CN113439101B - Polyamic acid composition, preparation method thereof, preparation method of polyamide imide film and polyamide imide film prepared by same - Google Patents
Polyamic acid composition, preparation method thereof, preparation method of polyamide imide film and polyamide imide film prepared by same Download PDFInfo
- Publication number
- CN113439101B CN113439101B CN201980086790.0A CN201980086790A CN113439101B CN 113439101 B CN113439101 B CN 113439101B CN 201980086790 A CN201980086790 A CN 201980086790A CN 113439101 B CN113439101 B CN 113439101B
- Authority
- CN
- China
- Prior art keywords
- polyamic acid
- chemical formula
- dianhydride
- compound
- solvent
- 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.)
- Active
Links
- 229920005575 poly(amic acid) Polymers 0.000 title claims abstract description 133
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 239000004962 Polyamide-imide Substances 0.000 title claims abstract description 48
- 229920002312 polyamide-imide Polymers 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 11
- -1 dicarbonyl compound Chemical class 0.000 claims abstract description 129
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000009477 glass transition Effects 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims description 75
- 239000002904 solvent Substances 0.000 claims description 52
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 42
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims 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 description 34
- 239000002253 acid Substances 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- LBVMWHCOFMFPEG-UHFFFAOYSA-N 3-methoxy-n,n-dimethylpropanamide Chemical compound COCCC(=O)N(C)C LBVMWHCOFMFPEG-UHFFFAOYSA-N 0.000 claims description 16
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 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 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000004984 aromatic diamines Chemical class 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- MBHINSULENHCMF-UHFFFAOYSA-N n,n-dimethylpropanamide Chemical compound CCC(=O)N(C)C MBHINSULENHCMF-UHFFFAOYSA-N 0.000 claims description 10
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 10
- 239000011877 solvent mixture Substances 0.000 claims description 9
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 8
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 8
- 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 description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002834 transmittance Methods 0.000 claims description 8
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 7
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 6
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 6
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 5
- HQSLKNLISLWZQH-UHFFFAOYSA-N 1-(2-propoxyethoxy)propane Chemical compound CCCOCCOCCC HQSLKNLISLWZQH-UHFFFAOYSA-N 0.000 claims description 4
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- OAXARSVKYJPDPA-UHFFFAOYSA-N tert-butyl 4-prop-2-ynylpiperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(CC#C)CC1 OAXARSVKYJPDPA-UHFFFAOYSA-N 0.000 claims description 4
- HJGCBFOTSZRRTP-UHFFFAOYSA-N 2-(1,1,1,3,3,3-hexafluoropropan-2-yl)-5-methylaniline Chemical compound NC=1C=C(C=CC=1C(C(F)(F)F)C(F)(F)F)C HJGCBFOTSZRRTP-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- DUTLDPJDAOIISX-UHFFFAOYSA-N 3-(1,1,1,3,3,3-hexafluoropropan-2-yl)aniline Chemical compound NC1=CC=CC(C(C(F)(F)F)C(F)(F)F)=C1 DUTLDPJDAOIISX-UHFFFAOYSA-N 0.000 claims description 3
- KZSXRDLXTFEHJM-UHFFFAOYSA-N 5-(trifluoromethyl)benzene-1,3-diamine Chemical compound NC1=CC(N)=CC(C(F)(F)F)=C1 KZSXRDLXTFEHJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 10
- 125000002723 alicyclic group Chemical group 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 46
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229920001721 polyimide Polymers 0.000 description 10
- 239000004642 Polyimide Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 235000010290 biphenyl Nutrition 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 6
- 150000003949 imides Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 210000005103 brain tumor initiating cell Anatomy 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 125000004989 dicarbonyl group Chemical group 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 3
- 229960000368 sulisobenzone Drugs 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- LRYZJEXQHWCLJY-UHFFFAOYSA-N 1-phenyl-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1C1=CC=CC=C1 LRYZJEXQHWCLJY-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-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
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229940095102 methyl benzoate Drugs 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- VBFVFTVNLQCICW-UHFFFAOYSA-N 1-(trifluoromethyl)-2-[2-(trifluoromethyl)phenyl]benzene Chemical compound FC(F)(F)C1=CC=CC=C1C1=CC=CC=C1C(F)(F)F VBFVFTVNLQCICW-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 210000005266 circulating tumour cell Anatomy 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- CVXXHXPNTZBZEL-UHFFFAOYSA-N methyl 4-carbonochloridoylbenzoate Chemical compound COC(=O)C1=CC=C(C(Cl)=O)C=C1 CVXXHXPNTZBZEL-UHFFFAOYSA-N 0.000 description 1
- ZLEFBGVPYZUUGI-UHFFFAOYSA-N methyl benzoate;2-methylbenzoic acid Chemical compound COC(=O)C1=CC=CC=C1.CC1=CC=CC=C1C(O)=O ZLEFBGVPYZUUGI-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007764 slot die coating Methods 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001392 ultraviolet--visible--near infrared spectroscopy 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
- C08G73/14—Polyamide-imides
-
- 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
- C08G73/1028—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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention relates to a method for preparing a polyamic acid composition, a method for preparing a polyamideimide film using the polyamic acid composition, and a polyamideimide film prepared by the preparation method, and more particularly, to a novel dicarbonyl compound, a method for preparing a polyamic acid composition having excellent optical characteristics, a high glass transition temperature, and a low thermal expansion coefficient by using a dicarbonyl compound comprising an aromatic ring and an alicyclic ring, a polyamic acid composition, a method for preparing a polyamideimide film using the polyamic acid composition, and a polyamideimide film prepared by the preparation method.
Description
Technical Field
The present invention relates to a method for preparing a polyamic acid composition, a method for preparing a polyamideimide film using the polyamic acid composition, and a polyamideimide film prepared by the preparation method, and more particularly, to a novel dicarbonyl compound, a method for preparing a polyamic acid composition having excellent optical characteristics, a high glass transition temperature, and a low thermal expansion coefficient by using a dicarbonyl compound comprising an aromatic ring and an alicyclic ring, a polyamic acid composition, a method for preparing a polyamideimide film using the polyamic acid composition, and a polyamideimide film prepared by the preparation method.
Background
The substrate material of a flexible display that is attracting attention as a new generation display device should be a material that is light and not fragile and bendable, and is easy to process without limitation of shape. Polymer materials, which are not only lighter than glass substrates used as display substrate materials, but also are not fragile and easy to prepare, are currently attracting attention as the most suitable materials for realizing flexible displays, and thus thin films can be prepared.
Existing flexible devices typically use Organic Light Emitting Diode (OLED) displays and use TFT processes at high process temperatures (300-500 ℃). Polymeric materials that withstand such high process temperatures are extremely limited. Therefore, in recent years, the use of polyimide resins having excellent heat resistance and dimensional stability is increasing as a candidate material for a plastic substrate for a transparent flexible display.
For use in flexible display substrates, not only excellent heat resistance and dimensional stability are necessary, but also excellent light transmittance, low refractive index, phase retardation characteristics for ensuring a display viewing angle are necessary. However, the color of conventional polyimides is brown or yellow, and the main reason for this is charge transfer complexes (Charge Transfer Complex, CTCs) caused by intramolecular (intra molecular) or intermolecular (inter molecular) interactions of the polyimide.
In order to impart excellent optical characteristics to the polyimide having brown or yellow color as described above, resonance effect is reduced by introducing a branched chain having a large volume or strong electronegativity, or a linking group (linkage group) capable of imparting flexibility into the chain is introduced (COO-, -O-, SO) 2 -, -CO-) such that the interaction is caused by intramolecular or intermolecular interactionsWith the resulting formation of charge transfer complexes minimized, light properties can be provided.
However, the polyimide improved by the method as described above has more excellent optical properties than the existing polyimide, but has disadvantages of low thermal and mechanical properties because the flexible structure or the groups having a large electronegativity for improving optical properties introduced into the main chain of the polyimide rather reduce thermal and mechanical properties.
In order to solve the problems as described above, a polyamideimide structure comprising amide groups in the main chain of polyimide has been proposed, which is known to have high thermal stability and mechanical properties due to the synergistic effect of polyamide and polyimide, and to have higher thermal properties due to hydrogen bonds between chains and to have excellent solubility in polar solvents of amide groups as compared with other polyimide. Based on these advantages, polyamideimides are being used in a variety of electronic material applications.
Disclosure of Invention
Technical problem to be solved
The present invention has been made to solve the above-described problems, and its specific objects are as follows.
The present invention aims to obtain a highly heat-resistant polyamideimide having excellent optical characteristics, glass transition temperature and low thermal expansion coefficient by using dicarbonyl compounds including novel dicarbonyl compounds comprising specific structures of aromatic rings and alicyclic rings.
Technical proposal
According to the present invention, there is provided a polyamic acid characterized in that the polyamic acid comprises a compound prepared from a dicarbonyl compound, a diamine compound, and an acid dianhydride compound, the dicarbonyl compound comprising one compound selected from the group consisting of the following chemical formula 1, chemical formula 2, chemical formula 3, chemical formula 4, chemical formula 5, chemical formula 6, chemical formula 7, and a combination thereof.
[ chemical formula 1]
[ chemical formula 2]
[ chemical formula 3]
[ chemical formula 4]
[ chemical formula 5]
[ chemical formula 6]
[ chemical formula 7]
The diamine compound may comprise one selected from the group consisting of fluorinated aromatic diamine monomers, non-fluorinated aromatic diamine monomers, and combinations thereof.
The diamine compound may comprise a compound selected from the group consisting of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl (TFMB), 4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (pPDA), m-phenylenediamine (mPDA), p-methylenedianiline (pMDA), m-methylenedianiline (mMDA), p-cyclohexanediamine (pCHDA), p-xylylenediamine (pXDA), m-xylylenediamine (mXDA), m-cyclohexanediamine (mCHDA), 4' -diaminodiphenyl sulfone (DDS) 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane (BAFP), 2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP) 2,2 '-bis (3-amino-4-tolyl) hexafluoropropane (BAMF), 2' -bis (3-aminophenyl) -hexafluoropropane (BAPF) 3, 5-Diaminobenzotrifluoride (DABF), 2 '-bis (trifluoromethyl) -4,4' -diaminodiphenyl ether (BTDE), 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHH), and combinations thereof.
The acid dianhydride compound may include one selected from the group consisting of fluorinated aromatic acid dianhydrides, non-fluorinated aromatic acid dianhydrides, and combinations thereof.
The fluorinated aromatic acid dianhydride may comprise one selected from 4,4' - (Hexafluoroisopropylidene) diphthalic anhydride (4, 4' - (hexafluorous mopolylidene) diphthalic anhydride,6 FDA), 4' - (4, 4' -Hexafluoroisopropylidene diphenoxy) bis- (phthalic anhydride) (4, 4' -hexafluorous mopolylidene) bis- (phthalic anhydride), 6-FDPDA), and combinations thereof.
The non-fluorinated aromatic acid dianhydride may comprise a compound selected from the group consisting of pyromellitic dianhydride (pyromellitic dianhydride, PMDA), 3',4,4' -biphenyltetracarboxylic dianhydride (3, 3', 4' -biphenyltetracarboxylic acid dianhydride, BPDA), 3', 4' -benzophenone tetracarboxylic dianhydride (3, 3', 4' -benzophenonetetracarboxylic dianhydride, BTDA), 4' -oxybisphthalic anhydride (4, 4' -oxydiphthalic anhydride, ODPA), 2-Bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride (2, 2-Bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, BPADA), 3', 4' -diphenyl sulfone tetracarboxylic dianhydride (3, 3',4,4' -Diphenyl sufone tetracarboxylic dianhydride, DSDA), ethylene glycol Bis (4-trimellitic anhydride), cyclobutane tetracarboxylic dianhydride (CBDA), 4- (2, 5-dioxytetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic dianhydride (TDA), benzophenone Tetracarboxylic Dianhydride (BTDA), oxydiphthalic Dianhydride (ODPA), bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride (BTDA), 3', 4-biphenyl tetracarboxylic dianhydride (s-BPDA), and combinations thereof.
The viscosity of any of the polyamic acids at 23℃may be 1000 to 10000 centipoise (cp).
According to the present invention, there is provided a polyamideimide film characterized in that the polyamideimide film comprises any one of the above-mentioned polyamic acids.
When the thickness of the polyamideimide film is 10 to 15 μm, a Yellow Index (y.i.) may be 10 or less, a thermal expansion coefficient (Coefficient of thermal expansion, c.t.e.) at 100 to 250 ℃ may be 20ppm/°c or less, a glass transition temperature may be 360 ℃ or more, and a light transmittance at a wavelength of 550nm may be 85% or more.
According to the present invention, there can be provided a method for producing a polyamic acid, characterized by comprising the steps of: mixing a diamine compound and a solvent to prepare a mixture; and adding a dicarbonyl compound and an acid dianhydride to the mixture and polymerizing to prepare a polyamic acid solution, wherein the dicarbonyl compound comprises one compound selected from the group consisting of the following chemical formula 1, chemical formula 2, chemical formula 3, chemical formula 4, chemical formula 5, chemical formula 6, chemical formula 7, and a combination thereof.
[ chemical formula 1]
[ chemical formula 2]
[ chemical formula 3]
[ chemical formula 4]
[ chemical formula 5]
[ chemical formula 6]
[ chemical formula 7]
In the step of preparing the mixture, the solvent may be selected from a polar solvent selected from m-cresol, N-methyl-2-pyrrolidone (NMP), N-Dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), diethyl acetate (DEA), 3-methoxy-N, N-Dimethylpropionamide (DMPA), N-Dimethylpropionamide (DPA), N-Dimethylpropionamide (DML), and combinations thereof, a low-boiling solvent selected from Tetrahydrofuran (THF), chloroform, TCM, and combinations thereof, and a low-hygroscopic solvent selected from γ -butyrolactone (GBL), 3-methoxy-N, N-Dimethylpropionamide (DMPA), N-Dimethylpropionamide (DPA), N-dimethyl lactonamide (DML), N-methyl-2-pyrrolidone (NMP), and combinations thereof, and a combination thereof, and the low-hygroscopic solvent may be selected from tetrahydrofuran (egl), chloroform, TCM, and combinations thereof, and the low-hygroscopic solvent may be selected from ethylene glycol (ege), ethylene glycol (dbe), ethylene glycol (dme), and combinations thereof.
The low hygroscopicity solvent may comprise: a first low hygroscopicity solvent mixture comprising 30-70 mole% of gamma-butyrolactone and 30-70 mole% of N-methyl-2-pyrrolidone, a second low hygroscopicity solvent mixture comprising 30-70 mole% of gamma-butyrolactone and 30-70 mole% of N, N-dimethylpropionamide, a third low hygroscopicity solvent mixture comprising 30-70 mole% of gamma-butyrolactone and 30-70 mole% of 3-methoxy-N, N-dimethylpropionamide, 100 mole% of N, N-dimethylpropionamide or 100 mole% of 3-methoxy-N, N-dimethylpropionamide.
The solvent may include one diffusible solvent selected from ethylene glycol monobutyl ether (EGBE), ethylene glycol dimethyl ether (EGME), ethylene Glycol Diethyl Ether (EGDE), ethylene glycol dipropyl ether (EGDPE), ethylene glycol dibutyl ether (EGDBE), and combinations thereof.
In the step of preparing the polyamic acid solution, the dicarbonyl compound may be contained in an amount of 20 to 100 mol% based on the diamine compound.
In the step of preparing the mixture, the mixing may be performed under a nitrogen atmosphere at a temperature of 25-30 ℃ for 30-60 minutes.
In the step of preparing the polyamic acid solution, one selected from the group consisting of a plasticizer, an antioxidant, a flame retardant, a dispersant, a viscosity modifier, a leveling agent, and a combination thereof may be further added to the mixture.
In the step of preparing the polyamic acid solution, the polymerization may be performed at a temperature of 10 to 70℃for 6 to 48 hours.
In the step of preparing a polyamic acid solution, the diamine compound, the dicarbonyl compound, and the acid dianhydride constitute a solid of the polyamic acid solution, and the content of the solid may be 10 to 40% by weight based on the polyamic acid solution.
In the step of preparing the polyamic acid solution, the acid dianhydride compound and the dicarbonyl compound may be contained in an amount of 100 to 105 mol% based on the diamine compound.
According to the present invention, there is provided a method for producing a polyamideimide film characterized in that any one of the above methods for producing a polyamic acid further comprises the steps of: coating the polyamic acid solution on a substrate to form a transparent coating; and heat-treating the transparent coating, wherein the heat-treatment is performed at a temperature of 100-450 ℃ in a nitrogen atmosphere for 30-120 minutes.
Advantageous effects
According to the present invention, it is possible to provide a polyamideimide film which can be effectively applied to a cover substrate for a flexible display, an optical film, a touch panel substrate material, a semiconductor material, or the like, and which is a transparent film and has excellent mechanical properties, high heat resistance properties, and low thermal expansion coefficient properties.
The effects of the present invention are not limited to the effects described above. It is to be understood that the effects of the present invention include all effects that can be inferred from the following description.
Best mode for carrying out the invention
Preparation example (method for preparing dicarbonyl Compound of chemical formula 1)
Process for preparing dicarbonyl compound of chemical formula 1
4,4'- {2,2' -bis (trifluoromethyl) - [1,1 '-biphenyl ] -4,4' -bis (iminocarbonyl) } bis (benzoyl chloride) (BTBC) as dicarbonyl compound of chemical formula 1 was synthesized by the following steps: synthesizing Methyl benzoate (Methyl benzoate) intermediate; synthesizing a Carboxylic acid (Carboxylic acid) intermediate; and synthesizing BTBC.
Step 1. Synthesis of methyl benzoate intermediate
100ml of dry NMP was added to a 1000ml round bottom flask under nitrogen atmosphere. TFMB (20.15 g,62.94 mmol) and Triethylamine (14.0 g,138.5 mmol) were added thereto and cooled to 0℃after complete dissolution. Methyl4- (chloroformyl) benzoate (25 g,125.9 mmol) was dissolved in 100ml NMP and slowly added to the TFMB solution. After the addition, the reaction mixture was heated to 50℃and stirred for 2 hours. Then, 200ml of water was added, and then the content was cooled to room temperature (20 ℃) and the precipitate was filtered. For the filtered precipitate, washing was performed with 300ml of water and further washing was performed with 50ml of dichloromethane (dichlormethane). Vacuum drying at 60 ℃ for 12 hours gave the title compound (38.5 g, 94.9%) as white. The white target compound obtained 1 The results of H-NMR are as follows.
1 H-NMR(400MHz,DMSO-d 6 ):δ10.84(s,2H),8.35(s,2H),8.14-8.12(d,8H),8.12-8.10(d,2H),7.42-7.40(d,2H),2.70(s,6H)
Step 2. Step of synthesizing Carboxylic acid intermediate
Methyl benzoate (20 g,31.0 mmol), KOH (3.8 g,68.2 mmol), 200ml ethanol, 100ml water were added to a 1000ml round bottom flask. The reaction solution was heated to 80℃and stirred for 4 hours. After the reaction, 500ml of water was added to the completely dissolved solution and cooled to room temperature (20 ℃). After cooling, 50ml of 1M HCl was slowly added to reduce the pH to below 2. The precipitate was stirred for 30 minutes and then filtered. For the filtered precipitate, washing was performed with 1000ml of water. Vacuum drying at 60 ℃ for 12 hours gave the title compound (15.45 g, 80.9%) as a white color. The white target compound obtained 1 The results of H-NMR are as follows.
1 H-NMR(400MHz,DMSO-d 6 ):δ13.3(brs,2H),10.81(s,2H),8.36(s,2H),8.13-8.12(d,2H),8.11-8.10(d,8H),7.42-7.40(d,2H)
Step 3, step of synthesizing BTBC
Into a 250ml round bottom flask was charged carboxylic acid (14.3 g,23.2 mmol), oxalyl chloride (14.7 g,116 mmol), 50ml of CHCl 3 The reaction solution was heated to 50℃and stirred for 5 hours. After the reaction, the solvent was removed by vacuum concentration. After concentration, 60ml of CHCl was added 3 Stirred for 30 minutes and filtered. For the filtered precipitate, 40ml of CHCl was used 3 Washing is performed. Vacuum drying at 60℃for 12 hours gave the title compound (9.5 g, 62.9%) as milky white. The milky white target compound obtained 1 H-NMR、 13 The results of C-NMR and FT-IR are as follows.
1 H-NMR(500MHz,DMSO-d6):δ10.83(s,2H),8.36(s,2H),8.13(d,2H),8.12-8.10(d,8H),7.41-7.40(d,2H)
13 C-NMR(500MHz,DMSO-d6):δ163.73,162.38,136.29,135.15,130.64,129.57,128.57,126.41,125.08,121.91,119.76,119.58,114.26
FT-IR(KBr,cm-1):3320,1690,1590,1520,725,553
Comparative example 1
As the composition shown in table 1 below, 3.22g (0.01 mol) of TFMB as a diamine compound was dissolved in 44.01g of DMPA as a solvent, and dissolved at room temperature under a nitrogen atmosphere for 30 minutes. Thereafter, 4.54g (0.01 mole) of 6FDA as an acid dianhydride compound was added, followed by stirring and polymerization for 24 hours, thereby preparing a polyamic acid solution. The polymerization temperature was maintained at 30℃and the solids were maintained at 15% by weight relative to the total weight of the polyamic acid solution. At this time, the viscosity was 4800cp as a result of measurement with a viscosity measuring device (Brookfield) DV2T, SC 4-27.
Example 1
As a composition shown in Table 1 below, 2.96g (0.009 mol) of TFMB as a diamine compound was dissolved in 42.5g of DMPA as a solvent, and dissolved at room temperature under a nitrogen atmosphere for 30 minutes. After that, 0.41g (0.001 mol) of 6FDA and 1.09g (0.004 mol) of BPDA were added as an acid dianhydride compound, followed by stirring at normal temperature for 1 hour. And, 3.05g (0.005 mol) of the compound of chemical formula 1 (BTBC) prepared in the preparation example was added, followed by stirring and polymerization at normal temperature for 3 hours, thereby preparing a polyamic acid solution. The solution of acetone and water was titrated in the prepared polyamic acid solution at a ratio of 2:1, and vacuum-dried at 80 ℃ for 12 hours, thereby obtaining 7.5g of polyamic acid as a solid powder.
The polyamic acid powder was added to 42.5g of DMPA and stirred for 4 hours, thereby preparing a polyamic acid solution. The polymerization temperature was maintained at 30℃and the solids were maintained at 15% by weight relative to the total weight of the polyamic acid solution. At this time, the viscosity was 4900cp as a result of measurement with a viscosity measuring device (Bowler-DV 2T, SC 4-27).
Example 2
As the compositions shown in Table 1 below, 3.77g (0.012 moles) of TFMB as a diamine compound was dissolved in 42.5g of DMPA as a solvent, and dissolved at room temperature under a nitrogen atmosphere for 30 minutes. Thereafter, 0.52g (0.001 mol) of 6FDA and 1.39g (0.005 mol) of BPDA were added as an acid dianhydride compound, followed by stirring at normal temperature for 1 hour. Thereafter, 1.82g (0.006 mol) of the compound of formula 2 (BPDC) was added, followed by stirring and polymerization at normal temperature for 3 hours, thereby preparing a polyamic acid solution. The solution of acetone and water was titrated in the prepared polyamic acid solution at a ratio of 2:1, and dried in vacuum at 80 ℃ for 12 hours, thereby obtaining 7.5g of polyamic acid as a solid powder.
The polyamic acid powder was added to 42.5g of DMPA and stirred for 4 hours, thereby preparing a polyamic acid solution. The polymerization temperature was maintained at 30℃and the solids were maintained at 15% by weight relative to the total weight of the polyamic acid solution. At this time, the viscosity was 6000cp as a result of measurement with a viscosity measuring device (Bowler-Nordheim DV2T, SC 4-27).
Example 3
As the compositions shown in Table 1 below, 3.47g (0.011 mol) of TFMB as a diamine compound was dissolved in 42.5g of DMPA as a solvent, and dissolved at room temperature under a nitrogen atmosphere for 30 minutes. Thereafter, 0.48g (0.001 mol) of 6FDA and 1.28g (0.004 mol) of BPDA were added as an acid dianhydride compound, followed by stirring at normal temperature for 1 hour. Thereafter, 2.27g (0.005 mol) of the compound of formula 3 (TFBC) was added, followed by stirring and polymerization at normal temperature for 3 hours, thereby preparing a polyamic acid solution. The solution of acetone and water was titrated in the prepared polyamic acid solution at a ratio of 2:1, and vacuum-dried at 80 ℃ for 12 hours, thereby obtaining 7.5g of polyamic acid as a solid powder.
The polyamic acid powder was added to 42.5g of DMPA and stirred for 4 hours, thereby preparing a polyamic acid solution. The polymerization temperature was maintained at 30℃and the solids were maintained at 15% by weight relative to the total weight of the polyamic acid solution. At this time, the viscosity was 4700cp as a result of measurement with a viscosity measuring device (Bowler-DV 2T, SC 4-27).
Example 4
As a composition shown in Table 1 below, 2.39g (0.007 mol) of TFMB as a diamine compound was dissolved in 42.5g of DMPA as a solvent, and dissolved at room temperature under a nitrogen atmosphere for 30 minutes. Thereafter, 5.38g (0.007 mol) of a compound of chemical formula 4 (BHIC) was added, followed by stirring and polymerization at normal temperature for 3 hours, thereby preparing a polyamic acid solution. The solution of acetone and water was titrated in the prepared polyamic acid solution at a ratio of 2:1, and vacuum-dried at 80 ℃ for 12 hours, thereby obtaining 7.5g of polyamic acid as a solid powder.
The polyamic acid powder was added to 42.5g of DMPA and stirred for 4 hours, thereby preparing a polyamic acid solution. The polymerization temperature was maintained at 30℃and the solids were maintained at 15% by weight relative to the total weight of the polyamic acid solution. At this time, the viscosity was 5600cp as a result of measurement with a viscosity measuring device (Bowler-femto DV2T, SC 4-27).
Example 5
As the compositions shown in Table 1 below, 2.42g (0.008 mol) of TFMB as a diamine compound was dissolved in 42.5g of DMPA as a solvent, and dissolved at room temperature under a nitrogen atmosphere for 30 minutes. Thereafter, 5.34g (0.008 mol) of the compound of formula 5 (BTIC) was added, followed by stirring and polymerization at normal temperature for 3 hours, thereby preparing a polyamic acid solution. The solution of acetone and water was titrated in the prepared polyamic acid solution at a ratio of 2:1, and vacuum-dried at 80 ℃ for 12 hours, thereby obtaining 7.5g of polyamic acid as a solid powder.
The polyamic acid powder was added to 42.5g of DMPA and stirred for 4 hours, thereby preparing a polyamic acid solution. The polymerization temperature was maintained at 30℃and the solids were maintained at 15% by weight relative to the total weight of the polyamic acid solution. At this time, the viscosity was 4700cp as a result of measurement with a viscosity measuring device (Bowler-DV 2T, SC 4-27).
Example 6
As the compositions shown in Table 1 below, 3.27g (0.01 mol) of TFMB as a diamine compound was dissolved in 42.5g of DMPA as a solvent, and dissolved at room temperature under a nitrogen atmosphere for 30 minutes. Thereafter, 0.45g (0.001 mol) of 6FDA and 1.20g (0.004 mol) of BPDA were added as an acid dianhydride compound, followed by stirring at normal temperature for 1 hour. Thereafter, 2.57g (0.005 mol) of a compound of formula 6 (BHCC) was added, followed by stirring and polymerization at normal temperature for 3 hours, thereby preparing a polyamic acid solution. The solution of acetone and water was titrated in the prepared polyamic acid solution at a ratio of 2:1, and vacuum-dried at 80 ℃ for 12 hours, thereby obtaining 7.5g of polyamic acid as a solid powder.
The polyamic acid powder was added to 42.5g of DMPA and stirred for 4 hours, thereby preparing a polyamic acid solution. The polymerization temperature was maintained at 30℃and the solids were maintained at 15% by weight relative to the total weight of the polyamic acid solution. At this time, the viscosity was 4100cp as a result of measurement with a viscosity measuring device (Bowler-DV 2T, SC 4-27).
Example 7
As the compositions shown in Table 1 below, 3.27g (0.01 mol) of TFMB as a diamine compound was dissolved in 42.5g of DMPA as a solvent, and dissolved at room temperature under a nitrogen atmosphere for 30 minutes. Thereafter, 0.45g (0.001 mol) of 6FDA and 1.20g (0.004 mol) of BPDA were added as an acid dianhydride compound, followed by stirring at normal temperature for 1 hour. Thereafter, 2.57g (0.005 mol) of the compound of formula 7 (CHIC) was added, followed by stirring and polymerization at normal temperature for 3 hours, thereby preparing a polyamic acid solution. The solution of acetone and water was titrated in the prepared polyamic acid solution at a ratio of 2:1, and vacuum-dried at 80 ℃ for 12 hours, thereby obtaining 7.5g of polyamic acid as a solid powder.
The polyamic acid powder was added to 42.5g of DMPA and stirred for 4 hours, thereby preparing a polyamic acid solution. The polymerization temperature was maintained at 30℃and the solids were maintained at 15% by weight relative to the total weight of the polyamic acid solution. At this time, the viscosity was 3900cp as a result of measurement with a viscosity measuring device (Bowler-DV 2T, SC 4-27).
TABLE 1
Experimental example
(1) Evaluation of physical Properties of Polyamide imide film
The polyamic acid solutions prepared in examples 1 to 7 and comparative example 1 were coated on a glass plate using a spin coater, and then heat-treated in a high-temperature convection oven. The heat treatment was performed under a nitrogen atmosphere, and the final film was obtained under conditions of a temperature and a time of 100 ℃/30 minutes, 350 ℃/30 minutes. Physical properties of the separately prepared polyamideimide films were measured by the methods described below, and the results are shown in table 2 below.
(a) Light Transmittance (Transmittance)
The light transmittance was measured at 550nm using an ultraviolet visible near infrared spectrophotometer (UV-Vis NIR Spectrophotometer) (Shimadsu) Inc., UV-1800).
(b) Yellow Index (YI)
The measurement was performed using a color difference meter (LabScan XE).
(c) Haze (haze)
Measurements were made using a Haze meter (Haze meter) (TOYOSEIKI, inc., HAZE-GARD).
(d) Thermal characteristics
Measurement of glass transition temperature (T) of film Using TMA 402F3 from Netzsch g ) Coefficient of Thermal Expansion (CTE). The Force (Force) of the tensile mode (tensile mode) was set at 0.1N, and the temperature was raised to 350℃at a rate of 5℃per minute at 30℃in terms of measurement temperature, and the average value in the range of 100 to 250℃was measured as the linear thermal expansion coefficient. Measurement of thermal decomposition temperature (T) Using TG 209F3 from Netzsch d ，1％)。
TABLE 2
As shown in the table 2, when dicarbonyl compounds of the structures of chemical formulas 1 to 7 are properly used, it is possible to have excellent light characteristics while having a high glass transition temperature and a low thermal expansion coefficient.
Accordingly, a transparent polyamideimide film having a yellowness index of 10 or less, a thermal expansion coefficient of 20 ppm/DEG C or less in a range of 100 to 250 ℃ and a glass transition temperature (Tg) of 360 ℃ or more and a light transmittance of 85% or more at a wavelength of 550nm based on a thickness of the film of 10 to 15 μm can be provided by the polyamic acid solution prepared according to the present invention.
Therefore, the polyamideimide film prepared according to the present invention satisfies excellent optical characteristics and heat resistance characteristics, and thus can be widely applied to substrates and protective films for Flexible displays such as displays for OLEDs, displays for liquid crystal elements, TFT substrates, flexible printed circuit substrates, flexible (Flexible) OLED surface illumination substrates, substrate materials for electronic papers, and the like.
Detailed Description
In this specification, it should be understood that the terms "comprises," "comprising," "includes," or "having," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, components, or groups thereof, but do not preclude the presence or addition of one or more other features or integers, steps, operations, elements, components, or groups thereof. Further, when a portion of a layer, a film, a region, a plate, or the like is described as being "on" another portion, this includes not only the case of being "directly over" another portion but also the case where there is another portion in between. On the other hand, when a portion of a layer, a film, a region, a plate, or the like is described as being "under" another portion, this includes not only the case of being "directly under" another portion but also the case where another portion exists in the middle thereof.
Unless otherwise indicated, with respect to all numbers, values, and/or expressions used in this specification to denote amounts of ingredients, reaction conditions, polymer compositions, and formulations, these numbers are essentially approximations reflecting the various uncertainties of measurements that occur when these values are obtained from other aspects, and thus should be understood to be modified in all instances by the term "about". Furthermore, when numerical ranges are disclosed in the present specification, such ranges are continuous and include all values from the minimum value to the maximum value (including the maximum value) of such ranges unless otherwise indicated. Further, when such a range refers to an integer, all integers from the minimum value to the maximum value (including the maximum value) are included unless otherwise indicated.
In this specification, when ranges of variables are recited, it is understood that the variables include all values within the recited ranges (including the endpoints of the ranges). For example, it is to be understood that a range of "5-10" includes not only values of 5, 6, 7, 8, 9, and 10, but also any subranges of 6-10, 7-10, 6-9, 7-9, etc., and also any values between integers such as 5.5, 6.5, 7.5, 5.5-8.5, and 6.5-9, etc., that fall within the recited ranges. Further, it is to be understood that a range of, for example, "10% -30%" includes not only all integers of 10%, 11%, 12%, 13% equivalent and up to 30% (including 30%), but also any sub-range of 10% -15%, 12% -18%, 20% -30%, etc., and also any value between integers such as 10.5%, 15.5%, 25.5%, etc. that fall within the range of the recited range.
The present invention relates to a method for producing a polyamic acid composition containing a novel dicarbonyl compound, a polyamic acid composition, a method for producing a polyamideimide film using the polyamic acid composition, and a polyamideimide film produced by the production method, and the polyamic acid composition, the polyamideimide film containing the polyamic acid composition, and the methods for producing the polyamic acid composition and the polyamideimide film are described below, respectively.
Polyamic acid composition
The polyamic acid of the present invention is characterized by being prepared from a dicarbonyl compound, a diamine compound, and an acid dianhydride compound, the dicarbonyl compound comprising one compound selected from the group consisting of the following chemical formula 1, chemical formula 2, chemical formula 3, chemical formula 4, chemical formula 5, chemical formula 6, chemical formula 7, and a combination thereof.
The components constituting the polyamic acid will be described.
Dicarbonyl compounds
The dicarbonyl compound of the present invention is characterized by comprising, as a novel dicarbonyl compound, one selected from the group consisting of 4,4'- {2,2' -bis (trifluoromethyl) - [1,1 '-biphenyl ] -4,4' -bis (iminocarbonyl) } bis (benzoyl chloride) (BTBC), benzophenone-4, 4 '-diacyl chloride (BPDC), 2' -bis (trifluoromethyl) - [1,1 '-biphenyl ] -4,4' -diacyl chloride (TFBC), 4'- [4,4' - (hexafluoroisopropylidene) diphthalimide ] bis (benzoyl chloride) (BHIC), [2,2 '-bis (trifluoromethyl) - [1,1' -biphenyl ] -4,4 '-bis (imide) ] bis (phthaloyl chloride) (BTIC), 4' - [1,2,4, 5-cyclohexane tetracarboxylic acid imide ] bis (benzoyl chloride) (BHCC), 1, 4-cyclohexyl-bis (imide) bis (phthaloyl chloride) (CHIC), and a combination thereof.
The dicarbonyl compound is represented by the following chemical formula 1, chemical formula 2, chemical formula 3, chemical formula 4, chemical formula 5, chemical formula 6, and chemical formula 7.
[ chemical formula 1]
4,4'- {2,2' -bis (trifluoromethyl) - [1,1 '-biphenyl ] -4,4' -bis (iminocarbonyl) } bis (benzoyl chloride) (BTBC)
[ chemical formula 2]
Benzophenone-4, 4' -diacyl chloride (BPDC)
[ chemical formula 3]
2,2' -bis (trifluoromethyl) - [1,1' -biphenyl ] -4,4' -diacyl chloride (TFBC)
[ chemical formula 4]
4,4'- [4,4' - (hexafluoroisopropylidene) diphthalimide ] bis (benzoyl chloride) (BHIC)
[ chemical formula 5]
[2,2' -bis (trifluoromethyl) - [1,1' -biphenyl ] -4,4' -bis (imide) ] bis (phthaloyl chloride) (BTIC)
[ chemical formula 6]
4,4' - [1,2,4, 5-cyclohexane tetracarboxylic acid imide ] bis (benzoyl chloride) (BHCC)
[ chemical formula 7]
1, 4-cyclohexyl-bis (imide) bis (phthaloyl chloride) (CHIC)
Diamine compound
The diamine compound of the present invention comprises one selected from the group consisting of fluorinated aromatic diamine monomers, non-fluorinated aromatic diamine monomers, and combinations thereof.
The fluorinated aromatic diamine monomer is preferably selected from the group consisting of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl (TFMB) 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane (BAFP), 2 '-bis (3-amino-4-tolyl) hexafluoropropane (BAMF) one of 2,2' -bis (3-aminophenyl) -hexafluoropropane (BAPF), 3, 5-Diaminobenzotrifluoride (DABF), 2 '-bis (trifluoromethyl) -4,4' -diaminodiphenyl ether (BTDE), 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHH), and combinations thereof.
The non-fluorinated aromatic diamine monomer is preferably one selected from the group consisting of 4,4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (pda), m-phenylenediamine (mda), p-methylenedianiline (pMDA), m-methylenedianiline (mda), p-cyclohexanediamine (pCHDA), p-xylylenediamine (pdda), m-xylylenediamine (mXDA), m-cyclohexanediamine (mCHDA), 4' -diaminodiphenyl sulfone (DDS), 2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), and combinations thereof.
Acid dianhydride compound
The acid dianhydride compound of the present invention is characterized by comprising one selected from the group consisting of fluorinated aromatic acid dianhydride, non-fluorinated aromatic acid dianhydride, and combinations thereof.
The fluorinated aromatic acid dianhydride is an aromatic acid dianhydride into which a fluorine substituent is introduced, and may be, for example, one selected from 4,4' - (Hexafluoroisopropylidene) diphthalic anhydride (4, 4' - (hexafluorochloroolipopropylene) diphthalic anhydride,6 FDA), 4' - (4, 4' -Hexafluoroisopropylidene diphenoxy) bis- (phthalic anhydride) (4, 4' -hexafluorochloroolipopropylene) bis- (phthalic anhydride), 6-FDPDA), and combinations thereof.
The non-fluorinated aromatic acid dianhydride is an aromatic acid dianhydride not having a fluorine substituent, and may be selected from pyromellitic dianhydride (pyromellitic dianhydride, PMDA), 3', 4' -biphenyl tetracarboxylic dianhydride (3, 3', 4' -biphenyltetracarboxylic acid dianhydride, BPDA), 3',4,4' -benzophenone tetracarboxylic dianhydride (3, 3', 4' -benzophenonetetracarboxylic dianhydride, BTDA), 4' -oxydiphthalic anhydride (4, 4' -oxydiphthalic anhydride, ODPA), 2-Bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride (2, 2-Bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, BPADA), 3',4,4' -diphenyl sulfone tetracarboxylic dianhydride (3, 3', 4' -Diphenyl sufone tetracarboxylic dianhydride, DSDA), ethylene glycol Bis (4-trimellitic anhydride), cyclobutane tetracarboxylic dianhydride (CBDA), 4- (2, 5-dioxytetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic dianhydride (TDA), benzophenone Tetracarboxylic Dianhydride (BTDA), oxydiphthalic Dianhydride (ODPA), bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride (BTDA), 3', 4-biphenyl tetracarboxylic dianhydride (s-BPDA), and combinations thereof.
The acid dianhydride of the present invention preferably comprises one selected from the group consisting of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, 4' - (4, 4' -hexafluoroisopropylidene diphenoxy) bis- (phthalic anhydride), cyclobutane tetracarboxylic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 4- (2, 5-dioxatetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, oxydiphthalic dianhydride, and combinations thereof.
The polyamic acid of the present invention comprising the dicarbonyl compound, the diamine compound, and the acid dianhydride compound is characterized in that the viscosity of the polyamic acid at 23 ℃ is 1000 to 10000cp. At this time, when the viscosity of the polyamic acid is less than 1000cp, it may be difficult to obtain a film thickness of an appropriate level when preparing a polyamideimide film, and when the viscosity of the polyamic acid exceeds 10000cp, there is a problem in that uniform coating cannot be achieved and the solvent cannot be removed effectively.
Process for preparing polyamic acid composition
In describing the method for producing the polyamic acid composition of the present invention, a part of the contents overlapping with the characteristics of the composition described in the composition of the above polyamic acid composition are excluded.
In order to obtain the polyamideimide film of the present invention, a polyamic acid (which is the same expression as that of a polyamic acid solution) is prepared, and specifically, a method for preparing a polyamic acid is characterized by comprising the steps of: mixing a diamine compound and a solvent to prepare a mixture; and adding a dicarbonyl compound and an acid dianhydride compound to the mixture and polymerizing to prepare a polyamic acid solution.
Step of preparing the mixture
The step of preparing the mixture is a step of adding a diamine compound to the prepared solvent and mixing to form a mixture.
The diamine compound comprises one selected from the group consisting of fluorinated aromatic diamine monomers, non-fluorinated aromatic diamine monomers, and combinations thereof.
The fluorinated aromatic diamine monomer preferably uses one selected from the group consisting of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl (TFMB), 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane (BAFP), and combinations thereof.
The non-fluorinated aromatic diamine monomer is preferably one selected from the group consisting of 4,4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (pda), m-phenylenediamine (mda), p-methylenedianiline (pMDA), m-methylenedianiline (mda), p-cyclohexanediamine (pCHDA), p-xylylenediamine (pdda), m-xylylenediamine (mXDA), m-cyclohexanediamine (mCHDA), 4' -diaminodiphenyl sulfone (DDS), 2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), and combinations thereof.
The mixing is carried out under nitrogen atmosphere at a temperature of 25-30 ℃ for 30-60 minutes.
The solvent to which the diamine compound is added may be selected from the group consisting of polar solvents, low boiling point solvents, low hygroscopic solvents, diffusive solvents, and combinations thereof. More specific examples will be described below (however, in the case of a solvent containing two or more characteristics among the solvents listed below, the description may be repeated).
The polar solvent may be selected from m-cresol, N-methyl-2-pyrrolidone (NMP), N-Dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), diethyl acetate (DEA), 3-methoxy-N, N-Dimethylpropionamide (DMPA), N-Dimethylpropionamide (DPA), N-Dimethylformamide (DML), and combinations thereof.
The low boiling point solvent may be selected from Tetrahydrofuran (THF), chloroform (TCM) and combinations thereof. The low boiling point solvent has high volatility, so that the solvent is easily removed when preparing a film, which can improve physical properties of the prepared film.
The low hygroscopicity solvent may be selected from gamma-butyrolactone (GBL), 3-methoxy-N, N-Dimethylpropionamide (DMPA), N-Dimethylpropionamide (DPA), N-Dimethylpropionamide (DML), N-methyl-2-pyrrolidone (NMP), and combinations thereof.
The low hygroscopic solvent minimizes the absorption of moisture in preparing the film, and thus plays an important role in improving the cloudiness phenomenon, and in order to improve the cloudiness phenomenon by solution casting at normal temperature, it is preferable to select a first low hygroscopic solvent mixture of gamma-butyrolactone (GBL) and N-methyl-2-pyrrolidone (NMP), a second low hygroscopic solvent mixture of gamma-butyrolactone (GBL) and N, N-Dimethylpropionamide (DPA), a third low hygroscopic solvent mixture of gamma-butyrolactone (GBL) and 3-methoxy-N, N-Dimethylpropionamide (DMPA), or 3-methoxy-N, N-Dimethylpropionamide (DMPA) and N, N-Dimethylpropionamide (DPA), respectively, singly.
When a mixture of the gamma-butyrolactone and N-methyl-2-pyrrolidone is used as the low hygroscopicity solvent, it is preferable to use 30 to 70 mol% of gamma-butyrolactone and 70 to 30 mol% of N-methyl-2-pyrrolidone. More preferably, 50 to 70 mole% of gamma-butyrolactone and 30 to 50 mole% of N-methyl-2-pyrrolidone are used.
When the mixture of gamma-butyrolactone and N, N-dimethylpropionamide is used as the low hygroscopicity solvent, 30 to 70 mol% of gamma-butyrolactone and 30 to 70 mol% of N, N-dimethylpropionamide are used. Preferably, 50-70 mole% of gamma-butyrolactone and 30-50 mole% of N, N-dimethylpropionamide are used.
When a mixture of the gamma-butyrolactone and 3-methoxy-N, N-dimethylpropionamide is used as the low hygroscopicity solvent, it is preferable to use 30 to 70 mole% of gamma-butyrolactone and 70 to 30 mole% of 3-methoxy-N, N-dimethylpropionamide. More preferably, 50 to 70 mole% of gamma-butyrolactone and 30 to 50 mole% of 3-methoxy-N, N-dimethylpropionamide are used.
When the N, N-dimethylpropionamide alone or 3-methoxy-N, N-dimethylpropionamide alone is selected as the low hygroscopicity solvent, 100 mol% alone is preferably used without adding other solvents.
The diffusible solvent may use one selected from ethylene glycol monobutyl ether (EGBE), ethylene glycol dimethyl ether (EGME), ethylene Glycol Diethyl Ether (EGDE), ethylene glycol dipropyl ether (EGDPE), ethylene glycol dibutyl ether (EGDBE), and combinations thereof.
The diffusible solvent plays an important role in improving wettability, improves the diffusibility of a solution at the time of solution casting, thus preventing shrinkage of the solution, and can obtain a film excellent in uniformity. For this purpose, from 10 to 40 mol% of ethylene glycol monobutyl ether may be used, preferably from 10 to 30 mol% of ethylene glycol monobutyl ether may be used.
Step of preparing polyamic acid solution
The step of preparing a polyamic acid solution is a step of adding a dicarbonyl compound and an acid dianhydride compound to the prepared mixture and preparing a polyamic acid solution by polymerization.
The dicarbonyl compound added is characterized by comprising one selected from the group consisting of 4,4'- {2,2' -bis (trifluoromethyl) - [1,1 '-biphenyl ] -4,4' -bis (iminocarbonyl) } bis (benzoyl chloride) (BTBC), benzophenone-4, 4 '-diacyl chloride (BPDC), 2' -bis (trifluoromethyl) - [1,1 '-biphenyl ] -4,4' -diacyl chloride (TFBC), 4'- [4,4' - (hexafluoroisopropylidene) diphthalimide ] bis (benzoyl chloride) (BHIC), [2,2 '-bis (trifluoromethyl) - [1,1' -biphenyl ] -4,4 '-bis (imide) ] bis (phthaloyl chloride) (BTIC), 4' - [1,2,4, 5-cyclohexane tetracarboxylic acid imide ] bis (benzoyl chloride) (BHCC), 1, 4-cyclohexyl-bis (imide) bis (phthaloyl chloride) (CHIC), and combinations thereof.
The dicarbonyl compound and the acid dianhydride compound are added in an amount of 100 to 105 mol% based on the diamine compound.
Preferably, the dicarbonyl compound is added in an amount of 20 to 100 mol% relative to the total content of the diamine compound. In this case, when the addition amount of the dicarbonyl compound is less than 20 mol%, the optical characteristics are increased, but there is a limitation in improving the heat resistance characteristics, and when the addition amount of the dicarbonyl compound exceeds 100 mol%, there is a problem in that the optical characteristics are lowered.
The added acid dianhydride compound may contain one selected from the group consisting of fluorinated aromatic acid dianhydride, non-fluorinated aromatic acid dianhydride, and combinations thereof, and specific examples are repeated as in the polyamic acid composition already described above, so that the description thereof is omitted.
In the present invention, the dicarbonyl compound, the diamine compound and the acid dianhydride compound constitute a solid in the polyamic acid solution, and in this case, the content of the solid is preferably 10 to 40% by weight based on the polyamic acid solution. More preferably, the solids content is 10-25 wt.%. At this time, when the content of the solid is less than 10% by weight, there is a limitation in increasing the thickness of the film in preparing the polyamideimide film, and when the content of the solid exceeds 40% by weight, there is a problem in that there is a limitation in adjusting the viscosity of the polyamic acid solution.
In the case of a diamine compound and an acid dianhydride compound constituting the solid, the content of the diamine compound is 95 to 100 mol% and the content of the acid dianhydride compound is 100 to 105 mol%.
The polymerization is preferably carried out at a temperature of from 10 to 70℃for from 6 to 48 hours.
In this step, a catalyst may be added in addition to the acid dianhydride to improve the reactivity. In this case, the catalyst to be used is not particularly limited as long as the reactivity can be improved within a range that does not violate the object of the present invention and does not significantly impair the effect. For example, the catalyst may be selected from Trimethylamine (Trimethylamine), xylene (Xylene), pyridine (Pyridine), quinoline (quinline), and combinations thereof. In the present invention, any one selected from plasticizers, antioxidants, flame retardants, dispersants, viscosity modifiers, leveling agents, and combinations thereof may be contained in addition to the catalyst, and may be selected and used as needed within a range not significantly impairing the objects and effects of the present invention.
Preparation method of polyamide imide film
The prepared polyamic acid solution is coated on a substrate to form a transparent coating layer, and the transparent coating layer is subjected to heat treatment, whereby the polyamideimide film of the present invention can be prepared.
Specifically, in the method for producing a polyamideimide film of the present invention, the polyamic acid solution of the present invention having a specific viscosity is coated on a prepared substrate such as glass, and at this time, the coating method used is not particularly limited. Examples of coating methods may be selected from spin coating, dip coating, solvent casting, slot die coating, spray coating, and combinations thereof.
The heat treatment may be carried out by convection through a conventional oven, and the heat treatment conditions are carried out at 100-450 ℃ for 30-120 minutes. Preferably, the heat treatment may be performed at a temperature and time of 30 minutes at 100 ℃ and 30 minutes at 350 ℃. This is a condition under which the characteristics of the polyamideimide film of the present invention used as an optical film can be maximized while the solvent is properly removed.
Polyamide imide film
The polyamic acid composition of the present invention is characterized by providing a polyamide imide film having excellent heat resistance and optical properties and having high transparency by optimizing the composition of dicarbonyl compound, diamine compound and acid dianhydride, and solvent (organic solvent) which does not cause clouding phenomenon, and the amount of use thereof. Specifically, the polyamideimide film of the present invention is produced by the method for producing a polyamideimide film, which is characterized in that when the polyamideimide film has a thickness of 10 to 15 μm, a yellow index (y.i.) is 5 or less, a glass transition temperature is 360 ℃ or more, a light transmittance at a wavelength of 550nm is 85% or more, and has high transparency. In this case, the polyamide-imide film of the present invention has a glass transition temperature of 380℃or higher, and a coefficient of thermal expansion (C.T.E.) at 100 to 250℃may have a value of 20 ppm/DEG C or lower.
The polyamideimide film of the present invention can be used in various fields, and particularly can be effectively applied to flexible devices, tablet computers, wearable devices, flexible OLED lighting substrate materials, etc. which require high transparency and high refractive index characteristics and require realization of efficient light sources.
Claims (20)
1. A polyamic acid characterized in that the polyamic acid is prepared from a dicarbonyl compound, a diamine compound, and an acid dianhydride compound, the dicarbonyl compound comprising one compound selected from the group consisting of the following chemical formula 1, chemical formula 3, chemical formula 5, chemical formula 6, chemical formula 7, and a combination thereof,
[ chemical formula 1]
[ chemical formula 3]
[ chemical formula 5]
[ chemical formula 6]
[ chemical formula 7]
2. The polyamic acid according to claim 1, wherein the diamine compound comprises one selected from the group consisting of a fluorinated aromatic diamine monomer, a non-fluorinated aromatic diamine monomer, and a combination thereof.
3. The polyamic acid according to claim 1, wherein, the diamine compound comprises a diamine compound selected from the group consisting of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl (TFMB), 4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (pPDA), m-phenylenediamine (mPDA), p-methylenedianiline (pMDA), m-methylenedianiline (mMDA), p-cyclohexanediamine (pCHDA), p-xylylenediamine (pXDA), m-xylylenediamine (mXDA), m-cyclohexanediamine (mCHDA), 4' -diaminodiphenyl sulfone (DDS) 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane (BAFP), 2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), 2 '-bis (3-amino-4-tolyl) hexafluoropropane (BAMF), 2' -bis (3-aminophenyl) -hexafluoropropane (BAPF) 3, 5-Diaminobenzotrifluoride (DABF), 2 '-bis (trifluoromethyl) -4,4' -diaminodiphenyl ether (BTDE), 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHH), and combinations thereof.
4. The polyamic acid according to claim 1, wherein the acid dianhydride compound comprises one selected from the group consisting of fluorinated aromatic acid dianhydride, non-fluorinated aromatic acid dianhydride, and combinations thereof.
5. The polyamic acid according to claim 4, wherein the fluorinated aromatic acid dianhydride comprises one selected from the group consisting of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA), 4' - (4, 4' -hexafluoroisopropylidene diphenoxy) bis- (phthalic anhydride) (6-FDPDA), and combinations thereof.
6. The polyamic acid according to claim 4, wherein the non-fluorinated aromatic acid dianhydride comprises a compound selected from the group consisting of pyromellitic dianhydride (PMDA), 3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), 3',4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 4 '-oxydiphthalic anhydride (ODPA), 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride (BPADA), 3',4,4 '-diphenyl sulfone tetracarboxylic dianhydride (DSDA), ethylene glycol bis (4-trimellitic anhydride), cyclobutane tetracarboxylic dianhydride (CBDA), 4- (2, 5-dioxytetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic dianhydride (TDA), benzophenone Tetracarboxylic Dianhydride (BTDA), oxydiphthalic Dianhydride (ODPA), bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride (BTDA), 3', 4-biphenyl tetracarboxylic dianhydride (s-BPDA), and combinations thereof.
7. The polyamic acid according to any one of claims 1 to 6, wherein the viscosity of the polyamic acid at 23 ℃ is 1000 to 10000 centipoise.
8. A polyamideimide film, characterized in that it comprises the polyamic acid according to any one of claims 1 to 7.
9. The polyamideimide film according to claim 8, wherein the polyamideimide film has a yellow index (y.i.) of 10 or less, a coefficient of thermal expansion (c.t.e.) of 20ppm/°c or less at 100 to 250 ℃, a glass transition temperature of 360 ℃ or more, and a light transmittance of 85% or more at a wavelength of 550nm when the polyamideimide film has a thickness of 10 to 15 μm.
10. A method of preparing a polyamic acid comprising the steps of:
mixing a diamine compound and a solvent to prepare a mixture; and
adding dicarbonyl compound and acid dianhydride to the mixture and polymerizing to prepare polyamic acid solution,
wherein the dicarbonyl compound comprises one compound selected from the group consisting of chemical formula 1, chemical formula 3, chemical formula 5, chemical formula 6, chemical formula 7, and a combination thereof,
[ chemical formula 1]
[ chemical formula 3]
[ chemical formula 5]
[ chemical formula 6]
[ chemical formula 7]
11. The method for producing polyamic acid according to claim 10, wherein in the step of producing a mixture, the solvent is selected from the group consisting of a polar solvent, a low boiling point solvent, a low hygroscopic solvent, a diffusible solvent and a combination thereof,
the polar solvent is selected from the group consisting of m-cresol, N-methyl-2-pyrrolidone (NMP), N-Dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), 3-methoxy-N, N-Dimethylpropionamide (DMPA), N-Dimethylpropionamide (DPA), N-Dimethylformamide (DML), and combinations thereof,
the low boiling point solvent is selected from Tetrahydrofuran (THF), chloroform (TCM) and combinations thereof,
the low hygroscopicity solvent is selected from the group consisting of gamma-butyrolactone (GBL), 3-methoxy-N, N-Dimethylpropionamide (DMPA), N-Dimethylpropionamide (DPA), N-Dimethylpropionamide (DML), N-methyl-2-pyrrolidone (NMP), and combinations thereof,
the diffusible solvent is one selected from ethylene glycol monobutyl ether (EGBE), ethylene glycol dimethyl ether (EGME), ethylene Glycol Diethyl Ether (EGDE), ethylene glycol dipropyl ether (EGDPE), ethylene glycol dibutyl ether (EGDBE), and combinations thereof.
12. The method for producing a polyamic acid according to claim 11, wherein the low-hygroscopicity solvent comprises: a first low hygroscopicity solvent mixture comprising 30-70 mole% of gamma-butyrolactone and 30-70 mole% of N-methyl-2-pyrrolidone, a second low hygroscopicity solvent mixture comprising 30-70 mole% of gamma-butyrolactone and 30-70 mole% of N, N-dimethylpropionamide, a third low hygroscopicity solvent mixture comprising 30-70 mole% of gamma-butyrolactone and 30-70 mole% of 3-methoxy-N, N-dimethylpropionamide, 100 mole% of N, N-dimethylpropionamide or 100 mole% of 3-methoxy-N, N-dimethylpropionamide.
13. The method of preparing polyamic acid according to claim 10, wherein the solvent comprises a diffusible solvent selected from the group consisting of ethylene glycol monobutyl ether (EGBE), ethylene glycol dimethyl ether (EGME), ethylene Glycol Diethyl Ether (EGDE), ethylene glycol dipropyl ether (EGDPE), ethylene glycol dibutyl ether (EGDBE), and combinations thereof.
14. The method for producing polyamic acid according to claim 10, wherein in the step of producing a polyamic acid solution, the dicarbonyl compound is contained in an amount of 20 to 100 mol% based on the diamine compound.
15. The method for preparing polyamic acid according to claim 10, wherein in the step of preparing the mixture, the mixing is performed under a nitrogen atmosphere at a temperature of 25 to 30 ℃ for 30 to 60 minutes.
16. The method for preparing polyamic acid according to claim 10, wherein in the step of preparing polyamic acid solution, one selected from the group consisting of a plasticizer, an antioxidant, a flame retardant, a dispersant, a viscosity modifier, a leveling agent, and a combination thereof is further added to the mixture.
17. The method for preparing polyamic acid according to claim 10, wherein in the step of preparing a polyamic acid solution, the polymerization is performed at a temperature of 10 to 70℃for 6 to 48 hours.
18. The method for producing a polyamic acid according to claim 10, wherein in the step of producing a polyamic acid solution, the diamine compound, the dicarbonyl compound, and the acid dianhydride constitute a solid of the polyamic acid solution, and the content of the solid is 10 to 40% by weight based on the polyamic acid solution.
19. The method for producing polyamic acid according to claim 10, wherein in the step of producing a polyamic acid solution, the acid dianhydride compound and the dicarbonyl compound are contained in an amount of 100 to 105 mol% based on the diamine compound.
20. A method for producing a polyamideimide film, characterized in that the method for producing a polyamic acid according to any one of claims 10 to 19 further comprises the steps of:
coating the polyamic acid solution on a substrate to form a transparent coating; and
the transparent coating layer is subjected to a heat treatment,
wherein the heat treatment is performed at a temperature of 100-450 ℃ in a nitrogen atmosphere for 30-120 minutes.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020190000243A KR102249475B1 (en) | 2019-01-02 | 2019-01-02 | manufacturing method of polyamic acid composition comprising novel dicarbonyl compounds, polyamic acid composition, manufacturing method of polyamide-imide film using the polyamic acid composition and polyamide-imide film using the same |
| KR10-2019-0000243 | 2019-01-02 | ||
| PCT/KR2019/015111 WO2020141713A1 (en) | 2019-01-02 | 2019-11-08 | Method for preparing polyamic acid composition containing novel dicarbonyl compound, polyamic acid composition, method for manufacturing polyamide-imide film using same, and polyamide-imide film produced by same manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113439101A CN113439101A (en) | 2021-09-24 |
| CN113439101B true CN113439101B (en) | 2023-08-11 |
Family
ID=71406756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980086790.0A Active CN113439101B (en) | 2019-01-02 | 2019-11-08 | Polyamic acid composition, preparation method thereof, preparation method of polyamide imide film and polyamide imide film prepared by same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7317123B2 (en) |
| KR (1) | KR102249475B1 (en) |
| CN (1) | CN113439101B (en) |
| WO (1) | WO2020141713A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI740758B (en) * | 2020-12-25 | 2021-09-21 | 律勝科技股份有限公司 | Polyamide-imide copolymer and film containing the same |
| CN114225721B (en) * | 2021-11-26 | 2023-06-27 | 山东东岳高分子材料有限公司 | Safe and environment-friendly method for preparing PVDF porous membrane |
| CN114940822B (en) * | 2022-05-17 | 2024-02-23 | 浙江中科玖源新材料有限公司 | Polyamide-imide film and flexible display |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100105182A (en) * | 2009-03-20 | 2010-09-29 | 김진우 | Process for making imide and aramid function containing novel polymer and application |
| KR20170011011A (en) * | 2015-07-21 | 2017-02-02 | 주식회사 엘지화학 | Polyamide-imide precursors and preparation method of same |
| KR20180009651A (en) * | 2016-07-19 | 2018-01-29 | 코오롱인더스트리 주식회사 | Polyamic acid, Polyimide Resin, Polyimide Film and Display Device Comprising Thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4586243B2 (en) | 2000-06-22 | 2010-11-24 | 住友ベークライト株式会社 | Insulating material manufacturing method |
| JP2012077144A (en) | 2010-09-30 | 2012-04-19 | Kaneka Corp | Polyamideimide resin, manufacturing method therefor, polyamideimide resin solution, polyamideimide film, and use thereof |
| JP2020109155A (en) | 2018-12-28 | 2020-07-16 | 住友化学株式会社 | Optical film, flexible display device and polyamide-imide resin |
-
2019
- 2019-01-02 KR KR1020190000243A patent/KR102249475B1/en active IP Right Grant
- 2019-11-08 JP JP2021538723A patent/JP7317123B2/en active Active
- 2019-11-08 WO PCT/KR2019/015111 patent/WO2020141713A1/en active Application Filing
- 2019-11-08 CN CN201980086790.0A patent/CN113439101B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100105182A (en) * | 2009-03-20 | 2010-09-29 | 김진우 | Process for making imide and aramid function containing novel polymer and application |
| KR20170011011A (en) * | 2015-07-21 | 2017-02-02 | 주식회사 엘지화학 | Polyamide-imide precursors and preparation method of same |
| KR20180009651A (en) * | 2016-07-19 | 2018-01-29 | 코오롱인더스트리 주식회사 | Polyamic acid, Polyimide Resin, Polyimide Film and Display Device Comprising Thereof |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis and characterization of fluorinated poly(imide–amide–sulfone)s;Bruma et.al.;《Journal of Applied Polymer Science》;19950502;527-532 * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102249475B1 (en) | 2021-05-12 |
| WO2020141713A1 (en) | 2020-07-09 |
| CN113439101A (en) | 2021-09-24 |
| KR20200084482A (en) | 2020-07-13 |
| JP2022516282A (en) | 2022-02-25 |
| JP7317123B2 (en) | 2023-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10815378B2 (en) | Polyamic acid resin and polyamideimide film | |
| JP6906054B2 (en) | A polyimide precursor resin composition having improved resin stability and heat resistance and transparency, a method for producing a polyimide film using the same, and a polyimide film produced by the same. | |
| TWI683837B (en) | Polyamide-imide precursor composition, polyamide-imide film and display device | |
| JP2021102770A (en) | Polyamic acid composition with improved adhesive strength and polyimide film comprising the same | |
| KR102497848B1 (en) | Poly(amide-imide) copolymer, method of preparing poly(amide-imede) copolymer, and article including poly(amide-imide)copolymer | |
| JP6862652B2 (en) | High-strength transparent polyamide-imide and its manufacturing method | |
| CN113439101B (en) | Polyamic acid composition, preparation method thereof, preparation method of polyamide imide film and polyamide imide film prepared by same | |
| KR20110010009A (en) | Manufacturing method of polyimide, polyimide manufactured by thereof and film manufactured using said polyimide | |
| US20180194900A1 (en) | Polyimide-polybenzoxazole precursor solution, polyimide-polybenzoxazole film, and preparation method therefor | |
| KR20150077177A (en) | Polyamic acid solution, transparent polyimide film, transparent substrate using the same | |
| CN113227207A (en) | Polyamic acid composition and transparent polyimide film using same | |
| KR20160003606A (en) | Polyamic acid solution, transparent polyimide film, transparent substrate using the same | |
| JP6935623B2 (en) | A highly transparent polyimide precursor resin composition having excellent optical characteristics and phase delay characteristics, a method for producing a polyimide resin film using the same, and a polyimide resin film produced by the same. | |
| US10316145B2 (en) | Polyamic acid composition, polyamideimide film thereof and method for preparing polyamideimide film | |
| JP2024028411A (en) | Polyamic acid composition and transparent polyimide film using the same | |
| JP7317122B2 (en) | Polyamic acid composition production method, polyamic acid composition, polyimide film production method using the same, and polyimide film produced by the production method | |
| TWI793414B (en) | Polyamide-imide block copolymers, preparation method thereof and polyamide-imide film comprising the same | |
| KR102276656B1 (en) | Composition of preparing poly(imide-benzoxasole)copolymer, poly(imide-benzoxasole)copolymer, article contatining poly(imide-benzoxasole)copolymer, and display device including same | |
| TWI842677B (en) | Polyamic acid resin and polyamideimide film | |
| US11970579B2 (en) | Polyamic acid resin and polyamideimide film | |
| KR102675752B1 (en) | Polyamic acid-imide composition and polyimide film formed from the same | |
| KR102339091B1 (en) | Polyamic acid composition, polyamideimide film thereof and method for preparing the polyamindeimide film | |
| KR20240008496A (en) | Polyamideimide film and optical multilayer structure comprising same | |
| KR20200027360A (en) | Polyamic acid-imide composition and polyimide film formed from the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |