2 in the formula.
- the weight average molecular weight means the weight average molecular weight in terms of polystyrene measured by the GPC method.
- a commonly known analyzer a detector such as a differential refraction detector, and a column for analysis may be used, and the temperature at which it is normally applied Conditions, solvents, and flow rates can be applied.
- the evaluation temperature is 160 ° C.
- the flow rate was 1 mL/min, and the sample was prepared at a concentration of 10 mg/10 mL, and then supplied in an amount of 200 ⁇ L, and the value of Mw can be obtained using a calibration curve formed using a polystyrene standard.
- the molecular weight of the polystyrene standard was 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.
- a polyimide resin including a repeating unit derived from a reaction product between three or more aromatic tetracarboxylic acids or derivatives thereof having different structures and an aromatic diamine, and transmittance at 450 nm and 550 nm wavelengths.
- a polyimide resin including a repeating unit derived from a reaction product between three or more aromatic tetracarboxylic acids or derivatives thereof having different structures and an aromatic diamine, and transmittance at 450 nm and 550 nm wavelengths.
- the coefficient of thermal expansion is -10 ppm/°C or more and 30 ppm/°C or less in the temperature range of 100°C or more and 400°C or less
- the glass transition temperature is 400°C or more
- a polyimide resin film can be provided.
- transmittance at wavelengths of 450 nm and 550 nm is 70% or more, respectively, and the thermal expansion coefficient is -10 ppm/°C or more and 30 ppm/ °C or less, and the glass transition temperature satisfies 400 °C or higher, excellent optical properties of colorless and transparent can be realized through low yellowness and excellent transmittance, and at the same time, high heat resistance properties can be realized by showing a low coefficient of thermal expansion. It was confirmed through experiments and the invention was completed.
- the polyimide resin refers to all of polyimide, and polyamic acid and polyamic acid ester, which are precursor polymers thereof. That is, the polyimide resin may include at least one selected from the group consisting of a polyamic acid repeating unit, a polyamic acid ester repeating unit, and a polyimide repeating unit. That is, the polyimide-based polymer may include one polyamic acid repeating unit, one polyamic acid ester repeating unit, one polyimide repeating unit, or a copolymer in which two or more repeating units thereof are mixed.
- At least one repeating unit selected from the group consisting of the polyamic acid repeating unit, the polyamic acid ester repeating unit, and the polyimide repeating unit may form the main chain of the polyimide resin.
- the polyimide resin film may include a cured product of the polyimide resin.
- the cured product of the polyimide resin means a product obtained through the curing process of the polyimide resin.
- the polyimide resin film may include a repeating unit including at least one selected from the group consisting of a repeating unit represented by the following Chemical Formula 1, a repeating unit represented by the following Chemical Formula 2, and a repeating unit represented by the following Chemical Formula 3;
- a polyimide repeating unit represented by the following formula (4); and a polyimide repeating unit represented by the following Chemical Formula 5; may include
- R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, the rest is hydrogen, and X 1 to X 3 are each independently a tetravalent functional group represented by Formula 6 below. a tetravalent organic group, wherein Y 1 to Y 3 are each independently a divalent organic group substituted with at least one fluorine-based functional group,
- Ar is a polycyclic aromatic divalent functional group
- X 1 ' is an aromatic tetravalent functional group having 8 or less carbon atoms
- Y 1 ' is an aromatic divalent functional group substituted with at least one fluorine-based functional group
- X 1 is an aromatic tetravalent functional group having 9 or more and 15 or less carbon atoms
- Y 1 is an aromatic divalent functional group in which at least one fluorine-based functional group is substituted.
- the polyimide resin is represented by Formula 4 together with a repeating unit including at least one selected from the group consisting of a repeating unit represented by Formula 1, a repeating unit represented by Formula 2, and a repeating unit represented by Formula 3 a polyimide repeating unit represented; and a polyimide repeating unit represented by Formula 5;
- a repeating unit including at least one selected from the group consisting of a repeating unit represented by Formula 1, a repeating unit represented by Formula 2, and a repeating unit represented by Formula 3 a polyimide repeating unit represented; and a polyimide repeating unit represented by Formula 5;
- X 1 to X 3 are each independently a tetravalent organic group including a tetravalent functional group represented by Formula 6, wherein X 1 to X 3 are tetracarboxylic acid used for synthesizing polyimide resin. It is a functional group derived from a dianhydride compound.
- Ar is a polycyclic aromatic divalent functional group.
- the polycyclic aromatic divalent functional group is a polycyclic aromatic hydrocarbon compound or a divalent functional group derived from a derivative compound thereof, and may include a fluorenylene group.
- the derivative compound includes all compounds in which one or more substituents are introduced or carbon atoms are replaced with heteroatoms.
- the polycyclic aromatic divalent functional group may include a fused cyclic divalent functional group containing at least two or more aromatic ring compounds. That is, in the multicyclic aromatic divalent functional group, at least two or more aromatic ring compounds may be contained in the functional group structure, and the functional group may have a fused ring structure.
- the aromatic ring compound may include an arene compound containing one or more benzene rings, or a hetero arene compound in which a carbon atom in the arene compound is replaced with a hetero atom.
- the aromatic ring compound may be contained in at least two or more of the polycyclic aromatic divalent functional group, and each of the two or more aromatic ring compounds may form a directly fused ring or a fused ring through another ring structure.
- each of the two or more aromatic ring compounds may form a directly fused ring or a fused ring through another ring structure.
- two benzene rings are each joined to a cycloalkyl ring structure, it can be defined that two benzene rings form a fused ring through the cycloalkyl ring.
- the fused cyclic divalent functional group containing at least two or more aromatic ring compounds is a divalent functional group derived from a fused cyclic compound containing at least two or more aromatic ring compounds or a derivative compound thereof, wherein the derivative compound has one or more substituents introduced therein. or a compound in which a carbon atom is replaced by a hetero atom.
- the tetravalent functional group represented by Chemical Formula 6 may include a functional group represented by the following Chemical Formula 6-1.
- Y 1 to Y 3 are each independently a divalent organic group substituted with at least one fluorine-based functional group, and Y 1 to Y 3 are polyamic acid, polyamic acid ester, or polyimide synthesis. It may be a functional group derived from a diamine compound used in the present invention.
- CTC charge transfer complex
- the divalent organic group in which at least one fluorine-based functional group is substituted may include a functional group represented by the following formula (7).
- P is an integer of 0 or more and 5 or less.
- the polyimide resin is a terminal anhydride group (-OC-O-CO-) of tetracarboxylic dianhydride and a terminal amino group (-NH 2 ) of an aromatic diamine substituted with at least one fluorine-based functional group.
- a bond between the nitrogen atom and the carbon atom of the anhydride group may be formed.
- the polyimide resin may include a combination of tetracarboxylic dianhydride represented by the following Chemical Formula 10 and aromatic diamine in which at least one fluorine-based functional group is substituted.
- Ar ' is a polycyclic aromatic divalent functional group.
- the polycyclic aromatic divalent functional group is a divalent functional group derived from a polycyclic aromatic hydrocarbon compound, and is a divalent functional group derived from a fluorenylene group or a derivative compound thereof, and may include a fluorenylene group.
- the derivative compound includes all compounds in which one or more substituents are introduced or carbon atoms are replaced with heteroatoms.
- tetracarboxylic dianhydride represented by Chemical Formula 10 examples include 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (9,9-Bis(3,4-dicarboxyphenyl)fluorene Dianhydride, BPAF) can be heard
- the aromatic diamine substituted with at least one fluorine-based functional group is a compound in which an amino group (-NH 2 ) is bonded to both terminals of an aromatic divalent functional group substituted with at least one or more fluorine-based functional groups, and a fluorine-based functional group is substituted with at least one aromatic diamine
- the description of the divalent functional group is the same as described above.
- the polyimide resin is a terminal anhydride group (-OC-O-CO-) of the tetracarboxylic acid dianhydride represented by Chemical Formula 10 and a terminal amino group (-NH 2 ) of an aromatic diamine in which at least one fluorine-based functional group is substituted. ), a bond between the nitrogen atom of the amino group and the carbon atom of the anhydride group may be formed.
- X 1 ′ may be an aromatic tetravalent functional group having 8 or less carbon atoms
- X 1 ′′ may be an aromatic tetravalent functional group having 9 or more carbon atoms and 15 or less carbon atoms.
- the aromatic tetravalent functional group may be one of the tetravalent functional groups represented by the following Chemical Formula 13.
- R 1 to R 6 are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms
- L 3 is a single bond, -O-, -CO-, -COO-, -S-, -SO-, -SO 2 -, -CR 7 R 8 -, -(CH 2 ) t -, -O(CH 2 ) t O-, -COO(CH 2 ) t OCO-, -CONH-, phenylene, or their Any one selected from the group consisting of combinations, wherein R 7 and R 8 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a halo alkyl group having 1 to 10 carbon atoms, and t is an integer from 1 to 10 .
- the aromatic tetravalent functional group having 8 or less carbon atoms may include a functional group represented by the following Chemical Formula 10.
- the polyimide resin may include a polyimide repeating unit including an aromatic tetravalent functional group having 8 or less carbon atoms including a functional group represented by Chemical Formula 10.
- aromatic tetravalent functional group having 9 or more and 15 or less carbon atoms may include a functional group represented by the following formula (11).
- L is a single bond, -O-, -CO-, -COO-, -S-, -SO-, -SO 2 -, -CR 7 R 8 -, -(CH 2 ) t -, - O(CH 2 ) t O-, -COO(CH 2 ) t OCO-, -CONH-, phenylene, or any one selected from the group consisting of a combination thereof, and t is an integer of 1 to 10.
- the polyimide resin may include a polyimide repeating unit including an aromatic tetravalent functional group having 9 or more and 15 or less carbon atoms including a functional group represented by Chemical Formula 11.
- aromatic tetravalent functional group having 9 or more and 15 or less carbon atoms may be a functional group represented by the following Chemical Formula 11-1.
- the polyimide resin is a functional group derived from a tetracarboxylic dianhydride compound used for synthesizing polyimide resin, a repeating unit including a tetravalent functional group represented by Formula 6, and a functional group represented by Formula 10. It may include a polyimide repeating unit including an aromatic tetravalent functional group of 8 or less, and a polyimide repeating unit including an aromatic tetravalent functional group having 9 or more and 15 or less carbon atoms including a functional group represented by Chemical Formula 11.
- the polymer is a repeating unit represented by Formula 1, wherein the functional group derived from tetracarboxylic acid dianhydride is a tetravalent functional group represented by Formula 6, a repeating unit represented by Formula 2, and a repeating unit represented by Formula 3 a first repeating unit containing a repeating unit comprising at least one selected from the group consisting of; a second repeating unit containing a polyimide repeating unit represented by Formula 4, wherein the functional group derived from tetracarboxylic dianhydride is an aromatic tetravalent functional group having 8 or less carbon atoms; and a third repeating unit containing a polyimide repeating unit represented by Formula 5, wherein the functional group derived from tetracarboxylic acid dianhydride is an aromatic tetravalent functional group having 9 to 15 carbon atoms; may include The first to third repeating units are randomly arranged in the polyimide-based polymer to form a random copolymer, or blocks between the first repeating
- the polymer including the first repeating unit to the third repeating unit can be prepared by reacting three or more different tetracarboxylic dianhydride compounds with a diamine compound.
- a block copolymer may be synthesized by synthesizing the coalesces or by sequentially adding them.
- the polyimide resin may include 51 mol% or more and 90 mol% or less of the polyimide repeating unit represented by Chemical Formula 4 with respect to 100 mol% of the total repeating unit.
- the thermal expansion coefficient is 35 ppm/° C. or higher, thereby reducing heat resistance, and the polyimide repeating unit represented by Chemical Formula 4 When it contains more than 90 mol%, there may be a problem in that the optical properties are remarkably poor.
- the polyimide resin film synthesized from the polyimide resin within the above numerical range has a glass transition temperature of 400 °C or higher, and the measured coefficient of thermal expansion is -10 ppm/°C or higher by raising the temperature in a temperature range of 100 °C or more and 400 °C or more. It is 30 ppm/°C or less, and transmittance at a wavelength of 450 nm in a thickness of 10 ⁇ m can satisfy 70% or more and 99% or less at the same time.
- the polyimide resin based on 100 mol% of the total repeating unit, at least one selected from the group consisting of the repeating unit represented by Formula 1, the repeating unit represented by Formula 2, and the repeating unit represented by Formula 3 5 mol% or more and 20 mol% or less, 10 mol% or more and 15 mol% or less, 10 mol% or more and 13 mol% or less, 10 mol% or more and 12.5 mol% or less, or 10 mol% or more and 12 mol% or less can be included as
- the polymer contains less than 5 mol% of a repeating unit including at least one selected from the group consisting of a repeating unit represented by Formula 1, a repeating unit represented by Formula 2, and a repeating unit represented by Formula 3 , haze, yellowness, and optical properties such as transmittance are poor, and there may be technical problems in that heat resistance is also lowered.
- the polyimide resin film synthesized from the polyimide resin within the above numerical range has a glass transition temperature of 400 °C or higher, and the measured coefficient of thermal expansion is -10 ppm/°C or higher by raising the temperature in a temperature range of 100 °C or more and 400 °C or more. It is 30 ppm/°C or less, and transmittance at a wavelength of 450 nm in a thickness of 10 ⁇ m can satisfy 70% or more and 99% or less at the same time.
- the polymer may include 1 mol% or more and 40 mol% or less, 5 mol% or more and 40 mol% or less, 5 mol% or more and 35 mol% or less of the polyimide repeating unit represented by Formula 5.
- the polymer contains 1 mol% or more and 40 mol% or less of the polyimide repeating unit represented by Chemical Formula 5, the polymer can exhibit excellent optical properties and realize high heat resistance.
- the polyimide resin film synthesized from the polyimide resin within the above numerical range has a glass transition temperature of 400 °C or higher, and the measured coefficient of thermal expansion is -10 ppm/°C or higher by raising the temperature in a temperature range of 100 °C or more and 400 °C or more. It is 30 ppm/°C or less, and transmittance at a wavelength of 450 nm in a thickness of 10 ⁇ m can satisfy 70% or more and 99% or less at the same time.
- a repeating unit comprising at least one selected from the group consisting of a repeating unit represented by Formula 1, a repeating unit represented by Formula 2, and a repeating unit represented by Formula 3, a polyimide repeating unit represented by Formula 4, and
- the polyimide repeating unit represented by Formula 5 is 70 mol% or more, or 80 mol% or more, or 90 mol% or more, or 70 mol% or more and 100 mol% or less, 80 mol% or more, based on the total repeating unit contained in the polyimide resin.
- % or more and 100 mol% or less 70 mol% or more and 90 mol% or less, 70 mol% or more and 99 mol% or less, 80 mol% or more and 99 mol% or less, 90 mol% or more and 99 mol% or less.
- the polyimide resin may be a repeating unit including at least one selected from the group consisting of the repeating unit represented by Chemical Formula 1, the repeating unit represented by Chemical Formula 2, and the repeating unit represented by Chemical Formula 3, and represented by Chemical Formula 4 It consists of only the polyimide repeating unit represented by the polyimide repeating unit and the polyimide repeating unit represented by Chemical Formula 5, or most of the repeating unit represented by Chemical Formula 1, the repeating unit represented by Chemical Formula 2, and the repeating unit represented by Chemical Formula 3 It may consist of a repeating unit including at least one selected from the group consisting of, a polyimide repeating unit represented by Chemical Formula 4, and a polyimide repeating unit represented by Chemical Formula 5.
- other diamines other than diamines capable of inducing an aromatic divalent functional group substituted with at least one fluorine-based functional group may not be mixed, or may be mixed in a fraction of less than 1 mol%.
- the polyimide resin film may include a compound represented by the following Chemical Formula 9.
- R 3 to R 5 are each independently hydrogen, a hydroxyl group, an alkyl group, or an aryl group.
- R 3 to R 5 may each independently be an aryl group.
- the compound represented by Formula 9 may include a compound represented by Formula 9-1 below.
- the compound represented by Formula 9 may be included in an amount of 0.5 wt% or more and 20 wt% or less based on the total weight of the polymer solid content.
- the polyimide resin film has a glass transition temperature of 400 °C or more, and a thermal expansion coefficient measured by increasing the temperature in a temperature range of 100 °C or more and 400 °C or less is -10 ppm/°C or more and 30 ppm/°C or less, and , the transmittance at a wavelength of 450 nm at a thickness of 10 ⁇ m can satisfy 70% or more and 99% or less at the same time.
- the polyimide resin film has a transmittance of 70% or more at wavelengths of 450 nm and 550 nm, respectively, and a thermal expansion coefficient of -10 ppm/°C or more and 30 ppm/°C or less in a temperature range of 100 ° C. or more and 400 ° C. or less, and glass
- the transition temperature may be 400 °C or higher.
- thermomechanical analysis device Q400, TA
- the film pulling force is set to 0.2N
- the temperature is 100 to 400 °C
- the inflection point shown in the temperature increase section in the first temperature increase process can be obtained as Tg.
- the polyimide resin film may have a thermal expansion coefficient of -10 ppm/°C or more, 0 ppm/°C or more, and 30 ppm/°C or less, 25 ppm/°C, measured by raising the temperature in a temperature range of 100 °C or more and 400 °C or less. or less, 23 ppm/°C or less, and -10 ppm/°C or more and 30 ppm/°C or less, or -10 ppm/°C or more and 25 ppm/°C or less, or -10 ppm/°C or more and 23 ppm/°C or less, or 0 It may be ppm/°C or more and 23 ppm/°C or less.
- the coefficient of thermal expansion is, for the polyimide resin film sample, set the film pulling force to 0.2 N or less and 1 °C/min or more and 10 °C/min or less, or 4 in a temperature range including a temperature range of 100 °C to 400 °C
- the change in thermal expansion when the temperature is raised at a temperature increase rate of °C/min or more and 6°C/min or less is measured by TMA (Q400 manufactured by TA).
- the polyimide resin film has a low coefficient of thermal expansion, it is possible to improve heat resistance by alleviating deformation due to heat, and when using it as a plastic substrate, when the metal layer formed on the plastic substrate is heat-treated, the plastic substrate is heated by heat. It can prevent damage and also suppress the occurrence of warpage in the metal thin film formed on the plastic substrate.
- the polyimide film may have a yellow index YI of 1.0 or more and 25.0 or less at a thickness of 10 ⁇ m. If the yellow index YI at a thickness of 10 ⁇ m of the polyimide resin film is excessively increased to more than 25.0, the degree of yellow discoloration of the polyimide film increases, thereby making it difficult to manufacture a colorless and transparent film.
- Examples of the YI measurement method and equipment of the embodiment are not specifically limited, and various methods used for conventional YI measurement can be applied without limitation. For example, it can be measured using a color meter (GRETAGMACBETH's Color-Eye 7000A).
- the polyimide resin film may have transmittance of 70% or more at wavelengths of 450 nm and 550 nm, respectively.
- the polyimide film may have a transmittance at a wavelength of 450 nm at a thickness of 10 ⁇ m, 70% or more, 71% or more, 99% or less, 95% or less, or 80% or less, and 70% or more 99 % or less, 71% or more and 99% or less, 71% or more and 95% or less, and 71% or more and 80% or less.
- the transmittance at a wavelength of 450 nm at a thickness of 10 ⁇ m of the polyimide resin film is less than 70%, the degree of yellow discoloration of the polyimide film increases, thereby making it difficult to manufacture a colorless and transparent film.
- the polyimide film may have a transmittance of 70% or more, 80% or more, 85% or more, 88% or more, and 99% or less, 95% or less, or 90% or less at a 550 nm wavelength at a thickness of 10 ⁇ m. and 70% or more and 99% or less, 80% or more and 99% or less, 85% or more and 99% or less, 88% or more and 95% or less, 88% or more and 90% or less.
- the transmittance at a wavelength of 550 nm at a thickness of 10 ⁇ m of the polyimide resin film is less than 70%, the degree of yellow discoloration of the polyimide film increases, thereby making it difficult to manufacture a colorless and transparent film.
- Examples of the transmittance measuring method and equipment of the embodiment are not specifically limited, and various methods used for conventional transmittance measurement can be applied without limitation.
- UV-vis spectroscopy model name: HR-100, Murakami Color Research Laboratory
- T transmittance
- the polyimide resin film may have a Td of 1% of 500 °C or higher, 550 °C or higher, and 600 °C or lower, 554 °C or lower, or 500 °C or higher 600 °C or lower, 550 °C or higher 600 °C or lower, 550 °C or higher. It may be 554 °C or less.
- the Td of 1% may be realized as the polyimide resin film of the embodiment includes the above-described polyimide resin.
- the Td of 1% may mean a temperature when the weight reduction rate for the initial polyimide resin film is 1%, and is not particularly limited, but may be measured using, for example, Discovery TGA manufactured by TA Instruments.
- the polyimide resin film may have an elongation of 15% or more, 16% or more, 25% or less, 24% or less, 15% or more and 25% or less, 15% or more and 24% or less, or 16% or more and 24% or more. may be below.
- the elongation may be realized as the polyimide resin film of the embodiment includes the polyimide resin described above.
- a sample having a size of 5 mm * 100 mm and a thickness of 10 ⁇ m was prepared for the polyimide resin film of the embodiment, and the distance between grips was measured at 30 mm and 10 mm/min using Instron’s 3365 model equipment. have.
- the polyimide resin film may have a tensile strength of 215 MPa or more, 218 MPa or more, 350 MPa or less, 330 MPa or less, 320 MPa or less, 215 MPa or more and 350 MPa or less, 215 MPa or more and 330 MPa or less, 215 MPa or more and 320 MPa or less, or 218 MPa or more and 320 MPa or less.
- the tensile strength may be realized as the polyimide resin film of the embodiment includes the polyimide resin described above.
- tensile strength a sample of 5 mm * 100 mm size and 10 ⁇ m in thickness was prepared for the polyimide resin film of the embodiment, and the gap between grips was measured at 30 mm and 10 mm/min speed using Instron's 3365 model equipment.
- the polyimide resin film may have a tensile modulus of 5.3 GPa or more, 5.5 GPa or more, 7.0 GPa or less, 6.8 GPa or less, 6.7 GPa or less, 5.3 GPa or more 7.0 GPa or less, 5.3 GPa or more 6.8 GPa or less, 5.5 GPa or more and 6.8 GPa or less, or 5.5 GPa or more and 6.7 GPa or less.
- the tensile modulus may be realized as the polyimide resin film of the embodiment includes the above-described polyimide resin.
- tensile modulus a sample of 5 mm * 100 mm size and 10 ⁇ m in thickness was prepared for the polyimide resin film of the embodiment, and the gap between grips was measured at 30 mm and 10 mm/min speed using Instron's 3365 model equipment.
- the weight average molecular weight (measured by GPC) of the polyimide resin is not particularly limited, but may be, for example, 1000 g/mol or more and 200000 g/mol or less, or 10000 g/mol or more and 200000 g/mol or less.
- the polyimide resin according to the present invention can exhibit excellent colorless and transparent properties while maintaining properties such as heat resistance and mechanical strength due to a rigid structure, and can be used in device substrates, display cover substrates, optical films, It can be used in various fields such as IC (integrated circuit) package, electrodeposition film, multi-layer flexible printed circuit (FRC), tape, touch panel, protective film for optical disk, etc. It can be particularly suitable for cover substrate for display .
- IC integrated circuit
- FRC multi-layer flexible printed circuit
- examples of the method for synthesizing the polyimide resin film are not particularly limited, for example, forming a coating film by applying a resin composition containing the polyimide resin to a substrate (step 1); drying the coating film (step 2); A method for producing a film, including the step of curing the dried coating film by heat treatment (step 3), may be used.
- Step 1 is a step of forming a coating film by applying the resin composition containing the above-described polyimide resin to a substrate.
- a method of applying the resin composition containing the polyimide resin to the substrate is not particularly limited, and for example, a method such as screen printing, offset printing, flexographic printing, and inkjet printing may be used.
- the resin composition containing the polyimide resin may be dissolved or dispersed in an organic solvent.
- an organic solvent for example, when polyimide resin is synthesize
- polyimide resin is obtained as powder, what was made to melt
- organic solvent examples include toluene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl Pyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, gamma-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3- Ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoa Milk ketone, methyl isopropyl ketone, cyclohexanone, ethylene
- the resin composition containing the polyimide resin may include a solid content in an amount to have an appropriate viscosity in consideration of fairness such as applicability during the film forming process.
- the content of the composition may be adjusted so that the content of the total resin is 5 wt% or more and 25 wt% or less, or 5 wt% or more and 20 wt% or less, or 5 wt% or more and 15 wt% or less .
- the resin composition containing the polyimide resin may further include other components in addition to the organic solvent.
- the resin composition containing the polyimide resin when the resin composition containing the polyimide resin is applied, the uniformity of the film thickness or the surface smoothness is improved, the adhesion to the substrate is improved, or the dielectric constant or the conductivity is changed. , or an additive capable of increasing compactness may be additionally included.
- Such additives may be exemplified by a surfactant, a silane-based compound, a dielectric or a crosslinking compound, and the like.
- Step 2 is a step of drying the coating film formed by applying the resin composition containing the polyimide resin to the substrate.
- the drying step of the coating film may be carried out by a heating means such as a hot plate, a hot air circulation furnace, an infrared furnace, and may be performed at a temperature of 50 °C or more and 150 °C or less, or 50 °C or more and 100 °C or less.
- a heating means such as a hot plate, a hot air circulation furnace, an infrared furnace, and may be performed at a temperature of 50 °C or more and 150 °C or less, or 50 °C or more and 100 °C or less.
- Step 3 is a step of curing the dried coating film by heat treatment.
- the heat treatment may be performed by a heating means such as a hot plate, a hot air circulation furnace, an infrared furnace, and may be performed at a temperature of 200 °C or higher, or 200 °C or higher and 300 °C or lower.
- the thickness of the polyimide resin film is not particularly limited, but can be freely adjusted within, for example, 0.01 ⁇ m or more and 1000 ⁇ m or less. When the thickness of the polyimide resin film increases or decreases by a specific value, physical properties measured in the polyimide resin film may also change by a specific value.
- a substrate for a flexible display device including the polyimide resin film of the other embodiment may be provided.
- the content regarding the polyimide resin film may include all of the content described above in the embodiment.
- a display device including the substrate may be a liquid crystal display device (LCD), an organic light emitting diode (OLED), a flexible display, or a rollable display or foldable display. ) and the like, but is not limited thereto.
- LCD liquid crystal display device
- OLED organic light emitting diode
- flexible display or a rollable display or foldable display.
- the display device may have various structures depending on the field of application and specific form, for example, a structure including a cover plastic window, a touch panel, a polarizing plate, a barrier film, a light emitting device (OLED device, etc.), a transparent substrate, etc. have.
- the polyimide resin film of another embodiment described above may be used for various purposes such as a substrate, an external protective film, or a cover window in these various display devices, and more specifically, it may be applied as a substrate.
- the substrate for the flexible display device may have a structure in which a device protection layer, a transparent electrode layer, a silicon oxide layer, a polyimide resin film, a silicon oxide layer, and a hard coating layer are sequentially stacked.
- the transparent polyimide substrate may include a silicon oxide layer formed between the transparent polyimide resin film and the cured layer in terms of improving solvent resistance, moisture permeability, and optical properties, and the silicon oxide layer is polysila. It may be produced by curing the cup.
- the silicon oxide layer is formed by coating and drying a solution containing polysilazane before forming a coating layer on at least one surface of the transparent polyimide resin film, and then curing the coated polysilazane.
- the substrate for a display device can provide a transparent polyimide cover substrate having excellent warpage characteristics and impact resistance, and solvent resistance, optical characteristics, moisture permeability and scratch resistance by including the device protection layer described above. have.
- a flexible display device including the polyimide resin film of the other embodiment may be provided.
- the content regarding the polyimide resin film may include all of the content described above in the embodiment.
- the flexible display device may include all kinds of devices using properties realized by light, for example, a display device.
- a display device include a liquid crystal display device (LCD), an organic light emitting diode (OLED), a flexible display, or a rollable display or foldable display. and the like, but is not limited thereto.
- the flexible display device may have various structures depending on the field of application and specific form, and for example, a structure including a cover plastic window, a touch panel, a polarizing plate, a barrier film, a light emitting device (OLED device, etc.), a transparent substrate, etc. can
- the polyimide resin film of the other embodiments described above may be used for various purposes such as a substrate, an external protective film, or a cover window in these various flexible display devices, and more specifically, may be applied to a substrate.
- a polyimide resin film capable of implementing excellent optical properties and high heat resistance, a substrate for a flexible display device using the same, and a flexible display device can be provided.
- the polyimide precursor composition was spin-coated on a glass substrate.
- the glass substrate coated with the polyimide precursor composition was placed in an oven, heated at a rate of 5 °C / min, and cured by holding at 80 °C for 5 to 30 minutes, 250 °C for 30 minutes, and 400 °C for 30 to 40 minutes. The process proceeded.
- the glass substrate was immersed in water to remove the film formed on the glass substrate and dried in an oven at 100° C. to prepare a polyimide film having a thickness of 10 ⁇ m.
- a polyimide precursor composition and a polyimide film were prepared in the same manner as in Example 1, except that the molar ratio of each monomer was changed as shown in Table 1 below.
- TPPO triphenylphosphine oxide
- Example 1 55 35 10 99.9 - Example 2 60 30 10 99.9 - Example 3 65 25 10 99.9 - Example 4 70 20 10 99.9 - Example 5 80 5 15 99.9 - Example 6 55 35 10 99.9 2 Example 7 60 30 10 99.9 2 Example 8 65 25 10 99.9 2 Example 9 70 20 10 99.9 2 Example 10 80 5 15 99.9 2 Comparative Example 1 45 45 10 99.9 - Comparative Example 2 50 49 10 99.9 - Comparative Example 3 45 45 10 99.9 2 Comparative Example 4 20 75 One 99.9 2
- the sample was loaded using an accessory.
- the length of the film actually measured was the same as 16 mm.
- the coefficient of linear thermal expansion of the polyimide-based film was measured as an average value in the range of 100 to 400°C from the growth of the test piece at a load of 0.2 N/film thickness of 10 ⁇ m and a temperature increase rate of 5°C/min. At this time, the inflection point seen in the temperature increase section in the first temperature raising process was taken as Tg.
- UV-vis spectroscopy (model name: HR-100, Murakami Color Research Laboratory) for the polyimide films prepared in Examples and Comparative Examples according to the measurement method of JIS K 7105 to light of wavelengths of 450 nm and 550 nm
- the transmittance (T) was measured and shown in Table 2 below.
- the temperature when the weight reduction rate of the first polyimide film was 1% in a nitrogen atmosphere was measured using Discovery TGA of TA Instruments, and it is shown in Table 2 below.
- the gap between grips was 30 mm and 10 mm/min using Instron's 3365 model equipment.
- the elongation (%), tensile strength (MPa) and tensile modulus (GPa) of each resin film were measured, and are shown in Table 2 below.
- Example 1 19 >400 76 87 550 20 299 5.5
- Example 2 14 >400 73 86 550 24 281 6.0
- Example 3 9 >400 73 86 552 20 271 6.2
- Example 4 5 >400 71 86 552 17 261 6.6
- Example 5 >400 73 86 552 24 263 6.7
- Example 6 23 >400 77 87 554 19 230 5.6
- Example 7 16 >400 76 87 554 20 263 6.0
- Example 8 11 >400 75 87 554 16 218 6.3
- Example 9 7 >400 75 87 554 24 317 6.7
- Example 10 8 >400 76 87 554 18 277 6.7 Comparative Example 1 36 >400 76 87 550 21 168 5.0
- the polyimide film obtained in Examples showed excellent optical properties and showed a small coefficient of thermal expansion, thereby suppressing shrinkage and expansion at high temperatures. excellence was confirmed.
- the polyimide films of Comparative Examples are inferior in optical properties and heat resistance to those of Examples, and in particular, the coefficient of thermal expansion is large, resulting in shrinkage and expansion at high temperatures as well as heat resistance, as well as mechanical properties such as tensile strength and tensile modulus. Also, it was confirmed that it was significantly inferior.
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Abstract
Description
구분 | PMDA (몰%) |
BPDA (몰%) |
BPAF (몰%) |
TFMB (몰%) |
TPPO (중량%) |
실시예1 | 55 | 35 | 10 | 99.9 | - |
실시예2 | 60 | 30 | 10 | 99.9 | - |
실시예3 | 65 | 25 | 10 | 99.9 | - |
실시예4 | 70 | 20 | 10 | 99.9 | - |
실시예5 | 80 | 5 | 15 | 99.9 | - |
실시예6 | 55 | 35 | 10 | 99.9 | 2 |
실시예7 | 60 | 30 | 10 | 99.9 | 2 |
실시예8 | 65 | 25 | 10 | 99.9 | 2 |
실시예9 | 70 | 20 | 10 | 99.9 | 2 |
실시예10 | 80 | 5 | 15 | 99.9 | 2 |
비교예1 | 45 | 45 | 10 | 99.9 | - |
비교예2 | 50 | 49 | 10 | 99.9 | - |
비교예3 | 45 | 45 | 10 | 99.9 | 2 |
비교예4 | 20 | 75 | 1 | 99.9 | 2 |
구분 | CTE (ppm/℃) |
Tg (℃) |
투과도(%) @450 nm |
투과도(%) @550 nm |
Td 1% | 연신율 (%) |
인장강도 (MPa) |
인장 모듈러스 (GPa) |
실시예1 | 19 | >400 | 76 | 87 | 550 | 20 | 299 | 5.5 |
실시예2 | 14 | >400 | 73 | 86 | 550 | 24 | 281 | 6.0 |
실시예3 | 9 | >400 | 73 | 86 | 552 | 20 | 271 | 6.2 |
실시예4 | 5 | >400 | 71 | 86 | 552 | 17 | 261 | 6.6 |
실시예5 | 6 | >400 | 73 | 86 | 552 | 24 | 263 | 6.7 |
실시예6 | 23 | >400 | 77 | 87 | 554 | 19 | 230 | 5.6 |
실시예7 | 16 | >400 | 76 | 87 | 554 | 20 | 263 | 6.0 |
실시예8 | 11 | >400 | 75 | 87 | 554 | 16 | 218 | 6.3 |
실시예9 | 7 | >400 | 75 | 87 | 554 | 24 | 317 | 6.7 |
실시예10 | 8 | >400 | 76 | 87 | 554 | 18 | 277 | 6.7 |
비교예1 | 36 | >400 | 76 | 87 | 550 | 21 | 168 | 5.0 |
비교예2 | 40 | >400 | 80 | 88 | 550 | 19 | 214 | 5.2 |
비교예3 | 42 | >400 | 79 | 88 | 552 | 16 | 193 | 5.0 |
비교예4 | 77 | >400 | 83 | 88 | 552 | 19 | 153 | 4.0 |
Claims (16)
- 상이한 구조를 갖는 3종 이상의 방향족 테트라카르복실산 또는 이의 유도체와 방향족 디아민 간의 반응물로부터 유래한 반복 단위를 포함한 폴리이미드 수지를 포함하고,450 nm 및 550nm 파장에서의 투과율이 각각 70 % 이상이고,100 ℃ 이상 400 ℃ 이하의 온도 범위에서 열팽창계수가 -10 ppm/℃ 이상 30 ppm/℃ 이하이고,유리전이온도가 400 ℃ 이상인, 폴리이미드 수지 필름.
- 제1항에 있어서,상기 폴리이미드 수지는하기 화학식 1로 표시되는 반복 단위, 하기 화학식 2로 표시되는 반복 단위 및 하기 화학식 3으로 표시되는 반복 단위로 이루어진 군에서 선택된 1종 이상을 포함한 반복 단위;하기 화학식 4로 표시되는 폴리이미드 반복단위; 및하기 화학식 5로 표시되는 폴리이미드 반복단위; 를 포함하는, 폴리이미드 수지 필름:[화학식 1][화학식 2][화학식 3]상기 화학식 1 내지 3에서,R1 및 R2 중 적어도 하나는 탄소수 1 내지 10의 알킬기이고, 나머지는 수소이며,X1 내지 X3는 각각 독립적으로 하기 화학식 6으로 표시되는 4가의 작용기를 포함하는 4가의 유기기이고,상기 Y1 내지 Y3은 각각 독립적으로 불소계 작용기가 적어도 1이상 치환된 2가의 유기기이며,[화학식6]상기 화학식 6에서,Ar은 다중고리 방향족 2가 작용기이고,[화학식 4]상기 화학식 4에서,X1’는 탄소수 8 이하의 방향족 4가의 작용기이며,Y1’은 불소계 작용기가 적어도 1이상 치환된 방향족 2가 작용기이고,[화학식 5]상기 화학식 5에서,X1”는 탄소수 9 이상 15 이하의 방향족 4가의 작용기이며,Y1”은 불소계 작용기가 적어도 1이상 치환된 방향족 2가 작용기이다.
- 제2항에 있어서,상기 화학식 6의 Ar에서,상기 다중고리 방향족 2가 작용기는적어도 2이상의 방향족 고리 화합물이 함유된 접합 고리형 2가 작용기를 포함하는, 폴리이미드 수지 필름.
- 제2항에 있어서,상기 화학식 6의 Ar에서,상기 다중고리 방향족 2가 작용기는 플루오레닐렌기를 포함하는, 폴리이미드 수지 필름.
- 제2항에 있어서,상기 폴리이미드 수지는,전체 반복 단위 100 몰%에 대하여,상기 화학식 4로 표시되는 폴리이미드 반복단위를 51 몰% 이상 90 몰% 이하로 포함하는, 폴리이미드 수지 필름.
- 제9항에 있어서,상기 폴리이미드 수지는,전체 반복 단위 100 몰%에 대하여,상기 화학식 1로 표시되는 반복 단위, 상기 화학식 2로 표시되는 반복 단위 및 상기 화학식 3으로 표시되는 반복 단위로 이루어진 군에서 선택된 1종 이상을 포함한 반복 단위를 5 몰% 이상 20 몰% 이하로 포함하는, 폴리이미드 수지 필름.
- 제10항에 있어서,상기 폴리이미드 수지는,전체 반복 단위 100 몰%에 대하여,상기 화학식 5로 표시되는 폴리이미드 반복단위를 1 몰% 이상 40 몰% 이하로 포함하는, 폴리이미드 수지 필름.
- 제12항에 있어서,상기 화학식 9로 표시되는 화합물은상기 중합체 고형분 전체 중량에 대하여 0.5 중량% 이상 20 중량% 이하로 포함되는, 폴리이미드 수지 필름.
- 제1항의 폴리이미드 수지 필름을 포함하는, 플렉서블 디스플레이 장치용 기판.
- 제1항의 폴리이미드 수지 필름을 포함하는, 플렉서블 디스플레이 장치.
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US18/250,172 US20240002602A1 (en) | 2020-11-18 | 2021-08-17 | Polyimide polymer film, substrate for flexible display device, and flexible display device using the same |
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