CN109384921B - 聚酰亚胺前体组合物及利用其的聚酰亚胺膜的制备方法 - Google Patents
聚酰亚胺前体组合物及利用其的聚酰亚胺膜的制备方法 Download PDFInfo
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- CN109384921B CN109384921B CN201810908279.1A CN201810908279A CN109384921B CN 109384921 B CN109384921 B CN 109384921B CN 201810908279 A CN201810908279 A CN 201810908279A CN 109384921 B CN109384921 B CN 109384921B
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- Prior art keywords
- dimethylpropionamide
- polyimide
- composition
- polyamic acid
- polyimide film
- Prior art date
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 86
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 239000004642 Polyimide Substances 0.000 title claims abstract description 42
- 239000002243 precursor Substances 0.000 title abstract description 19
- 238000004519 manufacturing process Methods 0.000 title description 6
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 36
- LBVMWHCOFMFPEG-UHFFFAOYSA-N 3-methoxy-n,n-dimethylpropanamide Chemical compound COCCC(=O)N(C)C LBVMWHCOFMFPEG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012046 mixed solvent Substances 0.000 claims abstract description 24
- MBHINSULENHCMF-UHFFFAOYSA-N n,n-dimethylpropanamide Chemical compound CCC(=O)N(C)C MBHINSULENHCMF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000654 additive Substances 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 6
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 3
- FAUAZXVRLVIARB-UHFFFAOYSA-N 4-[[4-[bis(oxiran-2-ylmethyl)amino]phenyl]methyl]-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC(CC=2C=CC(=CC=2)N(CC2OC2)CC2OC2)=CC=1)CC1CO1 FAUAZXVRLVIARB-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- ASQQEOXYFGEFKQ-UHFFFAOYSA-N dioxirane Chemical compound C1OO1 ASQQEOXYFGEFKQ-UHFFFAOYSA-N 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 27
- 238000002360 preparation method Methods 0.000 abstract description 14
- 238000000034 method Methods 0.000 description 37
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 239000010408 film Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 238000002834 transmittance Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- -1 6-hydroxy-phenyl Chemical group 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 5
- AHIPJALLQVEEQF-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1COC(C=C1)=CC=C1N(CC1OC1)CC1CO1 AHIPJALLQVEEQF-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
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- 239000000463 material Substances 0.000 description 3
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- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 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
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
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- 239000004065 semiconductor Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- FXGQUGCFZKMIJW-UHFFFAOYSA-N 2,4,5,6-tetrafluorobenzene-1,3-diamine Chemical compound NC1=C(F)C(N)=C(F)C(F)=C1F FXGQUGCFZKMIJW-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound 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
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- SSDBTLHMCVFQMS-UHFFFAOYSA-N 4-[4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 SSDBTLHMCVFQMS-UHFFFAOYSA-N 0.000 description 1
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 1
- BBTGUNMUUYNPLH-UHFFFAOYSA-N 5-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 BBTGUNMUUYNPLH-UHFFFAOYSA-N 0.000 description 1
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 229940039407 aniline Drugs 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
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- 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 1
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- 239000002798 polar solvent Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
Classifications
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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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Abstract
本发明公开可用于柔性基板的制备的聚酰亚胺前体组合物、利用其的聚酰亚胺膜制备方法以及包括聚酰亚胺膜的显示器器件。所述聚酰亚胺前体组合物,包含:混合溶剂,含有3‑甲氧基‑N,N‑二甲基丙酰胺(M3DMPA)和N,N‑二甲基丙酰胺(DMPA);以及聚酰胺酸或聚酰亚胺。
Description
技术领域
本发明涉及聚酰亚胺前体组合物及利用其的聚酰亚胺膜制备方法,更详细地,涉及可用于柔性基板的制备的聚酰亚胺前体组合物、利用其的聚酰亚胺膜制备方法及包含聚酰亚胺膜的显示器器件。
背景技术
最近,对容易实现大面积且可进行薄型及轻量化的平板显示器(Flat PanelDisplay;FPD)的需求正增加。这种平板显示器有液晶显示装置(Liquid Crystal Display;LCD)、等离子显示面板(Plasma Display Panel;PDP)、有机发光显示装置(Organic LightEmitting Display;OLED)等。但是,以往的平板显示器使用玻璃基板,因此没有柔性,其应用和用途受限。由此,作为新一代显示装置正积极研发代替没有柔性的玻璃基板,使用如塑料、箔等具有柔性的材料的基板而以能够弯曲的方式制备的柔性显示装置(FlexibleDisplay Device)。
柔性显示装置通常以高温的薄膜晶体管(TFT,Thin Film Transistor)工序制备。工序温度可根据包括于装置内的半导体层、绝缘膜及阻隔层的种类不同,通常,薄膜晶体管制造工序需要300℃至500℃左右的温度。但是,可承受这种工序温度的聚合物材料极其有限,主要使用具有优秀的耐热性而众所周知的聚酰亚胺。聚酰亚胺材质不仅具有优秀的热特性,而且,柔软且轻量,因此,聚酰亚胺基板作为可代替以往的玻璃基板的塑料基板备受关注。
有各种制备聚酰亚胺基板的工序,其中使用最多的方法为利用旋转机(spin)或狭缝式涂敷机(slit coater)将聚酰胺酸(Polyamic acid)高分子溶液以规定厚度涂敷于玻璃载体(Carrier Glass)之后通过对流炉(Convection Oven)或红外炉(IR Oven)进行热酰亚胺化反应及溶剂去除工艺而制备聚酰亚胺基板。柔性显示器生产工序在聚酰亚胺基板的上面形成薄膜晶体管背板、有机发光层等来制造产品之后,通过光绝缘膜去除(Laser LiftOff)方法从玻璃载体分离。聚酰亚胺材质容易弯曲,因此在将基板固定于玻璃载体的状态下进行后续工序。薄膜晶体管或蒸镀工序在较高的温度中进行,因此,若聚酰亚胺材质和玻璃载体的热膨胀系数的差异大,则具有玻璃载体被弯曲的忧虑,因此,具有相似的热膨胀系数尤为重要。
聚酰胺酸高分子溶液在极性溶剂中聚合二胺(Diamine)和二酐(Dianhydride)来制备,作为所述极性溶剂通常使用二甲基乙酰胺(Dimethylacetamide:DMAC,沸点:165.1℃)、二甲基甲酰胺(Dimethylformamide:DMF,沸点:153℃)、N-甲基吡咯烷酮(N-Methylpyrrolidone:NMP,沸点:202℃)等,但是,这些为环境限制对象,其使用受限,因此需要用其他的溶剂来代替。
并且,制备聚酰亚胺基板的热酰亚胺化工序根据炉中的高温固化(curing)过程决定工序时间(lead time),为了节省时间,进行缩短升温时间、缩短每个温度步骤中的维持时间等各种尝试。并且,当进行高温工序(120℃工序开始及450℃固化(cure)工序)及高速干燥时,由于溶剂快速挥发,在涂敷面产生缺陷,为改善这种问题,尝试各种方法。
发明内容
本发明的目的在于,提供利用代替环境限制对象溶剂的新混合溶剂的环保聚酰亚胺前体组合物。
本发明的另一目的在于,提供利用所述聚酰亚胺前体组合物来制备具有优秀的特性的聚酰亚胺膜的方法。
为了实现所述目的,本发明提供组合物,所述组合物包含:混合溶剂,含有3-甲氧基-N,N-二甲基丙酰胺(M3DMPA)和N,N-二甲基丙酰胺(DMPA);以及聚酰胺酸或聚酰亚胺。
本发明的组合物使用代替环境限制对象溶剂的新混合溶剂。通过使用新混合溶剂,可通过高温固化及速干工序缩短聚酰亚胺膜的制备工序时间(lead time)。并且,通过使用包含挥发度相不同的2种溶剂的混合溶剂获取透射率和表面特性良好的聚酰亚胺膜。
具体实施方式
以下,对本发明进行更加详细说明。
本发明的组合物,包含:混合溶剂,含有3-甲氧基-N,N-二甲基丙酰胺(M3DMPA)和N,N-二甲基丙酰胺(DMPA);以及聚酰胺酸或聚酰亚胺。
在本发明中使用的混合溶剂为挥发度不同的2种物质,混合有3-甲氧基-N,N-二甲基丙酰胺(3-Methoxy-N,N-dimethylpropionamide;M3DMPA,沸点:188.7℃)及N,N-二甲基丙酰胺(N,N-Dimethylpropionamide;DMPA,沸点:174-176℃),当进行高温工序时,防止溶剂的快速挥发引起的表面缺陷,并改善聚酰亚胺膜的透射率和表面特性。
所述3-甲氧基-N,N-二甲基丙酰胺(M3DMPA):N,N-二甲基丙酰胺(DMPA)的混合比率(重量比)为1:9至9:1,优选地,可为3:7至7:3,例如,可为5:5的重量比。其中,若所述3-甲氧基-N,N-二甲基丙酰胺(M3DMPA)的使用量过少,则存在在速干工序中具有膜表面不良的问题,若所述3-甲氧基-N,N-二甲基丙酰胺(M3DMPA)的使用量过多,则存在虽对于膜涂敷方面有利,但是具有透射度降低的问题。
在本发明的组合物中使用的聚酰胺酸为在分子内具有胺基和羧基的化合物,是通过加热胺基和羧基进行反应来形成亚胺基的高分子,可在所述混合溶剂中使二胺单体与二酐单体进行反应来制备。
作为所述二胺单体可使用对苯二胺(p-Phenylenediamine:PPDA),4,4'-二氨基二苯醚(4,4'-Oxydianiline:ODA),4,4'-亚甲基二苯胺(4,4'-Methylene dianiline:MDA),2,2'-二甲基-4,4'-二氨基联苯(m-Toli din;2,2'-Dimethyl-4,4'-Diaminobiphenyl),1,3-双(4'-氨基苯氧基)苯(1,3-BIS(4'-Aminophenoxy)benzene:TPE-R),以及含有氟基的2,2'-二(三氟甲基)二氨基联苯(2,2'-Bis(trifluoromethyl)benzidine:TFMB)、2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷(2,2-BIS[4-(4-Aminophenoxy)Phe nyl]Hexafluoropropane:HFBAPP)、2,2-双(3-氨基-4-羟基苯基)六氟聚苯胺丙烷(2,2-Bis(3-amino-4-hydroxy phenyl)hexafluoropropane:BIS-AP-AF)、1,3-二氨基-2,4,5,6-四氟苯(1,3-Diamino-2,4,5,6-Tetrafluorob enzene:DRFB),包含硫基的3,3'-二氨基二苯砜(3,3'-Diaminodiphen yl Sulfone:DDS)、4,4'-二氨基二苯硫醚(4,4'-DiaminodiphenylSulfi de:ASD)、双[4-(4-氨基苯氧基)苯基]砜(Bis[4-(4-amino phenoxy)phenyl]sulfone:BAPS)、2,2-双[4-(3-氨基苯氧基)苯]砜(2,2-Bis[4-(3-A mino phenoxy)Benzene]Sulfone:m-BAPS)等。其中,可混合1种或2种以上的单体来使用,为了确保高耐热特性,恰当的是作为芳香(Aro matic)结构单体的对苯二胺。
作为所述二酐(Dianhdride)单体恰当的是芳香族二酐(Dianhydr ide)化合物,可使用3,3',4,4'-二苯酮四酸二酐(3,3',4,4'-Benzophenone tetracarboxylicdianhydride:BTDA)、均苯四酸二酐(Pyromellitic d ianhydride:PMDA)、3,3',4,4'-联苯四羧酸二酐(3,3'4,4'-Biphenyl tetr acarboxylicacid dianhydride:BPDA)、2,2-双(3,4-无水二羧基苯基)-六氟丙烷二酐(2,2-Bis(3,4-anhydrodicarboxy phenyl)-hexafluoro propane dianhydride:6FDA)、2,3,3',4-联苯基四羧酸二酐(2,3,3',4-biphenyl t etracarboxylicacid dianhydride:a-BPDA)、4,4'-氧双邻苯二甲酸酐(4,4'-oxydiphthalic Anhydride:ODPA)、3,3',4,4'-二苯基砜四羧酸二酸酐(3,3',4,4'-Diphenylsulfone-tetracarboxylic Dianhydride:DSDA)、2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐(2,2-bis[4-(3,4-dicarboxy phen oxy)phenyl]propane dianhydride:BPADA)、4,4'-对苯二氧双邻苯二甲酸酐(Hydroquinone diphthalic anhydride:HQDA)等。其中,可混合1种或2种以上的单体来使用,为了确保高耐热特性,恰当的是3,3',4,4'-联苯四羧酸二酐(3,3'4,4'-Biphenyl tetracarboxylicacid dianhydride:BPDA)。
本发明的组合物可根据需要还包括添加剂。所述添加剂可为包含环氧多官能团的物质,与混合溶剂一起可起到改善涂敷面的缺陷的作用。例如,所述添加剂可使用由下述化学式表示的[化学式1-1]乙二醇二缩水甘油醚(Ethylene glycol diglycidyl ether)、[化学式1-2]N,N-二缩水甘油基-4-缩水甘油氧代苯胺(N,N-Diglycidyl-4-Glycidyloxy aniline)、[化学式1-3]1,4-双((2,3-环氧丙氧基)甲基)环己烷(1,4-Bis((2,3-epoxypropoxy)methyl)cyclohexane)、[化学式1-4]2,2’-[1,3-亚苯基双(氧亚甲基)]二环氧乙烷(2,2'-[1,3-Phenylenebis(oxymethylene)]dioxiran e)、[化学式1-5]4,4'-亚甲基双(N,N-二缩水甘油基苯胺)(4,4'-methyl ene bis(N,N-diglicidyl aniline))等,但并不限定于此,可将包含环氧多官能团的树脂用作添加剂。
相对于100重量份的聚酰胺酸或聚酰亚胺,可添加0.02重量份至1.2重量份的所述添加剂。其中,若所述添加剂的添加量过少,则会发生膜表面翘起来的问题,若过多,则存在膜的透射率降低(小于50%)的问题。
所述添加剂可在溶剂中溶解之后向本发明的组合物添加,溶解添加剂的溶剂可为包含3-甲氧基-N,N-二甲基丙酰胺(M3DMPA)和N,N-二甲基丙酰胺(DMPA)的混合溶剂,但并不限定于此,为了改善物性,可使用其他种类的溶剂。
[化学式1-1]
[化学式1-2]
[化学式1-3]
[化学式1-4]
[化学式1-5]
在本发明的组合物中,相对于100重量份的所述混合溶剂,所述聚酰胺酸或聚酰亚胺可为5重量份至30重量份,优选为8重量份至20重量份,更优选地,可为10重量份至15重量份。其中,若所述聚酰胺酸或聚酰亚胺的含量过少,则粘度低,因此难以获取厚度均匀的聚酰亚胺膜,当向高温炉(bake)投入时,因溶剂快速挥发而引起表面不良的可能性高,若所述聚酰胺酸或聚酰亚胺的含量过多,则粘度高,当进行狭缝式涂敷时,难以调整膜的厚度,从而形成相对厚的膜的可能性高。
在本发明的组合物中,组合物的粘度可为1000cP至20000cP。在粘度小于1000cP的情况下,低分子相对多,涂敷时的流动性高,从而可形成厚度薄的聚酰亚胺薄膜,在粘度大于20000cP的情况下,高分子多,流动性降低,因此形成相当厚的厚膜,从而难以获取适当的聚酰亚胺膜的厚度。
接着,对本发明的聚酰亚胺膜的制备方法进行说明。
为了根据本发明制备聚酰亚胺膜,首先,利用涂抹器(applicator)将所述组合物以如400μm厚度(wet厚度)涂敷于载体基板(carrier glass等)。此时,作为载体基板,可无特别限制地使用玻璃、金属基板或塑料基板等,其中,优选使用玻璃基板,所述玻璃基板在对聚酰亚胺前体的固化工序中具有优秀的热稳定性及化学稳定性,无须额外的离型剂处理也可容易以不损伤固化后形成的聚酰亚胺类膜的方式分离。所述涂敷工序可根据常规涂敷方法实施,具体可利用旋转涂敷法、杆式涂敷法、辊式涂敷法、气刀法、凹印法、逆转辊法、湿润辊法、刮刀法、喷射法、浸渍法或刷涂(brushing)法等。
所述组合物能够以使最终制备的聚酰亚胺膜作为显示基板具有适当的厚度的厚度范围内涂敷于基板的上侧。具体地,在溶剂蒸发及固化之后,能够以最终厚度成为1μm至30μm的量涂敷。在所述涂敷过程之后,在固化工序之前还可选择性地实施用于去除存在于组合物内的溶剂的干燥工序。所述干燥工序可根据常规方法实施,具体可在140℃以下或80℃至140℃的温度中实施。若干燥工序的实施温度低于80℃,则干燥工序时间变长,若干燥工序的实施温度高于140℃,则快速进行酰亚胺化而难以形成厚度均匀的聚酰亚胺膜。
另一方面,通过热酰亚胺化工序的固化工序消耗相当长的时间,因此,需减少固化工序时间才能增加生产量。因此,试图在炉没有完全被冷却的状态下,投入之后的涂敷基板来缩短工序时间。在本发明中,当进行固化工序时,可在冷却没有结束的炉,例如,在100℃的温度中的对流炉中到450℃为止以每分钟5℃至10℃的升温速度进行加热来制备聚酰亚胺膜。所述固化工序可根据情况加热至300℃至450℃的温度来进行。并且,所述固化工序可在如上所述的温度范围内通过按照步骤的热处理进行多步骤工序,例如,可在200℃的温度中进行第一次热处理、在300℃的温度中进行第二次热处理、在350℃的温度中进行第三次热处理来执行,但并不限定于此。并且,当进行所述固化工序时,固化时间并没有特别限制,作为一例,可以实施3分钟至60分钟。
并且,在所述固化工序之后,为了通过提高聚酰亚胺膜内聚酰亚胺类树脂的酰亚胺化率来形成具有优秀的物性特征的聚酰亚胺类膜,还可选择性地实施后续的热处理工序。所述后续热处理工序可在200℃以上或200℃至450℃的温度中实施1分钟至30分钟。并且,所述后续热处理工序可以实施1次,或还可以实施2次以上的多步骤。具体地,可以实施包括200℃至220℃温度中的第一热处理、300℃至350℃温度中的第二热处理及400℃至450℃温度中的第三热处理的3步骤。接着,可通过常规方法从载体基板剥离形成于冷却后的基板上的聚酰亚胺膜来完成。
在本发明的组合物与混合溶剂一同包含聚酰亚胺的情况下,为已经执行酰亚胺化的状态,因此,可通过在涂敷组合物之后蒸发溶剂来制备聚酰亚胺膜。例如,溶剂的蒸发可用200℃以上的温度加热来执行,但并不限定于此。
可提供包括所述聚酰亚胺膜的显示基板及器件。具体地,所述器件可为具有可挠性基板的任意太阳能电池(例如,柔性太阳能电池)、有机发光二极管(OLED)照明(例如,柔性有机发光二极管照明)、具有可挠性基板的任意半导体器件或具有可挠性基板的有机电致发光器件、电泳器件或液晶显示器件(LCD)等的柔性显示器件。
以下,通过具体实施例对本发明进行更详细地说明。下述实施例仅用于例示本发明,本发明并不限定于下述实施例。
[实施例1]制备聚酰亚胺前体组合物:
在以1:9(重量比)混合有3-甲氧基-N,N-二甲基丙酰胺(M3DMPA)和N,N-二甲基丙酰胺(DMPA)的529.2g的混合溶剂中在常温下完全溶解21.62g(0.2mol)的对苯二胺(PPDA)之后,投入58.84g(0.2mol)的3,3',4,4'-联苯四羧酸二酐(BPDA)来进行反应,搅拌18小时后结束,从而获取了相对于100重量份的混合溶剂包含15重量份的聚酰胺酸(聚酰亚胺前体)的组合物。为了确认高分子化顺利地进行而是否可以进行薄膜化,使用BrookField粘度计检测了组合物的粘度,所获取的聚酰胺酸组合物的粘度为13500cps。
[实施例2]制备聚酰亚胺前体组合物:
3-甲氧基-N,N-二甲基丙酰胺(M3DMPA)和N,N-二甲基丙酰胺(DMPA)的混合比率为3:7,除此之外,通过与实施例1相同的方法获取了聚酰胺酸(聚酰亚胺前体)组合物。所获取的聚酰胺酸组合物的粘度为13000cps。
[实施例3]制备聚酰亚胺前体组合物:
3-甲氧基-N,N-二甲基丙酰胺(M3DMPA)和N,N-二甲基丙酰胺(DMPA)的混合比率为5:5,除此之外,通过与实施例1相同的方法获取了聚酰胺酸(聚酰亚胺前体)组合物。所获取的聚酰胺酸组合物的粘度为12500cps。
[实施例4]制备聚酰亚胺前体组合物:
3-甲氧基-N,N-二甲基丙酰胺(M3DMPA)和N,N-二甲基丙酰胺(DMPA)的混合比率为7:3,除此之外,通过与实施例1相同的方法获取了聚酰胺酸(聚酰亚胺前体)组合物。所获取的聚酰胺酸组合物的粘度为13400cps。
[实施例5]制备聚酰亚胺前体组合物:
3-甲氧基-N,N-二甲基丙酰胺(M3DMPA)和N,N-二甲基丙酰胺(DMPA)的混合比率为9:1,除此之外,通过与实施例1相同的方法获取了聚酰胺酸(聚酰亚胺前体)组合物。所获取的聚酰胺酸组合物的粘度为13400cps。
[实施例1-1至1-5]制备聚酰亚胺膜:
根据所述聚酰胺酸单体固体成分的量对比表1的添加量,向由实施例1获取的聚酰胺酸组合物混合N,N-二缩水甘油基-4-缩水甘油氧代苯胺(N,N-Diglycidyl-4-Glycidyloxyaniline)并进行搅拌来制备了涂敷液组合物。利用涂抹器将所制备的涂敷液组合物以350μm的厚度(wet厚度)涂敷于玻璃载体(carrier glass),在对流炉中至450℃为止以每分钟8℃的升温速度加热来进行了热酰亚胺反应。对所获取聚酰亚胺膜的外部形态和光学特性等进行分析并示于表1。
[实施例2-1至2-5]制备聚酰亚胺膜:
根据所述聚酰胺酸单体固体成分的量对比表2的添加量,向由实施例2获取的聚酰胺酸组合物混合N,N-二缩水甘油基-4-缩水甘油氧代苯胺,除此之外,通过与实施例1-1相同的方法进行热酰亚胺反应,并对所获取的聚酰亚胺膜的外部形态和光学特性等进行分析并示于表2。
[实施例3-1至3-5]制备聚酰亚胺膜:
根据所述聚酰胺酸单体固体成分的量对比表3的添加量,向由实施例3获取的聚酰胺酸组合物混合N,N-二缩水甘油基-4-缩水甘油氧代苯胺,除此之外,通过与实施例1-1相同的方法进行热酰亚胺反应,并对所获取的聚酰亚胺膜的外部形态和光学特性等进行分析并示于表3。
[实施例4-1至4-5]制备聚酰亚胺膜:
根据所述聚酰胺酸单体固体成分的量对比表4的添加量,向由实施例4获取的聚酰胺酸组合物混合N,N-二缩水甘油基-4-缩水甘油氧代苯胺,除此之外,通过与实施例1-1相同的方法进行热酰亚胺反应,并对所获取的聚酰亚胺膜的外部形态和光学特性等进行分析并示于表4。
[实施例5-1至5-5]制备聚酰亚胺膜:
根据所述聚酰胺酸单体固体成分的量对比表5的添加量,向由实施例5获取的聚酰胺酸组合物混合N,N-二缩水甘油基-4-缩水甘油氧代苯胺,除此之外,通过与实施例1-1相同的方法进行热酰亚胺反应,并对所获取的聚酰亚胺膜的外部形态和光学特性等进行分析并示于表5。
[比较例1-1至1-5]制备聚酰亚胺膜:
作为溶剂仅使用3-甲氧基-N,N-二甲基丙酰胺(M3DMPA)来制备聚酰胺酸组合物,除此之外,通过与实施例1-1至1-5相同的方法进行了热酰亚胺反应,并对所获取的聚酰亚胺膜的外部形态和光学特性等进行分析并示于表6。
[比较例2-1至2-5]制备聚酰亚胺膜:
作为溶剂仅使用N,N-二甲基丙酰胺(DMPA)来制备聚酰胺酸组合物,除此之外,通过与实施例1-1至1-5相同的方法进行了热酰亚胺反应,并对所获取的聚酰亚胺膜的外部形态和光学特性等进行分析并示于表7。
<聚酰亚胺的物性分析>
[粘度检测]
使用旋转式高粘度用粘度计(美国博勒飞(BrookField)公司,Corn-Plate方式)在25℃的温度中测量3次之后测量得到平均值。
[膜厚度]
膜的厚度使用超声波厚度测量仪(Qnix4500)测量10次之后确认了平均值和标准偏差。
[透射度测量]
利用光学测量仪(Nippon Denshoku公司,COH-400)测量5次可见光区域中的平均透射度之后测量得到了平均值。
[机械物性-应力(Stress),变形率(Strain)]
为了测量聚酰亚胺膜的机械物性,利用了阿美特克公司(Ametek LLOYDInstrument)的万能试验机(UTM,Universal Test Machine)。准备5mm的宽度、70mm的长度以上的膜试片之后,将握柄尺寸(Grip To Grip size)设定为30mm,拉伸速率(TensionRate)以10mm/min速度测量10次之后确认了平均值及标准偏差。
【表1】
(3-甲氧基-N,N-二甲基丙酰胺(M3DMPA):N,N-二甲基丙酰胺(DMPA)=1:9)
【表2】
(3-甲氧基-N,N-二甲基丙酰胺:N,N-二甲基丙酰胺=3:7)
【表3】
(3-甲氧基-N,N-二甲基丙酰胺:N,N-二甲基丙酰胺=5:5)
【表4】
(3-甲氧基-N,N-二甲基丙酰胺:N,N-二甲基丙酰胺=7:3)
【表5】
(3-甲氧基-N,N-二甲基丙酰胺:N,N-二甲基丙酰胺=9:1)
【表6】
(3-甲氧基-N,N-二甲基丙酰胺=100%)
【表7】
(N,N-二甲基丙酰胺=100%)
从所述表1至表7可知,随着使用混合溶剂,聚酰亚胺膜的表面状态良好,且可呈现50%以上的透射率。但是,在添加剂的投入量少的情况下,透射度虽优秀,但是表面状态可能不良,在投入过量的添加剂的情况下,透射率小于50%,显著下降。
并且,在不使用本发明的混合溶剂而单独使用3-甲氧基-N,N-二甲基丙酰胺(M3DMPA)或N,N-二甲基丙酰胺(DMPA)的情况下,经确认膜表面状态均不良,由此可知,通过本发明的组合物包含混合溶剂具有可以改善聚酰亚胺膜的表面状态的效果。
尤其,在以快速的升温速度,例如,如实施例以8℃的升温速度进行速干处理的情况下,本发明中的使用混合溶剂的组合物具有所制备的膜表面状态良好的效果,相反,在使用如N,N-二甲基丙酰胺(DMPA)的1种溶剂的情况下,可确认膜的表面状态不佳。
进而,在膜厚度的标准偏差方面,通过使用本发明的混合溶剂,厚度的标准偏差为1以下,即,厚度的差异不大,因而形成膜时具有厚度的可靠性优秀的效果。
在应力(Stress)及变形率(Strain)方面,在使用本发明的混合溶剂的情况下,偏差分别为10以下、1以下,由此,使用混合溶剂而制备的聚酰亚胺膜的机械特性没有产生大的变动,因此可知聚酰亚胺膜的可靠性优秀。
Claims (4)
1.一种组合物,其特征在于,包含:
混合溶剂,含有3-甲氧基-N,N-二甲基丙酰胺和N,N-二甲基丙酰胺;
聚酰胺酸或聚酰亚胺,以及
添加剂,所述添加剂为包含环氧多官能团的树脂,
其中以1:9至9:1的重量比包含所述3-甲氧基-N,N-二甲基丙酰胺和所述N,N-二甲基丙酰胺,
其中相对于100重量份的所述混合溶剂,包含5重量份至30重量份的所述聚酰胺酸或聚酰亚胺,以及
其中相对于100重量份的所述聚酰胺酸或聚酰亚胺,包含0.02重量份至1.2重量份的所述添加剂。
2.根据权利要求1所述的组合物,其特征在于,所述添加剂为选自由乙二醇二缩水甘油醚、N,N-二缩水甘油基-4-缩水甘油氧代苯胺、1,4-双((2,3-环氧丙氧基)甲基)环己烷、2,2’-[1,3-亚苯基双(氧亚甲基)]二环氧乙烷以及4,4'-亚甲基双(N,N-二缩水甘油基苯胺)组成的组中的至少一者。
3.根据权利要求1所述的组合物,其特征在于,以3:7至7:3的重量比包含所述3-甲氧基-N,N-二甲基丙酰胺和N,N-二甲基丙酰胺。
4.根据权利要求1所述的组合物,其特征在于,粘度为1000cP至20000cP。
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