JP6503183B2 - Polyimide laminate, electronic device, and method of manufacturing electronic device - Google Patents
Polyimide laminate, electronic device, and method of manufacturing electronic device Download PDFInfo
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- JP6503183B2 JP6503183B2 JP2014261213A JP2014261213A JP6503183B2 JP 6503183 B2 JP6503183 B2 JP 6503183B2 JP 2014261213 A JP2014261213 A JP 2014261213A JP 2014261213 A JP2014261213 A JP 2014261213A JP 6503183 B2 JP6503183 B2 JP 6503183B2
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- Prior art keywords
- polyimide
- polyimide layer
- electronic device
- layer
- solution
- Prior art date
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- 229920001721 polyimide Polymers 0.000 title claims description 313
- 239000004642 Polyimide Substances 0.000 title claims description 300
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000011521 glass Substances 0.000 claims description 51
- 239000000758 substrate Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 38
- -1 tetracarboxylic acid dianhydride Chemical class 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 21
- 150000004985 diamines Chemical class 0.000 claims description 16
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 10
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003475 lamination Methods 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 132
- 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 20
- 238000010438 heat treatment Methods 0.000 description 17
- 239000002253 acid Substances 0.000 description 13
- 229920005575 poly(amic acid) Polymers 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004952 Polyamide Substances 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229920002647 polyamide Polymers 0.000 description 8
- 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 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 description 4
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012024 dehydrating agents Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 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
- 230000008859 change Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- FQYTUPYMTLWOOF-UHFFFAOYSA-N 1,3,4,6-tetramethylcyclohex-4-ene-1,3-diamine Chemical compound CC1C=C(C)C(C)(N)CC1(C)N FQYTUPYMTLWOOF-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 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 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- CEQNIRIQYOUDCF-UHFFFAOYSA-N 2,5-bis(trifluoromethyl)benzene-1,4-diamine Chemical compound NC1=CC(C(F)(F)F)=C(N)C=C1C(F)(F)F CEQNIRIQYOUDCF-UHFFFAOYSA-N 0.000 description 2
- 229940075142 2,5-diaminotoluene Drugs 0.000 description 2
- BWAPJIHJXDYDPW-UHFFFAOYSA-N 2,5-dimethyl-p-phenylenediamine Chemical compound CC1=CC(N)=C(C)C=C1N BWAPJIHJXDYDPW-UHFFFAOYSA-N 0.000 description 2
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 description 2
- ZQQOGBKIFPCFMJ-UHFFFAOYSA-N 2-(trifluoromethyl)benzene-1,4-diamine Chemical compound NC1=CC=C(N)C(C(F)(F)F)=C1 ZQQOGBKIFPCFMJ-UHFFFAOYSA-N 0.000 description 2
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical compound C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 2
- HGUYBLVGLMAUFF-UHFFFAOYSA-N 2-methoxybenzene-1,4-diamine Chemical compound COC1=CC(N)=CC=C1N HGUYBLVGLMAUFF-UHFFFAOYSA-N 0.000 description 2
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 2
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 2
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 2
- BDSPLIQKGRTNCG-UHFFFAOYSA-N 3,4-dimethylcyclohexa-1,5-diene-1,3-diamine Chemical group CC1C=CC(N)=CC1(C)N BDSPLIQKGRTNCG-UHFFFAOYSA-N 0.000 description 2
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-UHFFFAOYSA-N 0.000 description 2
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 2
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 2
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 2
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- FWOLORXQTIGHFX-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluoroaniline Chemical compound FC1=C(F)C(N)=C(F)C(F)=C1C1=C(F)C(F)=C(N)C(F)=C1F FWOLORXQTIGHFX-UHFFFAOYSA-N 0.000 description 2
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 2
- OMHOXRVODFQGCA-UHFFFAOYSA-N 4-[(4-amino-3,5-dimethylphenyl)methyl]-2,6-dimethylaniline Chemical compound CC1=C(N)C(C)=CC(CC=2C=C(C)C(N)=C(C)C=2)=C1 OMHOXRVODFQGCA-UHFFFAOYSA-N 0.000 description 2
- CBEVWPCAHIAUOD-UHFFFAOYSA-N 4-[(4-amino-3-ethylphenyl)methyl]-2-ethylaniline Chemical compound C1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=CC=2)=C1 CBEVWPCAHIAUOD-UHFFFAOYSA-N 0.000 description 2
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 2
- QBSMHWVGUPQNJJ-UHFFFAOYSA-N 4-[4-(4-aminophenyl)phenyl]aniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(C=2C=CC(N)=CC=2)C=C1 QBSMHWVGUPQNJJ-UHFFFAOYSA-N 0.000 description 2
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 2
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 2
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PJWQLRKRVISYPL-UHFFFAOYSA-N 4-[4-amino-3-(trifluoromethyl)phenyl]-2-(trifluoromethyl)aniline Chemical compound C1=C(C(F)(F)F)C(N)=CC=C1C1=CC=C(N)C(C(F)(F)F)=C1 PJWQLRKRVISYPL-UHFFFAOYSA-N 0.000 description 2
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 2
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 2
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 2
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005224 laser annealing Methods 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 2
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- ZFYCTASOLWEMCR-UHFFFAOYSA-N 1,3-dihydro-2-benzofuran-5-carboxamide Chemical compound NC(=O)C1=CC=C2COCC2=C1 ZFYCTASOLWEMCR-UHFFFAOYSA-N 0.000 description 1
- NMFFQLHSHIUFEZ-UHFFFAOYSA-N 1,3-dioxo-2-benzofuran-5-carboxamide Chemical compound NC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NMFFQLHSHIUFEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- FNJFWOJEIGPYAS-UHFFFAOYSA-N 4-[4-(9h-fluoren-1-yl)phenoxy]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C=2C3=C(C4=CC=CC=C4C3)C=CC=2)C=C1 FNJFWOJEIGPYAS-UHFFFAOYSA-N 0.000 description 1
- IXLCLXDFIPWZOF-UHFFFAOYSA-N 4-[9-(3,4-dicarboxyphenyl)fluoren-9-yl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1(C=2C=C(C(C(O)=O)=CC=2)C(O)=O)C2=CC=CC=C2C2=CC=CC=C21 IXLCLXDFIPWZOF-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
- FMACFWAQBPYRFO-UHFFFAOYSA-N 5-[9-(1,3-dioxo-2-benzofuran-5-yl)fluoren-9-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 FMACFWAQBPYRFO-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000006358 imidation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- JRDBISOHUUQXHE-UHFFFAOYSA-N pyridine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)N=C1C(O)=O JRDBISOHUUQXHE-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
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- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、ポリイミド積層体、電子デバイス、および電子デバイスの製造方法に関する。 The present invention relates to a polyimide laminate, an electronic device, and a method of manufacturing the electronic device.
近年、ディスプレイをはじめとする電子デバイスのフィルム上への形成が望まれている。従来のガラス基板上に用いた電子デバイスをフィルム上に形成することができれば、軽量化やフレキシブル化が可能となり、新たな用途に用いることができる様になる。例えば、有機ＥＬ表示素子や液晶表示素子などは一般的にガラス基板上に形成されているが、ガラス基板の代替材料としてフィルムを用いることでフレキシブルディスプレイを作ることが可能となり、軽量化とともに曲面上に表示できるデバイスが作製可能となる。その他、センサー、電池、太陽電池、トランジスタ、アクチュエーターなどの分野においてもフレキシブル化が望まれている。 In recent years, the formation of electronic devices such as displays on films has been desired. If an electronic device used on a conventional glass substrate can be formed on a film, weight reduction and flexibility can be achieved, and it can be used for new applications. For example, organic EL display elements and liquid crystal display elements are generally formed on a glass substrate, but it becomes possible to make a flexible display by using a film as a substitute material for a glass substrate, and on a curved surface along with weight reduction Devices that can be displayed on In addition, in the fields of sensors, batteries, solar cells, transistors, actuators, etc., it is also desired to be flexible.
ガラス代替となるフィルム材料としては、耐熱性、熱寸法安定性、透明性に優れるポリイミドが有用であると考えられている。一般的にポリイミドフィルムの耐熱温度は３００℃以上であり、シリコン系半導体における高温の製造プロセスに耐えうる。また、熱膨張係数が低く、高温に加熱された際の位置ずれが小さい等の特徴があり微細加工を必要とする電子デバイスの作製に於いては最も好ましいフィルムと考えられている。現在、ポリイミドを用いたフレキシブルデバイスにおいては、ガラス基板上にポリイミドフィルムを製膜し、その上に薄膜トランジスタや表示素子など全てを形成し、最後にガラス基板からポリイミドを剥離する方法が用いられている。その中でもフィルムディスプレイではＥＰＬａＲ法（基板側からレーザーを照射することによって剥離する方法）が主流として用いられているが、装置導入のコストが高く、尚且つ歩留まりが低いことが問題となっている。その為、装置の導入コストが安く、歩留りの高いポリイミドフィルムを基材とする電子デバイス（ポリイミド積層電子デバイス）の作製方法が望まれている。 As a film material to be a glass substitute, it is considered that a polyimide excellent in heat resistance, thermal dimensional stability, and transparency is useful. In general, the heat resistance temperature of the polyimide film is 300 ° C. or higher, and it can withstand the high temperature manufacturing process of a silicon-based semiconductor. In addition, it is considered to be the most preferable film in the production of an electronic device which has a low thermal expansion coefficient, a small positional deviation when heated to a high temperature, and the like and requires fine processing. Currently, in flexible devices using polyimide, a method is used in which a polyimide film is formed on a glass substrate, all thin film transistors, display elements, etc. are formed thereon, and finally the polyimide is peeled off from the glass substrate . Among them, the EPLaR method (a method of peeling by irradiating a laser from the substrate side) is mainly used as a film display, but the problem is that the cost for introducing the device is high and the yield is low. Therefore, there is a demand for a method for producing an electronic device (polyimide laminated electronic device) using a polyimide film as a substrate, which has a low introduction cost and high yield.
特許文献１においては、支持基材の上に形成したポリイミドフィルム積層体が剥離可能となるポリイミド積層体構造及びその製造方法についての記載がある。 In patent document 1, there is a description about the polyimide laminated body structure where the polyimide film laminated body formed on the support base material can peel, and its manufacturing method.
従来のポリイミドフィルムを基材とした電子デバイスの製造方法においては、上記の通りコストおよび歩留まりの点で問題がある。 In the conventional method for producing an electronic device based on polyimide film, there are problems in cost and yield as described above.
特許文献１に記載された技術は柔軟な支持基材を用いているため、表面に微細加工が必要な表示デバイスを形成する際に高温に加熱されると寸法変化が起き易く微細加工が難しい問題があり、更には、電子デバイスを形成後にポリイミドフィルムを具体的に剥離する方法の記載が無く剥離の際に応力等が発生して電子デバイスの破壊等が生じると考えられる。 Since the technology described in Patent Document 1 uses a flexible supporting substrate, when it is heated to a high temperature when forming a display device requiring microfabrication on the surface, dimensional change is likely to occur and micromachining is difficult. Furthermore, there is no description of a method for specifically peeling the polyimide film after forming the electronic device, and it is considered that stress or the like is generated at the time of peeling to cause destruction or the like of the electronic device.
すなわち、本発明の要旨は以下の通りである。 That is, the gist of the present invention is as follows.
１．ガラス基板、第１ポリイミド層、第２ポリイミド層の順に積層されているポリイミド積層体において、
前記第１ポリイミド層は、前記第２ポリイミド層と異なる組成のポリイミドから成り、前記第１ポリイミド層と前記第２ポリイミド層の間の剥離強度は、前記ガラス基板と前記第１ポリイミド層の間の剥離強度よりも弱いことを特徴とするポリイミド積層体。
1. In a polyimide laminate in which a glass substrate, a first polyimide layer, and a second polyimide layer are laminated in this order,
The first polyimide layer is made of polyimide different in composition from the second polyimide layer, and the peel strength between the first polyimide layer and the second polyimide layer is determined between the glass substrate and the first polyimide layer. A polyimide laminate characterized by being weaker than peel strength.
２．前記ガラス基板、前記第２ポリイミド層、前記第１ポリイミド層の順に熱膨張係数が大きい前記１に記載のポリイミド積層体。 2. The polyimide laminate according to the above 1, wherein the thermal expansion coefficient is large in the order of the glass substrate, the second polyimide layer, and the first polyimide layer.
３．前記第１ポリイミド層は、テトラカルボン酸二無水物とジアミンとを反応させて得られ、前記テトラカルボン酸二無水物は、ピロメリット酸無水物を含み、前記ジアミンは、ジアミノジフェニルエーテルを含む前記１または２に記載のポリイミド積層体。 3. The first polyimide layer is obtained by reacting tetracarboxylic acid dianhydride with diamine, and the tetracarboxylic acid dianhydride contains pyromellitic anhydride, and the diamine contains diaminodiphenyl ether. Or the polyimide laminated body as described in 2.
４．電子デバイスが前記第２ポリイミド層上に積層されている前記１〜３のいずれか１つに記載のポリイミド積層体。 4. 5. The polyimide laminate according to any one of the above 1 to 3, wherein an electronic device is laminated on the second polyimide layer.
５．前記４記載の電子デバイスを積層してなるポリイミド積層体を第１ポリイミド層から剥離したポリイミド積層電子デバイス。 5. The polyimide laminated electronic device which peeled the polyimide laminated body formed by laminating | stacking the electronic device of said 4 from the 1st polyimide layer.
６．第１ポリイミド溶液又は第１ポリイミド前駆体溶液をガラス基板上に塗布して第１ポリイミド層を形成し、第２ポリイミド溶液又は第２ポリイミド前駆体溶液を前記第１ポリイミド層上に塗布して第２ポリイミド層を形成し、電子デバイスを前記第２のポリイミド層上に形成し、前記第２ポリイミド層を前記第１ポリイミド層から剥離させるポリイミド積層電子デバイスの製造方法であって、前記第１ポリイミド溶液又は第１ポリイミド前駆体溶液は、前記第２ポリイミド溶液又は第２ポリイミド前駆体溶液と異なる組成のポリイミド溶液又は前駆体溶液であることを特徴とするポリイミド積層電子デバイスの製造方法。 6. A first polyimide solution or a first polyimide precursor solution is coated on a glass substrate to form a first polyimide layer, and a second polyimide solution or a second polyimide precursor solution is coated on the first polyimide layer to form a first polyimide layer. 2. A method for producing a polyimide laminated electronic device, comprising: forming a polyimide layer; forming an electronic device on the second polyimide layer; and peeling the second polyimide layer from the first polyimide layer, the first polyimide A method for producing a polyimide laminated electronic device, wherein the solution or the first polyimide precursor solution is a polyimide solution or a precursor solution having a composition different from that of the second polyimide solution or the second polyimide precursor solution.
７．前記第１ポリイミド層と前記第２ポリイミド層の間の剥離強度は、前記ガラス基板と前記第１ポリイミド層の間の剥離強度よりも弱い前記６に記載のポリイミド積層電子デバイスの製造方法。 7. The method for producing a polyimide laminated electronic device according to the above 6, wherein the peel strength between the first polyimide layer and the second polyimide layer is weaker than the peel strength between the glass substrate and the first polyimide layer.
８．前記ガラス基板、前記第２ポリイミド層、前記第１ポリイミド層の順に熱膨張係数が大きい前記６または７に記載のポリイミド積層電子デバイスの製造方法。 8. The method for producing a polyimide laminated electronic device according to 6 or 7, wherein the thermal expansion coefficient is large in the order of the glass substrate, the second polyimide layer, and the first polyimide layer.
９．前記第１ポリイミド層は、テトラカルボン酸二無水物とジアミンとを反応させて得られ、前記テトラカルボン酸二無水物は、ピロメリット酸無水物を含み、前記ジアミンは、ジアミノジフェニルエーテルを含む前記６〜８のいずれか１つに記載のポリイミド積層電子デバイスの製造方法。 9. The first polyimide layer is obtained by reacting tetracarboxylic acid dianhydride with diamine, the tetracarboxylic acid dianhydride containing pyromellitic anhydride, and the diamine containing diaminodiphenyl ether. The manufacturing method of the polyimide laminated electronic device as described in any one of -8.
本発明のポリイミド積層体は、ガラス基板上に形成した第１ポリイミド層とその上に形成した第２ポリイミド層からなり、熱寸法安定性に優れると共に、ポリイミド界面で簡便に剥離することが出来るため、ディスプレイ、センサー、電池、太陽電池、トランジスタ、アクチュエーター等の電子デバイスを低コストかつ歩留まり良く作製することができる。 The polyimide laminate of the present invention comprises a first polyimide layer formed on a glass substrate and a second polyimide layer formed thereon, and has excellent thermal dimensional stability and can be easily peeled off at the polyimide interface. , Electronic devices such as displays, sensors, batteries, solar cells, transistors, and actuators can be manufactured at low cost with high yield.
以下において、本発明を詳しく説明する。 The present invention will be described in detail below.
本願発明におけるポリイミド積層体の一例を図１に示す。ポリイミド積層体は、ガラス基板１、第１ポリイミド層２、第２ポリイミド層３が順に積層されている。 An example of the polyimide laminated body in this invention is shown in FIG. In the polyimide laminate, a glass substrate 1, a first polyimide layer 2, and a second polyimide layer 3 are sequentially laminated.
本発明におけるガラス基板は、ソーダライムガラス、ホウ珪酸ガラス、無アルカリガラスを用いることができる。特に、無アルカリガラスは不純物が少なく、熱膨張係数が小さい為、寸法安定性が高い点で好ましい。 As the glass substrate in the present invention, soda lime glass, borosilicate glass and alkali-free glass can be used. In particular, non-alkali glass is preferable from the viewpoint of high dimensional stability because it has few impurities and a small thermal expansion coefficient.
本願発明における第１ポリイミド層とは、テトラカルボン酸二無水物とジアミンとを反応させて得られるポリイミドである。 The first polyimide layer in the present invention is a polyimide obtained by reacting tetracarboxylic acid dianhydride with diamine.
使用するテトラカルボン酸二無水物は特に限定されないが、ピロメリット酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物、９，９−ビス（３，４−ジカルボキシフェニル）フルオレン二無水物、９，９’−ビス［４−（３，４−ジカルボキシフェノキシ）フェニル］フルオレン二無水物、３，３’，４，４’−ビフェニルエーテルテトラカルボン酸二無水物、２，３，５，６−ピリジンテトラカルボン酸二無水物、３，４，９，１０−ペリレンテトラカルボン酸二無水物、４，４’−スルホニルジフタル酸二無水物、パラテルフェニル−３，４，３’，４’−テトラカルボン酸二無水物、メタテルフェニル−３，３’，４，４’−テトラカルボン酸二無水物、３，３’，４，４’−ジフェニルエーテルテトラカルボン酸二無水物、４，４‘−（ヘキサフルオロイソプロピリデン）ジフタル酸無水物等が好適に用いることができる。これらのテトラカルボン酸二無水物は１種類のみ用いても良く、２種類以上用いても良い。第１ポリイミド層のポリイミドは、密着強度や熱膨張係数を制御しやすい構造であるピロメリット酸無水物を用いることが特に好ましい。 The tetracarboxylic acid dianhydride to be used is not particularly limited, but pyromellitic acid dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyl Tetracarboxylic acid dianhydride, 3,3 ′, 4,4′-diphenyl sulfone tetracarboxylic acid dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9′- Bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic acid dianhydride, 2,3,5,6-pyridine tetracarboxylic acid Acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 4,4'-sulfonyldiphthalic acid dianhydride, paraterphenyl-3,4,3 ', 4'-tetracarbonide acid Anhydride, metaterphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride, 4,4 ′-(hexafluoro) Isopropylidene) diphthalic anhydride and the like can be suitably used. These tetracarboxylic dianhydrides may be used alone or in combination of two or more. As the polyimide of the first polyimide layer, it is particularly preferable to use pyromellitic anhydride which is a structure that can easily control the adhesion strength and the thermal expansion coefficient.
第１ポリイミド層のポリイミドに使用するジアミンについても特に限定されないが、ｐ−フェニレンジアミン、２−メチル−１，４−フェニレンジアミン、２−トリフルオロメチル−１，４−フェニレンジアミン、２−メトキシ−１，４−フェニレンジアミン、２，５−ジメチル−１，４−フェニレンジアミン、２，５−ビス（トリフルオロメチル）−１，４−フェニレンジアミン、ｍ−フェニレンジアミン、２，４−ジアミノトルエン、２，５−ジアミノトルエン、２，４−ジアミノキシレン、２，４−ジアミノデュレン、４，４’−ジアミノジフェニルメタン、４，４’−メチレンビス（２−メチルアニリン）、４，４’−メチレンビス（２−エチルアニリン）、４，４’−メチレンビス（２，６−ジメチルアニリン）、４，４’−メチレンビス（２，６−ジエチルアニリン）、４，４’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルエーテル、３，３’−ジアミノジフェニルエーテル、２，４’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルスルホン、３，３’−ジアミノジフェニルスルホン、４，４’−ジアミノベンゾフェノン、３，３’−ジアミノベンゾフェノン、４，４’−ジアミノベンズアニリド、ベンジジン、３，３’−ジヒドロキシベンジジン、３，３’−ジメトキシベンジジン、３，３’−ジクロロベンジジン、ｏ−トリジン、ｍ−トリジン、２，２’−ビス（トリフルオロメチル）ベンジジン、３，３’−ビス（トリフルオロメチル）ベンジジン、オクタフルオロベンジジン、３，３’，５，５’−テトラメチルベンジジン、２，２’，５，５’−テトラクロロベンジジン、１，４−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（３−アミノフェノキシ）ベンゼン、４，４’−ビス（４−アミノフェノキシ）ビフェニル、ビス（４−（３−アミノフェノキシ)フェニル）スルホン、ビス（４−（４−アミノフェノキシ)フェニル）スルホン、２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパン、２，２−ビス（４−（４−アミノフェノキシ）フェニル）ヘキサフルオロプロパン、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン、ｐ−ターフェニレンジアミン、２，２’−ビス（トリフルオロメチル）ベンジジン等が好適に用いることができる。これらは１種類のみ用いても良く、２種類以上用いても良い。第１ポリイミド層のポリイミドは、密着強度や熱膨張係数を制御しやすい構造であるジアミノジフェニルエーテルを用いることが特に好ましい。 The diamine used for the polyimide of the first polyimide layer is also not particularly limited, but p-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2-trifluoromethyl-1,4-phenylenediamine, 2-methoxy- 1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,5-bis (trifluoromethyl) -1,4-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,4-diaminodurene, 4,4'-diaminodiphenylmethane, 4,4'-methylenebis (2-methylaniline), 4,4'-methylenebis (2 -Ethylaniline), 4,4'-methylenebis (2,6-dimethylaniline), 4,4'-methyl Bis (2,6-diethylaniline), 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 2,4'-diaminodiphenylether, 4,4'-diaminodiphenylsulfone 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzanilide, benzidine, 3,3'-dihydroxybenzidine, 3,3'- Dimethoxybenzidine, 3,3'-dichlorobenzidine, o-tolidine, m-tolidine, 2,2'-bis (trifluoromethyl) benzidine, 3,3'-bis (trifluoromethyl) benzidine, octafluorobenzidine, 3 , 3 ', 5,5'-Tetramethylbenzidine 2,2 ', 5,5'-tetrachlorobenzidine, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-amino) Phenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, 2,2- Bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, p -Terphenylene diamine, 2,2'-bis (trifluoromethyl) benzidine etc. can be used suitably. These may be used alone or in combination of two or more. As the polyimide of the first polyimide layer, it is particularly preferable to use diaminodiphenyl ether, which is a structure that facilitates control of adhesion strength and thermal expansion coefficient.
第１ポリイミド層は、ポリイミド溶液又は前駆体であるポリアミド酸溶液から形成される。塗布した溶液がポリイミド前駆体であるポリアミド酸の場合、イミド化する方法は特に限定はされないが、熱イミド化や、脱水剤とイミド化剤を用いる化学イミド化などを用いることができる。化学イミド化を行う場合、イミド化剤としては、特に限定されないが、３級アミンを用いることができる。脱水剤としては具体的には無水酢酸、プロピオン酸無水物、ｎ−酪酸無水物、安息香酸無水物、トリフルオロ酢酸無水物等を具体例として挙げることができる。 The first polyimide layer is formed of a polyimide solution or a polyamide acid solution which is a precursor. When the solution applied is a polyamic acid which is a polyimide precursor, the method of imidization is not particularly limited, but thermal imidization, chemical imidization using a dehydrating agent and an imidizing agent, or the like can be used. When chemical imidization is performed, the imidization agent is not particularly limited, but tertiary amines can be used. Specific examples of the dehydrating agent include acetic anhydride, propionic acid anhydride, n-butyric acid anhydride, benzoic acid anhydride, trifluoroacetic acid anhydride and the like.
第１ポリイミド層は、ポリイミド溶液または前駆体溶液はスリットコーターやスピンコーターを用いた方法、キャスト法などによりガラス基板上に塗布し、ホットプレートやオーブンなどを用いて乾燥することで第１ポリイミド層が得られる。 The first polyimide layer is formed by applying a polyimide solution or a precursor solution on a glass substrate by a method using a slit coater or a spin coater, a cast method or the like, and drying using a hot plate or an oven. Is obtained.
本願発明における第２ポリイミド層とは、テトラカルボン酸二無水物とジアミンとを反応させて得られるポリイミドである。 The second polyimide layer in the present invention is a polyimide obtained by reacting tetracarboxylic acid dianhydride with diamine.
使用するテトラカルボン酸二無水物は特に限定されないが、ピロメリット酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物、１，４，５，８−ナフタレンテトラカルボン酸二無水物、２，３，６，７−ナフタレンテトラカルボン酸二無水物、１，２，５，６−ナフタレンテトラカルボン酸二無水物、４，４’−オキシジフタル酸無水物、９，９−ビス（３，４−ジカルボキシフェニル）フルオレン二無水物、９，９’−ビス［４−（３，４−ジカルボキシフェノキシ）フェニル］フルオレン二無水物、３，３’，４，４’−ビフェニルエーテルテトラカルボン酸二無水物、２，３，５，６−ピリジンテトラカルボン酸二無水物、３，４，９，１０−ペリレンテトラカルボン酸二無水物、４，４’−スルホニルジフタル酸二無水物、パラテルフェニル−３，４，３’，４’−テトラカルボン酸二無水物、メタテルフェニル−３，３’，４，４’−テトラカルボン酸二無水物、３，３’，４，４’−ジフェニルエーテルテトラカルボン酸二無水物、４，４‘−（ヘキサフルオロイソプロピリデン）ジフタル酸無水物、Ｎ，Ｎ’−［２，２’−ビス（トリフルオロメチル）ビフェニル−４，４’−ジイル］ビス（１，３−ジオキソ−１，３−ジヒドロイソベンゾフラン−５−カルボキサミド）等が挙げられる。これらは１種類のみ用いても良く、２種類以上用いても良い。 The tetracarboxylic acid dianhydride to be used is not particularly limited, but pyromellitic acid dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyl Tetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7- Naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic anhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene 2 Anhydride, 9,9'-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic acid dianhydride, 2,3 5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 4,4'-sulfonyldiphthalic acid dianhydride, paraterphenyl-3,4,3 ', 4'-tetracarboxylic acid dianhydride, metaterphenyl-3,3', 4,4'-tetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenylethertetracarboxylic acid dianhydride 4,4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, N, N'-[2,2'-bis (trifluoromethyl) biphenyl-4,4'-diyl] bis (1,3-dioxo) And 1,3-dihydroisobenzofuran-5-carboxamide and the like. These may be used alone or in combination of two or more.
第２ポリイミド層のポリイミドは熱膨張係数が低く寸法安定性に優れ、密着強度が低くなるポリイミドであることが好ましく、そのようなポリイミドを得る為には、テトラカルボン酸二無水物として、ピロメリット酸無水物、３，３’，４，４’−ビフェニルテトラカルボン酸ニ無水物、Ｎ，Ｎ’−［２，２’−ビス（トリフルオロメチル）ビフェニル−４，４’−ジイル］ビス（１，３−ジオキソ−１，３−ジヒドロイソベンゾフラン−５−カルボキサミド）、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物を用いることが好ましい。 The polyimide of the second polyimide layer is preferably a polyimide having a low thermal expansion coefficient and excellent dimensional stability and a low adhesion strength. In order to obtain such a polyimide, pyromellitic acid is used as a tetracarboxylic acid dianhydride. Acid anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride, N, N ′-[2,2′-bis (trifluoromethyl) biphenyl-4,4′-diyl] bis ( It is preferred to use 1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide), 3,3 ′, 4,4′-benzophenonetetracarboxylic acid dianhydride.
第２ポリイミド層のポリイミドに使用するジアミンについても特に限定されないが、ｐ−フェニレンジアミン、２−メチル−１，４−フェニレンジアミン、２−トリフルオロメチル−１，４−フェニレンジアミン、２−メトキシ−１，４−フェニレンジアミン、２，５−ジメチル−１，４−フェニレンジアミン、２，５−ビス（トリフルオロメチル）−１，４−フェニレンジアミン、ｍ−フェニレンジアミン、２，４−ジアミノトルエン、２，５−ジアミノトルエン、２，４−ジアミノキシレン、２，４−ジアミノデュレン、４，４’−ジアミノジフェニルメタン、４，４’−メチレンビス（２−メチルアニリン）、４，４’−メチレンビス（２−エチルアニリン）、４，４’−メチレンビス（２，６−ジメチルアニリン）、４，４’−メチレンビス（２，６−ジエチルアニリン）、４，４’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルエーテル、３，３’−ジアミノジフェニルエーテル、２，４’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルスルホン、３，３’−ジアミノジフェニルスルホン、４，４’−ジアミノベンゾフェノン、３，３’−ジアミノベンゾフェノン、４，４’−ジアミノベンズアニリド、ベンジジン、３，３’−ジヒドロキシベンジジン、３，３’−ジメトキシベンジジン、３，３’−ジクロロベンジジン、ｏ−トリジン、ｍ−トリジン、２，２’−ビス（トリフルオロメチル）ベンジジン、３，３’−ビス（トリフルオロメチル）ベンジジン、オクタフルオロベンジジン、３，３’，５，５’−テトラメチルベンジジン、２，２’，５，５’−テトラクロロベンジジン、１，４−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（３−アミノフェノキシ）ベンゼン、４，４’−ビス（４−アミノフェノキシ）ビフェニル、ビス（４−（３−アミノフェノキシ)フェニル）スルホン、ビス（４−（４−アミノフェノキシ)フェニル）スルホン、２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパン、２，２−ビス（４−（４−アミノフェノキシ）フェニル）ヘキサフルオロプロパン、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン、ｐ−ターフェニレンジアミン、２，２’−ビス（トリフルオロメチル）ベンジジン等が挙げられる。これらは１種類のみ用いても良く、２種類以上用いても良い。 The diamine used for the polyimide of the second polyimide layer is also not particularly limited, but p-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2-trifluoromethyl-1,4-phenylenediamine, 2-methoxy- 1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,5-bis (trifluoromethyl) -1,4-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,4-diaminodurene, 4,4'-diaminodiphenylmethane, 4,4'-methylenebis (2-methylaniline), 4,4'-methylenebis (2 -Ethylaniline), 4,4'-methylenebis (2,6-dimethylaniline), 4,4'-methyl Bis (2,6-diethylaniline), 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 2,4'-diaminodiphenylether, 4,4'-diaminodiphenylsulfone 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzanilide, benzidine, 3,3'-dihydroxybenzidine, 3,3'- Dimethoxybenzidine, 3,3'-dichlorobenzidine, o-tolidine, m-tolidine, 2,2'-bis (trifluoromethyl) benzidine, 3,3'-bis (trifluoromethyl) benzidine, octafluorobenzidine, 3 , 3 ', 5,5'-Tetramethylbenzidine 2,2 ', 5,5'-tetrachlorobenzidine, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-amino) Phenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, 2,2- Bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, p -Terphenylene diamine, 2,2'-bis (trifluoromethyl) benzidine etc. are mentioned. These may be used alone or in combination of two or more.
第２ポリイミド層のポリイミドは熱膨張係数が低く寸法安定性に優れ、密着強度が低くなるポリイミドであることが好ましく、そのようなポリイミドを得る為には、ジアミンとして、ｐ−フェニレンジアミン、ジアミノジフェニルエーテル、２，２’−ビス（トリフルオロメチル）ベンジジン等を用いることが好ましい。
第２ポリイミド層は、ポリイミド溶液又は前駆体であるポリアミド酸溶液から形成される。塗布した溶液がポリイミド前駆体であるポリアミド酸の場合、イミド化する方法は特に限定はされないが、熱イミド化や、脱水剤とイミド化剤を用いる化学イミド化などを用いることができる。化学イミド化を行う場合、イミド化剤としては、特に限定されないが、３級アミンを用いることができる。脱水剤としては具体的には無水酢酸、プロピオン酸無水物、ｎ−酪酸無水物、安息香酸無水物、トリフルオロ酢酸無水物等を具体例として挙げることができる。
The polyimide of the second polyimide layer is preferably a polyimide having a low thermal expansion coefficient and excellent dimensional stability and a low adhesion strength. In order to obtain such a polyimide, p-phenylenediamine, diaminodiphenylether as a diamine is preferable. It is preferable to use 2,2,2'-bis (trifluoromethyl) benzidine and the like.
The second polyimide layer is formed of a polyimide solution or a polyamide acid solution which is a precursor. When the solution applied is a polyamic acid which is a polyimide precursor, the method of imidization is not particularly limited, but thermal imidization, chemical imidization using a dehydrating agent and an imidizing agent, or the like can be used. When chemical imidization is performed, the imidization agent is not particularly limited, but tertiary amines can be used. Specific examples of the dehydrating agent include acetic anhydride, propionic acid anhydride, n-butyric acid anhydride, benzoic acid anhydride, trifluoroacetic acid anhydride and the like.
第２ポリイミド層は、第１ポリイミド層と第２ポリイミド層の間の剥離強度が、ガラス基板と第１ポリイミド層の間の剥離強度よりも弱いものであれば特に限定されない。また、ガラス基板、第２ポリイミド層、第１ポリイミド層の順に熱膨張係数が大きくなる様な第２ポリイミド層が好ましい。 The second polyimide layer is not particularly limited as long as the peel strength between the first polyimide layer and the second polyimide layer is weaker than the peel strength between the glass substrate and the first polyimide layer. In addition, it is preferable to use a second polyimide layer whose thermal expansion coefficient is increased in the order of the glass substrate, the second polyimide layer, and the first polyimide layer.
第２ポリイミド層は、上記第２ポリイミド層を構成しうるポリイミド溶液又は前駆体溶液を、前記第１ポリイミド層上に、スリットコーターやスピンコーターを用いた方法や、キャスト法などによりポリイミド溶液または前駆体を塗布し、ホットプレートやオーブンなどを用いて乾燥することで第２ポリイミド層が得られる。 For the second polyimide layer, a polyimide solution or precursor solution that can constitute the second polyimide layer is formed on the first polyimide layer by a method using a slit coater or a spin coater, or by a cast method or the like. The second polyimide layer is obtained by applying a body and drying using a hot plate, an oven or the like.
本発明における積層体を形成する第１、第２のポリイミド層の厚みは１μｍ〜２００μｍが好ましく、特に好ましくは、３μｍ〜１００μｍの範囲であることがポリイミドにより発生する応力を下げることができ、ガラス基材の反りを低減でき、残留応力により自然にポリイミド層が剥離することを避けることができるので好ましい。 The thickness of the first and second polyimide layers forming the laminate in the present invention is preferably 1 μm to 200 μm, and particularly preferably in the range of 3 μm to 100 μm because stress generated by the polyimide can be reduced, and glass It is preferable because warpage of the substrate can be reduced, and peeling of the polyimide layer spontaneously due to residual stress can be avoided.
本発明における第１ポリイミド層と第２ポリイミド層が異なるとは、具体的にはポリイミドを構成する酸二無水物並びに、ジアミンが、第１並びに、第２ポリイミドにおいて、同一種を同一割合で用いているポリイミドで無い場合を指す。 Specifically, in the present invention, the first polyimide layer and the second polyimide layer are different from each other. Specifically, the acid dianhydride constituting the polyimide and the diamine use the same species in the same proportion in the first and second polyimides. Refers to the case where it is not polyimide.
本発明における、前記第１ポリイミド層と前記第２ポリイミド層の間の剥離強度は、前記ガラス基板と前記第１ポリイミド層の間の剥離強度よりも弱いことが好ましく、特に、剥離強度は、ＪＩＳ０２３７の方法に基づく９０°方向の剥離強度を測定した場合において、第１ポリイミド層と第２ポリイミド層の間の剥離強度は、０．０１Ｎ／ｃｍ以上、０．２５Ｎ／ｃｍ以下が好ましく、０．０１Ｎ／ｃｍ以上、０．２０Ｎ／ｃｍ以下であることが剥離する際に電子デバイス等に影響を与えず良好に剥離できるので特に好ましい。 In the present invention, the peel strength between the first polyimide layer and the second polyimide layer is preferably weaker than the peel strength between the glass substrate and the first polyimide layer, and in particular, the peel strength is JIS JIS 0237. The peel strength between the first polyimide layer and the second polyimide layer is preferably 0.01 N / cm or more and 0.25 N / cm or less, and the peel strength between the first polyimide layer and the second polyimide layer is preferably 0. It is particularly preferable that the pressure is not less than 01 N / cm and not more than 0.20 N / cm because the electronic device can be favorably peeled without affecting the electronic device or the like.
また、ガラス基板と第１ポリイミド層の間の剥離強度は、第１のポリイミド層と第２のポリイミド層の密着強度より大きければ特に指定されないが、０．２５Ｎ／ｃｍ以上であることが好ましく、特に好ましくは０．４０Ｎ／ｃｍ以上があることが積層体製造プロセスにおいて剥離が生じにくいため好ましい。このような密着力を達成するために、第１ポリイミド層を構成するポリイミドには、シランカップリング剤を含有していても良い。シランカップリング剤は特に限定されないが、例えば、３−アミノプロピルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシランなどが好適に用いることができる。 The peel strength between the glass substrate and the first polyimide layer is not particularly specified as long as it is greater than the adhesion strength between the first polyimide layer and the second polyimide layer, but is preferably 0.25 N / cm or more. In particular, it is preferable to have 0.40 N / cm or more because peeling is less likely to occur in the laminate manufacturing process. In order to achieve such adhesion, the polyimide constituting the first polyimide layer may contain a silane coupling agent. Although a silane coupling agent is not specifically limited, For example, 3-aminopropyl trimethoxysilane, 3-glycidoxy propyl trimethoxysilane, etc. can be used suitably.
本発明における熱膨張係数はガラス基板、第２ポリイミド層、第１ポリイミド層の順に大きいことが好ましい。この様な順序で熱膨膨張係数が大きい場合、第１ポリイミド層と第２ポリイミド層界面に赤外線照射や加熱を行った際に、僅かな応力が生じ、剥離を容易にする。 The thermal expansion coefficient in the present invention is preferably larger in the order of the glass substrate, the second polyimide layer, and the first polyimide layer. When the thermal expansion coefficient is large in this order, a slight stress is generated when infrared radiation or heating is performed on the interface between the first polyimide layer and the second polyimide layer, which facilitates peeling.
本願発明における第１ポリイミド層の熱膨張係数は、第２ポリイミド層の熱膨張係数より大きければ特に限定されないが１０〜６０ｐｐｍ／Ｋであることが好ましく、特に好ましくは、２５〜６０ｐｐｍ／Ｋである。 The thermal expansion coefficient of the first polyimide layer in the present invention is not particularly limited as long as it is larger than the thermal expansion coefficient of the second polyimide layer, but it is preferably 10 to 60 ppm / K, particularly preferably 25 to 60 ppm / K. .
第２ポリイミド層の熱膨張係数は第１ポリイミド層の熱膨張係数より小さければ特に限定されないが、１〜２５ｐｐｍ／Ｋであることが好ましく、第２ポリイミド層の上にデバイスを形成する際に位置ずれが小さくなるといった点から、１〜２０ｐｐｍ／Ｋであることが特に好ましい。 The thermal expansion coefficient of the second polyimide layer is not particularly limited as long as it is smaller than the thermal expansion coefficient of the first polyimide layer, but is preferably 1 to 25 ppm / K, and is preferably located when forming a device on the second polyimide layer It is particularly preferable that the amount is 1 to 20 ppm / K, in order to reduce the deviation.
このような熱膨張係数に制御することで、第１ポリイミド層と第２ポリイミド層を剥離する際に応力が生じるために好ましい。 By controlling to such a thermal expansion coefficient, since a stress arises when peeling a 1st polyimide layer and a 2nd polyimide layer, it is preferable.
本発明においては、特に、第1ポリイミド層が、ピロメリット酸二無水物とジアミノジフェニルエーテルからなるポリイミドであることが好ましく、このポリイミドを用いることで、熱膨張係数を最適な値に制御できると共に、ガラスとの密着力を向上させることが出来るので好ましい。 In the present invention, in particular, the first polyimide layer is preferably a polyimide composed of pyromellitic dianhydride and diaminodiphenyl ether. By using this polyimide, the thermal expansion coefficient can be controlled to an optimum value, It is preferable because the adhesion to glass can be improved.
ポリイミド積層体からポリイミドフィルムを剥離する方法を図２に示す。本発明における第１ポリイミド層１２と第２ポリイミド層１３の剥離方法は特に限定されないが、機械的に剥離する方法もしくは、ポリイミド積層体を急加熱する方法を用いることができる。特に急加熱する方法は、剥離界面に応力が生じ剥離を容易にする点で好ましい。急加熱の方法は特に限定されず、ホットプレートを用いて加熱する方法や、熱風を用いて加熱する方法、赤外線照射装置を用いて加熱する方法などが挙げられるが、フラッシュランプ等の急速加熱処理装置を用いて第１ポリイミド層１２をガラス基板１１を介して赤外線照射して急速加熱を行うことで剥離する方法が好ましく用いられる。本方法を用いることで瞬間的に第１ポリイミド層１２と第２ポリイミド層１３の界面に応力が生じ、ポリイミド界面の接着強度を急激に低下させることができるので好ましい。また本方法を用いることでポリイミドに電子デバイスを形成した後に剥離する場合においても、電子デバイスを劣化させることが無いので好ましい。 The method of peeling a polyimide film from a polyimide laminated body is shown in FIG. Although the peeling method in particular of the 1st polyimide layer 12 in the present invention and the 2nd polyimide layer 13 is not limited, a method of exfoliating mechanically or a method of rapidly heating a polyimide layered product can be used. In particular, the rapid heating method is preferable in that stress is generated at the peeling interface to facilitate peeling. The method of rapid heating is not particularly limited, and the method of heating using a hot plate, the method of heating using hot air, the method of heating using an infrared irradiation device, etc. may be mentioned. It is preferable to use a method in which the first polyimide layer 12 is exposed to infrared radiation through the glass substrate 11 using an apparatus to perform rapid heating, thereby peeling it. By using this method, a stress is generated instantaneously at the interface between the first polyimide layer 12 and the second polyimide layer 13 and the adhesive strength at the polyimide interface can be sharply reduced, which is preferable. Moreover, even when peeling after forming an electronic device to polyimide by using this method, since an electronic device is not degraded, it is preferable.
特に、本願発明において好ましく用いられるフラッシュランプ等の急速加熱処理装置は、近赤外光、中間赤外光、遠赤外光の少なくとも１つの光を含むことを特徴とする光を発生させる装置であって、特に好ましくはフラッシュランプアニール装置、赤外線ランプアニール装置、レーザーアニール装置を用いることが好ましい。本装置を用いることで、ガラス基材１１を通過させて第１ポリイミド層１２を効果的に加熱することが出来るので好ましい。 In particular, a rapid thermal processing apparatus such as a flash lamp preferably used in the present invention is an apparatus generating light characterized by containing at least one of near infrared light, mid infrared light and far infrared light. In particular, it is preferable to use a flash lamp annealing apparatus, an infrared lamp annealing apparatus, or a laser annealing apparatus. The use of this device is preferable because the first polyimide layer 12 can be effectively heated while passing through the glass substrate 11.
本発明における電子デバイスを積層したポリイミド積層体の模式図を図３に示す。ポリイミド積層体は、ガラス基板２１、第１ポリイミド層２２、第２ポリイミド層２３、電子デバイス２４が順に積層されている。尚、本発明におけるポリイミド積層電子デバイス２５の一実施形態は、第２ポリイミド層２３及び電子デバイス２４が積層された電子デバイスである。尚、第２ポリイミド層は１層であっても良いし、多層であっても良い。具体的には、第１ポリイミド溶液又は第１ポリイミド前駆体溶液をガラス基板２１上に塗布して第１ポリイミド層２２を形成し、第２ポリイミド溶液又は第２ポリイミド前駆体溶液を前記第１ポリイミド層２２上に塗布して第２ポリイミド層２３を形成し、電子デバイス２４を前記第２のポリイミド層２３上に形成し、前記第２ポリイミド層２３を前記第１ポリイミド層２２から剥離させるポリイミド積層電子デバイス２５の製造方法である。特に、本発明においては、前記第１ポリイミド溶液又は第１ポリイミド前駆体溶液は、前記第２ポリイミド溶液又は第２ポリイミド前駆体溶液と異なる組成のポリイミド溶液又は前駆体溶液であることが剥離を容易にして歩留りを向上させる上で好ましい。 The schematic diagram of the polyimide laminated body which laminated | stacked the electronic device in this invention is shown in FIG. In the polyimide laminate, a glass substrate 21, a first polyimide layer 22, a second polyimide layer 23, and an electronic device 24 are sequentially stacked. In addition, one embodiment of the polyimide laminated electronic device 25 in the present invention is an electronic device in which the second polyimide layer 23 and the electronic device 24 are laminated. The second polyimide layer may be a single layer or a multilayer. Specifically, a first polyimide solution or a first polyimide precursor solution is applied onto the glass substrate 21 to form a first polyimide layer 22, and a second polyimide solution or a second polyimide precursor solution is used as the first polyimide. The polyimide lamination is applied on the layer 22 to form a second polyimide layer 23, and the electronic device 24 is formed on the second polyimide layer 23, and the second polyimide layer 23 is peeled off from the first polyimide layer 22. This is a method of manufacturing the electronic device 25. In particular, in the present invention, the first polyimide solution or the first polyimide precursor solution is a polyimide solution or a precursor solution having a composition different from that of the second polyimide solution or the second polyimide precursor solution, so that peeling is easy. To improve the yield.
本発明における、ポリイミド積層電子デバイスの具体的な製造方法に関する模式図を図４に示す。
本方法により作製された電子デバイスは、前記第２ポリイミド層３３または第２ポリイミド層３３上に形成された電子デバイス３４を前記第１ポリイミド層３２から剥離することでポリイミド積層電子デバイス３５が得られる。ポリイミド積層電子デバイス３５を剥離させる方法については特に限定されないが、機械的に剥離する方法もしくは、ポリイミド積層体を急加熱する方法を用いることができる。特に急加熱する方法は、剥離界面に応力が生じ剥離を容易にする点で好ましい。急加熱の方法は特に限定されず、ホットプレートを用いて加熱する方法や、熱風を用いて加熱する方法、赤外線照射装置を用いて加熱する方法などが挙げられるが、フラッシュランプ等の急速加熱処理装置を用いて第１ポリイミド層３２をガラス基板３１を介して赤外線照射して急速加熱を行うことで剥離する方法が好ましく用いられる。本方法を用いることで瞬間的に第１ポリイミド層３２と第２ポリイミド層３３の界面に応力が生じ、ポリイミド界面の接着強度を急激に低下させることができるので好ましい。また本方法を用いることでポリイミドに電子デバイスを形成した後に剥離する場合においても、電子デバイスを劣化させることが無いので好ましい。
The schematic diagram regarding the specific manufacturing method of a polyimide lamination | stacking electronic device in this invention is shown in FIG.
The electronic device produced by this method can obtain a polyimide laminated electronic device 35 by peeling the electronic device 34 formed on the second polyimide layer 33 or the second polyimide layer 33 from the first polyimide layer 32. . Although it does not specifically limit about the method to peel the polyimide lamination | stacking electronic device 35, The method of peeling mechanically or the method of rapidly heating a polyimide laminated body can be used. In particular, the rapid heating method is preferable in that stress is generated at the peeling interface to facilitate peeling. The method of rapid heating is not particularly limited, and the method of heating using a hot plate, the method of heating using hot air, the method of heating using an infrared irradiation device, etc. may be mentioned. It is preferable to use a method in which the first polyimide layer 32 is exposed to infrared radiation through the glass substrate 31 using an apparatus to perform rapid heating and peeling. By using this method, a stress is generated instantaneously at the interface between the first polyimide layer 32 and the second polyimide layer 33, and the adhesive strength at the polyimide interface can be sharply reduced, which is preferable. Moreover, even when peeling after forming an electronic device to polyimide by using this method, since an electronic device is not degraded, it is preferable.
特に、本願発明において好ましく用いられるフラッシュランプ等の急速加熱処理装置は、近赤外光、中間赤外光、遠赤外光の少なくとも１つの光を含むことを特徴とする光を発生させる装置であって、特に好ましくはフラッシュランプアニール装置、赤外線ランプアニール装置、レーザーアニール装置を用いることが好ましい。本装置を用いることで、ガラス基材３１を通過させて第１ポリイミド層３２を効果的に加熱することが出来るので好ましい。 In particular, a rapid thermal processing apparatus such as a flash lamp preferably used in the present invention is an apparatus generating light characterized by containing at least one of near infrared light, mid infrared light and far infrared light. In particular, it is preferable to use a flash lamp annealing apparatus, an infrared lamp annealing apparatus, or a laser annealing apparatus. The use of this device is preferable because the first polyimide layer 32 can be effectively heated while passing through the glass substrate 31.
本発明におけるポリイミド積層体上に形成する電子デバイスは、ディスプレイ、センサー、電池、太陽電池、トランジスタ、アクチュエーターなどが好適に挙げられる。更に、本発明におけるポリイミド積層電子デバイスとは、ディスプレイ、センサー、電池、太陽電池、トランジスタ、アクチュエーターなどをポリイミドフィルム表面に積層したポリイミド積層電子デバイスが好適に挙げられる。 As the electronic device formed on the polyimide laminate in the present invention, a display, a sensor, a battery, a solar cell, a transistor, an actuator and the like are suitably mentioned. Furthermore, the polyimide laminated electronic device in the present invention preferably includes a polyimide laminated electronic device in which a display, a sensor, a battery, a solar cell, a transistor, an actuator and the like are laminated on the surface of a polyimide film.
以下、本発明を実施例に基づいて具体的に説明する。ただし、本発明は、これらの実施例によって限定されるものではなく、本発明の趣旨を逸脱しない範囲で実施形態の変更が可能である。 Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited by these examples, and modifications of the embodiment can be made without departing from the spirit of the present invention.
（特性の評価方法）
（剥離強度）
剥離強度はＪＩＳＺ０２３７にもとづいて９０度剥離強度を求めた。
(Characteristic evaluation method)
(Peeling strength)
Peeling strength calculated | required 90 degree peeling strength based on JISZ0237.
（剥離性）
ガラス基材面からフラッシュランプアニール装置（菅原研究所製ＥＳ−Ｚ５８１５）により急速加熱を行った後に、第２ポリイミド層の端部をカッターで切れ目を入れ、第２ポリイミド層が第１ポリイミド層から容易に剥離できた場合を○、剥離できなかった場合を×とした。
(Peelability)
After rapid heating from a glass substrate surface by a flash lamp annealing apparatus (ES-Z5815 manufactured by Kashihara Lab.), The end of the second polyimide layer is cut with a cutter, and the second polyimide layer starts from the first polyimide layer The case where it was able to peel easily was made into (circle) and the case where it was not able to peel was made into x.
（熱膨張係数）
熱膨張係数は、ブルカーエイエックスエス社製熱機械分析装置（ＴＭＡ４０００）を用いて、熱機械分析により、試験片に一定荷重（膜厚１μｍ当たり０．５ｇ）をかけ、昇温速度５℃／分における試験片の伸び値より、１００〜３００℃の範囲での平均値として、ポリイミドフィルムの線熱膨張係数を求めた。
(Thermal expansion coefficient)
The thermal expansion coefficient applies a constant load (0.5 g per 1 μm of film thickness) to the test piece by thermomechanical analysis using a thermomechanical analyzer (TMA 4000) manufactured by Bruker AXS Co., and the temperature rising rate is 5 ° C. / From the elongation value of the test piece in minutes, the linear thermal expansion coefficient of the polyimide film was determined as an average value in the range of 100 to 300 ° C.
（合成例１）
ステンレス製撹拌棒を備えた撹拌機、窒素導入管を備えた３Ｌのガラス製セパラブルフラスコに、重合用溶媒として脱水したＮ−Ｎ’ジメチルアセトアミド（以下ＤＭＡｃと称する）３６５．００ｇを投入し、４，４’−ジアミノジフェニルエーテル（以下ＯＤＡと称する）を４５．０７ｇ加え、氷浴中で３０分間攪拌した。ＯＤＡが均一に溶解した後に、ピロメリット酸二無水物（以下ＰＭＤＡと称する）を４６．６３ｇ加え、反応を続けた。さらに２．４４ｇのＰＭＤＡと１１．６４ｇのＤＭＡｃを少量加え、粘度が上昇した時点で反応を終了した。この反応溶液におけるジアミン及びテトラカルボン酸二無水物の合計の固形分濃度は２０重量％であった。溶液の粘度が変化しなくなったことを確認した後にＤＭＡｃでさらに希釈し、作業しやすい粘度に調整した。本方法で得られたポリアミド酸溶液は固形分濃度が１２重量％であった。本合成例で得られたポリアミド酸溶液をポリアミド酸Ａ溶液、ポリアミド酸をイミド化して得られるポリイミドをポリイミドＡと称する。
Synthesis Example 1
Into a 3 L glass separable flask equipped with a stirrer equipped with a stainless steel stir bar and a nitrogen introduction tube, 365.00 g of dehydrated N-N'dimethylacetamide (hereinafter referred to as DMAc) as a solvent for polymerization is charged. 45.07 g of 4,4'-diaminodiphenyl ether (hereinafter referred to as "ODA") was added and stirred in an ice bath for 30 minutes. After the ODA was uniformly dissolved, 46.63 g of pyromellitic dianhydride (hereinafter referred to as PMDA) was added, and the reaction was continued. Furthermore, a small amount of 2.44 g of PMDA and 11.64 g of DMAc were added, and the reaction was terminated when the viscosity increased. The solid concentration of the total of diamine and tetracarboxylic acid dianhydride in this reaction solution was 20% by weight. After confirming that the viscosity of the solution did not change, the solution was further diluted with DMAc and adjusted to a working viscosity. The polyamic acid solution obtained by this method had a solid content concentration of 12% by weight. The polyamide acid solution obtained in this synthesis example is called a polyamide acid A solution, and the polyimide obtained by imidizing the polyamide acid is called polyimide A.
（合成例２）
ステンレス製撹拌棒を備えた撹拌機、窒素導入管を備えた５００ｍＬのガラス製セパラブルフラスコに、トリメリット酸無水物クロライド６７．４ｇ（０．３２ｍｍｏｌ）を入れ、酢酸エチル１９０ｇとｎ−ヘキサン１９０ｇからなる混合溶媒を加えて溶解させ、溶液１を調製した。更に別の容器に２，２’−ビス（トリフルオロメチル）ベンジジン２５．６ｇ（０．０８ｍｍｏｌ）を酢酸エチル７２ｇとｎ−ヘキサン７２ｇからなる混合溶媒を加えて溶解させ、脱酸剤としてプロピレンオキサイド９．２ｇを加えて溶液２を調製した。
(Composition example 2)
In a 500 mL glass separable flask equipped with a stirrer equipped with a stainless steel stir bar and a nitrogen introduction tube, 67.4 g (0.32 mmol) of trimellitic anhydride chloride was placed, and 190 g of ethyl acetate and 190 g of n-hexane were added. Mixed solvent was added and dissolved to prepare solution 1. Furthermore, 25.6 g (0.08 mmol) of 2,2'-bis (trifluoromethyl) benzidine is dissolved in another container by adding a mixed solvent consisting of 72 g of ethyl acetate and 72 g of n-hexane, and propylene oxide is used as a deacidifying agent. 9.2 g was added to prepare solution 2.
エタノールアイスバス中で−２０℃程度に冷却下で、溶液１に攪拌下溶液２を滴下して３時間攪拌し、その後室温で１２時間攪拌した。析出物を濾別し、酢酸エチル／ｎ−ヘキサン混合溶媒（体積比１：１）でよく洗浄した。その後、濾別し、６０℃で１２時間、さらに１２０℃で１２時間真空乾燥して収率７０％で白色の生成物を得た。ＦＴ−ＩＲにて３３８０ｃｍ−1（アミド基ＮＨ伸縮振動）、３１０５ｃｍ−1（芳香族Ｃ−Ｈ伸縮振動）、１８５７ｃｍ−1、１７８１ｃｍ−1（酸無水物基Ｃ＝Ｏ伸縮振動）、１６７７ｃｍ−1（アミド基Ｃ＝Ｏ伸縮振動）のピーク、また、１Ｈ−ＮＭＲで、δ１１．０６ｐｐｍ（ｓ、ＮＨ、２Ｈ）、δ８．６５ｐｐｍ（ｓ、フタルイミド上、３位ＣａｒｏｍＨ、２Ｈ）、δ８．３７ｐｐｍ（フタルイミド上、５および６位ＣａｒｏｍＨ、４Ｈ）、δ７．４６ｐｐｍ（ｄ、中央ビフェニル上、６および６’位ＣａｒｏｍＨ、２Ｈ）、δ８．１３ｐｐｍ（ｄ、中央ビフェニル上、５および５’位ＣａｒｏｍＨ、２Ｈ）、δ８．２７ｐｐｍ（ｓ、中央ビフェニル上、３および３’位ＣａｒｏｍＨ、２Ｈ）のピークを確認することができたことから、目的物であるアミド基含有テトラカルボン酸二無水物（以下酸二無水物モノマーＢとする）得られたことを確認した。この化合物の融点をＤＳＣで測定したところ、２７４℃であった。 While cooling to about -20 ° C in an ethanol ice bath, Solution 2 was added dropwise to Solution 1 with stirring and stirred for 3 hours, and then stirred at room temperature for 12 hours. The precipitate was separated by filtration and washed well with an ethyl acetate / n-hexane mixed solvent (volume ratio 1: 1). Then, it was separated by filtration and vacuum dried at 60 ° C. for 12 hours and further at 120 ° C. for 12 hours to obtain a white product in 70% yield. FT-IR at 3380 cm -1 (amide NH stretching vibration), 3105cm -1 (aromatic C-H stretching vibration), 1857cm -1, 1781cm -1 (acid anhydride group C = O stretching vibration), 1677cm - 1 (Amid group C = O stretching vibration) peak, and in 1 H-NMR, δ 11.06 ppm (s, NH, 2H), δ 8.65 ppm (s, phthalimide, 3-position Carom H, 2H), δ 8.37 ppm (5 and 6 positions Ca rom H, 4 H on phthalimide), δ 7.46 ppm (d, C arom H, 2 H on 6 and 6 ′ positions on central biphenyl), δ 8.13 ppm (d, on central biphenyl) 5 and 5 'positions C arom H, 2H), δ8.27ppm (s, on the central biphenyl, 3 and 3' C arom H, it was possible to confirm the peak of 2H) Et al., It was confirmed that the obtained amide group-containing tetracarboxylic acid dianhydride as the target compound (hereinafter referred to as an acid dianhydride monomer B). The melting point of this compound was measured by DSC and found to be 274 ° C.
ステンレス製撹拌棒を備えた撹拌機、窒素導入管を備えた、３Ｌのガラス製セパラブルフラスコに、２，２’−ビス（トリフルオロメチル）ベンジジン３２．０ｇ（０．１０ｍｏｌ）を入れ、重合用溶媒として脱水したＮ，Ｎ−ジメチルホルムアミド（以下、ＤＭＦ）２９６ｇを仕込み攪拌した後、この溶液に、上記の合成したアミド基含有テトラカルボン酸二無水物（酸二無水物モノマーＢ）６６．８ｇ（０．１０ｍｏｌ）を加え、室温で２４時間攪拌し、ポリアミド酸を得た。なお、この反応溶液におけるジアミン化合物及びテトラカルボン酸二無水物の仕込み濃度は、全反応液に対して２５重量％となっていた。 In a 3 L glass separable flask equipped with a stirrer equipped with a stainless steel stir bar and a nitrogen inlet tube, 32.0 g (0.10 mol) of 2,2'-bis (trifluoromethyl) benzidine was added to polymerize 296 g of dehydrated N, N-dimethylformamide (hereinafter referred to as DMF) as a solvent for the reaction is added and stirred, and then the above synthesized amido group-containing tetracarboxylic acid dianhydride (acid dianhydride monomer B) 66. 8 g (0.10 mol) was added and stirred at room temperature for 24 hours to obtain a polyamic acid. The concentration of the diamine compound and tetracarboxylic acid dianhydride in the reaction solution was 25% by weight based on the total reaction solution.
上記溶液にＤＭＦを加え固形分濃度を２０重量％とし、イミド化触媒としてピリジンを１５．８ｇ（０．２０ｍｏｌ）添加して、完全に分散させた。分散させた溶液中に無水酢酸を２４．５ｇ（０．２４ｍｏｌ）を添加して攪拌し、１００℃で４時間攪拌したのち、室温まで冷却した。上記ポリイミド樹脂溶液にＤＭＦを加え固形分濃度を１５重量％とし、１２００ｇのイソプロピルアルコールをポリイミド樹脂溶液に加えた後、約３０分間撹拌した。その後、ポリイミドスラリーを取り出し、更に、８００ｇのイソプロピルアルコールを添加して完全に固形分を抽出した。９００ｇのイソプロパノ−ルで抽出した固形分の洗浄を４回行った。そして得られた固形分を真空乾燥装置で１５０℃２４時間真空乾燥して、ポリイミド樹脂として取り出した。 DMF was added to the above solution to adjust the solid content concentration to 20% by weight, and 15.8 g (0.20 mol) of pyridine was added as an imidation catalyst to completely disperse. After 24.5 g (0.24 mol) of acetic anhydride was added to the dispersed solution, the mixture was stirred, stirred at 100 ° C. for 4 hours, and cooled to room temperature. After adding DMF to the said polyimide resin solution and setting solid content density | concentration to 15 weight%, and adding 1200 g of isopropyl alcohol to a polyimide resin solution, it stirred for about 30 minutes. Thereafter, the polyimide slurry was taken out, and further 800 g of isopropyl alcohol was added to completely extract the solid content. The solid extracted with 900 g of isopropanol was washed four times. Then, the obtained solid content was vacuum dried with a vacuum dryer at 150 ° C. for 24 hours, and taken out as a polyimide resin.
３Ｌパラブルフラスコ中にＤＭＡｃ９００ｇを投入し、さらに得られたポリイミド樹脂を１００ｇ添加し、固形分濃度１０重量％の第２ポリイミド溶液を得た。得られたポリイミド溶液をポリイミドＢ溶液、本構造を有するポリイミドをポリイミドＢと称する。 900 g of DMAc was charged into a 3 L parallel flask, and 100 g of the obtained polyimide resin was further added to obtain a second polyimide solution having a solid content concentration of 10% by weight. The obtained polyimide solution is referred to as a polyimide B solution, and a polyimide having the present structure is referred to as polyimide B.
（合成例３）
ステンレス製撹拌棒を備えた撹拌機、窒素導入管を備えた３Ｌのガラス製セパラブルフラスコに、重合用溶媒として脱水したＤＭＡｃ１３３８ｇを投入し、パラフェニレンジアミン（以下ＰＤＡと称する）を５８．４８ｇ、ＯＤＡを０．８７ｇ加え、油浴で５０℃に加熱し３０分間攪拌した。ＯＤＡとＰＤＡが均一に溶解した後に、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物（以下ＢＰＤＡと称する）１５７．１９ｇを加え、原料が溶解したことを確認した後に溶液の濃度を約８０℃に調整した。さらに一定の温度で加熱しながら攪拌を３時間続けて粘度を下げ、さらにＤＭＡｃ１５３．８ｇ加えて攪拌し、ポリアミド酸溶液を得た。この反応溶液におけるジアミン及びテトラカルボン酸二無水物の合計の固形分濃度は１５重量％であった。
(Composition example 3)
In a 3-liter glass separable flask equipped with a stirrer with a stainless steel stir bar and a nitrogen inlet tube, 1338 g of dehydrated DMAc was charged as a polymerization solvent, and 58.48 g of paraphenylene diamine (hereinafter referred to as PDA), 0.87 g of ODA was added, heated to 50 ° C. with an oil bath and stirred for 30 minutes. After ODA and PDA were uniformly dissolved, 157.19 g of 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride (hereinafter referred to as BPDA) was added, and after confirming that the raw materials were dissolved, The concentration was adjusted to about 80 ° C. Stirring was further continued while heating at a constant temperature for 3 hours to lower the viscosity, and 153.8 g of DMAc was further added and stirred to obtain a polyamic acid solution. The solid content concentration of the total of diamine and tetracarboxylic dianhydride in this reaction solution was 15% by weight.
上記ポリアミド酸溶液を水浴で速やかに冷却し、溶液の温度を約５０℃に調整した。次に３−アミノプロピルトリエトキシシランの１％ＤＭＡｃ溶液を１０．９ｇ加え５時間攪拌した。溶液の粘度が変化しなくなったことを確認した後にＤＭＡｃでさらに希釈し、作業しやすい粘度に調整した。本方法で得られたポリアミド酸溶液は固形分濃度が１３ｗｔ％であった。 The above polyamic acid solution was quickly cooled with a water bath, and the temperature of the solution was adjusted to about 50 ° C. Next, 10.9 g of a 1% DMAc solution of 3-aminopropyltriethoxysilane was added and stirred for 5 hours. After confirming that the viscosity of the solution did not change, the solution was further diluted with DMAc and adjusted to a working viscosity. The polyamic acid solution obtained by this method had a solid content concentration of 13 wt%.
本合成例で得られたポリアミド酸溶液をポリアミド酸Ｃ溶液、ポリアミド酸をイミド化して得られるポリイミドをポリイミドＣと称する。 The polyamide acid solution obtained in this synthesis example is referred to as a polyamide acid C solution, and the polyimide obtained by imidizing the polyamide acid is referred to as polyimide C.
＜ポリイミド積層体の製造＞
ガラス基板にはＥａｇｌｅＸＧ（Ｃｏｒｎｉｎｇ社製）を用いた（縦×横×厚み：１０ｃｍ×１０ｃｍ×０．５ｍｍ）。ガラス基板は６ｗｔ％セミクリーンＭ−ＬＯ（横浜油脂製）で２０分、超純水で１０分、アセトンで２０分、２−プロパノールで２０分の順番に超音波洗浄を行った後に、１００℃のオーブンで乾燥を行った。
<Production of polyimide laminate>
As a glass substrate, Eagle X G (manufactured by Corning) was used (length × width × thickness: 10 cm × 10 cm × 0.5 mm). The glass substrate is subjected to ultrasonic cleaning in the following order: 6 wt% semi clean M-LO (Yokohama Yushi Co., Ltd.) for 20 minutes, ultra pure water for 10 minutes, acetone for 20 minutes, and 2-propanol for 20 minutes. Drying was done in the oven.
（実施例１）
第１ポリイミド層にはポリイミドＡを、第２ポリイミド層にはポリイミドＢを用いた。
Example 1
Polyimide A was used for the first polyimide layer, and polyimide B was used for the second polyimide layer.
ガラス基板上にポリアミド酸Ａ溶液をスピンコートした後に、８０℃で２０分、１５０℃で３０分、３００℃で１時間、４００℃で１時間の条件でホットプレート上にて乾燥を行い、第１ポリイミド層を得た（２０μｍ）。この第１ポリイミド層の上に、第２ポリイミド溶液としてポリイミドＢ溶液をスピンコートし、８０℃で２０分、１５０℃で１時間、３００℃で１時間の条件でホットプレート上にて乾燥を行うことで、第２ポリイミド層を第１ポリイミド層の上に形成した（２０μｍ）。この様にしてポリイミド積層体を得た。 After spin coating a solution of polyamic acid A on a glass substrate, drying is performed on a hot plate under the conditions of 80 ° C. for 20 minutes, 150 ° C. for 30 minutes, 300 ° C. for 1 hour, and 400 ° C. for 1 hour. 1 Polyimide layer was obtained (20 μm). Polyimide B solution is spin coated on the first polyimide layer as a second polyimide solution, and dried on a hot plate under the conditions of 80 ° C. for 20 minutes, 150 ° C. for 1 hour, and 300 ° C. for 1 hour Thus, the second polyimide layer was formed on the first polyimide layer (20 μm). Thus, a polyimide laminate was obtained.
得られたポリイミド積層体の剥離強度、剥離性、熱膨張係数を評価した結果を表1に示す。 The results of evaluating the peel strength, peelability, and thermal expansion coefficient of the obtained polyimide laminate are shown in Table 1.
（実施例２）
＜ポリイミド積層体の製造＞
第１ポリイミド層にはポリイミドＡを、第２ポリイミド層にはポリイミドＣを用いた。
(Example 2)
<Production of polyimide laminate>
Polyimide A was used for the first polyimide layer, and polyimide C was used for the second polyimide layer.
ガラス基板上にポリアミド酸Ａ溶液をスピンコートした後に、８０℃で２０分、１５０℃で３０分、３００℃で１時間、４００℃で１時間の条件でホットプレート上にて乾燥を行い、第１ポリイミド層を得た（２０μｍ）。この第１ポリイミド層の上に、ポリアミド酸Ｃ溶液をスピンコートし、８０℃で２０分、１５０℃で３０分、３００℃で１時間、４００℃で１時間の条件でホットプレート上にて乾燥を行うことで、第２ポリイミド層を第１ポリイミド層の上に形成した（２０μｍ）。この様にしてポリイミド積層体を得た。 After spin coating a solution of polyamic acid A on a glass substrate, drying is performed on a hot plate under the conditions of 80 ° C. for 20 minutes, 150 ° C. for 30 minutes, 300 ° C. for 1 hour, and 400 ° C. for 1 hour. 1 Polyimide layer was obtained (20 μm). A solution of polyamic acid C is spin coated on the first polyimide layer and dried on a hot plate under the conditions of 80 ° C. for 20 minutes, 150 ° C. for 30 minutes, 300 ° C. for 1 hour, and 400 ° C. for 1 hour To form a second polyimide layer on the first polyimide layer (20 μm). Thus, a polyimide laminate was obtained.
実施例１と同様に、得られたポリイミド積層体の剥離強度、剥離性、熱膨張係数を評価した結果を表1に示す。 The peel strength, peelability, and thermal expansion coefficient of the obtained polyimide laminate were evaluated in the same manner as in Example 1. Table 1 shows the results.
（比較例１）
＜ポリイミド積層体の製造＞
第１ポリイミド層にはポリイミドＡを、第２ポリイミド層にはポリイミドＡを用いた。
ガラス基板上にポリアミド酸Ａ溶液をスピンコートした後に、８０℃で２０分、１５０℃で３０分、３００℃で１時間、４００℃で１時間の条件でホットプレート上にて乾燥を行い、第１ポリイミド層を得た（２０μｍ）。この第１ポリイミド層の上に、ポリアミド酸Ａ溶液をスピンコートした後に、８０℃で２０分、１５０℃で３０分、３００℃で１時間、４００℃で１時間の条件でホットプレート上にて乾燥を行うことで、第２ポリイミド層を第１ポリイミド層の上に形成した（２０μｍ）。この様にしてポリイミド積層体を得た。実施例１と同様に、得られたポリイミド積層体の剥離強度、剥離性、熱膨張係数を評価した結果を表1に示す。
(Comparative example 1)
<Production of polyimide laminate>
Polyimide A was used for the first polyimide layer, and polyimide A was used for the second polyimide layer.
After spin coating a solution of polyamic acid A on a glass substrate, drying is performed on a hot plate under the conditions of 80 ° C. for 20 minutes, 150 ° C. for 30 minutes, 300 ° C. for 1 hour, and 400 ° C. for 1 hour. 1 Polyimide layer was obtained (20 μm). A solution of polyamic acid A is spin coated on the first polyimide layer, and then heated on a hot plate under the conditions of 80 ° C. for 20 minutes, 150 ° C. for 30 minutes, 300 ° C. for 1 hour, and 400 ° C. for 1 hour. By drying, a second polyimide layer was formed on the first polyimide layer (20 μm). Thus, a polyimide laminate was obtained. The peel strength, peelability, and thermal expansion coefficient of the obtained polyimide laminate were evaluated in the same manner as in Example 1. Table 1 shows the results.
実施例１〜２のポリイミド積層体は、剥離することができた。このことにより、電子デバイスを積層したポリイミド積層電子デバイスを作製した際に、電子デバイスの劣化を防ぐことができ、歩留り良く生産することができることが明らかになった。これに対して比較例１記載の通り、第１ポリイミド層と第２ポリイミド層が同一の場合であって、熱膨張係数の差が無く、しかも、第２のポリイミド積層体の熱膨張係数が大きい場合においては、剥離することができず、ポリイミド積層電子デバイスを歩留り良く生産できないことが明らかになった。 The polyimide laminates of Examples 1 and 2 were able to be peeled off. By this, when producing the polyimide lamination | stacking electronic device which laminated | stacked the electronic device, it became clear that deterioration of an electronic device can be prevented and it can manufacture with a sufficient yield. On the other hand, as described in Comparative Example 1, the first polyimide layer and the second polyimide layer are the same, there is no difference in the thermal expansion coefficient, and the thermal expansion coefficient of the second polyimide laminate is large. In the case, it was revealed that it was not possible to exfoliate, and it was not possible to produce polyimide laminated electronic devices with high yield.
１ ガラス基板
２ 第１ポリイミド層
３ 第２ポリイミド層
１１ ガラス基板
１２ 第１ポリイミド層
１３ 第２ポリイミド層
２１ ガラス基板
２２ 第１ポリイミド層
２３ 第２ポリイミド層
２４ 電子デバイス
２５ ポリイミド積層電子デバイス
３１ ガラス基板
３２ 第１ポリイミド層
３３ 第２ポリイミド層
３４ 電子デバイス
３５ ポリイミド積層電子デバイス
DESCRIPTION OF SYMBOLS 1 glass substrate 2 1st polyimide layer 3 2nd polyimide layer 11 glass substrate 12 1st polyimide layer 13 2nd polyimide layer 21 glass substrate 22 1st polyimide layer 23 2nd polyimide layer 24 electronic device 25 polyimide laminated electronic device 31 glass substrate 32 first polyimide layer 33 second polyimide layer 34 electronic device
35 Polyimide Stacked Electronic Device
Claims (6)
前記第１ポリイミド層は、前記第２ポリイミド層と異なる組成のポリイミドから成り、前記第１ポリイミド層と前記第２ポリイミド層との間の剥離強度は、０．０１Ｎ／ｃｍ以上、０．２５Ｎ／ｃｍ以下であり、
前記ガラス基板と前記第１ポリイミド層との間の剥離強度は、０．２５Ｎ／ｃｍ以上であり、
前記第１ポリイミド層の熱膨張係数は、２５〜６０ｐｐｍ／Ｋであり、
前記第２ポリイミド層の熱膨張係数は、１〜２０ｐｐｍ／Ｋであり、
前記第１ポリイミド層は、テトラカルボン酸二無水物とジアミンとを反応させて得られ、前記テトラカルボン酸二無水物は、ピロメリット酸無水物を含み、前記ジアミンは、ジアミノジフェニルエーテルを含むことを特徴とするポリイミド積層体。 In a polyimide laminate in which a glass substrate, a first polyimide layer, and a second polyimide layer are laminated in this order,
The first polyimide layer is made of polyimide having a composition different from that of the second polyimide layer, and the peel strength between the first polyimide layer and the second polyimide layer is 0.01 N / cm or more, 0.25 N / cm. cm or less,
The peel strength between the glass substrate and the first polyimide layer is 0.25 N / cm or more.
The thermal expansion coefficient of the first polyimide layer is 25 to 60 ppm / K,
The thermal expansion coefficient of the second polyimide layer is 1 to 20 ppm / K,
The first polyimide layer is obtained by reacting tetracarboxylic acid dianhydride with diamine, the tetracarboxylic acid dianhydride containing pyromellitic anhydride, and the diamine containing diaminodiphenyl ether. Characteristic polyimide laminate.
電子デバイスを前記第２のポリイミド層上に形成し、前記第２ポリイミド層を前記第１ポリイミド層から剥離させるポリイミド積層電子デバイスの製造方法であって、
前記第１ポリイミド溶液又は第１ポリイミド前駆体溶液は、前記第２ポリイミド溶液又は第２ポリイミド前駆体溶液と異なる組成のポリイミド溶液又は前駆体溶液であり、
前記第１ポリイミド層と前記第２ポリイミド層の間の剥離強度は、０．０１Ｎ／ｃｍ以上、０．２５Ｎ／ｃｍ以下であり、前記ガラス基板と前記第１ポリイミド層の間の剥離強度は、０．２５Ｎ／ｃｍ以上であり、
前記第１ポリイミド層の熱膨張係数は、２５〜６０ｐｐｍ／Ｋであり、
前記第２ポリイミド層の熱膨張係数は、１〜２０ｐｐｍ／Ｋであり、
前記第１ポリイミド層は、テトラカルボン酸二無水物とジアミンとを反応させて得られ、前記テトラカルボン酸二無水物は、ピロメリット酸無水物を含み、前記ジアミンは、ジアミノジフェニルエーテルを含むことを特徴とするポリイミド積層電子デバイスの製造方法。 A first polyimide solution or a first polyimide precursor solution is coated on a glass substrate to form a first polyimide layer, and a second polyimide solution or a second polyimide precursor solution is coated on the first polyimide layer to form a first polyimide layer. 2 form a polyimide layer,
A method of manufacturing a polyimide-laminated electronic device, comprising forming an electronic device on the second polyimide layer and peeling the second polyimide layer from the first polyimide layer,
The first polyimide solution or the first polyimide precursor solution is a polyimide solution or a precursor solution of a composition different from that of the second polyimide solution or the second polyimide precursor solution,
The peel strength between the first polyimide layer and the second polyimide layer is 0.01 N / cm or more and 0.25 N / cm or less, and the peel strength between the glass substrate and the first polyimide layer is More than 0.25 N / cm,
The thermal expansion coefficient of the first polyimide layer is 25 to 60 ppm / K,
The thermal expansion coefficient of the second polyimide layer is 1 to 20 ppm / K,
The first polyimide layer is obtained by reacting tetracarboxylic acid dianhydride with diamine, the tetracarboxylic acid dianhydride containing pyromellitic anhydride, and the diamine containing diaminodiphenyl ether. The manufacturing method of the polyimide lamination | stacking electronic device characterized by the above-mentioned.
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| KR102630960B1 (en) * | 2016-12-15 | 2024-01-29 | 엘지디스플레이 주식회사 | Flexible substrate, flexible display device including the same, and manufacturing method thereof |
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| JP2018099800A (en) * | 2016-12-20 | 2018-06-28 | 東洋紡株式会社 | Laminate, laminate production method, and flexible device production method |
| JP6878870B2 (en) * | 2016-12-20 | 2021-06-02 | 東洋紡株式会社 | Laminates, methods for manufacturing laminates and methods for manufacturing flexible devices |
| JP6784329B2 (en) | 2017-05-29 | 2020-11-11 | 東洋紡株式会社 | Laminated body of polyimide film and inorganic substrate |
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