CN118005921A - High-transparency polyimide film material for flexible display and preparation method thereof - Google Patents
High-transparency polyimide film material for flexible display and preparation method thereof Download PDFInfo
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- CN118005921A CN118005921A CN202410152518.0A CN202410152518A CN118005921A CN 118005921 A CN118005921 A CN 118005921A CN 202410152518 A CN202410152518 A CN 202410152518A CN 118005921 A CN118005921 A CN 118005921A
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- Prior art keywords
- polyimide film
- film material
- polyimide
- bis
- flexible display
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 144
- 239000000463 material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000004642 Polyimide Substances 0.000 claims abstract description 57
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 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 32
- -1 dicarboxymethyl phenyl phosphine oxide Chemical compound 0.000 claims abstract description 27
- 150000004985 diamines Chemical class 0.000 claims abstract description 23
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 14
- 239000004952 Polyamide Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 7
- 229920002647 polyamide Polymers 0.000 claims abstract description 7
- 239000011521 glass Substances 0.000 claims description 56
- 239000002904 solvent Substances 0.000 claims description 44
- 239000002002 slurry Substances 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000012986 modification Methods 0.000 claims description 18
- 230000004048 modification Effects 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 14
- 239000009719 polyimide resin Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000012024 dehydrating agents Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 8
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 238000003892 spreading Methods 0.000 claims description 6
- 230000007480 spreading Effects 0.000 claims description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 claims description 4
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 4
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- IPFOLFNDBVVUNS-UHFFFAOYSA-N 2-(trifluoromethyl)benzene-1,3-diamine Chemical group NC1=CC=CC(N)=C1C(F)(F)F IPFOLFNDBVVUNS-UHFFFAOYSA-N 0.000 claims description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 3
- ROXBONJQHNRKST-UHFFFAOYSA-N 4-[4-(9H-fluoren-1-yl)phenoxy]aniline Chemical compound NC1=CC=C(OC2=CC=C(C=C2)C2=CC=CC=3C4=CC=CC=C4CC2=3)C=C1 ROXBONJQHNRKST-UHFFFAOYSA-N 0.000 claims description 3
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- HDGLPTVARHLGMV-UHFFFAOYSA-N 2-amino-4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenol Chemical compound NC1=CC(C(C(F)(F)F)C(F)(F)F)=CC=C1O HDGLPTVARHLGMV-UHFFFAOYSA-N 0.000 claims description 2
- VFNUTEMVQGLDAG-NKVSQWTQSA-N 2-methoxy-4-[(Z)-(5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-ylhydrazinylidene)methyl]phenol Chemical compound COC1=CC(\C=N/NC2=NC=NC3=C2C2=C(CCCC2)S3)=CC=C1O VFNUTEMVQGLDAG-NKVSQWTQSA-N 0.000 claims description 2
- NJCOLSAFYMXOGO-UHFFFAOYSA-N 3-(trifluoromethyl)benzene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C(F)(F)F)=C1C(O)=O NJCOLSAFYMXOGO-UHFFFAOYSA-N 0.000 claims description 2
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 claims description 2
- LACZRKUWKHQVKS-UHFFFAOYSA-N 4-[4-[4-amino-2-(trifluoromethyl)phenoxy]phenoxy]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1C(F)(F)F LACZRKUWKHQVKS-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- SNHKMHUMILUWSJ-UHFFFAOYSA-N 5-(1,3-dioxo-3a,4,5,6,7,7a-hexahydro-2-benzofuran-5-yl)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CC2C(=O)OC(=O)C2CC1C1CC2C(=O)OC(=O)C2CC1 SNHKMHUMILUWSJ-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- SNCJAJRILVFXAE-UHFFFAOYSA-N 9h-fluorene-2,7-diamine Chemical compound NC1=CC=C2C3=CC=C(N)C=C3CC2=C1 SNCJAJRILVFXAE-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 2
- VWTPHVKCTOTYPZ-UHFFFAOYSA-N NC(C=C1)=CC(C(F)(F)F)=C1OC(C=C1)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C21 Chemical compound NC(C=C1)=CC(C(F)(F)F)=C1OC(C=C1)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C21 VWTPHVKCTOTYPZ-UHFFFAOYSA-N 0.000 claims 1
- KSVUZILQRILGSW-UHFFFAOYSA-N cyclohexyloxymethanamine Chemical compound NCOC1CCCCC1 KSVUZILQRILGSW-UHFFFAOYSA-N 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 8
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000007259 addition reaction Methods 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 238000006482 condensation reaction Methods 0.000 abstract description 2
- 238000012856 packing Methods 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 3
- 230000021615 conjugation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical group C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 description 1
- ZPSUIVIDQHHIFH-UHFFFAOYSA-N 3-(trifluoromethyl)-4-[2-(trifluoromethyl)phenyl]benzene-1,2-diamine Chemical group FC(F)(F)C1=C(N)C(N)=CC=C1C1=CC=CC=C1C(F)(F)F ZPSUIVIDQHHIFH-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000004804 winding 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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a high-transparency polyimide film material for flexible display and a preparation method thereof, wherein a plurality of diamine and dianhydride monomers containing specific structures or groups are selected to prepare polyamide acid through a quaternary copolymerization mode, and finally polyimide for flexible display is prepared through chemical imidization; the polyimide has the advantages that the movement of a molecular chain can be restrained by introducing a crosslinking structure into polyimide, so that the CTE of the film is effectively reduced, the rigidity of the polyimide molecular chain is improved and the movement of the polyimide molecular chain is restrained by introducing a micro-branched crosslinking structure on the surface of the film, the amino grafted polyimide film and carboxyl of dicarboxymethyl phenyl phosphine oxide undergo condensation reaction, and then 4,4' -dimercapto diphenyl ether is added for amino-mercapto addition reaction, so that the CTE value of the polyimide film is effectively reduced; meanwhile, the introduction of the micro-branched cross-linked structure prevents the close packing of molecular chains, which is beneficial to the low dielectric property of the polyimide film.
Description
Technical Field
The invention relates to the field of flexible display, in particular to a high-transparency polyimide film material for flexible display and a preparation method thereof.
Background
With the continuous development of society, more and more electronic products are applied to aspects of industrial production and air-field life, and with the continuous innovation of technology, many high-tech electronic products are gradually developed towards small-size integration and light weight, and most of the high-tech electronic products are equipped with intelligent display systems, so that the electronic products are gradually developed towards integration and intelligent innovation, and simultaneously, higher requirements are also put on the performances of display systems, particularly display screens, in electronic equipment. Most of traditional display screens are made of inorganic glass materials, so that the mechanical strength of the display screens is not high, and the display screens are extremely easy to damage in the use process; in addition, the traditional glass screen cannot be ultrathin and heavy, which is not beneficial to the application of the glass screen in light-weight, miniaturization and integrated electronic products, and the glass display screen is hard and cannot be flexible, so that the application of the glass display screen in some foldable electronic products and special-shaped displays is limited. The polyimide as a novel special polymer material can perfectly overcome the defects of the glass display, thereby realizing perfect substitution of the traditional glass display screen.
Polyimide is used as a special polymer material, has the characteristics of high temperature resistance, corrosion resistance, high strength and the like, and can be made into homogeneous ultrathin film materials with different thickness requirements according to requirements. Moreover, through the design and the molecular chain structure of the modified polyimide, the high transparency and the high flexibility of the polyimide film material can be effectively realized, so that the high transparent polyimide for flexible display can be prepared, the effective replacement of the traditional glass screen is realized, and the development of high and new electronic products is promoted.
Chinese patent CN117343325A: the polyimide is prepared by polymerizing dianhydride and diamine, wherein the dianhydride is fluorine-containing dianhydride or alicyclic dianhydride, and the hydroxyl-containing diamine in the polyimide accounts for more than 10 percent of the total molar weight of diamine participating in polymerization, and has a general formula shown in the following structural formula: the polyimide film material prepared by the invention improves the glass transition temperature of the transparent polyimide material, and simultaneously can reduce the thermal expansion coefficient of the material and improve the transparency of the material, so that the polyimide film material can better meet the application of downstream industries.
Chinese patent CN116675887a: the preparation process of transparent polyimide film includes the following steps: polyimide is dissolved in a solvent to obtain polyimide solution; and casting the polyimide solution onto a flexible substrate film in a slit coating mode, primarily drying at 100-180 ℃ to obtain a primary film with the solvent content of 10-25%, standing for 24 hours, stripping the primary film from the flexible substrate film, stretching and tensioning the primary film, secondarily drying at 200-300 ℃ to remove residual solvent in the film, and winding to obtain the transparent polyimide film. According to the preparation method, the polyimide solution is cast onto the flexible substrate film to be primarily dried to obtain the primary film, the primary film is kept stand for a certain time and then is peeled off from the flexible substrate film, and then the secondary drying is carried out under stretching and tensioning, so that the problem of warping of the film can be effectively avoided, and the prepared CPI film is low in yellowness, high in transparency and high in flatness.
Chinese patent CN114231029B: belongs to the technical field of functional polymer materials, and in particular relates to a cross-linking type high-transparency polyimide film and a preparation method thereof, wherein the cross-linking type high-transparency polyimide film is prepared by polycondensation reaction of novel alicyclic structure-containing triamine monomer 1,3, 5-tri (2-trifluoromethyl-4-amino-benzamide) cyclohexane and aromatic dianhydride monomer, and an amide group, an alicyclic structure and a fluorine-containing group are introduced into a cross-linking type polyimide molecular chain. The cross-linked high-transparency polyimide film prepared by the invention has the characteristics of high transparency, low expansion, low dielectric property, low expansion and high heat resistance, the light transmittance at 400nm is more than 85%, the yellowness index is less than 2, the thermal expansion coefficient is reduced to be below 20 ppm/DEG C, the dielectric constant is less than 3, the glass transition temperature is more than 300 ℃, and the cross-linked high-transparency polyimide film has wide application in the photoelectric fields of electronic microelectronics and the like. The invention has simple preparation process, excellent processing performance and simple film forming process, and is suitable for industrial production.
The traditional aromatic polyimide is prepared by polymerizing diamine with strong electrophilicity and dianhydride with strong nucleophilicity, polymer molecular chains are closely stacked, strong conjugation exists between aromatic rings, and the strong interaction between the aromatic rings can lead the traditional aromatic polyimide to present characteristic yellow and poor transmittance in a visible light region while endowing the polyimide with excellent characteristics, so that the application of the polyimide film in bottom-light-emitting flexible display is limited.
Disclosure of Invention
The invention provides a high-transparency polyimide film material for flexible display and a preparation method thereof, wherein the polyimide has the performances of high transparency, high solubility, high mechanical strength, high internal temperature, high chemical stability, film forming and the like, can be applied to the field of flexible display screens, and is used for solving the replacement problems of novel integrated, special-shaped, light-weight and other electronic product display screens.
A high transparent polyimide for flexible display has the following chemical structure:
Wherein n is 0.1 to 0.9, m=1 to n, wherein A1 is a diamine intermediate structure which is any one of the following structures:
b1 is a dianhydride intermediate structure, which is any one of the following structures:
another object of the present invention is to provide a method for preparing a highly transparent polyimide film material for flexible display, which comprises the following steps:
s1: weighing 100-200 parts by weight of solvent and 6-12 parts by weight of diamine monomer, and stirring in a reaction kettle to dissolve the solvent and the diamine monomer;
s2: continuously adding 10-15 parts of dianhydride monomer, and reacting for 4-8 hours at the temperature of 0-10 ℃ to obtain transparent viscous polyamide acid slurry with certain solid content;
S3: continuously adding 4-8 parts of catalyst and 5-10 parts of dehydrating agent, heating to 20-40 ℃, and reacting for 4-8 hours under the stirring state; obtaining transparent polyimide slurry;
s4: injecting polyimide slurry into 800-1200 parts of phase inversion liquid, and soaking for 8-10 hours;
S5: heating the soaked resin to 80-150 ℃, and drying for 6-12h to obtain polyimide resin;
S6: adding 5-10 parts of polyimide resin into 20-40 parts of solvent to prepare slurry with the solid content of 20-30wt%, pouring the slurry onto a clean glass plate, and spreading the polyimide slurry on the glass plate uniformly by using a scraper with the opening thickness of 10-50 mu m;
S7: placing the glass plate coated with polyimide obtained in the step S4 on a horizontal heat table, and preserving heat at 70-100 ℃ for 4-10 hours to preliminarily evaporate the solvent to form a solid film on the glass plate; then the temperature of the heat table is increased to 120-160 ℃, the heat preservation time is continued for 4-8h, the film is formed, and most of the solvent contained in the film material is removed; transferring the glass plate coated with the polyimide film obtained in the step S6 into a vacuum oven, heating to 200-220 ℃, keeping the temperature for 4-8 hours to completely remove the solvent in the film material, and curing to form a film;
S8: naturally cooling the glass plate coated with the polyimide film obtained in the step S7 to room temperature, putting the glass plate into plasma equipment, and performing plasma modification in an ammonia atmosphere for 20-40min to obtain an amino grafted polyimide film;
S9: adding 100-150 parts by weight of an amino grafted polyimide film, 0.003-0.04 part by weight of dicarboxymethyl phenyl phosphine oxide, 1000-2000 parts by weight of toluene, stirring at 70-80 ℃ for reacting for 10-20min, adding 0.03-0.4 part by weight of 4,4' -dimercaptodiphenyl ether and 0.6-2 parts by weight of sodium tert-butoxide, and stirring at 70-80 ℃ for reacting for 30-60min; after the reaction is finished, taking out, drying, putting into plasma equipment, and performing plasma modification in an argon atmosphere for 30-50min to obtain a polytetrafluoroethylene filter screen containing phosphino groups; then placing the mixture in distilled water for soaking for 3-6 hours; the film material naturally falls off from the glass plate, and the water stain on the surface of the film material is carefully wiped by using water absorbing paper, so that the high-transparency polyimide film material which can be used for flexible display is obtained.
Further, the method comprises the steps of, the diamine monomer is 2, 6-diamino benzotrifluoride, 2-bis (3-amino-4-hydroxy phenyl) hexafluoropropane (6 FAP), 2' -bis (trifluoromethyl) -4,4' -diamino diphenyl ether, 2' -bis (trifluoromethyl) diaminobiphenyl 4,4' -diaminoanilide, 4' -diaminodiphenyl ether (ODA), 1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene, 2, 7-diaminofluorene, 9-bis [4- (4-aminophenoxy) phenyl ] fluorene (BAOFL), and 4,4' -diaminoanilide, 4' -diaminodiphenyl ether (ODA), 1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene 2, 7-diaminofluorene, 9-bis [4- (4-aminophenoxy) phenyl ] fluorene (BAOFL); the solvent is one or more of N, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), tetrahydrofuran, p-chlorophenol (PCP), 1, 3-dimethyl-2-imidazolidinone (DMI) and dimethyl sulfoxide (DMSO).
Further, the dianhydride monomer is 5,5 '-oxybis- (cis-5-norbornane-exo-2, 3' -dicarboxylic anhydride), exo-2, 2', 3' -bis (cis-5-norbornane) dicarboxylic anhydride, 5 '-hexafluoroisopropylidenedi- (cis-5-norbornane-exo-2, 3' -dicarboxylic anhydride), CPODA, hexafluorodianhydride (6 FDA), 2 '-difluoromethyl-4, 4',5 '-biphenyl tetracarboxylic dianhydride, 3', at least one of 4,4 '-biphenyltetracarboxylic dianhydride (BPDA), cyclobutanetetracarboxylic dianhydride (CBDA), 3, 6-bis (trifluoromethyl) -1,2,4, 5-tetracarboxylic dianhydride, 6-trifluoromethyl-1, 2,4, 5-benzene tetracarboxylic dianhydride, 4' -oxydiphthalic anhydride (ODPA), 4 '-oxydiphthalic anhydride (2-trifluoromethylphenyl) phthalic anhydride, 3',4 '-tetracarboxylic acid-2, 2' -bis (trifluoromethyl) diphenylether diamine, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (HPMDA), dicyclohexyl-3, 4,3',4' -tetracarboxylic dianhydride (HBPDA), bisphenol a diether dianhydride (BPADA), bisphenol F diether dianhydride (BPFDA).
Further, the catalyst is at least one of isoquinoline, pyridine, picoline and triethylamine.
Further, the dehydrating agent is at least one of acetic anhydride, trifluoroacetic anhydride and propionic anhydride.
Further, the phase conversion liquid is at least one of distilled water, methanol, ethanol and toluene.
Further, the solvent is at least one of DMAc, DMF, NMP, and the solid content is 10-30wt%.
Further, the plasma modification conditions of the S8 and the S9 are as follows: the frequency of the plasma radio frequency equipment is 100-200kHz, and the output power is 100-150W; the gas flow rate is 10-22ml/min.
Description of the drawings:
FIG. 1 is an infrared spectrum of example 3;
FIG. 2 is a differential thermal scan curve of example 3.
The technical effects are as follows:
compared with the prior art, the high-transparency polyimide film material for flexible display and the preparation method thereof have the following remarkable effects:
1. The dianhydride with the norbornene structure, the diamine containing the fluoromethyl with high electron withdrawing effect and other monomers containing alicyclic are used for preparing polyimide, and the introduction of the alicyclic and fluoromethyl effectively suppresses the electron conjugation effect and the electron transfer effect in a polyimide molecular chain, so that the light transmittance of the polyimide is effectively improved;
2. The introduction of the large-volume monomer containing fluorenyl also increases the compatibility between molecular chains, further inhibits the electron transfer between the molecular chains and further improves the light transmittance of polyimide;
3. The hydroxyl-containing monomer introduced into the polyimide provided by the invention can generate chemical hydrogen bond crosslinking between polyimide molecules, so that the thermal expansion coefficient of the polyimide film is effectively reduced;
4. According to the invention, the monomer containing the ether bond structure is introduced, so that the flexibility of a molecular chain is enhanced, and the flexibility of a final film material is greatly improved;
5. The high-transparency flexible polyimide has very good application prospect and large-scale industrialized popularization potential in the aspect of flexible display of the tip;
6. The polyimide has the advantages that the movement of a molecular chain can be restrained by introducing a crosslinking structure into polyimide, so that the CTE of the film is effectively reduced, the rigidity of the polyimide molecular chain is improved and the movement of the polyimide molecular chain is restrained by introducing a micro-branched crosslinking structure on the surface of the film, the amino grafted polyimide film and carboxyl of dicarboxymethyl phenyl phosphine oxide undergo condensation reaction, and then 4,4' -dimercapto diphenyl ether is added for amino-mercapto addition reaction, so that the CTE value of the polyimide film is effectively reduced; meanwhile, the introduction of the micro-branched cross-linked structure prevents the close packing of molecular chains, which is beneficial to the low dielectric property of the polyimide film.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example test method:
1. Glass transition temperature test: testing by adopting a TA company Q800 type dynamic mechanical analyzer (DMTA); adopting a film stretching clamp, testing the temperature of the film stretching clamp at the test frequency of 1Hz and the heating rate of 3 ℃/min, testing the temperature of the film stretching clamp at the test temperature of between room temperature and 450 ℃, and taking the temperature corresponding to the peak value of the loss angle tan delta curve as the glass transition temperature of the polymer;
2. Detecting the mechanical properties of the film by adopting an Instron electronic universal material tester;
3. light transmittance test: testing with reference to standard GB/T2410-2008;
4. The linear thermal expansion coefficient of the polyimide resin layer is tested by adopting a thermo-mechanical analyzer (TMA) under the nitrogen atmosphere, the heating rate is 10 ℃/min, and the value is taken at 50-250 ℃;
5. Dielectric constant test: performing dielectric property test by using a broadband dielectric impedance spectrometer (concept 40); testing temperature 25 ℃ and relative humidity 30%; and (3) frequency conversion test: the test frequency range is 10 0-106 Hz; and (3) temperature change test: the test temperature is 30-280 ℃ (test frequency 10 kHz).
Example 1
A high transparent polyimide film material for flexible display and a preparation method thereof, which comprises the following operation steps:
s1: weighing 100g of solvent and 6g of diamine monomer, and stirring in a reaction kettle to dissolve the solvent and the diamine monomer;
s2: continuously adding 10g of dianhydride monomer, and reacting for 4 hours at the temperature of 0 ℃ to obtain transparent viscous polyamide acid slurry with certain solid content;
s3: continuously adding 4g of catalyst and 5g of dehydrating agent, heating to 20 ℃, and reacting for 4h under the stirring state; obtaining transparent polyimide slurry;
S4: injecting polyimide slurry into 800g of phase inversion liquid, and soaking for 8 hours;
S5: heating the soaked resin to 80 ℃, and drying for 6 hours to obtain polyimide resin;
S6: adding 5g of polyimide resin into 20g of solvent to prepare slurry with the solid content of 20wt%, pouring the slurry onto a clean glass plate, and uniformly spreading the polyimide slurry on the glass plate by using a scraper with the opening thickness of 10 mu m;
S7: placing the glass plate coated with polyimide obtained in the step S4 on a horizontal heat table, preserving heat at the temperature of 70 ℃ for 4 hours, and forming a solid film on the glass plate by primarily evaporating the solvent; then the temperature of the heat table is increased to 120 ℃, the heat preservation time is continued for 4 hours, and most of the solvent contained in the film material is formed and removed; transferring the glass plate coated with the polyimide film obtained in the step S6 into a vacuum oven, heating to 200 ℃, keeping the temperature for 4 hours to completely remove the solvent in the film material, and curing to form a film;
S8: naturally cooling the glass plate coated with the polyimide film obtained in the step S7 to room temperature, putting the glass plate into plasma equipment, and performing plasma modification in an ammonia atmosphere for 20min to obtain an amino grafted polyimide film;
S9: adding 100g of amino grafted polyimide film, 0.003g of dicarboxymethyl phenyl phosphine oxide and 1000g of toluene into a reaction kettle, stirring and reacting for 10min at 70 ℃, adding 0.03g of 4,4' -dimercaptodiphenyl ether and 0.6g of sodium tert-butoxide, and stirring and reacting for 30min at 70 ℃; after the reaction is finished, taking out, drying, putting into plasma equipment, performing plasma modification in an argon atmosphere, and treating for 30min to obtain a polytetrafluoroethylene filter screen containing phosphine groups; then placing the mixture in distilled water for soaking for 3 hours; the film material naturally falls off from the glass plate, and the water stain on the surface of the film material is carefully wiped by using water absorbing paper, so that the high-transparency polyimide film material which can be used for flexible display is obtained.
The diamine monomer is 2, 6-diamino benzotrifluoride.
The dianhydride monomer is 5,5 '-oxybis- (cis-5-norbornane-exo-2, 3' -dicarboxylic anhydride).
The catalyst is isoquinoline.
The dehydrating agent is acetic anhydride.
The phase inversion liquid is distilled water.
The solvent is DMAc, and the solid content is 10wt%.
The plasma modification conditions of S8 and S9 are as follows: the frequency of the plasma radio frequency equipment is 100kHz, and the output power is 100W; the gas flow rate was 10ml/min.
Example 2
A high transparent polyimide film material for flexible display and a preparation method thereof, which comprises the following operation steps:
s1: weighing 140g of solvent and 8g of diamine monomer, and stirring in a reaction kettle to dissolve the solvent and the diamine monomer;
S2: continuously adding 12g of dianhydride monomer, and reacting for 5 hours at the temperature of 5 ℃ to obtain transparent viscous polyamide acid slurry with certain solid content;
S3: continuously adding 5g of catalyst and 6g of dehydrating agent, heating to 25 ℃, and reacting for 5h under the stirring state; obtaining transparent polyimide slurry;
s4: injecting polyimide slurry into 900g of phase inversion liquid, and soaking for 9h;
S5: heating the soaked resin to 100 ℃, and drying for 8 hours to obtain polyimide resin;
s6: adding 6g of polyimide resin into 25g of solvent to prepare slurry with the solid content of 25wt%, pouring the slurry onto a clean glass plate, and uniformly spreading the polyimide slurry on the glass plate by using a scraper with the opening thickness of 20 mu m;
S7: placing the glass plate coated with polyimide obtained in the step S4 on a horizontal heat table, preserving heat at the temperature of 80 ℃ for 6 hours, and forming a solid film on the glass plate by primarily evaporating the solvent; then the temperature of the heat table is increased to 130 ℃, the heat preservation time is continued for 5 hours, and most of the solvent contained in the film material is formed and removed; transferring the glass plate coated with the polyimide film obtained in the step S6 into a vacuum oven, heating to 205 ℃, keeping the temperature for 5 hours to completely remove the solvent in the film material, and curing to form a film;
S8: naturally cooling the glass plate coated with the polyimide film obtained in the step S7 to room temperature, putting the glass plate into plasma equipment, performing plasma modification in an ammonia atmosphere, and treating for 25min to obtain an amino grafted polyimide film;
S9: 110g of amino grafted polyimide film, 0.01g of dicarboxymethyl phenyl phosphine oxide and 1300g of toluene are added into a reaction kettle, stirred and reacted for 15min at 75 ℃, and then 0.1g of 4,4' -dimercaptodiphenyl ether and 1g of sodium tert-butoxide are added, stirred and reacted for 40min at 75 ℃; after the reaction is finished, taking out, drying, putting into plasma equipment, and performing plasma modification in an argon atmosphere for 35min to obtain a polytetrafluoroethylene filter screen containing phosphine groups; then placing the mixture in distilled water for soaking for 4 hours; the film material naturally falls off from the glass plate, and the water stain on the surface of the film material is carefully wiped by using water absorbing paper, so that the high-transparency polyimide film material which can be used for flexible display is obtained.
The diamine monomer is 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6 FAP).
The dianhydride monomer is external-2, 2', 3' -bi (cis-5-norbornane) dicarboxylic dianhydride.
The catalyst is pyridine.
The dehydrating agent is trifluoroacetic anhydride.
The phase inversion liquid is methanol.
The solvent is DMF, and the solid content is 15wt%.
The plasma modification conditions of S8 and S9 are as follows: the frequency of the plasma radio frequency equipment is 150kHz, and the output power is 110W; the gas flow rate was 15ml/min.
Example 3
A high transparent polyimide film material for flexible display and a preparation method thereof, which comprises the following operation steps:
s1: 180g of solvent and 10g of diamine monomer are weighed and stirred in a reaction kettle to be dissolved;
s2: continuously adding 14g of dianhydride monomer, and reacting for 7 hours at the temperature of 5 ℃ to obtain transparent viscous polyamide acid slurry with certain solid content;
S3: continuously adding 7g of catalyst and 9g of dehydrating agent, heating to 35 ℃, and reacting for 7h under the stirring state; obtaining transparent polyimide slurry;
S4: injecting polyimide slurry into 1100g of phase inversion liquid, and soaking for 9h;
s5: heating the soaked resin to 130 ℃, and drying for 10 hours to obtain polyimide resin;
S6: adding 9g of polyimide resin into 35g of solvent to prepare slurry with the solid content of 25wt%, pouring the slurry onto a clean glass plate, and uniformly spreading the polyimide slurry on the glass plate by using a scraper with the opening thickness of 40 mu m;
S7: placing the glass plate coated with polyimide obtained in the step S4 on a horizontal heat table, preserving heat at 90 ℃ for 8 hours, and forming a solid film on the glass plate by primarily evaporating the solvent; then the temperature of the heat table is increased to 150 ℃, the heat preservation time is continued for 7 hours, the film is formed, and most of the solvent contained in the film material is removed; transferring the glass plate coated with the polyimide film obtained in the step S6 into a vacuum oven, heating to 215 ℃, keeping the temperature for 7 hours to completely remove the solvent in the film material, and curing to form a film;
s8: naturally cooling the glass plate coated with the polyimide film obtained in the step S7 to room temperature, putting the glass plate into plasma equipment, and performing plasma modification in an ammonia atmosphere for 35min to obtain an amino grafted polyimide film;
S9: adding 140g of amino grafted polyimide film, 0.03g of dicarboxymethyl phenyl phosphine oxide and 1800g of toluene into a reaction kettle, stirring and reacting for 15min at 75 ℃, adding 0.3g of 4,4' -dimercaptodiphenyl ether and 1.5g of sodium tert-butoxide, and stirring and reacting for 50min at 75 ℃; after the reaction is finished, taking out, drying, putting into plasma equipment, and performing plasma modification in an argon atmosphere for 45min to obtain a polytetrafluoroethylene filter screen containing phosphine groups; then placing the mixture in distilled water for soaking for 5 hours; the film material naturally falls off from the glass plate, and the water stain on the surface of the film material is carefully wiped by using water absorbing paper, so that the high-transparency polyimide film material which can be used for flexible display is obtained.
The diamine monomer is 2,2 '-di (trifluoromethyl) -4,4' -diaminodiphenyl ether.
The dianhydride monomer is 5,5 '-hexafluoroisopropylidene bis- (cis-5-norbornane-external-2, 3' -dicarboxylic anhydride).
The catalyst is picoline.
The dehydrating agent is trifluoroacetic anhydride.
The phase inversion liquid is ethanol.
The solvent is DMF and the solid content is 25wt%.
The plasma modification conditions of S8 and S9 are as follows: the frequency of the plasma radio frequency equipment is 150kHz, and the output power is 140W; the gas flow rate was 20ml/min.
Example 4
A high transparent polyimide film material for flexible display and a preparation method thereof, which comprises the following operation steps:
s1: 200g of solvent and 12g of diamine monomer are weighed and stirred in a reaction kettle to be dissolved;
S2: continuously adding 15g of dianhydride monomer, and reacting for 8 hours at the temperature of 10 ℃ to obtain transparent viscous polyamide acid slurry with certain solid content;
S3: continuously adding 8g of catalyst and 10g of dehydrating agent, heating to 40 ℃, and reacting for 8h under the stirring state; obtaining transparent polyimide slurry;
S4: injecting polyimide slurry into 1200g of phase inversion liquid, and soaking for 10h;
S5: heating the soaked resin to 150 ℃, and drying for 12 hours to obtain polyimide resin;
S6: adding 10g of polyimide resin into 40g of solvent to prepare slurry with the solid content of 30wt%, pouring the slurry onto a clean glass plate, and uniformly spreading the polyimide slurry on the glass plate by using a scraper with the opening thickness of 50 mu m;
S7: placing the glass plate coated with polyimide obtained in the step S4 on a horizontal heat table, preserving heat at 100 ℃ for 10 hours, and forming a solid film on the glass plate by primarily evaporating the solvent; then the temperature of the heat table is increased to 160 ℃, the heat preservation time is continued for 8 hours, and most of the solvent contained in the film material is formed and removed; transferring the glass plate coated with the polyimide film obtained in the step S6 into a vacuum oven, heating to 220 ℃, keeping the temperature for 8 hours to completely remove the solvent in the film material, and curing to form a film;
S8: naturally cooling the glass plate coated with the polyimide film obtained in the step S7 to room temperature, putting the glass plate into plasma equipment, and performing plasma modification in an ammonia atmosphere for 40 minutes to obtain an amino grafted polyimide film;
S9: 150g of amino grafted polyimide film, 0.04g of dicarboxymethyl phenyl phosphine oxide and 2000g of toluene are added into a reaction kettle, stirred and reacted for 20min at 80 ℃, and then 0.4g of 4,4' -dimercaptodiphenyl ether and 2g of sodium tert-butoxide are added into the reaction kettle, stirred and reacted for 60min at 80 ℃; after the reaction is finished, taking out, drying, putting into plasma equipment, and performing plasma modification in an argon atmosphere for 50min to obtain a polytetrafluoroethylene filter screen containing phosphine groups; then placing the mixture in distilled water for soaking for 6 hours; the film material naturally falls off from the glass plate, and the water stain on the surface of the film material is carefully wiped by using water absorbing paper, so that the high-transparency polyimide film material which can be used for flexible display is obtained.
The diamine monomer is 2,2' -di (trifluoromethyl) diaminobiphenyl.
The dianhydride monomer is hexafluorodianhydride (6 FDA).
The catalyst is triethylamine.
The dehydrating agent is propionic anhydride.
The phase inversion liquid is toluene.
The solvent is NMP, and the solid content is 30wt%.
The plasma modification conditions of S8 and S9 are as follows: the frequency of the plasma radio frequency equipment is 200kHz, and the output power is 150W; the gas flow rate was 22ml/min.
Comparative example 1
This comparative example was conducted in the same manner as in example 1 except that no dicarboxymethylphenyl phosphine oxide was added.
Comparative example 2
This comparative example was conducted in the same manner as in example 1 except that 4,4' -dimercaptodiphenyl ether was not added.
Comparative example 3
This comparative example was conducted in the same manner as in example 1 except that sodium t-butoxide was not added.
Test results
Through the data analysis of the examples and the comparative examples, the high-transparency polyimide film material for flexible display prepared by the invention has the advantages of high light transmittance, low thermal expansion coefficient, better flexibility, low dielectric property and the like.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept, and the scope of protection of the present invention should not be construed as limited to the specific forms set forth in the examples, nor is it intended that the scope of protection of the present invention be limited to only equivalent technical means as would occur to those skilled in the art based on the inventive concept.
Claims (8)
1. A high transparent polyimide film material for flexible display and a preparation method thereof, which comprises the following operation steps:
s1: weighing 100-200 parts by weight of solvent and 6-12 parts by weight of diamine monomer, and stirring in a reaction kettle to dissolve the solvent and the diamine monomer;
s2: continuously adding 10-15 parts of dianhydride monomer, and reacting for 4-8 hours at the temperature of 0-10 ℃ to obtain transparent viscous polyamide acid slurry with certain solid content;
s3: continuously adding 4-8 parts of catalyst and 5-10 parts of dehydrating agent, heating to 20-40 ℃, and reacting for 4-8 hours under the stirring state to obtain transparent polyimide slurry;
s4: injecting polyimide slurry into 800-1200 parts of phase inversion liquid, and soaking for 8-10 hours;
S5: heating the soaked resin to 80-150 ℃, and drying for 6-12h to obtain polyimide resin;
S6: adding 5-10 parts of polyimide resin into 20-40 parts of solvent to prepare slurry with the solid content of 20-30wt%, pouring the slurry onto a clean glass plate, and spreading the polyimide slurry on the glass plate uniformly by using a scraper with the opening thickness of 10-50 mu m;
S7: placing the glass plate coated with polyimide obtained in the step S4 on a horizontal heat table, and preserving heat at 70-100 ℃ for 4-10 hours to preliminarily evaporate the solvent to form a solid film on the glass plate; then the temperature of the heat table is increased to 120-160 ℃, the heat preservation time is continued for 4-8h, the film is formed, and most of the solvent contained in the film material is removed; transferring the glass plate coated with the polyimide film obtained in the step S6 into a vacuum oven, heating to 200-220 ℃, keeping the temperature for 4-8 hours to completely remove the solvent in the film material, and curing to form a film;
S8: naturally cooling the glass plate coated with the polyimide film obtained in the step S7 to room temperature, putting the glass plate into plasma equipment, and performing plasma modification in an ammonia atmosphere for 20-40min to obtain an amino grafted polyimide film;
S9: adding 100-150 parts by weight of an amino grafted polyimide film, 0.003-0.04 part by weight of dicarboxymethyl phenyl phosphine oxide, 1000-2000 parts by weight of toluene, stirring at 70-80 ℃ for reacting for 10-20min, adding 0.03-0.4 part by weight of 4,4' -dimercaptodiphenyl ether and 0.6-2 parts by weight of sodium tert-butoxide, and stirring at 70-80 ℃ for reacting for 30-60min; after the reaction is finished, taking out, drying, putting into plasma equipment, and performing plasma modification in an argon atmosphere for 30-50min to obtain a polytetrafluoroethylene filter screen containing phosphino groups; then placing the mixture in distilled water for soaking for 3-6 hours; the film material naturally falls off from the glass plate, and the water stain on the surface of the film material is carefully wiped by using water absorbing paper, so that the high-transparency polyimide film material which can be used for flexible display is obtained.
2. The high-transparency polyimide film material for flexible display and the preparation method thereof according to claim 1, wherein the high-transparency polyimide film material is characterized in that: the diamine monomer is 2, 6-diamino benzotrifluoride, 2-bis (3-amino-4-hydroxy phenyl) hexafluoropropane (6 FAP), 2' -bis (trifluoromethyl) -4,4' -diamino diphenyl ether, 2' -bis (trifluoromethyl) diaminobiphenyl 4,4' -diaminoanilide, 4' -diaminodiphenyl ether (ODA), 1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene, 2, 7-diaminofluorene, 9-bis [4- (4-aminophenoxy) phenyl ] fluorene (BAOFL), and 9, 9-bis [4- (4-aminomethoxycyclohexane) phenyl ] fluorene, 9-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] fluorene, 9-bis [4- (2-trifluoromethyl-4-aminomethoxycyclohexane) phenyl ] fluorene at least one of 9, 9-bis (4-amino-5-trifluoromethylcyclohexyl) fluorene, 9-bis (4-amino-5-trifluoromethylphenyl) fluorene, 9-bis (4-aminophenyl) fluorene, and 9, 9-bis (4-aminocyclohexyl) fluorene; the solvent is one or more of N, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), tetrahydrofuran, p-chlorophenol (PCP), 1, 3-dimethyl-2-imidazolidinone (DMI) and dimethyl sulfoxide (DMSO).
3. The high-transparency polyimide film material for flexible display and the preparation method thereof according to claim 1, wherein the high-transparency polyimide film material is characterized in that: the dianhydride monomer is 5,5 '-oxybis- (cis-5-norbornane-exo-2, 3' -dicarboxylic anhydride), exo-2, 2', 3' -bi (cis-5-norbornane) dicarboxylic anhydride, 5 '-hexafluoroisopropylidene bis- (cis-5-norbornane-exo-2, 3' -dicarboxylic anhydride), CPODA, hexafluorodianhydride (6 FDA), 2 '-difluoromethyl-4, 4',5 '-biphenyl tetracarboxylic dianhydride, 3', at least one of 4,4 '-biphenyltetracarboxylic dianhydride (BPDA), cyclobutanetetracarboxylic dianhydride (CBDA), 3, 6-bis (trifluoromethyl) -1,2,4, 5-tetracarboxylic dianhydride, 6-trifluoromethyl-1, 2,4, 5-benzene tetracarboxylic dianhydride, 4' -oxydiphthalic anhydride (ODPA), 4 '-oxydiphthalic anhydride (2-trifluoromethylphenyl) phthalic anhydride, 3',4 '-tetracarboxylic acid-2, 2' -bis (trifluoromethyl) diphenylether diamine, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (HPMDA), dicyclohexyl-3, 4,3',4' -tetracarboxylic dianhydride (HBPDA), bisphenol a diether dianhydride (BPADA), bisphenol F diether dianhydride (BPFDA).
4. The high-transparency polyimide film material for flexible display and the preparation method thereof according to claim 1, wherein the high-transparency polyimide film material is characterized in that: the catalyst is at least one of isoquinoline, pyridine, picoline and triethylamine.
5. The high-transparency polyimide film material for flexible display and the preparation method thereof according to claim 1, wherein the high-transparency polyimide film material is characterized in that: the dehydrating agent is at least one of acetic anhydride, trifluoroacetic anhydride and propionic anhydride.
6. The high-transparency polyimide film material for flexible display and the preparation method thereof according to claim 1, wherein the high-transparency polyimide film material is characterized in that: the phase inversion liquid is at least one of distilled water, methanol, ethanol and toluene.
7. The high-transparency polyimide film material for flexible display and the preparation method thereof according to claim 1, wherein the high-transparency polyimide film material is characterized in that: the solvent is at least one of DMAc, DMF, NMP, and the solid content is 10-30wt%.
8. The high-transparency polyimide film material for flexible display and the preparation method thereof according to claim 1, wherein the high-transparency polyimide film material is characterized in that: the plasma modification conditions of S8 and S9 are as follows: the frequency of the plasma radio frequency equipment is 100-200kHz, and the output power is 100-150W; the gas flow rate is 10-22ml/min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070069082A (en) * | 2005-12-27 | 2007-07-02 | 듀폰 도레이 컴파니, 리미티드 | Highly adhesive polyimide film with the improved heat shrinkability |
| WO2012050072A1 (en) * | 2010-10-13 | 2012-04-19 | 東洋紡績株式会社 | Polyimide film, method for manufacturing same, and method for manufacturing layered product |
| CN109563300A (en) * | 2016-07-25 | 2019-04-02 | 宇部兴产株式会社 | The manufacturing method of Porous polyimide film and the Porous polyimide film manufactured by this method |
| CN110709245A (en) * | 2017-05-29 | 2020-01-17 | 东洋纺株式会社 | Laminate of polyimide film and inorganic substrate |
| KR20210086902A (en) * | 2019-12-31 | 2021-07-09 | (주)아이컴포넌트 | Optical transparent film for foldable display |
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- 2024-02-03 CN CN202410152518.0A patent/CN118005921A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070069082A (en) * | 2005-12-27 | 2007-07-02 | 듀폰 도레이 컴파니, 리미티드 | Highly adhesive polyimide film with the improved heat shrinkability |
| WO2012050072A1 (en) * | 2010-10-13 | 2012-04-19 | 東洋紡績株式会社 | Polyimide film, method for manufacturing same, and method for manufacturing layered product |
| CN109563300A (en) * | 2016-07-25 | 2019-04-02 | 宇部兴产株式会社 | The manufacturing method of Porous polyimide film and the Porous polyimide film manufactured by this method |
| CN110709245A (en) * | 2017-05-29 | 2020-01-17 | 东洋纺株式会社 | Laminate of polyimide film and inorganic substrate |
| KR20210086902A (en) * | 2019-12-31 | 2021-07-09 | (주)아이컴포넌트 | Optical transparent film for foldable display |
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