WO2016140559A1 - 광전소자의 플렉시블 기판용 폴리이미드 필름용 조성물 - Google Patents
광전소자의 플렉시블 기판용 폴리이미드 필름용 조성물 Download PDFInfo
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- WO2016140559A1 WO2016140559A1 PCT/KR2016/002263 KR2016002263W WO2016140559A1 WO 2016140559 A1 WO2016140559 A1 WO 2016140559A1 KR 2016002263 W KR2016002263 W KR 2016002263W WO 2016140559 A1 WO2016140559 A1 WO 2016140559A1
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- Prior art keywords
- polyimide
- group
- polyimide precursor
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 137
- 239000000758 substrate Substances 0.000 title claims abstract description 68
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 230000009975 flexible effect Effects 0.000 title claims abstract description 23
- 230000005693 optoelectronics Effects 0.000 title claims abstract description 10
- 239000004642 Polyimide Substances 0.000 claims abstract description 78
- 239000002243 precursor Substances 0.000 claims abstract description 74
- 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 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 21
- 150000004985 diamines Chemical class 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 35
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 239000011521 glass Substances 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000005192 partition Methods 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 150000003512 tertiary amines Chemical group 0.000 claims description 4
- 238000002834 transmittance Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 22
- 239000010408 film Substances 0.000 description 26
- -1 siloxane repeating unit Chemical group 0.000 description 23
- 125000000962 organic group Chemical group 0.000 description 21
- 239000000243 solution Substances 0.000 description 17
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 14
- 229920005575 poly(amic acid) Polymers 0.000 description 14
- 239000009719 polyimide resin Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 150000004678 hydrides Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 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 6
- 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 6
- 238000001035 drying Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- BCJIMAHNJOIWKQ-UHFFFAOYSA-N 4-[(1,3-dioxo-2-benzofuran-4-yl)oxy]-2-benzofuran-1,3-dione Chemical compound O=C1OC(=O)C2=C1C=CC=C2OC1=CC=CC2=C1C(=O)OC2=O BCJIMAHNJOIWKQ-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004618 QSPR study Methods 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 description 4
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 4
- 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 4
- 238000006358 imidation reaction Methods 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 125000003367 polycyclic group Chemical group 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000011160 research Methods 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
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000007611 bar coating method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000002837 carbocyclic group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- NYRFBMFAUFUULG-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=C(N)C=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=CC(N)=C1 NYRFBMFAUFUULG-UHFFFAOYSA-N 0.000 description 1
- NQZOFDAHZVLQJO-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(OC=3C=CC(OC=4C=C(N)C=CC=4)=CC=3)=CC=2)=C1 NQZOFDAHZVLQJO-UHFFFAOYSA-N 0.000 description 1
- UCQABCHSIIXVOY-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]phenoxy]aniline Chemical group NC1=CC=CC(OC=2C=CC(=CC=2)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 UCQABCHSIIXVOY-UHFFFAOYSA-N 0.000 description 1
- JERFEOKUSPGKGV-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfanylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(SC=3C=CC(OC=4C=C(N)C=CC=4)=CC=3)=CC=2)=C1 JERFEOKUSPGKGV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- YSMXOEWEUZTWAK-UHFFFAOYSA-N 3-[4-[[4-(3-aminophenoxy)phenyl]methyl]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(CC=3C=CC(OC=4C=C(N)C=CC=4)=CC=3)=CC=2)=C1 YSMXOEWEUZTWAK-UHFFFAOYSA-N 0.000 description 1
- MGENSHRLAKPCSM-UHFFFAOYSA-N 3-methylcyclohexane-1,1,2,2-tetracarboxylic acid Chemical compound CC1CCCC(C(O)=O)(C(O)=O)C1(C(O)=O)C(O)=O MGENSHRLAKPCSM-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- YARZEPAVWOMMHZ-UHFFFAOYSA-N 4-(3,4-dicarboxy-4-phenylcyclohexa-1,5-dien-1-yl)phthalic acid Chemical compound OC(=O)C1C=C(C=2C=C(C(C(O)=O)=CC=2)C(O)=O)C=CC1(C(O)=O)C1=CC=CC=C1 YARZEPAVWOMMHZ-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- QNLCDRXVEPWSBQ-UHFFFAOYSA-N 4-(4,5-dicarboxy-5-phenylcyclohexa-1,3-dien-1-yl)phthalic acid Chemical compound OC(=O)C1=CC=C(C=2C=C(C(C(O)=O)=CC=2)C(O)=O)CC1(C(O)=O)C1=CC=CC=C1 QNLCDRXVEPWSBQ-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
- 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 1
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- LDFYRFKAYFZVNH-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 LDFYRFKAYFZVNH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- TZKDBUSJDGKXOE-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfinylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 TZKDBUSJDGKXOE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PJCCVNKHRXIAHZ-UHFFFAOYSA-N 4-[4-[[4-(4-aminophenoxy)phenyl]methyl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1CC(C=C1)=CC=C1OC1=CC=C(N)C=C1 PJCCVNKHRXIAHZ-UHFFFAOYSA-N 0.000 description 1
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- 239000004971 Cross linker Substances 0.000 description 1
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- HKWWRLBGQRLBRM-UHFFFAOYSA-N [4-[4-(4-aminophenoxy)benzoyl]phenyl]-[4-(4-aminophenoxy)phenyl]methanone Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(=O)C=2C=CC(=CC=2)C(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HKWWRLBGQRLBRM-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
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- 125000003282 alkyl amino group Chemical group 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- BBRLKRNNIMVXOD-UHFFFAOYSA-N bis[4-(3-aminophenoxy)phenyl]methanone Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)C(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 BBRLKRNNIMVXOD-UHFFFAOYSA-N 0.000 description 1
- LSDYQEILXDCDTR-UHFFFAOYSA-N bis[4-(4-aminophenoxy)phenyl]methanone Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 LSDYQEILXDCDTR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- NAJAZZSIKSSBGH-UHFFFAOYSA-N butane-1,1,1,2-tetracarboxylic acid Chemical group CCC(C(O)=O)C(C(O)=O)(C(O)=O)C(O)=O NAJAZZSIKSSBGH-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- FGQOVSPPSXYIBT-UHFFFAOYSA-N cyclopropane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CC1(C(O)=O)C(O)=O FGQOVSPPSXYIBT-UHFFFAOYSA-N 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 125000005549 heteroarylene group Chemical group 0.000 description 1
- 125000006588 heterocycloalkylene group Chemical group 0.000 description 1
- JNWGOCSTXJQFEP-UHFFFAOYSA-N hexane-1,1,1,2-tetracarboxylic acid Chemical compound CCCCC(C(O)=O)C(C(O)=O)(C(O)=O)C(O)=O JNWGOCSTXJQFEP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000019988 mead Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MIVZUXGHPJSKRI-UHFFFAOYSA-N pentane-1,1,1,2-tetracarboxylic acid Chemical compound CCCC(C(O)=O)C(C(O)=O)(C(O)=O)C(O)=O MIVZUXGHPJSKRI-UHFFFAOYSA-N 0.000 description 1
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- 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
-
- 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
- C08G73/12—Unsaturated polyimide precursors
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the present invention relates to a composition for a polyimide film for flexible substrates of an optoelectronic device, and more particularly to a composition for producing polyimide film excellent in dimensional stability that does not increase the stress of the substrate even at high heat treatment.
- polyimide (PI) resin is easy to synthesize, can make thin film, and has the advantage of not needing a crosslinker for curing.
- PI polyimide
- a polyimide (PI) film prepared by filming the polyimide resin is generally a polyimide resin.
- a polyimide resin is prepared by solution polymerization of an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate to prepare a polyamic acid derivative, and then, at a high temperature. It refers to a high heat resistant resin produced by imidation by ring closure dehydration.
- the substrate for a flexible display is manufactured through a process of forming a film by coating a polyimide resin solution on a glass substrate and then subjecting it to high temperature heat treatment. At this time, due to the difference in the coefficient of thermal expansion (CTE) between the lower glass substrate and the polyimide film layer, there is a problem that the organic glass pin is bent after film formation. If the substrate is bent, it becomes difficult to stack the elements on the film and subsequent processing may become impossible.
- CTE coefficient of thermal expansion
- the present invention is to provide a composition for forming a polyimide film, which has high transparency and isotropy and is excellent in heat resistance and can improve warpage due to a difference in thermal expansion coefficient with a lower substrate.
- the present invention also provides a polyimide film having high transparency and isotropy and heat resistance from the polyimide composition.
- the present invention also provides a laminate in which the polyimide film is formed on a substrate and the stress is reduced even after high temperature heat treatment.
- the present invention also provides an optoelectronic device comprising the polyimide film as a flexible substrate.
- a polyimide precursor composition for a flexible substrate of a photovoltaic device containing a polyimide precursor derived from a diamine or an acid dianhydride comprising the structure of Formula 1:
- R 1 and R 2 are each independently a single bond, an alkylene group having 1 to 5 carbon atoms, or a divalent aromatic group having 6 or more carbon atoms,
- R 3 and Each R 4 is independently an alkyl group of 1 to 5,
- R 5 and R 6 are each independently an aryl group having 4 to 10 carbon atoms
- At least one of R 7 and R 8 is an alkenyl group having 2 to 10 carbon atoms
- n1, m2 and m3 are each independently an integer of 1 or more.
- the polyimide precursor derived from diamine or acid dianhydride including the structure of Formula 1 may be 50% by weight or less based on the total weight of the polyimide precursor.
- the polyimide precursor derived from the diamine or acid dianhydride including the structure of Formula 1 may have a molecular weight of 600 or more and 7,000 or less.
- m1, m2, m3 in Formula 1 may be an integer of 1 to 10.
- the composition may be a polyimide precursor is dissolved in a solvent having a positive partition coefficient.
- the solvent may include an amine-based first solvent and a non-amine-based second solvent.
- the volume ratio of the amine-based first solvent and the non-amine-based second solvent may be 50 to 90:10 to 50.
- the amine-based first solvent may be a tertiary amine substituted with an alkyl group of 2 or more carbon atoms.
- non-amine solvent may be toluene or tetrahydrofuran.
- the polyimide precursor composition may further include silica-based particles.
- a polyimide film for a flexible substrate of a photoelectric device obtained by applying the composition on a glass substrate and then curing.
- the film may have an average transmittance of 80% or more with respect to light having a wavelength of 350 nm to 760 nm.
- the polyimide film may have a modulus of 4 GPa or less and a tensile stress of 150 MPa or less.
- the coefficient of thermal expansion (CTE) of the polyimide film may be 30 ppm or more and 200 ppm or less at 100 to 250 ° C.
- a laminate in which a polyimide film is formed on a glass substrate which is obtained by applying the composition on a glass substrate and then curing the composition.
- the laminate may be less than 60 MPa stress received by the substrate after the heat treatment process of 100 ⁇ 350 °C.
- the present invention also provides an optoelectronic device comprising the polyimide film as a flexible substrate.
- the present invention also provides a flexible display comprising the polyimide film as a flexible substrate.
- the polyimide film obtained by applying and curing the precursor composition according to the present invention on a substrate has high transparency and heat resistance, and the stress of the substrate does not rise even in high heat treatment, and thus the dimensional stability is excellent.
- the polyimide precursor composition according to the present invention may be applied to an organic light emitting diode (OLED) or a liquid crystal display (LCD), an electronic paper, or a flexible display substrate in an electronic device such as a solar cell. It is useful for manufacturing.
- 1 is a graph showing the principle of stress reduction after the high temperature process of the polyimide structure according to the present invention.
- the carbocyclic group includes both an alicyclic ring group and an aromatic ring group, and is meant to include their hetero rings.
- the "hetero” refers to a functional group containing 1 to 3 hetero atoms selected from the group consisting of N, O, S, P, and Si.
- C4 to C20 condensed polycyclic carbon ring group means a form in which two or more carbon rings are condensed with each other.
- C6 to C30 non-condensed polycyclic carbon ring group interconnected by a linker means a form in which two or more carbon rings are connected by a linker.
- the linker is a single bond, -O-, -CO-, -S-, -SO 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -CONH-, -COO-,- (CH 2) n1 -, and -O (CH 2) and the like n2 O-, -OCO (CH 2) n3 OCO-.
- substituted means a substituent selected from the group consisting of halogen, C1 to C15 haloalkyl group, nitro group, cyano group, C1 to C15 alkoxy group and C1 to C10 lower alkylamino group. It means substituted.
- * denotes a bonding position
- the elastic modulus Young's modulus or modulus
- the coefficient of thermal expansion of the polyimide film formed on the substrate were adjusted to an appropriate range, and as a result, the elastic modulus of 4 GPa or less and 30 to By having a thermal expansion coefficient of 200 ppm, the warpage after the high temperature heat treatment of the substrate could be improved.
- the polyimide precursor composition for a flexible substrate of an optoelectronic device is characterized by containing a polyimide precursor derived from a diamine or an acid dianhydride containing the structure of the following formula (1).
- R 1 and R 2 are each independently a single bond, an alkylene group having 1 to 5 carbon atoms, or a divalent aromatic group having 6 or more carbon atoms,
- R 3 and Each R 4 is independently an alkyl group of 1 to 5,
- R 5 and R 6 are each independently an aryl group having 4 to 10 carbon atoms
- At least one of R 7 and R 8 is an alkenyl group having 2 to 10 carbon atoms
- n1, m2 and m3 are each independently an integer of 1 or more.
- the repeating unit having the structure of Formula 1 includes a repeating unit substituted with an alkyl group, a siloxane repeating unit substituted with an aryl group, and a siloxane repeating unit substituted with an alkenyl group together, thereby producing a polyimide film having an elastic modulus of 4 GPa or less and 30 It can be made to have a thermal expansion coefficient of 200ppm.
- the order of the repeating unit substituted with the alkyl group, the siloxane repeating unit substituted with the aryl group, and the siloxane repeating unit substituted with the alkenyl group may be arbitrarily changed, or may be alternately positioned.
- a highly heat-resistant elastic polyimide by having a repeating unit substituted with an alkenyl group, and when applied to a display substrate, as shown in FIG.
- reducing the stress caused by thermal expansion-contraction of the mead can improve the substrate warpage phenomenon caused by the difference in thermal expansion coefficient with the substrate.
- a polyimide precursor derived from a diamine or an acid dianhydride comprising the structure of Formula 1 above, It can be used up to 50% by weight based on the weight.
- the content may be included 10 wt% or more and 40 wt% or less, and in another embodiment 10 wt% or more and 30 wt% or less.
- the molecular weight of the polyimide precursor may be 500 or more and 7,000 or less, preferably 500 or more and 5,000 or less.
- R 1 and R 2 may each independently be a single bond, an alkylene group having 1 to 5 carbon atoms, or a divalent aromatic group having 6 or more carbon atoms, and preferably an alkylene group having 3 or more carbon atoms. have.
- R 3 and R 4 is each independently an alkyl group of 1 to 5, and preferably may be a methyl or ethyl group.
- R 5 and R 6 are each independently an aryl group having 4 to 10 carbon atoms, preferably a phenyl group.
- At least one of R 7 and R 8 is an alkenyl group having 2 to 10 carbon atoms, preferably an ethenyl or propenyl group.
- the other alkenyl group may be an alkyl group having 1 to 5 carbon atoms.
- m1, m2, m3 in Formula 1 may be each independently an integer of 1 to 10, specifically m1 may be 3 to 9, m2 is 2 to 9, m3 may be an integer of 1 to 5. .
- the polyimide precursor may be formed from a mixture of a precursor of a polyimide having a structure of Formula 2 and a precursor of a polyimide having a structure of Formula 3.
- X 1 is a tetravalent organic group containing an aromatic, alicyclic or aliphatic group derived from an acid dianhydride
- Y 1 is a divalent organic group including a divalent organic group derived from a diamine represented by the following Formula 1a,
- p is an integer of 1 or more indicating a repeating unit.
- R 1 to R 8 and m1 to m3 are the same as those described in Chemical Formula 1.
- X 2 is a tetravalent organic group containing an aromatic, alicyclic or aliphatic group derived from an acid dianhydride
- Y 2 is a divalent organic comprising an aromatic, cycloaliphatic or aliphatic group derived from diamine,
- q is an integer of 1 or more indicating a repeating unit.
- At least one of Y 1 and Y 2 is a divalent organic group selected from the group consisting of aromatic, alicyclic and aliphatic groups derived from diamine, and has a substituent containing one or more fluoro atoms Can be.
- X 1 and X 2 are tetravalent organic groups represented by the following Formula 4, respectively, and Y 1 and Y 2 are represented by Formula 5 or Formula 6, respectively. May include one or more structures selected from organic groups.
- R 7 , R 8 , R 9 , and R 10 are each independently selected from a hydrogen atom, a halogen atom, or a hydroxy group,
- A is a single bond, -O-, -NH-, -CO-, -S-, -SO 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -CONH-, -COO -,-(CH 2 ) n 1- , -O (CH 2 ) n 2 O-, or -OCO (CH 2 ) n 3 OCO-, n 1 , n 2 and n 3 are each an integer from 1 to 10 ego,
- R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are each independently selected from a hydrogen atom, a halogen atom, or a hydroxy group.
- the content of the monomer including the siloxane structure of Formula 1 may be 5 mol% or more or 50 mol% or less, preferably 5 to 40 mol%. If less than 5 mol%, the warpage prevention effect of the substrate of the polyimide film is lowered, and if more than 50 mol%, the molecular weight decrease and heat resistance of the polyimide may be lowered, which means that the polyimide precursor is not less than 350 °C In the heat treatment process under high temperature conditions, the mechanical and thermal properties of the polyimide film may be reduced.
- the precursor including the polyimide structure of Formula 2 may further include a monomer having a tetravalent organic group of Formula 4 and a divalent organic group selected from Formula 5 or 6, the content of which is at least 10 mol% or at most 50 mol%, respectively. , Preferably 25 mol% to 50 mol%, more preferably 35 mol% to 50 mol%.
- the content of the monomer having a tetravalent organic group of Formula 4 and a divalent organic group of Formula 5 or 6 is 5 mol% or more or 50 mol% or less, preferably 20 to 50 mol%, More preferably, it may be included in an amount of 40 mol% to 50 mol%. According to the content ratio of the compounds of Formulas 4 to 6, the flexibility of the polyimide and the flowability during the high temperature process may be improved, and the heat resistance of the polyimide molecule may be improved during the high temperature process.
- X 1 , X 2 is a substituted or unsubstituted C4 to C20 carbocyclic group; Substituted or unsubstituted C4 to C20 condensed polycyclic carbocyclic group; And C6 to C30 non-condensed polycyclic carbon ring group interconnected by a substituted or unsubstituted linker; may further include one tetravalent organic group selected from the group consisting of.
- X 1 and X 2 may be one tetravalent organic group selected from the group consisting of Formulas 7a to 7d.
- R 31 to R 35 each independently represent an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, etc.) or 1 to 10 carbon atoms.
- Fluoroalkyl group for example, fluoromethyl group, perfluoroethyl group, trifluoromethyl group, etc.
- a 1 may be an integer of 0 or 2
- b 1 may be an integer of 0 to 4
- c 1 may be an integer of 0 to 8
- d 1 and e 1 may be each independently an integer of 0 to 3
- a 1 is a single bond, —O—, —CR 46 R 47 —, —C ( ⁇ O) —, —C ( ⁇ O) NH—, —S—, —SO 2 —, a phenylene group, or a combination thereof It may be selected from the group consisting of, wherein R 46 and R 47 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group) , Pentyl group, hexyl group, etc.) and a fluoroalkyl group having 1 to 10 carbon atoms (for example, fluoromethyl group, fluoroethyl group, trifluoromethyl group, etc.).
- R 46 and R 47 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propy
- X 1 and X 2 may be each independently selected from the group consisting of tetravalent organic groups of the formula 8a to 8t.
- x is an integer of 1 to 3.
- the aromatic tetravalent organic groups represented by Formulas 8a to 8n have one or more hydrogen atoms in the tetravalent organic group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group). Or a pentyl group, hexyl group, or the like) or a fluoroalkyl group having 1 to 10 carbon atoms (for example, a fluoromethyl group, a perfluoroethyl group, a trifluoromethyl group, and the like).
- 1 to 10 carbon atoms eg, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group.
- a pentyl group, hexyl group, or the like or a fluoroalkyl group having 1 to 10 carbon atoms (for example, a fluoromethyl group, a perfluoroe
- the tetravalent organic group derived from the acid dianhydride is butanetetracarboxylic dione hydride, pentanetetracarboxylic dione hydride, hexanetetracarboxylic dione hydride, cyclopentanetetracarboxylic dione hydride , Bicyclopentanetetracarboxylic dianhydride, cyclopropanetetracarboxylic dianhydride, methylcyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dione Hydride, 3,4,9,10-perylenetetracarboxylic dione hydride, 4,4'-sulfonyldiphthalic dione hydride, 3,3 ', 4,4'-biphenyltetracarboxylic Dionhydride, 1,2,5,6-naphthalenetetracarboxylic dionehydride,
- Y 1 and Y 2 are substituted or unsubstituted C1 to C20 alkylene groups, substituted or unsubstituted C5 to C40 arylene groups, It further includes one divalent organic group selected from the group consisting of a substituted or unsubstituted C3 to C40 heteroarylene group, a substituted or unsubstituted C5 to C40 cycloalkylene group, and a substituted or unsubstituted C5 to C40 heterocycloalkylene group. can do.
- the Y 2 may be one divalent organic group selected from the group consisting of Formulas 9a to 9d.
- L 1 is a single bond, -O-, -CO-, -S-, -SO 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -CONH-, -COO-,-(CH 2 ) n 1- , -O (CH 2 ) n 2 O-, -OCH 2 -C (CH 3 ) 2 -CH 2 O- or COO (CH 2 ) n 3 OCO- , N 1 , n 2 and n 3 are each an integer of 1 to 10.
- L 2 and L 3 may be the same as or different from each other, and each of a single bond, -O-, -CO-, -S-, -SO 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -CONH-, -COO-,-(CH 2 ) n 1- , -O (CH 2 ) n 2 O-, -OCH 2 -C (CH 3 ) 2 -CH 2 O- Or COO (CH 2 ) n 3 OCO—, wherein n 1 , n 2 and n 3 are each an integer from 1 to 10.
- L 4 , L 5, and L 6 may be the same as or different from each other, and each single bond, —O—, —CO—, —S—, —SO 2 —, —C (CH 3 ) 2 ⁇ , -C (CF 3 ) 2- , -CONH-, -COO-,-(CH 2 ) n 1- , -O (CH 2 ) n 2 O-, -OCH 2 -C (CH 3 ) 2 -CH 2 O- or COO (CH 2 ) n 3 OCO-, wherein n 1 , n 2 and n 3 are each an integer of 1 to 10.
- Y 2 may be selected from the group consisting of divalent organic groups of Formulas 10a to 10q.
- At least one hydrogen atom in the divalent functional group of Formulas 10a to 10q is an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, etc.).
- a fluoroalkyl group having 1 to 10 carbon atoms e.g., a fluoromethyl group, a perfluoroethyl group, a trifluoromethyl group, etc.
- an aryl group having 6 to 12 carbon atoms e.g., a phenyl group, naphthalenyl group, etc. It may be substituted with a substituent selected from the group consisting of a sulfonic acid group and a carboxylic acid group.
- diamine which has the said divalent organic group 4,4'- diamino diphenyl ether, 4,4'- diamino diphenyl sulfide, 4,4'- diamino diphenyl sulfone, 4, 4'-diaminobenzophenone, bis [4- (4-aminophenoxy) phenyl] methane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis (4-aminophenoxy) benzene, 4,4'-bis (4- Aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phen
- Production of polyamic acid through the polymerization reaction of the above acid dianhydride and diamine can be carried out according to a conventional polyamic acid polymerization production method such as solution polymerization. Specifically, it can be prepared by dissolving the diamine in an organic solvent, followed by polymerization by adding an acid dianhydride to the resulting mixed solution. At this time, the reaction may be carried out in anhydrous conditions, the temperature during the polymerization reaction may be carried out at 25 to 50 °C, preferably 40 to 45 °C.
- the composition may be a polyimide precursor is dissolved in a hydrophobic solvent exhibiting a positive partition coefficient.
- the distribution coefficient is calculated using an ACD / LogP module of ACD / Percepta platform of ACD / Labs (where ACD / LogP module is based on Quantitative Structure-Property Relationship (QSPR) methodology using a molecular 2D structure).
- QSPR Quantitative Structure-Property Relationship
- the distribution coefficient LogP value may be 0.01 to 3, or 0.01 to 2, or 0.01 to 1.
- the solution of the polyimide or its precursor is prepared using a hydrophobic solvent having a positive distribution coefficient value
- the dispersibility of the polyimide precursor is increased in the solvent, making it easy to prepare an amorphous polyimide polymer.
- a hydrophobic solvent having a positive value of the partition coefficient may be a mixed solvent of a two-component solvent of an amine-based first solvent and a non-amine-based second solvent.
- the polyimide precursor of Formula 1 tends to dissolve better when a non-amine hydrophobic solvent is present because of its high hydrophobicity.
- the first solvent and the second solvent can be used in a volume ratio of 50 to 90:10 to 50.
- the amine hydrophobic solvent may be a tertiary amine substituted with an alkyl group having 2 or more carbon atoms, and more preferably, a tertiary amine having two or more alkyl groups having 2 to 6 carbon atoms. More specifically, for example, N, N-diethylacetamide, N, N-diethylformamide, N-ethylpyrrolidone Or a mixture thereof. According to the researches of the present inventors, in particular, it was confirmed that the transparency of the film is improved when using N, N-diethylformamide.
- non-amine hydrophobic solvent examples include, but are not limited to, toluene and tetrahydrofuran.
- the content of the organic solvent may be 100 to 1000 parts by weight based on 100 parts by weight of tetracarboxylic dianhydride and diamine solids in the polyimide resin precursor composition.
- the content of the organic solvent is too small, the viscosity of the composition may be too high to reduce the coating property, when the content is too high, the drying of the composition may not be easy, and the mechanical properties of the film to be produced may be reduced. Can be.
- a polyamic acid which is a precursor of the polyimide is produced.
- the polyamic acid is an acid or a derivative of the acid including a -CO-NH- group and a CO-OR group (wherein R is a hydrogen atom or an alkyl group) according to the reaction of an acid anhydride group and an amino group, and another embodiment of the present invention.
- R is a hydrogen atom or an alkyl group
- X 1 and Y 1 are the same as defined above.
- the imidation process is performed with respect to the polyamic acid obtained as a result of the said polymerization reaction.
- the imidization process may be specifically carried out by a chemical imidization or thermal imidization method.
- chemical imidization includes acid anhydrides such as acetic anhydride, propionic anhydride, benzoic anhydride or acid chlorides thereof; It can be implemented using dehydrating agents, such as carbodiimide compounds, such as dicyclohexyl carbodiimide. At this time, the dehydrating agent may be preferably used in an amount of 0.1 to 10 moles with respect to 1 mole of the acid dianhydride.
- the heating step at a temperature of 60 to 120 °C at the time of the chemical imidization may be carried out together.
- thermal imidization it may be carried out by heat treatment at a temperature of 80 to 400 ° C, wherein the azeotropic removal of water generated as a result of the dehydration reaction using benzene, toluene, xylene, etc. is also performed. More preferred.
- the chemical or thermal imidization process is carried out under a base catalyst such as pyridine, isoquinoline, trimethylamine, triethyl amine, N, N-dimethylaminopyridine, imidazole, 1-methylpiperidine, 1-methylpiperazine, etc.
- a base catalyst such as pyridine, isoquinoline, trimethylamine, triethyl amine, N, N-dimethylaminopyridine, imidazole, 1-methylpiperidine, 1-methylpiperazine, etc.
- the base catalyst may be used in an amount of 0.1 to 5 moles per 1 mole of the acid dianhydride.
- the polyimide resin precursor composition may further include a thermal crosslinking agent, a curing accelerator, a phosphorus-based flame retardant, an antifoaming agent, a leveling agent, a gel inhibitor, or a mixture thereof.
- a thermal crosslinking agent such as a curing accelerator, a phosphorus-based flame retardant, an antifoaming agent, a leveling agent, a gel inhibitor, or a mixture thereof.
- additives may be used without limitation as long as they are known to be used in the polyimide resin precursor composition, and may be used in appropriate amounts in consideration of physical properties of the polyimide resin precursor composition or film obtained therefrom.
- the polyimide precursor composition may comprise silica-based particles.
- the polyamic acid and the silica-based particles as described above are mixed and then reacted, or the polyamic acid and the silane-based compound are reacted to produce a polyamic acid polymer, and then the alkoxysilane is reacted to react the polyamic acid polymer and the silica-based particle.
- Composites comprising particles can be prepared.
- the silica-based particles may be chemically bonded to one or more substituents of R1 to R8 of the formula (1). When the silica-based particles are included, mechanical properties are improved and thermal stability is excellent, thereby preventing warpage of the substrate and chemical resistance may be improved.
- the acid dianhydride and the diamine react to form a polyamic acid, and the polyamic acid thus formed may be imidized to provide a polyimide resin.
- the viscosity of the polyimide precursor composition according to the invention may be 10,000 to 20,000 cP.
- the composite material which consists of a glass substrate, a metal substrate, a plastic substrate, or these 2 or more types is also mentioned as said board
- Plastic substrates include polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly (meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, And various plastic films such as polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, and polytrifluoroethylene.
- plastic films such as polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, and polytrifluoroethylene.
- the thickness of the substrate is preferably from 5 to 150 ⁇ m, among them excellent in thermal and chemical stability during the curing process for the polyimide precursor, and easily separated without damage to the polyimide film formed after curing, without a separate release agent treatment Glass substrates that may be desirable.
- a drying step for removing the solvent present in the polyimide-based solution prior to the curing process may be optionally further performed.
- the coating method of the polyimide resin precursor composition is not particularly limited, and for example, a spray method, a roll coating method, a rotary coating method, a slit coating method, an extrusion coating method, a curtain coating method, a die coating method, a wire bar coating method or Methods such as the knife coating method can be used.
- drying of the said polyimide resin precursor composition changes with each component, the kind of organic solvent, and content ratio, it is preferable to carry out for 30 second-15 minutes at 60-100 degreeC. Specifically, it may be carried out at a temperature of 140 ° C or less, or 80 to 140 ° C.
- the implementation temperature of a drying process is less than 80 degreeC, a drying process becomes long, and when it exceeds 140 degreeC, imidation advances rapidly and it is difficult to form polyimide film of uniform thickness.
- the curing process may be carried out by heat treatment at a temperature of 80 to 500 °C, it may also be carried out by a multi-stage heat treatment at various temperatures within the temperature range.
- the polyimide precursor composite may be cured at a temperature of 400 to 500 °C, preferably 450 to 500 °C.
- the curing process may be carried out by a multi-step heat treatment at various temperatures within the above temperature range.
- the curing time in the curing process is not particularly limited, and may be carried out for 30 minutes to 6 hours as an example.
- the film thickness of the polyimide film after drying and hardening is 5-95 micrometers, Preferably it is 10-50 micrometers, More preferably, it is 10-20 micrometers. If the film thickness of the film is 5 ⁇ m or less, the insulation is not good, and if the film thickness exceeds 95 ⁇ m, the transmittance and resolution may decrease.
- a subsequent heat treatment step may be optionally further performed to increase the imidation ratio of the polyimide resin in the polyimide film to form a polyimide film having the above-described physical properties.
- the subsequent heat treatment process is preferably carried out at 200 ° C. or higher, or at 200 to 500 ° C., preferably at 400 ° C. to 500 ° C. for 1 to 30 minutes.
- the subsequent heat treatment process may be performed once or may be performed in multiple stages two or more times. Specifically, it may be carried out in three steps including a first heat treatment at 200 to 220 ° C., a second heat treatment at 300 to 450 ° C., and a third heat treatment at 400 to 550 ° C.
- the laminate in which the polyimide film is formed on the substrate may have a stress of 60 MPa or less after the heat treatment at 100 to 350 ° C. That is, the stress applied to the substrate during the high temperature heat treatment may be reduced due to the difference in thermal expansion coefficient with the film, and thus the substrate warpage may be improved.
- the thermal expansion coefficient (CTE) of the polyimide film may be 30 ppm or more and 200 ppm or less, 100 ppm or less according to another embodiment, or 100 ppm or less according to another embodiment at 100 to 250 ° C.
- the polyimide film can be produced by peeling the polyimide film formed on the substrate from the substrate according to a conventional method.
- the step of preparing the display and the solar cell substrate from the polyimide film prepared as described above may be carried out by peeling the polyimide film formed on the support according to a conventional method.
- the resulting polyimide film has an average transmittance of 80% or more for light with a wavelength of 350 nm to 760 nm, a modulus of 4 GPa or less, a tensile stress of 150 MPa or less, and a coefficient of thermal expansion (CTE) of 30 ppm at 100 to 250 ° C. It may be more than 200 ppm.
- the polyimide precursor composition of the present invention having the thermal expansion coefficient and elastic modulus adjusted as described above can significantly improve the warpage of the substrate in a high temperature heat treatment process, thereby providing a flexible substrate in an electronic device such as an OLED or LCD, electronic paper, or solar cell. It may be particularly useful for manufacturing.
- the ACD / LogP module of the ACD / Percepta platform of ACD / Labs (where ACD / LogP module is calculated based on the Quantitative Structure-Property Relationship (QSPR) methodology based on the molecular 2D structure) is calculated.
- the partition coefficient (LogP value) at °C is as follows.
- P_PDMS_V The structure of P_PDMS_V is represented by the following Chemical Formula 13.
- x repeating units may increase intramolecular flexibility
- y repeating units may improve intermolecular compatibility
- z repeating units may affect improving chemical resistance.
- the order of the x, y, z repeating units may be arbitrarily changed and may be alternately positioned.
- the molecular structure of the polyimide precursor is as shown in the following formula (14).
- a precursor composition was prepared in the same manner as in Example 1, except that the precursor (P_PDMS_V) content of Formula 2 was 30 wt%.
- a precursor composition was prepared in the same manner as in Example 1, except that the precursor (P_PDMS_V) content of Formula 2 was 50% by weight.
- Oxydiphthalic anhydride (ODPA) was used instead of BPDA, and the precursor composition was prepared in the same manner as in Example 1 except that the precursor (P_PDMS_V) content of Chemical Formula 2 was 30% by weight.
- a precursor composition was prepared in the same manner as in Comparative Example 1 except that Oxydiphthalic anhydride (ODPA) was used instead of BPDA.
- ODPA Oxydiphthalic anhydride
- a precursor composition was prepared in the same manner as in Comparative Example 1 except that 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluropropane (BAPP) was used instead of TFMB.
- BAPP 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluropropane
- the prepared polyimide precursor solution was spin coated onto a glass substrate to a thickness of about 10 microns.
- the glass substrate coated with the polyimide precursor solution was placed in an oven and heated at a rate of 3 ° C./min, and the curing process was performed by maintaining the mixture at 80, 120, 180, and 250 ° C. for 30 minutes to 1 hour.
- Yellowness (YI) was measured by Color Eye 7000A.
- CTE coefficient of thermal expansion
- Zwick's UTM was used to measure the mechanical properties of the film (modulus, maximum stress, maximum elongation). After the film was cut to 5 mm horizontally and 60 mm or longer, the distance between the grips was set to 40 mm, and the value measured while pulling the sample at a speed of 20 mm / min was confirmed.
- Thickness direction retardation was measured using Axoscan. The film was cut to a certain size to measure the thickness, and then the thickness was measured while calibrating in the direction of the C-plate to compensate for the phase difference value by measuring the phase difference with Axoscan.
- Example 1 Example 2
- Example 3 Thickness ( ⁇ m) 11.2 11.5 10.8 10.3 YI 5 4 3.3 2.4 CTE (ppm / K) / 250 ⁇ 100 °C 23 92 148 158 Modulus (GPa) 5.0 3.5 1.8 0.5
- the polyimide film made of the polyimide composition according to the present invention has a coefficient of thermal expansion of 30 or more and 200 or less and a modulus of 4 GPa or less, and compared to Comparative Example 1 in a glass substrate. It can be seen that the stress applied is greatly reduced. In addition, it can be confirmed that other physical properties such as transparency and isotropy are also good. In addition, as shown in Table 3, in Comparative Example 3 has a soft segment has a low modulus value, but it can be confirmed that the stress value is higher than the embodiment using the structure according to the present invention.
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Abstract
Description
용매 | DEF | DMF | DEAc | DMAc | NMP | NEP |
LogP (25℃) | 0.05 | -1.01 | 0.32 | -0.75 | -0.28 | 0.22 |
비점(℃) | 176-177 | 152-154 | 182-186 | 165 | 202-204 | 97 |
구분 | 비교예 1 | 실시예 1 | 실시예 2 | 실시예 3 | |
두께(μm) | 11.2 | 11.5 | 10.8 | 10.3 | |
YI | 5 | 4 | 3.3 | 2.4 | |
CTE(ppm/K)/250~100℃ | 23 | 92 | 148 | 158 | |
모듈러스(GPa) | 5.0 | 3.5 | 1.8 | 0.5 | |
최대인장강도(MPa) | 200 | 105 | 40 | 20 | |
최대연신율(%) | 25 | 30 | 12 | 70 | |
글래스스트레스(Bow), μm | 66 | 55 | 39 | 7.5 | |
C.R. test | Stripper | ○ | ○ | ○ | ○ |
Developer | ○ | ○ | ○ | ○ |
구분 | 두께(μm) | 최대인장강도(MPa) | C.R. test(r.t. 30min) | 모듈러스(GPa) | Rth, nm | |
Stripper | Developer | |||||
비교예 2 | 11.3 | 82.6 | ○ | ○ | 4.1 | 225 |
실시예 4 | 11.2 | 43.8 | ○ | ○ | 2.2 | 40 |
비교예 3 | 16.0 | 63.1 | - | - | 2.3 | 15 |
Claims (18)
- 화학식 1의 구조를 포함하는 다이아민 또는 산이무수물로부터 유래된 폴리이미드 전구체를 함유하는 광전소자의 플렉시블 기판용 폴리이미드 전구체 조성물:[화학식 1]상기 식에서, 상기 R1 및 R2는 각각 독립적으로 단일 결합, 탄소수 1 내지 5의 알킬렌기 또는 탄소수 6 이상의 2가 방향족기이고,R3 및 R4는 각각 독립적으로 1 내지 5의 알킬기이며,R5 및 R6는 각각 독립적으로 탄소수 4 내지 10의 아릴기이고,R7 및 R8 중 적어도 하나는 탄소수 2 내지 10의 알케닐기이며,m1, m2 및 m3은 각각 독립적으로 1 이상의 정수이다.
- 제1항에 있어서,상기 화학식 1의 구조를 포함하는 다이아민 또는 산이무수물로부터 유래된 폴리이미드 전구체를, 폴리이미드 전구체 총중량을 기준으로 50중량% 이하 함유하는 것인 폴리이미드 플렉시블 기판용 폴리이미드 전구체 조성물.
- 제1항에 있어서,상기 화학식 1의 구조를 포함하는 다이아민 또는 산이무수물로부터 유래된 폴리이미드 전구체는 분자량이 600 이상 7,000 이하인 것인 폴리이미드 전구체 조성물.
- 제1항에 있어서,상기 화학식 1에서 m1, m2 및 m3은 각각 독립적으로 1 내지 10의 정수인 것인 폴리이미드 전구체 조성물.
- 제1항에 있어서,상기 조성물은 분배계수가 양수인 값을 나타내는 용매에 폴리이미드 전구체가 용해되어 있는 것인 폴리이미드 전구체 조성물.
- 제5항에 있어서,상기 용매는 아민계 제1 용매와 비아민계 제2 용매를 포함하는 것인 폴리이미드 전구체 조성물.
- 제6항에 있어서,상기 아민계 제1 용매와 비아민계 제2 용매의 부피비가 50~90 : 10~50 인 것인 폴리이미드 전구체 조성물.
- 제6항에 있어서,상기 아민계 제1 용매가 탄소수 2 이상의 알킬기로 치환된 3차아민인 것인 폴리이미드 전구체 조성물.
- 제6항에 있어서,상기 비아민계 용매는 톨루엔 또는 테트라하이드로퓨란인 것인 폴리이미드 전구체 조성물.
- 제1항에 있어서, 실리카계 입자를 더 포함하는 폴리이미드 전구체 조성물.
- 제1항 내지 제10항 중 어느 한 항의 조성물을 유리기판 상에 도포한 후 경화시켜 얻은 광전소자의 플렉시블 기판용 폴리이미드 필름.
- 제11항에 있어서, 모듈러스 4GPa 이하, 인장스트레스 150 MPa 이하, 열팽창계수(CTE)가 100 내지 250℃에서 30ppm 이상 200pm 이하인 광전소자의 플렉시블 기판용 폴리이미드 필름.
- 제11항에 있어서, 상기 필름은 350nm~760nm 파장의 빛에 대한 평균투과도가 80% 이상인 것인 폴리이미드 필름.
- 제1항 내지 제10항 중 어느 한 항의 조성물을 유리기판 상에 도포한 후 경화시켜 얻은, 유리 기판 상에 폴리이미드 필름이 형성된 적층체.
- 제14항에 있어서, 상기 적층체는 100~350℃의 열처리 공정 후 기판이 받는 스트레스가 60 MPa 이하인 것인 적층체.
- 제14항에 있어서, 상기 폴리이미드 필름은 모듈러스 4GPa 이하, 인장스트레스 150 MPa 이하, 열팽창계수(CTE)가 100 내지 250℃에서 30ppm 이상 200ppm 이하인 것인 적층체.
- 제11항에 따른 폴리이미드 필름을 플렉시블 기판으로 포함하는 광전소자.
- 제11항에 따른 폴리이미드 필름으로 제조된 플렉시블 기판을 포함하는 플렉시블 디스플레이.
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JP2016551162A JP6501312B2 (ja) | 2015-03-05 | 2016-03-07 | 光電素子のフレキシブル基板用ポリイミドフィルム用組成物 |
EP16745600.3A EP3266808B1 (en) | 2015-03-05 | 2016-03-07 | Composition for polyimide film for flexible substrate of optoelectronic device |
CN201680000859.XA CN106133025B (zh) | 2015-03-05 | 2016-03-07 | 用于生产光电器件的柔性板的聚酰亚胺膜的组合物 |
US15/126,416 US10544266B2 (en) | 2015-03-05 | 2016-03-07 | Composition for the production of polyimide film for flexible board of photoelectronic device |
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KR1020160027035A KR101993652B1 (ko) | 2015-03-05 | 2016-03-07 | 광전소자의 플렉시블 기판용 폴리이미드 필름용 조성물 |
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