CN109689732A - Resin stability, heat resistance improve, with transparent polyimide precursor resin composition, using the polyimides film manufacturing method of the composition, and the polyimide film manufactured by the method - Google Patents
Resin stability, heat resistance improve, with transparent polyimide precursor resin composition, using the polyimides film manufacturing method of the composition, and the polyimide film manufactured by the method Download PDFInfo
- Publication number
- CN109689732A CN109689732A CN201680088588.8A CN201680088588A CN109689732A CN 109689732 A CN109689732 A CN 109689732A CN 201680088588 A CN201680088588 A CN 201680088588A CN 109689732 A CN109689732 A CN 109689732A
- Authority
- CN
- China
- Prior art keywords
- moles
- acid dianhydride
- resin
- aromatic diamine
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- 239000011347 resin Substances 0.000 title claims abstract description 36
- 229920005989 resin Polymers 0.000 title claims abstract description 36
- 239000004642 Polyimide Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000002243 precursor Substances 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 title claims description 40
- 239000011342 resin composition Substances 0.000 title description 6
- 239000002253 acid Substances 0.000 claims abstract description 36
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 33
- 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 29
- 239000003960 organic solvent Substances 0.000 claims abstract description 29
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 50
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 45
- 229920005575 poly(amic acid) Polymers 0.000 claims description 38
- -1 fluorinated aromatic acid dianhydride Chemical class 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 25
- 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 claims description 18
- 239000011521 glass Substances 0.000 claims description 16
- 239000004615 ingredient Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 11
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004383 yellowing Methods 0.000 claims description 9
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 7
- 125000003368 amide group Chemical group 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 150000004985 diamines Chemical class 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 230000009466 transformation Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- BXEMXLDMNMKWPV-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1.C1=CC=NC=C1 BXEMXLDMNMKWPV-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims 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 claims 2
- DLEPYXFUDLQGDW-UHFFFAOYSA-N FC(F)(F)NC1=CC=C(C2=CC=C(NC(F)(F)F)C=C2)C=C1 Chemical compound FC(F)(F)NC1=CC=C(C2=CC=C(NC(F)(F)F)C=C2)C=C1 DLEPYXFUDLQGDW-UHFFFAOYSA-N 0.000 claims 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 206010018612 Gonorrhoea Diseases 0.000 abstract description 23
- 239000004952 Polyamide Substances 0.000 abstract description 4
- 229920002647 polyamide Polymers 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 125000006159 dianhydride group Chemical class 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- WJRMKXJMFGANCA-UHFFFAOYSA-N 2-(1,1,1,3,3,3-hexafluoro-2-phenoxypropan-2-yl)aniline Chemical compound NC1=C(C=CC=C1)C(C(F)(F)F)(C(F)(F)F)OC1=CC=CC=C1 WJRMKXJMFGANCA-UHFFFAOYSA-N 0.000 description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 159000000032 aromatic acids Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- MHAJTXGUWATIOJ-UHFFFAOYSA-N 2-(2-amino-1,1,1,3,3,3-hexafluoropropan-2-yl)phenol Chemical compound OC1=C(C=CC=C1)C(C(F)(F)F)(C(F)(F)F)N MHAJTXGUWATIOJ-UHFFFAOYSA-N 0.000 description 1
- JGGPAWVFHBAOFC-UHFFFAOYSA-N 3-[4-amino-2-(trifluoromethyl)phenyl]-2-(trifluoromethyl)aniline Chemical group FC(C1=C(C=CC(=C1)N)C1=C(C(=CC=C1)N)C(F)(F)F)(F)F JGGPAWVFHBAOFC-UHFFFAOYSA-N 0.000 description 1
- USICOLXYLHLXHM-UHFFFAOYSA-N 3-[5-amino-2-(trifluoromethyl)phenyl]-4-(trifluoromethyl)aniline Chemical group NC1=CC=C(C(F)(F)F)C(C=2C(=CC=C(N)C=2)C(F)(F)F)=C1 USICOLXYLHLXHM-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 1
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N Adamantane Natural products C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- LKRUZYNPJUZODM-UHFFFAOYSA-N adamantane-1,3-dicarbonyl chloride Chemical compound C1C(C2)CC3CC1(C(=O)Cl)CC2(C(Cl)=O)C3 LKRUZYNPJUZODM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical class CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- KGVBVOYQIKFIGA-UHFFFAOYSA-N n,n-dimethylmethanamine Chemical compound CN(C)C.CN(C)C KGVBVOYQIKFIGA-UHFFFAOYSA-N 0.000 description 1
- XYQUZYVBQYBQDB-UHFFFAOYSA-N naphthalene-1,5-dicarbonyl chloride Chemical compound C1=CC=C2C(C(=O)Cl)=CC=CC2=C1C(Cl)=O XYQUZYVBQYBQDB-UHFFFAOYSA-N 0.000 description 1
- NZZGQZMNFCTNAM-UHFFFAOYSA-N naphthalene-2,6-dicarbonyl chloride Chemical compound C1=C(C(Cl)=O)C=CC2=CC(C(=O)Cl)=CC=C21 NZZGQZMNFCTNAM-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-UHFFFAOYSA-N norbornene Chemical compound C1C2CCC1C=C2 JFNLZVQOOSMTJK-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000007764 slot die coating Methods 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- RKFCDGOVCBYSEW-AUUKWEANSA-N tmeg Chemical compound COC=1C(OC)=CC(C(OC(C=2OC)=C34)=O)=C3C=1OC(=O)C4=CC=2O[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O RKFCDGOVCBYSEW-AUUKWEANSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 1
- 238000010792 warming Methods 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
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1021—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the catalyst used
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
- C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
-
- 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
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- 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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
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- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The present invention relates to provided by optimizing aromatic diamine for improving heat resistance and mechanical property and acid dianhydride and not occurring the organic solvent of gonorrhoea phenomenon with outstanding engineering properties, high-fire resistance, low thermal coefficient of expansion, and the transparent polyamide acid precursors resin combination of gonorrhoea phenomenon and the polyimides film manufacturing method using it, and the polyimide film manufactured by this method does not occur in solution-cast.
Description
[technical field]
The present invention relates to outstanding engineering properties, high-fire resistance, low thermal coefficient of expansion, and while pouring solution do not occur it is white
The polyimide precursor resin composition with the transparency of turbid phenomenon and the polyimide film manufacturer for utilizing the composition
Method, and the polyimide film manufactured by the method, can usefully be suitable for display substrate materials flexible, semiconductor material
Material.
[background technique]
Baseplate material as next generation display device by the display flexible favored, high molecular material flexible
It attracts attention.
Device flexible generally uses Organic Light Emitting Diode (OLED) display, uses high engineering temperature (300~500
DEG C) TFT engineering.The high molecular material for being resistant to engineering temperature high in this way is extremely limited, wherein also mainly used as heat-resisting
Outstanding high molecular polyimides (PI) resin of property.
Organic Light Emitting Diode (OLED) display is by coated with resins on the glass substrate, thermmohardening and membranization, through all
Display is manufactured from the method for glass substrate removing after the process in stage.In such manufacturing process, on the glass substrate
When coated with resins, it is important in the resin stability of room temperature.When being unable to ensure the stability of resin, because of the reunion of resin,
Uniform film can not be made in gonorrhoea phenomenon etc. after curing, and product defects as a result can occur.In addition, in subsequent handling, because
TFT is deposited thermal shock (thermal shock) caused by the high-temperature of process and product defects can also occur.Accordingly it is desirable to have
There are the resin stability in room temperature, high-fire resistance and low thermal coefficient of expansion (Coefficien Thermal Expansion；CTE)
Polyimide resin (PI).
KR published patent the 2015-108812nd discloses with low thermal expansion rate and high thermal decomposition temperature and thermal characteristics is excellent
Film that is elegant and being applicable to the base of display material or the polyamic acid solution of protective layer and the utilization solution, but it is unable to ensure
The stability of resin, because of the reunion of resin, uniform film can not be made in gonorrhoea phenomenon etc. after curing, and product as a result occurs and lacks
It falls into.
In addition, KR published patent the 2013-35691st discloses for manufacturing combined polymerization polyamide-imines film group
Close object and manufacturing method, but its occur by-product and must the process through removing by-product, to have in the economy of process
Limitation.
In this regard, needing to be not only the excellent in stability of resin, also there is high-fire resistance, low thermal coefficient of expansion, outstanding machine
The it is proposed of the fairly simple manufacturing method of the polyimide compositions of tool intensity and manufacturing process.
(advanced technical literature)
(patent document)
(patent document 1) 1: KR published patent the 2015-108812nd
(patent document 2) 2: KR published patent the 2013-35691st
[detailed description of the invention]
[technical task]
In this regard, the present inventor has found to improve, in manufacture heat resistance with most suitable machinery spy to solve the above-mentioned problems
Property polyimide film on more effectively the composition of aromatic diamine and acid dianhydride compounds and the organic molten of gonorrhoea phenomenon does not occur
The composition of agent, discovery is compared to previous polyimide film with more the transparency, resin stability, high-fire resistance, low thermal expansion system
Several polyimide precursor resin compositions, thereby completing the present invention.
To the present invention is intended to provide can be used as has the transparency, resin stability, high-fire resistance, low thermal coefficient of expansion
The polyimide precursor resin composition that uses of display substrate materials flexible.
In addition, the present invention is intended to provide the method for manufacturing polyimide resin film using the composition.
In addition, the present invention is intended to provide by the manufacturing method manufacture on the basis of 10~15 μm of film thickness, glass turn
Temperature is 300 DEG C or more, is 25ppm/ DEG C hereinafter, at 550nm wavelength in the thermal expansion coefficient within the scope of 100~300 DEG C
Transmitance be 85% or more, the yellowing (Yellow Index, Y.I.) at 550nm wavelength is 7 polyimides trees below
Adipose membrane.
[project solution]
The transparent polyimide precursor resin combination that the present invention provides resin stability, high-fire resistance improves, feature
It is, it is described in the polyimide precursor resin composition of acid dianhydride compounds and organic solvent comprising aromatic diamine ingredient
Aromatic diamine ingredient (A) includes: bis- (the trifluoromethyl) -4,4'- benzidine bases of 2,2'- as fluorinated aromatic diamine monomer
(TFMB), alternatively, N- (4- aminophenyl) -4- aminobenzamide (DBA) as the diamine monomer with amide groups, or
Person, these mixture, the acid dianhydride compounds (B) are comprising 4, the 4'- (hexafluoro different sub- third as fluorinated aromatic acid dianhydride
Base) diphthalic anhydrides (6FDA) and the pyromellitic acid anhydride (PMDA) as nonfluorinated aromatics acid dianhydride, alternatively, 3',
The mixture of 4,4'- biphenyl tetracarboxylic dianhydrides (BPDA), the organic solvent (C) are gamma-butyrolacton (GBL) and N- methyl-
The mixture of 2-Pyrrolidone (NMP), alternatively, gamma-butyrolacton (GBL) and 3- methoxyl group-N, N- dimethylpropane amide
(DMPA) mixture or individual 3- methoxyl group-N, N- dimethylpropane amide (DMPA).
In addition, the present invention provides the manufacturing method of clear polyimides resin film, which is characterized in that the utilization combination
The polyamic acid solution of object manufacture is heat-treated and manufactures film.
In addition, the present invention provide by the manufacturing method manufacture on the basis of 10~15 μm of film thickness, Glass Transition temperature
Degree is 300 DEG C or more, is 25ppm/ DEG C hereinafter, saturating at 550nm wavelength in the thermal expansion coefficient within the scope of 100~300 DEG C
The rate of mistake is 85% or more, and the yellowing (Yellow Index, Y.I.) at 550nm wavelength is 7 clear polyimides trees below
Adipose membrane.
[invention effect]
By the present invention, compared with previous polyamic acid solution, gonorrhoea phenomenon does not occur when pouring solution, in the tree of room temperature
Rouge stability is outstanding, transparent when by thermmohardening manufacture film, and provides outstanding mechanical property and optical characteristics, heat-resistant quality,
Display substrate materials flexible, semiconductor material etc. can be usefully suitable for.
In addition, the present invention when manufacturing polyamic acid solution, compares conventional art, without the generation and removing work of by-product
Sequence, to also ensure that competitiveness in process.
[brief description]
When Fig. 1 is shown in room temperature and pours polyamic acid solution on the glass substrate, using embodiment 1 organic solvent (GBL:
NMP=70 moles of %:30 moles of %) when gonorrhoea phenomenon (ordinary temperature stability).
When Fig. 2 is shown in room temperature and pours polyamic acid solution on the glass substrate, using embodiment 2 organic solvent (GBL:
DMPA=70 moles of %:30 moles of %) when gonorrhoea phenomenon (ordinary temperature stability).
When Fig. 3 is shown in room temperature and pours polyamic acid solution on the glass substrate, using the organic solvent of comparative example 3, (NMP is mono-
Only 100 moles of % of object) when gonorrhoea phenomenon (ordinary temperature stability).
[embodiment]
Polyimide precursor resin composition of the invention (hereinafter also referred to ' polyamic acid composition ') be characterized in that,
Heat resistance is improved, gonorrhoea phenomenon does not occur for the composition of aromatic diamine and acid dianhydride compounds with most suitable mechanical property
Organic solvent composition and these usage amount optimization and provide with high-fire resistance, low thermal coefficient of expansion, outstanding machine
The transparent polyimide film of tool intensity.Polyimide precursor composition according to the present invention, i.e., ' polyamic acid composition ' refer to
For manufacturing the composition of the polyamic acid solution used in polyimide film manufacture.
Specifically, polyamic acid composition according to the present invention includes: comprising fluorinated aromatic diamine or there is amide groups
Diamine compound or these mixture aromatic diamine ingredient (A), include fluorinated aromatic acid dianhydride and nonfluorinated aromatic acid
The acid dianhydride compounds (B) of dianhydride compound include gamma-butyrolacton (GBL) and n-methyl-2-pyrrolidone (NMP) or 3- first
The organic solvent (C) and catalysts (D) of oxygroup-N, N- dimethylpropane amide (DMPA).Each ingredient is illustrated then
It is as follows.
(A) aromatic diamine ingredient
Aromatic diamine ingredient in the present invention includes the 2,2'- bis- (trifluoromethyls)-as fluorinated aromatic diamine monomer
4,4'- benzidine bases (TFMB), alternatively, N- (4- aminophenyl) -4- amino as the diamine monomer with amide groups
Benzamide (DBA), alternatively, these mixture.
Specifically, bis- (trifluoromethyl) -4, the 4'- benzidines of 2, the 2'- as fluorinated aromatic diamine monomer
Base (TFMB) is 30~100 moles of %, N- (4- aminophenyl) -4- aminobenzamide relative to all diamine compounds
(DBA) it is 5~50 moles of % relative to all diamine compounds, also may include the nonfluorinated aromatic diamine of surplus.
It include in the case where importing the fluorinated aromatic diamine of fluoro substituents, because of molecule in the aromatic diamine ingredient (A)
Charge between chain between fluoro substituents mobile effect (Charge Transfer effect) and to can provide optical characteristics outstanding
Polyimide film.
In addition, being used in mixed way N- (4- aminophenyl) -4- aminobenzamide together with such fluorinated aromatic diamine
(DBA) it in the case where, can provide due to the rigidity of aromatic structure and amide structure with outstanding heat resistance and low thermal expansion system
Several polyimide films.
The case where using fluorinated aromatic diamine and N- (4- aminophenyl) -4- aminobenzamide with as aromatic diamine ingredient
In, be used only fluorinated aromatic diamine the case where compared with, can manufacture both maintained optical characteristics and thermal characteristics simultaneously raising polyamides
Imines film.
As long as aromatic diamine of the fluorinated aromatic diamine containing fluorine, is not particularly limited.For example, can be used selected from following
More than one: bis- (the trifluoromethyl) -4,4'- benzidine bases of 2,2'- (2,2'-Bis (trifluoromethyl) -4,
4'-Diaminobiphenyl, TFMB), double hydroxy amino phenyl hexafluoropropane (bisaminohydroxyphebyl
Hexafluoropropane, DBOH), double aminophenoxy phenyl hexafluoropropane (bis aminophenoxy phenyl
Hexafluoropropane, 4BDAF), 2,2'- bis- (trifluoromethyl) -4,3'- benzidine bases (2,2'-Bis
(trifluoromethyl) -4,3'-Diaminobiphenyl) and 2, bis- (trifluoromethyl) -5,5'- benzidine bases of 2'-
(2,2'-Bis(trifluoromethyl)-5,5'-Diaminobiphenyl)。
But in the present invention, it is preferred to use the bis- (fluoroforms of 2,2'- that can improve permeability and heat-resistant quality simultaneously
Base) -4,4'- benzidine base (TFMB).
At this point, the TFMB is 30~100 moles of %, preferably on the basis of 100 moles of % of all two amine compounds
50~90 moles of %, in the range in the case where use, because of the mobile effect of charge between intermolecular fluoro substituents
(Charge Transfer effect) and the optical characteristics that can further improve polyimide film.
In addition, in the present invention, being not only the fluorinated aromatic diamine monomer as above-mentioned TFMB, also may include nonfluorinated
Aromatic diamine monomer.At this point, being used in such a way that the fluorinated aromatic diamine and nonfluorinated aromatics amount up to 100 moles of %.
On the other hand, for the outstanding heat-resistant quality of polyimide resin, low thermal coefficient of expansion and may include can have
Or form the compound of amide structure.As the compound that can form such amide structure, there is acetyl halide compound (acid
Halide), dicarboxylic acid compound (dicarboxylic acid).For example, being selected from more than one following: p- terephthalyl chloride
(p-terephthaloyl chloride, TPC), different phthalyl dichloro (isophthaloyl dichloride, IPC),
1,3- adamantane, two formyl dichloro (1,3-Adamantanedicarbonyl dichloride, ADC), 5- norbornene -2,3-
Dimethyl chloride (5-Norbonene-2,3-dicarbonyl chloride, NDC), 4,4'- benzoyl dichloros (4,4'-
Benzoyl dichloride, BDC), Isosorbide-5-Nitrae-naphthalene dicarboxylic dihydrazides dichloro (Isosorbide-5-Nitrae-naphthalene dicarboxylic acid
Dichloride, Isosorbide-5-Nitrae-NaDC), 2,6- naphthalene dicarboxylic dihydrazides dichloro (2,6-naphthalene dicarboxylic acid
Dichloride, 2,6-NaDC), 1,5- naphthalene, two formyl dichloro (1,5-naphthalene dicarboxylic acid
Dichloride, 1,5-NaDC), terephthalic acid (TPA) (Terephthalic acid, TPA), different phthalic acid
(Isophthalic acid, IPA) phthalic acid (Phthalic acid, PA), 4,4'- diphenyldicarboxylic acids (4,4 '-
Biphenyl dicarboxylic acid, BDA) and naphthalene dicarboxylic acids (Naphthalene dicarboxylic acid,
NaDA)。
But such compound generates the HCl, H as by-product while forming amide structure2O etc., from
And membrane property can be reduced when manufacturing imines film.
Thus in the present invention, can be by the inclusion of N- (the 4- aminobenzene used as the diamine compound with amide groups
Base) -4- aminobenzamide (N- (4-aminophenyl) -4-aminobenzamide, DBA), the spot of no coupling product to
Strand imports amide groups and realizes heat-resistant quality and low thermal coefficient of expansion characteristic.N- (4- aminophenyl) -4- aminobenzoyl
The content of amine (DBA) is not particularly limited, on the basis of two amine compounds, 100 moles of %, can be 5~50 moles of %, preferably 5
~20 moles of %.
(B) acid dianhydride compounds
Aromatics acid dianhydride compounds of the invention include 20~80 moles of % of fluorinated aromatic acid dianhydride and nonfluorinated aromatic acid
80~20 moles of % of dianhydride compound.
In the case where being used in mixed way fluorinated aromatic acid dianhydride and nonfluorinated aromatics acid dianhydride compounds as the present invention,
The optical characteristics and heat-resistant quality of polyimide film can improve simultaneously.It can be made because of the fluoro substituents of the fluorinated aromatic acid dianhydride
The outstanding polyimide film of optical characteristics is made, it is outstanding to manufacture heat-resistant quality because of the molecular structure of the rigidity of aromatics acid dianhydride
Polyimide film.
Fluorinated aromatic acid dianhydride is the aromatics acid dianhydride for importing fluoro substituents, for example, can be used selected from it is following it is a kind of with
It is upper: 4,4'- (hexafluoroisopropylidenyl) diphthalic anhydrides (4,4'- (Hexafluoroisopropylidene)
Diphthalic anhydride, 6FDA)) and 4,4'- (4,4'- hexafluoroisopropylidenyl, two phenoxy group) double-(phthalic acid
Acid anhydride) (4,4'- (4,4'-Hexafluoroisopropylidenediphenoxy) bis- (phthalic anhydride, 6-
FDPDA), in the present invention, as fluorinated aromatic acid dianhydride, it is preferable to use 6FDA.
Such fluorinated aromatic acid dianhydride is 20~80 moles of %, preferably on the basis of total 100 moles of % of acid dianhydride
For 40~70 moles of %, the high transmission degree of achievable polyimide film and low yellowing in the range.
Next, nonfluorinated aromatics acid dianhydride is the aromatics acid dianhydride for not importing fluoro substituents, can be used selected from following
More than one: pyromellitic acid anhydride (pyromellitic dianhydride, PMDA), 3,3', 4,4'- xenyl tetrabasic carboxylic acids
Dianhydride (3,3'4,4'-biphenyltetracarboxylic acid dianhydride, BPDA), 3,3', 4,4'- hexichol first
Ketone tetracarboxylic dianhydride (3,3', 4,4'-benzophenonetetracarboxylic dianhydride, BTDA), 4,4' oxygroups
Diphthalic anhydrides (4,4 '-oxydiphthalic anhydride, ODPA), 2,2- bis- [4-3,4- di carboxyl phenyloxies]
Phenyl] propane acid anhydride (2,2-Bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride,
BPADA), 3,3', 4,4'- diphenyl sulphur tetracarboxylic anhydride (3,3', 4,4'-Diphenyl sufone tetracarboxylic
Dianhydride, DSDA) and ethylidene glycol bis- (4- trimellitic anhydrides) (ethylene glycol bis (4-
Trimellitate anhydride), TMEG), in the present invention, as nonfluorinated aromatics acid dianhydride, it is preferable to use PMDA or
BPDA or these mixture.
At this point, nonfluorinated aromatics acid dianhydride is on the basis of total 100 moles of % of acid dianhydride, and it is 80~20 moles of %, it is excellent
30~50 moles of % are selected as, to further decrease heat-resisting spy while the high transmission degree for maintaining polyimide film and low yellowing
Property.
(C) organic solvent
Organic solvent in the present invention is just like m- cresols, n-methyl-2-pyrrolidone (NMP), N, N- dimethyl formyl
Amine (DMF), dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO), diethacetic acid ester (DEA), 3- methoxyl group-N, N- bis-
Polar solvent as methylpropane amide (DMPA) etc., such as tetrahydrofuran (THF), low boiling point solvent as chloroform etc. or such as
The low water absorbable solvent of gamma-butyrolacton (GBL) equally.
The organic solvent being used in the present invention plays an important role in the improvement of gonorrhoea phenomenon, wherein gonorrhoea phenomenon
It can be confirmed by FIG. 1 to FIG. 3.When Fig. 1 is shown in room temperature and pours polyamic acid solution on the glass substrate, to 70 moles of % of GBL and
The ordinary temperature stability (no gonorrhoea phenomenon) of the organic solvent of 30 moles of % of NMP, Fig. 2 are shown to 70 moles of % and DMPA30 of GBL
The ordinary temperature stability (no gonorrhoea phenomenon) of the organic solvent of mole %.Fig. 3 is shown to the organic molten of 100 moles of % of the independent object of NMP
The gonorrhoea phenomenon of agent.
To in the present invention, in order to improve on gonorrhoea phenomenon when room temperature pours solution, it is preferable to use gamma-butyrolacton
(GBL) and the mixture of n-methyl-2-pyrrolidone (NMP), alternatively, gamma-butyrolacton (GBL) and 3- methoxyl group-N, N- diformazan
The mixture of base propane amide (DMPA) or individual 3- methoxyl group-N, N- dimethylpropane amide (DMPA).
At this point, the usage amount of organic solvent is that it is preferable to use 30~70 moles of % of gamma-butyrolacton (GBL) and N- methyl -2-
70~30 moles of % of pyrrolidones (NMP) or 3- methoxyl group-N, N- dimethylpropane amide (DMPA).More preferably γ-Ding Nei
50~70 moles of % of ester (GBL) and n-methyl-2-pyrrolidone (NMP) or 3- methoxyl group-N, N- dimethylpropane amide
(DMPA) 30~50 moles of %.Alternatively, 100 moles of % of individual gamma-butyrolacton (GBL) can be used.
(D) catalysts
Catalysts of the invention can also include to be selected from Trimethylamine (Trimethylamine) according to reactivity, and two
Toluene (Xylene), is also not necessarily limited to this by a kind or more of pyridine (Pyridine) and quinoline (Quinoline).In addition, polyamide
Acid composition can include plasticizer, antioxygen as needed in the range of not significantly damage the objects and effects of the present invention on a small quantity
Agent, fire retardant, dispersing agent, viscosity modifier, the additive of levelling agent etc..
In addition, utilizing aromatic diamine ingredient as polyamic acid composition according to the present invention, acid dianhydride compounds have
Solvent and catalysts polymerization obtained from polyamic acid solution relative to polyamic acid solution all weight and include
Solid point 10~40 weight %, preferably 10~25 weight %.In the case where solid divides less than 10 weight %, film mentions when manufacturing
There is limitation on the thickness of high film, in the case where solid point is more than 40 weight %, has office on adjusting polyamic acid resin viscosity
Limit, to be formed within the above range.
Specifically, the polyamic acid solution uses organic solvent preferably in a manner of 10~40wt% of solid content
Content, by 100~105 moles of % mixing of 95~100 moles of % of aromatic diamine ingredient and acid dianhydride compounds at 10~70 DEG C
Temperature condition is implemented 24~48 hours.At this point, reaction temperature can be changed according to the monomer used.
Herein, acid dianhydride compounds are excessively added with -5~5 moles of % and are made preferably with respect to aromatic diamine ingredient
Target viscosities are reached, reason for this is that suitable viscosity-adjusting agent and storage stability ensures.
The viscosity for the polyamic acid solution that reaction in this way generates is preferably within the scope of 1,000~7,000cP.Viscous
It is problematic on obtaining suitable fixed horizontal film thickness in the case where degree is less than 1,000cP, in the case where more than 7,000cP,
Uniform coating and the removing of effective solvent are upper problematic, thus it is preferred that within the above range.
In addition, transparent polyimide film and its manufacturing method are as follows in the present invention.Present invention offer will be by described above
Polyamic acid composition manufacture polyamic acid solution hot imidization and the transparent polyimide film that manufactures.It is according to the present invention
Polyamic acid solution has viscosity, is heat-treated and manufactures after being coated with glass substrate with suitable method when film manufactures.The coating
Method can unlimitedly use known conventional method, there is such as spin coating (Spincoating), dip coated (Dip
Coating), pour solvent (Solvent casting), slot coated (Slot die coating), spray (Spray
Coating) etc., it is without being limited thereto.
Polyamic acid composition of the invention can be heat-treated in high temperature convection furnace and manufacture into polyimide film.At this point,
Heat treatment condition is carried out in nitrogen atmosphere, is implemented 30~120 minutes in 100~450 DEG C of conditions.More preferably in 100 DEG C/30min,
220 DEG C/30min, the temperature and time condition of 350 DEG C/30mim obtains film.It is such reason for this is that suitable solvent removing
With can be by the maximized imidization of characteristic.
Since transparent polyimide film of the invention is manufactured using the polyamic acid composition, the same of high transparency is presented
When have low thermal coefficient of expansion.
Polyimide film of the invention is on the basis of 10~15 μm of film thickness, and glass transformation temperature is 300 DEG C or more,
Thermal expansion coefficient within the scope of 100~300 DEG C is down to 25ppm/ DEG C hereinafter, preferably 15ppm/ DEG C hereinafter, at 550nm wavelength
Transmitance be up to 85% or more, the yellowing (Yellow Index, Y.I.) at 550nm wavelength is down to 7 hereinafter, preferably 5
Below.The defect (defect) of material on substrate caused by polyimide film of the invention can inhibit expansion and shrink.In addition, this
The polyimide film of invention is due to being applicable to display flexible with bloom permeability and low yellowing.
Polyimide film of the invention can use in the field of multiplicity, especially, can be used as required high transparency and resistance to
Hot OLED display, liquid crystal display, TFT substrate, print circuit substrate flexible, (Flexible) OLED table flexible
Face illuminating board, (Flexible) base plate for displaying and protective film flexible as Electronic Paper baseplate material provide.
Hereinafter, the present invention is described in more detail by embodiment.But these embodiments are only intended to illustrate the present invention, this
The range of invention is not limited by these.
[embodiment]
[comparative example 1]
As composition shown in the following table 1, by the PPD 2.547g (0.024mole) and TFMB as two amine system monomers
17.606g (0.055mole) is dissolved in NMP 142.1g, the GBL 58.5g as organic solvent, molten in room temperature in nitrogen atmosphere
Solution 30 minutes~1 hour.Hereafter, 6FDA 24.798g (0.056mole) and PMDA5.212g of the addition as dianhydride system monomer
(0.024mol) and after polymerizeing 24 hours, further add GBL 83.6g, stirring 24 hours and to manufacture polyamic acid solution (anti-
It answers temperature: 30 DEG C, maintaining all weight relative to reaction dissolvent at this point, solid is divided and reach 15 weight %).Use viscosity
Measurement equipment (Brookfield DV2T, SC4-27) be measured as a result, viscosity is 5,700cP.
[comparative example 2~3]
Other than using the content ratio of organic solvent of table 1, polyamic acid is manufactured with method identical with comparative example 1
Solution.
[Examples 1 to 5]
Other than using the content ratio of organic solvent of table 1, polyamic acid is manufactured with method identical with comparative example 1
Solution.
[experimental example 1: property measurement]
(1) room temperature gonorrhoea phenomenon is evaluated
The polyamic acid solution prepared in Examples 1 to 5 and comparative example 1~3 is dripped on glass plate, preparation is utilized
Bar coater applies certain thickness (solid point 15% benchmark, at 100 μm of the thickness of solution 15 μm after heat treatment), wet at 25 DEG C of temperature
The atmosphere of degree > 90% observes gonorrhoea phenomenon after placing 30 minutes.Gonorrhoea phenomenon generation level is commented with 0~5 numeralization
Valence (0: not occurring, 5: serious to occur).
(2) film manufacture and properties evaluations
After being coated with polyamic acid solution on a glass using bar coater, it is heat-treated in high temperature convection furnace.Heat
Treatment conditions are carried out in nitrogen atmosphere, and in 100 DEG C/30min, 220 DEG C/30min, the temperature and time condition of 350 DEG C/30min is obtained
To most telolemma.The property of the film obtained in this way with following method measurement and will be as the result is shown in the following table 2.
(a) permeability (Transmittance) and phase difference (delay)
Using permeability of the UV-Vis NIR spectrophotometric determination at 550nm, equipped using double refraction determining
Phase difference (the R of (Retarder, Otsuka RETs-100) measurement in-planeο), the phase difference (R of thickness directionυθ)。
(b) yellowing (Yellowness Index, YI)
It is measured using colorimeter (LabScan XE).
(c) turbidity (haze)
It is measured using nephelometer (TOYOSEIKI society, HAZE-GARD).
(d) thermal characteristics
Utilize the glass transformation temperature (T of the TMA 402F3 measurement film of Netzsch companyη), thermal expansion coefficient (CTE).It will
The power of tension mode is set as 0.05N, measuring temperature is warming up to 350 DEG C from 30 DEG C with the speed of 5/min, with 100~300 DEG C
In the range of average value measure thermal linear expansion coefficient.Thermal decomposition temperature is measured using the TG 209F3 of Netzsch company
(Tδ, 1%).
(e) mechanical property
Use the engineering properties of the UTM measurement film of Instron company.The width of film test piece is 10mm, the setting of grid interval
For 100mm, it is measured with the speed pulling test piece of 50mm/min.
[table 1]
As shown in Table 1, the GBL and NMP of organic solvent will be used as to use with specified ratio 70:30 (mole %)
It can confirm in the case where embodiment 1, gonorrhoea phenomenon not occur when pouring room temperature after solution on a glass, there is stability.
In addition we know, GBL and DMPA is mixed as shown in embodiment 2~4, or DMPA is used alone as described in Example 5
In the case where gonorrhoea phenomenon does not occur yet.
Since the rate of water absorption of GBL is low, GBL content increases, and it is more effective that control occurs for gonorrhoea.And it is found that
DMPA also inhibits effective for gonorrhoea phenomenon because of identical reason.In addition can be observed, in the optical characteristics of film, thermal characteristics, machine
Also the characteristic of peer-level is compared and presented in tool characteristic with comparative example 1~3.
Can be confirmed by such result, with the content of organic solvent according to the present invention by GBL and NMP, GBL and DMPA
In the case where with specified content use, it can ensure to the reduction without membrane property the resin stability in room temperature.
[comparative example 4]
As composition shown in the following table 2, the TFMB 21.186g (0.066mole) as two amine system monomers is dissolved in
As NMP 86.7g, the GBL 117.3g of organic solvent, in nitrogen atmosphere, in normal-temperature dissolution 30 minutes~1 hour.Hereafter it adds
As dianhydride system monomer 6FDA29.881g (0.067mole) and after polymerizeing 24 hours, further add GBL 85.0g and stir
It mixes 24 hours and manufactures polyamic acid solution and (reaction temperature: 30 DEG C, maintain at this point, solid is divided relative to reaction dissolvent
All weight and reach 15 weight %).With viscosimetric analysis equipment (Brookfield DV2T, SC4-27) be measured as a result,
Viscosity is 4,200cP.
[embodiment 6]
As composition shown in the following table 2, by the PPD 2.589g (0.024mole) and TFMB as two amine system monomers
17.899g (0.056mole) is dissolved in NMP 86.7g, the GBL 117.3g as organic solvent, molten in room temperature in nitrogen atmosphere
Solution 30 minutes~1 hour.Hereafter 6FDA 25.210g (0.057mole) and PMDA5.299g of the addition as dianhydride system monomer
(0.024mol) and after polymerizeing 24 hours, further add GBL 85.0g and stir 24 hours and to manufacture polyamic acid solution (anti-
It answers temperature: 30 DEG C, maintaining all weight relative to reaction dissolvent at this point, solid divides and reach 15 weight %).It is surveyed with viscosity
Fixed equipment (Brookfield DV2T, SC4-27) be measured as a result, viscosity is 6,400cP.
[embodiment 7]
As composition shown in the following table 2, by the TFMB 22.244g (0.069mole) as two amine system monomers, DBA
0.842g (0.004mol) is dissolved in the NMP86.7g as organic solvent, GBL 117.3g, in nitrogen atmosphere, in normal-temperature dissolution 30
Minute~1 hour.Hereafter 6FDA 23.063g (0.052mole) and PMDA 4.848g of the addition as dianhydride system monomer
(0.022mol) and after polymerizeing 24 hours, further add GBL 85.0g and stir 24 hours and to manufacture polyamic acid solution (anti-
It answers temperature: 30 DEG C, maintaining all weight relative to reaction dissolvent at this point, solid divides and reach 15 weight %).It is surveyed with viscosity
Fixed equipment (Brookfield DV2T, SC4-27) be measured as a result, viscosity is 4,800cP.
[embodiment 8]
As composition shown in the following table 2, the TFMB 24.320g (0.076mole) as two amine system monomers is dissolved in
As NMP 86.7g, the GBL 117.3g of organic solvent, in nitrogen atmosphere, in normal-temperature dissolution 30 minutes~1 hour.Hereafter it adds
As dianhydride system monomer 6FDA17.110g (0.038mole) and PMDA 5.035g (0.038mol) and after polymerizeing 24 hours,
It further adds GBL 85.0g and stirs 24 hours and manufacture polyamic acid solution and (reaction temperature: 30 DEG C, tieed up at this point, solid divides
It holds in all weight relative to reaction dissolvent and reaches 15 weight %).With viscosimetric analysis equipment (Brookfield DV2T,
SC4-27) being measured as a result, viscosity is 6,600cP.
[embodiment 9]
As composition shown in the following table 2, by the PPD 2.094g (0.019mole) and TFMB as two amine system monomers
18.610g (0.058mole), DBA 0.881g (0.004mol) are dissolved in NMP 86.7g, GBL as organic solvent
117.3g, in nitrogen atmosphere, in normal-temperature dissolution 30 minutes~1 hour.Hereafter 6FDA 24.298g of the addition as dianhydride system monomer
(0.055mole) and PMDA 5.115g (0.023mol) and polymerize 24 hours after, further add GBL 85.0g and stir 24
Hour and manufacture polyamic acid solution (reaction temperature: 30 DEG C, at this point, solid point maintains the entirety weight relative to reaction dissolvent
It measures and reaches 15 weight %).With viscosimetric analysis equipment (Brookfield DV2T, SC4-27) be measured as a result, viscosity is
6,800cP
[experimental example 2: property measurement]
Using the polyamic acid solution prepared in embodiment 6~9 and comparative example 4, surveyed with method identical with experimental example 1
Qualitative matter and be shown in the following table 2.
[table 2]
As shown in table 2, can confirm in the case where embodiment 6~8, as the PMDA of acid dianhydride monomer, BPDA and work
Content for the PPD of diamine monomer, DBA increases, and higher permeability is presented, and thermal characteristics improves.In addition, as diamines
Monomer and use TFMB simultaneously, can confirm in the case where the embodiment 9 of PPD, DBA, can not be realized by-product occurs because of DBA resistance to
Thermal characteristics and low thermal coefficient of expansion characteristic.
As a result, by polyamic acid solution produced by the present invention with 10~15 μm of benchmark of thickness of film, it is possible to provide turn for glass
Temperature is 300 DEG C or more, is 25ppm/ DEG C hereinafter, at 550nm wavelength in the thermal expansion coefficient within the scope of 100~300 DEG C
Transmitance be 85% or more, the yellowing (Yellow Index, Y.I.) at 550nm wavelength is that 7 transparent polyamides below are sub-
Amine film.
To meet the transparency, resin stability, high-fire resistance, low thermal expansion by polyimide film produced by the present invention
Coefficient and engineering properties are widely portable to such as OLED display, liquid crystal display, TFT substrate, print circuit base flexible
Plate, (Flexible) OLED surface illumination substrate flexible, (Flexible) flexible as Electronic Paper baseplate material are aobvious
Show device substrate and protective film.
Claims (9)
1. the transparent polyimide precursor resin combination that resin stability, high-fire resistance improve, it includes aromatic diamine ingredient,
Acid dianhydride compounds and organic solvent, wherein
The aromatic diamine ingredient (A) includes:
Bis- (trifluoromethyl) -4,4'- benzidine bases (TFMB) of 2,2'- as fluorinated aromatic diamine monomer, or
As N- (4- aminophenyl) -4- aminobenzamide (DBA) of the diamine monomer with amide groups, or
The mixture of above-mentioned TFMB and DBA,
The acid dianhydride compounds (B) are the mixtures comprising following substance:
As fluorinated aromatic acid dianhydride 4,4'- (hexafluoroisopropylidenyl) diphthalic anhydrides (6FDA) and
Pyromellitic acid anhydride (PMDA) or 3,3', 4,4'- biphenyl tetracarboxylic dianhydride as nonfluorinated aromatics acid dianhydride
(BPDA),
The organic solvent (C) is
The mixture of gamma-butyrolacton (GBL) and n-methyl-2-pyrrolidone (NMP), or
The mixture of gamma-butyrolacton (GBL) and 3- methoxyl group-N, N- dimethylpropane amide (DMPA), or
Individual 3- methoxyl group-N, N- dimethylpropane amide (DMPA).
2. the transparent polyimide precursor resin combination that the resin stability of claim 1, high-fire resistance improve, wherein described
Aromatic diamine ingredient (A) includes
Bis- (the trifluoromethyl) -4,4'- benzidine bases of 2,2'- relative to all 30~100 moles of % of diamine compound
(TFMB), and
Relative to N- (4- aminophenyl) -4- aminobenzamide (DBA) of all 5~50 moles of % of diamine compound,
It also include the nonfluorinated aromatic diamine of surplus.
3. the transparent polyimide precursor resin combination that the resin stability of claim 1, high-fire resistance improve, wherein described
Acid dianhydride compounds (B) include
Relative to the fluorinated aromatic acid dianhydride of 20~80 moles of % of all acid dianhydride compounds, and
Nonfluorinated aromatics acid dianhydride relative to 80~20 moles of % of all acid dianhydride compounds.
4. the transparent polyimide precursor resin combination that the resin stability of claim 1, high-fire resistance improve, wherein described
Organic solvent (C) includes:
The gamma-butyrolacton (GBL) of 30~70 moles of %, and
The n-methyl-2-pyrrolidone (NMP) or 3- methoxyl group-N, N- dimethylpropane amide (DMPA) of 70~30 moles of %.
5. the transparent polyimide precursor resin combination that the resin stability of claim 1, high-fire resistance improve, wherein described
Polyimide compositions also include the catalysts (D) selected from following a kind or more: Trimethylamine
(Trimethylamine), dimethylbenzene (Xylene), pyridine (Pyridine) and quinoline (Quinoline).
6. the manufacturing method of clear polyimides resin film comprising to the composition system of any one using Claims 1 to 55
The polyamic acid solution made is heat-treated and manufactures film forming.
7. the manufacturing method of the clear polyimides resin film of claim 6, wherein the polyamic acid solution
Organic solvent content is used in a manner of 10~40wt% of solid content,
It is manufactured by 95~100 moles of % aromatic diamine ingredients of mixing and 100~105 moles of % acid dianhydride compounds.
8. the manufacturing method of the clear polyimides resin film of claim 6, wherein the polyamic acid solution be 1000~
7000cP。
9. by method for claim 6 manufacture clear polyimides resin film, wherein based on 10~15 μm film thickness and
Glass transformation temperature is 300 DEG C or more,
Thermal expansion coefficient within the scope of 100~300 DEG C be 25ppm/ DEG C hereinafter,
Transmitance at 550nm wavelength is 85% or more,
Yellowing (Yellow Index, Y.I.) at 550nm wavelength is 7 or less.
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| KR1020160107257A KR101899902B1 (en) | 2016-08-23 | 2016-08-23 | Transparent polyimide precursor resin composition improving stability of resin and heat-resistance, method for manufacturing polyimide film using the same, and polyimide film thereof |
| KR10-2016-0107257 | 2016-08-23 | ||
| PCT/KR2016/010435 WO2018038309A1 (en) | 2016-08-23 | 2016-09-20 | Polyimide precursor resin composition with improved resin stability and heat resistance and having transparency, method for producing polyimide film using same, and polyimide film produced thereby |
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| JP (1) | JP6906054B2 (en) |
| KR (1) | KR101899902B1 (en) |
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| CN113121824A (en) * | 2019-12-31 | 2021-07-16 | 株式会社东进世美肯 | Polyimide film, polyimide composition, and display element |
| CN114685789A (en) * | 2020-12-25 | 2022-07-01 | 律胜科技股份有限公司 | Polyimide and film formed therefrom |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015122032A1 (en) * | 2014-02-14 | 2015-08-20 | 旭化成イーマテリアルズ株式会社 | Polyimide precursor and resin composition containing same |
| WO2016010003A1 (en) * | 2014-07-17 | 2016-01-21 | 旭化成イーマテリアルズ株式会社 | Resin precursor, resin composition containing same, polyimide resin membrane, resin film, and method for producing same |
| JP2016098260A (en) * | 2014-11-18 | 2016-05-30 | 住友ベークライト株式会社 | Polyamide solution |
| CN105637016A (en) * | 2014-05-30 | 2016-06-01 | 株式会社Lg化学 | Polyimide-based solution and polyimide-based film prepared by using same |
| CN107429057A (en) * | 2015-03-13 | 2017-12-01 | 旭化成株式会社 | Polyimide precursor resin composition |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5109374B2 (en) * | 2006-10-24 | 2012-12-26 | 日立化成工業株式会社 | Polyamideimide resin solution and production method thereof, resin composition and coating composition |
| KR101225842B1 (en) * | 2007-08-27 | 2013-01-23 | 코오롱인더스트리 주식회사 | Colorless polyimide film |
| KR101230418B1 (en) * | 2011-04-05 | 2013-02-06 | 한국화학연구원 | Cross-linked Polyimide film and Preparation method for the same |
| KR102196058B1 (en) * | 2013-07-05 | 2020-12-29 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Polyimide resin |
| JP6287608B2 (en) * | 2013-09-02 | 2018-03-07 | 株式会社リコー | Ink composition for ink jet recording, recording apparatus and recorded matter |
| JP2015218179A (en) | 2014-05-14 | 2015-12-07 | 日本精化株式会社 | Tetracarboxylic acid dianhydride, and polyimide obtained by using the same |
| JP2016027085A (en) * | 2014-06-26 | 2016-02-18 | デクセリアルズ株式会社 | Polyimide, polyamide acid, and methods for producing the polyimide and the polyamide acid, and photosensitive resin composition |
| CN104151823B (en) * | 2014-09-02 | 2019-02-26 | 长春聚明光电材料有限公司 | Kapton and preparation method thereof |
| KR102158223B1 (en) * | 2014-11-17 | 2020-09-22 | 에스케이이노베이션 주식회사 | Polyamic acid solution, polyimde film, and method for manufacturing the same |
-
2016
- 2016-08-23 KR KR1020160107257A patent/KR101899902B1/en active IP Right Grant
- 2016-09-20 JP JP2019532897A patent/JP6906054B2/en active Active
- 2016-09-20 WO PCT/KR2016/010435 patent/WO2018038309A1/en active Application Filing
- 2016-09-20 CN CN201680088588.8A patent/CN109689732B/en active Active
-
2017
- 2017-08-22 TW TW106128437A patent/TWI713782B/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015122032A1 (en) * | 2014-02-14 | 2015-08-20 | 旭化成イーマテリアルズ株式会社 | Polyimide precursor and resin composition containing same |
| CN105637016A (en) * | 2014-05-30 | 2016-06-01 | 株式会社Lg化学 | Polyimide-based solution and polyimide-based film prepared by using same |
| WO2016010003A1 (en) * | 2014-07-17 | 2016-01-21 | 旭化成イーマテリアルズ株式会社 | Resin precursor, resin composition containing same, polyimide resin membrane, resin film, and method for producing same |
| JP2016098260A (en) * | 2014-11-18 | 2016-05-30 | 住友ベークライト株式会社 | Polyamide solution |
| CN107429057A (en) * | 2015-03-13 | 2017-12-01 | 旭化成株式会社 | Polyimide precursor resin composition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110760062A (en) * | 2019-10-15 | 2020-02-07 | 李南文 | Optical film, transparent substrate, image display device and solar cell |
| CN113121824A (en) * | 2019-12-31 | 2021-07-16 | 株式会社东进世美肯 | Polyimide film, polyimide composition, and display element |
| CN112194790A (en) * | 2020-06-16 | 2021-01-08 | 中国科学院长春应用化学研究所 | Low-thermal-expansion transparent polyimide film and preparation method thereof |
| CN112194790B (en) * | 2020-06-16 | 2022-03-29 | 中国科学院长春应用化学研究所 | Low-thermal-expansion transparent polyimide film and preparation method thereof |
| CN114685789A (en) * | 2020-12-25 | 2022-07-01 | 律胜科技股份有限公司 | Polyimide and film formed therefrom |
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| Publication number | Publication date |
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| KR101899902B1 (en) | 2018-09-18 |
| JP6906054B2 (en) | 2021-07-21 |
| TW201817776A (en) | 2018-05-16 |
| CN109689732B (en) | 2022-02-11 |
| WO2018038309A1 (en) | 2018-03-01 |
| KR20180022217A (en) | 2018-03-06 |
| JP2019528368A (en) | 2019-10-10 |
| TWI713782B (en) | 2020-12-21 |
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