CN114423823B - Polyimide precursor composition and method for producing flexible electronic device - Google Patents
Polyimide precursor composition and method for producing flexible electronic device Download PDFInfo
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- CN114423823B CN114423823B CN202080065533.1A CN202080065533A CN114423823B CN 114423823 B CN114423823 B CN 114423823B CN 202080065533 A CN202080065533 A CN 202080065533A CN 114423823 B CN114423823 B CN 114423823B
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- polyimide
- polyimide precursor
- valent
- substrate
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 345
- 239000004642 Polyimide Substances 0.000 title claims abstract description 226
- 239000002243 precursor Substances 0.000 title claims abstract description 159
- 239000000203 mixture Substances 0.000 title claims abstract description 98
- 238000004519 manufacturing process Methods 0.000 title claims description 33
- -1 phosphorus compound Chemical class 0.000 claims abstract description 77
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 55
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 55
- 239000011574 phosphorus Substances 0.000 claims abstract description 47
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims description 78
- 125000003118 aryl group Chemical group 0.000 claims description 57
- 239000000178 monomer Substances 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 49
- 125000002723 alicyclic group Chemical group 0.000 claims description 42
- 239000011521 glass Substances 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 38
- 125000003545 alkoxy group Chemical group 0.000 claims description 35
- 239000000126 substance Substances 0.000 claims description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- 239000004065 semiconductor Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 22
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 20
- 125000001931 aliphatic group Chemical group 0.000 claims description 17
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 239000004020 conductor Substances 0.000 claims description 13
- 125000004437 phosphorous atom Chemical group 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 7
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 6
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 4
- 150000001408 amides Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims 1
- 229920005575 poly(amic acid) Polymers 0.000 description 78
- 239000010408 film Substances 0.000 description 53
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 47
- 150000004985 diamines Chemical class 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 31
- 230000015572 biosynthetic process Effects 0.000 description 29
- 238000003786 synthesis reaction Methods 0.000 description 28
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 25
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 25
- 150000001875 compounds Chemical class 0.000 description 22
- 238000002834 transmittance Methods 0.000 description 19
- 239000012456 homogeneous solution Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 12
- 125000000962 organic group Chemical group 0.000 description 12
- 125000001153 fluoro group Chemical group F* 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 11
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- OVASAEXSPYGGES-UHFFFAOYSA-N C1C2C(C(OC3=O)=O)C3C1CC2(C1=O)CCC21CC1CC2C2C(=O)OC(=O)C12 Chemical compound C1C2C(C(OC3=O)=O)C3C1CC2(C1=O)CCC21CC1CC2C2C(=O)OC(=O)C12 OVASAEXSPYGGES-UHFFFAOYSA-N 0.000 description 7
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 7
- 239000004973 liquid crystal related substance Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 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 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004805 Cyclohexane-1,2-dicarboxylic acid Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 3
- BEQVQKJCLJBTKZ-UHFFFAOYSA-N diphenylphosphinic acid Chemical compound C=1C=CC=CC=1P(=O)(O)C1=CC=CC=C1 BEQVQKJCLJBTKZ-UHFFFAOYSA-N 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000005340 laminated glass Substances 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- UIZIZIPEEWDBCL-UHFFFAOYSA-N (4-aminophenyl) 4-[4-(4-aminophenoxy)carbonylphenyl]benzoate Chemical compound C1=CC(N)=CC=C1OC(=O)C1=CC=C(C=2C=CC(=CC=2)C(=O)OC=2C=CC(N)=CC=2)C=C1 UIZIZIPEEWDBCL-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 2
- NYYLZXREFNYPKB-UHFFFAOYSA-N 1-[ethoxy(methyl)phosphoryl]oxyethane Chemical compound CCOP(C)(=O)OCC NYYLZXREFNYPKB-UHFFFAOYSA-N 0.000 description 2
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 2
- HDGLPTVARHLGMV-UHFFFAOYSA-N 2-amino-4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenol Chemical compound NC1=CC(C(C(F)(F)F)C(F)(F)F)=CC=C1O HDGLPTVARHLGMV-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- XTEBLARUAVEBRF-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)aniline Chemical compound NC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 XTEBLARUAVEBRF-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- APXJLYIVOFARRM-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C(C(O)=O)=C1 APXJLYIVOFARRM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- DEYFWGXTPWNADC-UHFFFAOYSA-N 6-[2-phenylethyl(propyl)amino]-5,6,7,8-tetrahydronaphthalen-1-ol Chemical compound C1CC2=C(O)C=CC=C2CC1N(CCC)CCC1=CC=CC=C1 DEYFWGXTPWNADC-UHFFFAOYSA-N 0.000 description 2
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- 101000729827 Homo sapiens Barrier-to-autointegration factor-like protein Proteins 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
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- 238000005229 chemical vapour deposition Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
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- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
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- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
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- 150000003457 sulfones Chemical class 0.000 description 2
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- SIOVKLKJSOKLIF-HJWRWDBZSA-N trimethylsilyl (1z)-n-trimethylsilylethanimidate Chemical compound C[Si](C)(C)OC(/C)=N\[Si](C)(C)C SIOVKLKJSOKLIF-HJWRWDBZSA-N 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- GWNMOARSGRXJMV-UHFFFAOYSA-N (1-cycloheptylcycloheptyl)oxymethanediamine Chemical compound C1CCCCCC1C1(OC(N)N)CCCCCC1 GWNMOARSGRXJMV-UHFFFAOYSA-N 0.000 description 1
- YIDVLWDHYNWHMH-UHFFFAOYSA-N (4-hydroxyphenyl)phosphonic acid Chemical compound OC1=CC=C(P(O)(O)=O)C=C1 YIDVLWDHYNWHMH-UHFFFAOYSA-N 0.000 description 1
- JDGFELYPUWNNGR-UHFFFAOYSA-N 1,2,3,3a,4,5,6,6a-octahydropentalene-1,3,4,6-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C2C(C(=O)O)CC(C(O)=O)C21 JDGFELYPUWNNGR-UHFFFAOYSA-N 0.000 description 1
- LERDAFCBKALCKT-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(2,3,4-trifluorophenyl)benzene Chemical group FC1=C(F)C(F)=CC=C1C1=C(F)C(F)=C(F)C(F)=C1F LERDAFCBKALCKT-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
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Classifications
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Abstract
Disclosed is a polyimide precursor composition which contains a polyimide precursor, a phosphorus compound having a P (=O) OH structure OR a P (=O) OR structure (wherein R is an alkyl group having 4 OR more carbon atoms), and a solvent. By using the composition, flexible electronic devices can be manufactured by an industrially simple apparatus.
Description
Technical Field
The present invention relates to a polyimide precursor composition suitable for use in electronic devices such as substrates for flexible devices, and a method for producing flexible electronic devices.
Background
Polyimide films are widely used in the fields of electric/electronic devices, semiconductors, etc. because of their excellent heat resistance, chemical resistance, mechanical strength, electrical characteristics, dimensional stability, etc. On the other hand, in recent years, with the advent of a highly informative society, development of optical materials such as optical fibers and optical waveguides in the field of optical communication, liquid crystal alignment films and protective films for color filters in the field of display devices has been advanced. In particular, in the field of display devices, research on plastic substrates having light weight and excellent flexibility and development of displays capable of being bent or rolled up are actively being conducted as substitutes for glass substrates.
In a display such as a liquid crystal display or an organic EL display, a semiconductor element such as a TFT for driving each pixel is formed. Therefore, heat resistance and dimensional stability are required for the substrate. Polyimide films are expected to be used as substrates for display applications because of their excellent heat resistance, chemical resistance, mechanical strength, electrical characteristics, dimensional stability, and the like.
Polyimide is generally colored in a tan color, and therefore, is limited in use in a transmissive device such as a liquid crystal display having a backlight, but in recent years, a polyimide film having excellent transparency in addition to mechanical characteristics and thermal characteristics has been developed, and the desire for use as a substrate for display applications has been further improved (see patent documents 1 to 3).
In general, it is difficult to maintain planarity of a flexible film, and therefore it is difficult to uniformly and precisely form semiconductor elements such as TFTs, fine wirings, and the like on the flexible film. For example, patent document 4 describes "a method for manufacturing a flexible device as a display device or a light receiving device, which includes the steps of: a step of forming a polyimide resin film in a solid state by applying a specific precursor resin composition onto a carrier substrate to form a film; forming a circuit on the resin film; and a step of peeling the solid resin film having the circuit formed on the surface thereof from the carrier substrate.
In addition, in patent document 5, as a method of manufacturing a flexible device, there is disclosed a method including: after forming elements and circuits necessary for devices on a polyimide film/glass substrate laminate obtained by forming a polyimide film on a glass substrate, laser light is irradiated from the glass substrate side to peel the glass substrate.
Prior art literature
Patent literature
Patent document 1: international publication No. 2012/01590
Patent document 2: international publication No. 2013/179727
Patent document 3: international publication No. 2014/038715
Patent document 4: japanese patent application laid-open No. 2010-202729
Patent document 5: international publication No. 2018/221607
Patent document 6: international publication No. 2012/173204
Patent document 7: international publication No. 2015/080139
Disclosure of Invention
Problems to be solved by the invention
The mechanical peeling described in patent document 4 has an advantage of simplicity without additional equipment, but the peeling strength between the polyimide film and the glass substrate is excessively high, and when the polyimide film is peeled from the glass substrate, there is a case where the element and the circuit formed on the polyimide film are damaged. On the other hand, the laser lift-off described in patent document 5 has an advantage that the laser lift-off can ensure high adhesion between the polyimide film and the glass substrate at the time of forming the element and the circuit, and can reduce the lift-off strength at the time of lift-off, so that the damage to the element and the circuit is small. However, a laser irradiation device and the like are required, and the equipment cost increases.
Incidentally, patent document 6 describes a composition in which monoethyl phosphate (example 4), monolauryl phosphate (example 5) and polyphosphoric acid (example 6) are added to a polyimide precursor solution obtained from 3,3', 4' -biphenyltetracarboxylic dianhydride and p-phenylenediamine, respectively, but does not describe the reduction of the peel strength of a polyimide film formed on a substrate from the substrate and the production of a flexible electronic device by the addition of these phosphorus compounds.
Further, patent document 7 describes an example in which phosphoric acid (comparative example 2) and tributyl phosphate (comparative example 4) are added to a polyimide precursor solution having a specific component as comparative examples, but it is not described at all that the peel strength of a polyimide film formed on a substrate from the substrate is reduced by the addition of these phosphorus compounds.
The present invention has been made in view of the conventional problems, and a main object thereof is to provide a polyimide precursor composition which can be used for producing a flexible electronic device by industrially simple equipment and steps, and a method for producing a flexible electronic device.
Means for solving the problems
Summary of the main disclosures of the application are as follows.
1. A polyimide precursor composition (wherein the following condition (A)) is satisfied, characterized by comprising:
a polyimide precursor;
A phosphorus compound having a P (=o) OH structure OR a P (=o) OR structure (wherein R is an alkyl group having 4 OR more carbon atoms) in an amount of more than 0.001 mol% and less than 5mol% relative to the total monomer units of the polyimide precursor; and
And (3) a solvent.
(A) The above polyimide precursor is not a polyimide precursor obtained from only 3,3', 4' -biphenyltetracarboxylic dianhydride and p-phenylenediamine.
2. The composition according to item 1 above, wherein the content of the phosphorus compound is 0.01 mol% or more based on the total monomer units of the polyimide precursor.
3. The composition according to item 1 or 2 above, wherein the phosphorus compound does not contain a compound having an aryl group directly bonded to P.
4. The composition according to any one of the above 1 to 3, wherein the molecular weight of the phosphorus compound is less than 400.
5. The composition according to any one of the above items 1 to 4, wherein the polyimide precursor comprises a repeating unit selected from the group consisting of a structure represented by the following general formula (I) and a structure in which at least 1 amide structure in the general formula (I) is imidized.
[ Chemical 1]
(In the general formula I, X 1 is a 4-valent aliphatic group or aromatic group, Y 1 is a 2-valent aliphatic group or aromatic group, and R 1 and R 2 are, independently of each other, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkylsilyl group having 3 to 9 carbon atoms.)
6. The composition according to item 5 above, wherein the content of the repeating unit represented by the general formula (I) in which X 1 is a 4-valent group having an alicyclic structure and Y 1 is a 2-valent group having an alicyclic structure is 50 mol% or less based on the total repeating units.
7. The composition according to the above item 5, wherein X 1 in the general formula (I) is a 4-valent group having an aromatic ring, and Y 1 is a 2-valent group having an aromatic ring.
8. The composition according to the above item 5, wherein X 1 in the general formula (I) is a 4-valent group having an alicyclic structure, and Y 1 is a 2-valent group having an aromatic ring.
9. The composition according to the above item 5, wherein X 1 in the general formula (I) is a 4-valent group having an aromatic ring, and Y 1 is a 2-valent group having an alicyclic structure.
10. The composition according to item 5 above, wherein the content of the repeating unit represented by the general formula (I) in which X 1 is a 4-valent group having an alicyclic structure (wherein X 1 is a 4-valent group having an alicyclic structure and Y 1 is a 2-valent group having an alicyclic structure) is 50 mol% or less based on the total repeating units, is contained in an amount exceeding 60% of the total repeating units.
11. A method of manufacturing a flexible electronic device, comprising:
(a) A step of applying a polyimide precursor composition containing a polyimide precursor, a phosphorus compound having a P (=o) OH structure OR a P (=o) OR structure (wherein R is an alkyl group having 4 OR more carbon atoms), and a solvent to a substrate;
(b) A step of producing a laminate in which a polyimide film is laminated on the base material by heating the polyimide precursor on the base material;
(c) Forming at least 1 layer selected from a conductor layer and a semiconductor layer on the polyimide film of the laminate; and
(D) And peeling the base material from the polyimide film by an external force.
12. The method according to item 11, wherein the polyimide precursor composition is any one of the polyimide precursor compositions according to items 1 to 10.
13. The production method according to any one of the above 11 or 12, wherein the substrate is a glass plate.
14. The method according to any one of claims 11 to 13, wherein laser irradiation is not performed in the step of peeling the base material from the polyimide film.
15. A method for reducing peel strength of a laminate, which is a method for reducing peel strength between a polyimide film and a substrate of a laminate having the substrate and the polyimide film formed on the substrate, characterized by comprising the steps of,
The polyimide precursor composition for forming the polyimide film contains a phosphorus compound having a P (=o) OH structure OR a P (=o) OR structure (wherein R is an alkyl group having 4 OR more carbon atoms).
16. The method according to item 15, wherein the polyimide precursor composition is the polyimide precursor composition according to any one of items 1 to 10.
17. The method according to any one of the above 15 or 16, wherein the substrate is a glass plate.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a polyimide precursor composition that can be used for manufacturing flexible electronic devices by industrially simple equipment and processes can be provided. Further, according to the present invention, a simple method for manufacturing a flexible electronic device using a polyimide film as a substrate can be provided. When the polyimide precursor composition of the present invention is used, the peel strength between the substrate and the polyimide film can be suitably reduced. Therefore, a flexible electronic device can be manufactured by a simple apparatus and process, and the device can be manufactured with a good yield with little possibility of damage.
Detailed Description
In the present application, a "flexible (electronic) device" means that the device itself is flexible, and generally, a semiconductor layer (a transistor, a diode, or the like as an element) is formed on a substrate to complete the device. A "flexible (electronic) device" is different from a conventional device such as COF (Chip On Film) in which a "hard" semiconductor element such as an IC Chip is mounted On an FPC (flexible printed circuit board). However, there is no problem in that a "hard" semiconductor element such as an IC chip is mounted on a flexible substrate, or is electrically connected or fused for use in order to operate or control the "flexible (electronic) device" of the present application. Examples of flexible (electronic) devices that can be preferably used include liquid crystal displays, organic EL displays, display devices such as electronic papers, solar cells, and light receiving devices such as CMOS.
Hereinafter, the polyimide precursor composition of the present invention will be described, and a method for manufacturing a flexible electronic device will be described.
Polyimide front body composition >
A polyimide precursor composition for forming a polyimide film contains a polyimide precursor, a phosphorus compound, and a solvent. Both the polyimide precursor and the phosphorus compound are dissolved in a solvent.
In the present application, the term "polyimide precursor" is used in the sense of a precursor capable of forming polyimide in a polyimide film. That is, the term "polyimide precursor" includes polyamic acid and derivative (precisely defined by formula (I)), partially imidized polyamic acid and derivative partially imidized, and polyimide, all dissolved in a solvent.
The polyimide precursor has a repeating unit represented by the following general formula (I). Particularly preferred are polyamic acids wherein R 1 and R 2 are hydrogen atoms.
[ Chemical 2]
(In the general formula I, X 1 is a 4-valent aliphatic group or aromatic group, Y 1 is a 2-valent aliphatic group or aromatic group, and R 1 and R 2 are, independently of each other, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkylsilyl group having 3 to 9 carbon atoms.)
In addition, the partially imidized polyimide precursor comprises at least 1 imidized repeating unit out of 2 amide structures in the general formula (I).
The polyimide formed from the polyimide precursor having the repeating unit represented by the general formula (I) has the repeating unit represented by the following general formula (II).
[ Chemical 3]
(Wherein X 1 is a 4-valent aliphatic group or aromatic group, and Y 1 is a 2-valent aliphatic group or aromatic group.)
In the case of a soluble polyimide, the polyimide can be contained as a "polyimide precursor" in the polyimide precursor composition.
Hereinafter, the chemical structure of such polyimide will be described using the structure of X 1 and Y 2 in the repeating units (formulae (I) and (II)) and the monomers (tetracarboxylic acid component, diamine component, and other components) used for production, and the production method will be described.
In the present specification, the tetracarboxylic acid component includes tetracarboxylic acid, tetracarboxylic dianhydride, and tetracarboxylic acid derivatives such as tetracarboxylic silyl ester, tetracarboxylic ester, and tetracarboxylic acid chloride, which are used as raw materials for producing polyimide. Although not particularly limited, the use of tetracarboxylic dianhydride in the production is simple, and in the following description, an example of the use of tetracarboxylic dianhydride as the tetracarboxylic acid component will be described. The diamine component is a diamine compound having 2 amino groups (-NH 2) used as a raw material for producing polyimide.
In the present specification, the polyimide film refers to both a film formed on a (carrier) substrate and present in a laminate, and a film obtained by peeling off the substrate. In addition, a material obtained by heat-treating (imidizing) a polyimide precursor composition, which is a material constituting a polyimide film, may be referred to as a "polyimide material".
The polyimide contained in the polyimide film is not particularly limited, and the tetracarboxylic acid component and the diamine component are suitably composed of a polyimide selected from the group consisting of aromatic compounds and aliphatic compounds. The aliphatic compound of the diamine component is preferably an alicyclic compound. Examples of the polyimide include wholly aromatic polyimide, semi-alicyclic polyimide, and wholly alicyclic polyimide.
However, the polyimide material obtained is not particularly limited, and it is preferable that X 1 in the general formula (I) is a 4-valent group having an aromatic ring and Y 1 is a 2-valent group having an aromatic ring because of excellent heat resistance. In addition, since the obtained polyimide material is excellent in heat resistance and transparency, it is preferable that X 1 be a 4-valent group having an alicyclic structure and Y 1 be a 2-valent group having an aromatic ring. In addition, since the obtained polyimide material is excellent in heat resistance and dimensional stability, it is preferable that X 1 be a 4-valent group having an aromatic ring and Y 1 be a 2-valent group having an alicyclic structure.
From the viewpoints of characteristics of the obtained polyimide material, such as transparency, mechanical characteristics, and heat resistance, the content of the repeating unit represented by the formula (I) in which X 1 is a 4-valent group having an alicyclic structure and Y 1 is a 2-valent group having an alicyclic structure is preferably 50 mol% or less, more preferably 30 mol% or less, or less than 30 mol%, and still more preferably 10 mol% or less, relative to the total repeating units.
In one embodiment, the total content of 1 or more of the repeating units of the formula (I) in which X 1 is a 4-valent group having an aromatic ring and Y 1 is a 2-valent group having an aromatic ring is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 100 mol% relative to the total of the repeating units. In this embodiment, in particular, in the case of polyimide materials requiring high transparency, the polyimide preferably contains fluorine atoms. That is, the polyimide preferably contains 1 or more of the repeating units of the above general formula (I) in which X 1 is a 4-valent group having an aromatic ring containing a fluorine atom and/or the repeating units of the above general formula (I) in which Y 1 is a 2-valent group having an aromatic ring containing a fluorine atom.
In one embodiment, in the polyimide, the total content of 1 or more of the repeating units of the above general formula (I) in which X 1 is a 4-valent group having an alicyclic structure and Y 1 is a 2-valent group having an aromatic ring is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 100 mol% relative to the total of the repeating units.
In one embodiment, in the polyimide, the total content of 1 or more of the repeating units of the formula (I) in which X 1 is a 4-valent group having an aromatic ring and Y 1 is a 2-valent group having an alicyclic structure is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 100 mol% relative to the total of the repeating units.
< X 1 and tetracarboxylic acid component >
The 4-valent group having an aromatic ring of X 1 is preferably a 4-valent group having an aromatic ring of 6 to 40 carbon atoms.
Examples of the 4-valent group having an aromatic ring include the following groups.
[ Chemical 4]
(Wherein Z 1 is a direct bond or any of the following 2-valent groups.
[ Chemical 5]
Wherein Z 2 in the formula is a 2-valent organic group, Z 3、Z4 is each independently an amide bond, an ester bond, a carbonyl bond, and Z 5 is an organic group containing an aromatic ring. )
Specifically, Z 2 is an aliphatic hydrocarbon group having 2 to 24 carbon atoms or an aromatic hydrocarbon group having 6 to 24 carbon atoms.
Specifically, Z 5 is an aromatic hydrocarbon group having 6 to 24 carbon atoms.
The following 4-valent group is particularly preferable as the 4-valent group having an aromatic ring because the polyimide film obtained can achieve both high heat resistance and high transparency.
[ Chemical 6]
(Wherein Z 1 is a direct bond or a hexafluoroisopropylidene bond.)
Here, since the obtained polyimide film can achieve high heat resistance, high transparency, and low linear thermal expansion coefficient, Z 1 is more preferably a direct bond.
In addition, as a preferable group, in the above formula (9), Z 1 is represented by the following formula (3A):
[ chemical 7]
Compounds containing fluorenyl groups are shown. Z 11 and Z 12 are each independently preferably identical and are a single bond or a 2-valent organic group. As Z 11 and Z 12, an organic group containing an aromatic ring is preferable, and a structure represented by formula (3 A1) is preferable, for example.
[ Chemical 8]
( Z 13 and Z 14 are independently of each other a single bond, -COO-, -OCO-or-O-, where in the case where Z 14 is bonded to the fluorenyl group, it is preferable that Z 13 is-COO-, -OCO-or-O-, and Z 14 is a single bond; r 91 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, preferably a methyl group, and n is an integer of 0 to 4, preferably 1. )
Examples of the tetracarboxylic acid component providing a repeating unit of the general formula (I) wherein X 1 is a 4-valent group having an aromatic ring include 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane, 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic acid, pyromellitic acid, 3',4' -benzophenone tetracarboxylic acid, 3',4' -biphenyl tetracarboxylic acid, 2, 3',4' -biphenyltetracarboxylic acid, 4' -oxo-diphthalic acid, bis (3, 4-dicarboxyphenyl) sulfone, m-terphenyl-3, 4,3',4' -tetracarboxylic acid, p-terphenyl-3, 4,3',4' -tetracarboxylic acid, dicarboxyphenyl dimethylsilane, dicarboxyphenoxydiphenyl sulfide, sulfonyl diphthalic acid, tetracarboxylic dianhydrides thereof, tetracarboxylic silyl esters, tetracarboxylic acid chlorides, and the like. Examples of the tetracarboxylic acid component providing a repeating unit of the general formula (I) wherein X 1 is a 4-valent group having an aromatic ring containing a fluorine atom include derivatives such as 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane, tetracarboxylic dianhydride thereof, tetracarboxylic silyl ester, tetracarboxylic ester, and tetracarboxylic acid chloride. Further, as a preferable compound, (9H-fluorene-9, 9-diyl) bis (2-methyl-4, 1-phenylene) bis (1, 3-dioxo-1, 3-dihydroisobenzofuran-5-carboxylate) may be mentioned. The tetracarboxylic acid component may be used alone, or two or more kinds may be used in combination.
The 4-valent group having an alicyclic structure of X 1 is preferably a 4-valent group having an alicyclic structure of 4 to 40 carbon atoms, more preferably at least one aliphatic 4 to 12-membered ring, and still more preferably an aliphatic 4-membered ring or an aliphatic 6-membered ring. Examples of the 4-valent group having a preferable aliphatic 4-membered ring or aliphatic 6-membered ring include the following groups.
[ Chemical 9]
( Wherein R 31~R38 is each independently a direct bond or a 2-valent organic group. R 41~R47 each independently represents a member selected from the group consisting of: -CH 2-、-CH=CH-、-CH2CH2 -, -O-, -S-, a member of the group consisting of. R 48 is an organic group containing an aromatic or alicyclic structure. )
Specific examples of R 31、R32、R33、R34、R35、R36、R37、R38 include a direct bond, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an oxygen atom (-O-), a sulfur atom (-S-), a carbonyl bond, an ester bond, and an amide bond.
Examples of the organic group containing an aromatic ring of R 48 include the following groups.
[ Chemical 10]
(Wherein W 1 is a direct bond or a 2-valent organic group, n 11~n13 each independently represents an integer of 0 to 4, and R 51、R52、R53 each independently represents an alkyl group having 1 to 6 carbon atoms, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group.)
Specific examples of W 1 include a direct bond, a 2-valent group represented by the following formula (5), and a 2-valent group represented by the following formula (6).
[ Chemical 11]
(R 61~R68 in formula (6) each independently represents a direct bond or any one of the 2-valent groups represented by the above formula (5))
The following groups are particularly preferred as the 4-valent group having an alicyclic structure, since the polyimide obtained can achieve high heat resistance, high transparency, and low linear thermal expansion coefficient.
[ Chemical 12]
Examples of the tetracarboxylic acid component providing a repeating unit of the formula (I) wherein X 1 is a 4-valent group having an alicyclic structure include 1,2,3, 4-cyclobutanetetracarboxylic acid, isopropylidenediphenoxydiphthalic acid, cyclohexane-1, 2,4, 5-tetracarboxylic acid, [1,1 '-bis (cyclohexane) ] -3,3',4 '-tetracarboxylic acid, [1,1' -bis (cyclohexane) ] -2, 3',4' -tetracarboxylic acid, [1,1 '-bis (cyclohexane) ] -2,2',3,3 '-tetracarboxylic acid, 4' -methylenebis (cyclohexane-1, 2-dicarboxylic acid), 4'- (propane-2, 2-diyl) bis (cyclohexane-1, 2-dicarboxylic acid), 4' -oxybis (cyclohexane-1, 2-dicarboxylic acid), 4 '-thiobis (cyclohexane-1, 2-dicarboxylic acid), 4' -sulfonylbis (cyclohexane-1, 2-dicarboxylic acid) 4,4'- (dimethylsilanediyl) bis (cyclohexane-1, 2-dicarboxylic acid), 4' - (tetrafluoropropane-2, 2-diyl) bis (cyclohexane-1, 2-dicarboxylic acid), octahydropentalene-1, 3,4, 6-tetracarboxylic acid, bicyclo [2.2.1] heptane-2, 3,5, 6-tetracarboxylic acid, 6- (carboxymethyl) bicyclo [2.2.1] heptane-2, 3, 5-tricarboxylic acid, bicyclo [2.2.2] octane-2, 3,5, 6-tetracarboxylic acid, bicyclo [2.2.2] oct-5-ene-2, 3,7, 8-tetracarboxylic acid, tricyclo [4.2.2.02,5] decane-3, 4,7, 8-tetracarboxylic acid, tricyclo [4.2.2.02,5] dec-7-ene-3, 4,9, 10-tetracarboxylic acid, 9-oxatricyclo [4.2.1.02,5] nonane-3, 4,7, 8-tetracarboxylic acid, norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane 5,5",6 "-tetracarboxylic acid, (4 arH,8 ach) -decahydro-1 t,4t:5c,8 c-dimethylnaphthalene-2 c,3c,6c,7 c-tetracarboxylic acid, (4 arH,8 ach) -decahydro-1 t,4t:5c,8 c-dimethylnaphthalene-2 t,3t,6c,7 c-tetracarboxylic acid, and derivatives thereof such as tetracarboxylic dianhydride, tetracarboxylic silyl ester, tetracarboxylic acid chloride, and the like. The tetracarboxylic acid component may be used alone, or two or more kinds may be used in combination.
< Y 1 and diamine component >
The 2-valent group having an aromatic ring of Y 1 is preferably a 2-valent group having an aromatic ring with 6 to 40 carbon atoms, more preferably with 6 to 20 carbon atoms.
Examples of the 2-valent group having an aromatic ring include the following groups.
[ Chemical 13]
(Wherein W 1 is a direct bond or a 2-valent organic group, n 11~n13 each independently represents an integer of 0 to 4, and R 51、R52、R53 each independently represents an alkyl group having 1 to 6 carbon atoms, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group.)
Specific examples of W 1 include a direct bond, a 2-valent group represented by the following formula (5), and a 2-valent group represented by the following formula (6).
[ Chemical 14]
[ 15]
(R 61~R68 in formula (6) each independently represents a direct bond or any one of the 2-valent groups represented by the above formula (5))
Here, since the obtained polyimide can be given a combination of high heat resistance, high transparency, and low linear thermal expansion coefficient, W 1 is particularly preferably a direct bond or a polyimide selected from the group consisting of the following formulae: -NHCO-, -CONH-, -COO-, -OCO-, and a member of the group shown. In addition, W 1 is also particularly preferably R 61~R68 is a direct bond or is selected from the formulae: -NHCO-, -CONH-, -COO-, -OCO-, and any of the above-mentioned 2-valent groups represented by the formula (6).
In addition, as a preferable group, in the above formula (4), W 1 is represented by the following formula (3B):
[ 16]
The fluorenyl-containing group compound shown. Z 11 and Z 12 are each independently preferably identical and are a single bond or a 2-valent organic group. As Z 11 and Z 12, an organic group containing an aromatic ring is preferable, and a structure represented by formula (3B 1) is preferable, for example.
[ Chemical 17]
( Z 13 and Z 14 are independently of each other a single bond, -COO-, -OCO-or-O-, where in the case where Z 14 is bonded to the fluorenyl group, it is preferable that Z 13 is-COO-, -OCO-or-O-, and Z 14 is a single bond; r 91 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, preferably a phenyl group, and n is an integer of 0 to 4, preferably 1. )
As another preferable group, in the above formula (4), there may be mentioned a compound in which W 1 is a phenylene group, that is, a terphenylenediamine compound, and particularly, all of the compounds are preferably para-bonded.
As another preferable group, in the above formula (4), there may be mentioned a compound wherein R 61 and R 62 are 2, 2-propylene groups in the structure in which W 1 is the first 1 phenyl ring of the formula (6).
As another preferable group, in the above formula (4), a compound represented by the following formula (3B 2) is given as W 1.
[ Chemical 18]
Examples of the diamine component providing a repeating unit of the general formula (I) wherein Y 1 is a 2-valent group having an aromatic ring include p-phenylenediamine, m-phenylenediamine, benzidine, 3' -diaminobiphenyl, 2' -bis (trifluoromethyl) benzidine, 3' -bis (trifluoromethyl) benzidine, m-toluidine, 4' -diaminobenzidine, 3,4' -diaminobenzidine, N, N ' -bis (4-aminophenyl) terephthalamide, N ' -p-phenylenebis (p-aminobenzamide), 4-aminophenoxy-4-diaminobenzoate, bis (4-aminophenyl) terephthalate, biphenyl-4, 4' -dicarboxylic acid bis (4-aminophenyl) ester, p-phenylene bis (p-aminophenyl) ester, bis (4-aminophenyl) - [1,1' -biphenyl ] -4,4' -dicarboxylate, [1,1' -biphenyl ] -4,4' -diylbis (4-aminobenzoate), 4' -oxydiphenylamine, 3' -oxydiphenylamine, p-methylenebis (phenylenediamine), 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, 4' -bis (3-aminophenoxy) biphenyl, 2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane, bis (4-aminophenyl) sulfone, and 3,3' -bis (trifluoromethyl) benzidine, 3' -bis ((aminophenoxy) phenyl) propane, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4- (4-aminophenoxy) diphenyl) sulfone, bis (4- (3-aminophenoxy) diphenyl) sulfone, octafluorobiphenyl, 3 '-dimethoxy-4, 4' -diaminobiphenyl, 3 '-dichloro-4, 4' -diaminobiphenyl, 3 '-difluoro-4, 4' -diaminobiphenyl, 2, 4-bis (4-aminoanilino) -6-amino-1, 3, 5-triazine, 2, 4-bis (4-aminoanilino) -6-methylamino-1, 3, 5-triazine, 2, 4-bis (4-aminoanilino) -6-ethylamino-1, 3, 5-triazine, 2, 4-bis (4-aminoanilino) -6-anilino-1, 3, 5-triazine. Examples of the diamine component providing a repeating unit of the general formula (I) wherein Y 1 is a 2-valent group having an aromatic ring containing a fluorine atom include 2,2' -bis (trifluoromethyl) benzidine, 3' -bis (trifluoromethyl) benzidine, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane, and 2,2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane. Further, preferable diamine compounds include 4,4' - ((9H-fluorene-9, 9-diyl) bis ([ 1,1' -biphenyl ] -5, 2-diyl)) bis (oxy)) diamine, [1,1':4', 1' -terphenyl ] -4, 4' -diamine, and 4,4' - ([ 1,1' -binaphthyl ] -2,2' -diylbis (oxy)) diamine. The diamine component may be used alone, or two or more kinds may be used in combination.
The 2-valent group having an alicyclic structure of Y 1 is preferably a 2-valent group having an alicyclic structure of 4 to 40 carbon atoms, more preferably at least one aliphatic 4 to 12-membered ring, and still more preferably an aliphatic 6-membered ring.
Examples of the 2-valent group having an alicyclic structure include the following groups.
[ Chemical 19]
( Wherein V 1、V2 is each independently a direct bond or a 2-valent organic group, n 21~n26 is each independently an integer of 0to 4, R 81~R86 is each independently an alkyl group having 1to 6 carbon atoms, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group, and R 91、R92、R93 is each independently selected from the group consisting of the formulae: -CH 2-、-CH=CH-、-CH2CH2 -, -O-, -S-, a member of the group consisting of. )
Specifically, V 1、V2 is a direct bond or a 2-valent group represented by the above formula (5).
The following groups are particularly preferred as the 2-valent group having an alicyclic structure, since the polyimide obtained can achieve both high heat resistance and low linear thermal expansion coefficient.
[ Chemical 20]
As the 2-valent group having an alicyclic structure, the following groups are preferable.
[ Chemical 21]
Examples of the diamine component providing a repeating unit of the general formula (I) in which Y 1 is a 2-valent group having an alicyclic structure include 1, 4-diaminocyclohexane, 1, 4-diamino-2-methylcyclohexane, 1, 4-diamino-2-ethylcyclohexane, 1, 4-diamino-2-n-propylcyclohexane, 1, 4-diamino-2-isopropylcyclohexane, 1, 4-diamino-2-n-butylcyclohexane, 1, 4-diamino-2-isobutylcyclohexane, 1, 4-diamino-2-sec-butylcyclohexane, 1, 4-diamino-2-tert-butylcyclohexane, 1, 2-diaminocyclohexane, 1, 3-diaminocyclobutane, 1, 4-bis (aminomethyl) cyclohexane, 1, 3-bis (aminomethyl) cyclohexane, diaminobicycloheptane, diaminooxybicycloheptane, diaminomethoxybicycloheptane, isophorone diamine, diaminotricyclodecane, diaminomethyltriayclodecane, bis (3, 3 '-iminocyclohexane), bis (3, 6' -iminodiacetyl) methane, and 1,3 '-bis (3, 6' -tetramethyl) cyclohexane. The diamine component may be used alone, or two or more kinds may be used in combination.
In a preferred embodiment of the invention involving polyimide precursors, the polyimide precursor is not one derived solely from 3,3', 4' -biphenyltetracarboxylic acid derivative (dianhydride) and p-phenylenediamine. Preferably, the proportion of the repeating units of X 1 derived from 3,3', 4' -biphenyltetracarboxylic acid derivative (s-BPDA or the like) and Y 1 derived from p-phenylenediamine (PPD) in the general formula (I) is 25 mol% or less, more preferably 10 mol% or less, and still more preferably 0mol% or less of the total repeating units (excluding at least one of s-BPDA or the like and PPD).
In a preferred embodiment of the invention relating to polyimide precursors, the polyimide precursors and polyimides are not polyimide precursors and polyimides obtained from only tetracarboxylic acid derivatives (dianhydrides) having an aromatic ring and containing no fluorine atom and diamine compounds having an aromatic ring and containing no fluorine atom. That is, it is preferable that at least one of X 1 and Y 1 containing the general formula (I) is a repeating unit of a group having an alicyclic structure or a group having an aromatic ring containing a fluorine atom. Preferably, the proportion of the repeating units of the general formula (I) in which X 1 is a group having an aromatic ring (excluding a fluorine-containing group) and Y 1 is a group having an aromatic ring (excluding a fluorine-containing group) is 25 mol% or less, more preferably 10 mol% or less, and still more preferably 0 mol% or less of the total repeating units (at least one of X 1 and Y 1 is not a group having an aromatic ring and does not contain a fluorine atom).
As the tetracarboxylic acid component and the diamine component which provide the repeating unit represented by the above general formula (I), any of aliphatic tetracarboxylic acids other than alicyclic (in particular, dianhydride) and/or aliphatic diamines may be used, and the content thereof is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less (including 0%) with respect to 100 mol% of the total of the tetracarboxylic acid component and the diamine component.
Among them, in a preferred embodiment of the present invention, X 1 of the general formula (I) is a repeating unit having a 4-valent group of an alicyclic structure at a ratio exceeding 60%, more preferably 70% or more, still more preferably 80% or more, still more preferably 90% or more, particularly preferably 100% by mole of the total repeating units. In the case of alicyclic structure less than 100%, the remainder is preferably a 4-valent group having an aromatic ring. Preferred 4-valent groups having an alicyclic structure and 4-valent groups having an aromatic ring are as described above. Further, Y 1 may be any one of a 2-valent group having an aromatic ring and a 2-valent group having an alicyclic structure, and as described above, X 1 is a 4-valent group having an alicyclic structure, and Y 1 is a 2-valent group having an alicyclic structure, and the content of the repeating unit represented by formula (I) is preferably 50 mol% or less, more preferably 30 mol% or less, still more preferably 10 mol% or less, with respect to the total repeating units.
In another preferred embodiment of the present invention, polyimide (and polyimide material) having a breaking strength of 80MPa or more when formed into a film is preferred. The breaking strength may be, for example, a value obtained from a film having a film thickness of about 5 to 100. Mu.m. The breaking strength is a value obtained for a film obtained by heating a polyimide precursor solution composition or a coating film of the polyimide solution composition preferably at a maximum temperature of 310 ℃.
The polyimide precursor can be produced from the above-described tetracarboxylic acid component and diamine component. The polyimide precursor (polyimide precursor containing at least one of the repeating units represented by the above formula (I)) used in the present invention can be classified into:
1) Polyamic acid (R 1 and R 2 are hydrogen);
2) Polyamic acid esters (at least a portion of R 1 and R 2 are alkyl groups);
3) 4) a polyamic acid silyl ester (at least a portion of R 1 and R 2 is an alkylsilyl group).
The polyimide precursor can be easily produced by the following production method according to the classification. However, the method for producing the polyimide precursor used in the present invention is not limited to the following production method.
1) Polyamic acid
The polyimide precursor can be suitably obtained in the form of a polyimide precursor solution by reacting, in a solvent, tetracarboxylic dianhydride as a tetracarboxylic acid component and a diamine component in a ratio of about equimolar, preferably a molar ratio of the diamine component to the tetracarboxylic acid component [ the number of moles of the diamine component/the number of moles of the tetracarboxylic acid component ] of preferably 0.90 to 1.10, more preferably 0.95 to 1.05, at a relatively low temperature of, for example, 120 ℃ or less, while suppressing imidization.
More specifically, the polyimide precursor is obtained by dissolving a diamine in an organic solvent or water, slowly adding a tetracarboxylic dianhydride to the solution while stirring, and stirring at a temperature in the range of 0 to 120 ℃, preferably 5 to 80 ℃ for 1 to 72 hours. In the case of a reaction at 80 ℃ or higher, the molecular weight varies depending on the temperature history during polymerization, and imidization is performed by heat, so that there is a possibility that a polyimide precursor cannot be stably produced. The order of addition of the diamine and the tetracarboxylic dianhydride in the above production method is preferable because it is easy to increase the molecular weight of the polyimide precursor. The order of addition of the diamine and the tetracarboxylic dianhydride in the above production method may be reversed, and it is preferable to reduce the amount of precipitate. When water is used as the solvent, an imidazole such as 1, 2-dimethylimidazole or a base such as triethylamine is preferably added in an amount of 0.8 times or more equivalent to the carboxyl group of the polyamide acid (polyimide precursor) to be produced.
2) Polyamic acid esters
The tetracarboxylic dianhydride is reacted with an arbitrary alcohol to obtain a dicarboxylic acid diester, and then reacted with a chlorinating agent (thionyl chloride, oxalyl chloride, etc.) to obtain a diester dicarboxylic acid chloride. The diester dicarboxylic acid chloride and diamine are stirred at a temperature in the range of-20 to 120 ℃, preferably-5 to 80 ℃ for 1 to 72 hours, thereby obtaining a polyimide precursor. In the case of a reaction at 80 ℃ or higher, the molecular weight varies depending on the temperature history during polymerization, and imidization is performed by heat, so that there is a possibility that a polyimide precursor cannot be stably produced. Further, a polyimide precursor can be easily obtained by dehydrating condensation of a dicarboxylic acid diester and a diamine using a phosphorus-based condensing agent, a carbodiimide condensing agent, or the like.
The polyimide precursor obtained by this method is stable, and therefore, can be purified by adding a solvent such as water or alcohol for reprecipitation.
3) Polyamic acid silyl ester (indirect method)
The diamine is reacted with a silylating agent in advance to give a silylated diamine. Purification of the silylated diamine is carried out by distillation or the like as needed. Then, the silylated diamine is dissolved in the dehydrated solvent in advance, and the tetracarboxylic dianhydride is slowly added while stirring, and stirred at a temperature ranging from 0 to 120 ℃, preferably from 5 to 80 ℃ for 1 to 72 hours, thereby obtaining a polyimide precursor. In the case of a reaction at 80 ℃ or higher, the molecular weight varies depending on the temperature history during polymerization, and imidization is performed by heat, so that there is a possibility that a polyimide precursor cannot be stably produced.
4) Polyamic acid silyl ester (direct method)
The polyamic acid solution obtained in the method of 1) is mixed with a silylating agent and stirred at a temperature ranging from 0 to 120 ℃, preferably from 5 to 80 ℃ for 1 to 72 hours, thereby obtaining a polyimide precursor. In the case of a reaction at 80 ℃ or higher, the molecular weight varies depending on the temperature history during polymerization, and imidization is performed by heat, so that there is a possibility that a polyimide precursor cannot be stably produced.
The silylating agent used in the method of 3) and the method of 4) is preferably a chlorine-free silylating agent because it is not necessary to purify the silylated polyamic acid or the polyimide obtained. Examples of the silylating agent containing no chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane. N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferable for the reason of no fluorine atom and low cost.
In the silylation reaction of diamine in the method of 3), an amine catalyst such as pyridine, piperidine, and triethylamine may be used to promote the reaction. The catalyst can be directly used as a polymerization catalyst of polyimide precursor.
The solvent used in the preparation of the polyimide precursor is preferably water, or an aprotic solvent such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, dimethylsulfoxide, or the like, and any kind of solvent may be used without any problem as long as it can dissolve the raw material monomer components and the polyimide precursor to be produced, and therefore the structure thereof is not particularly limited. As the solvent, water, or an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, a cyclic ester solvent such as gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, gamma-caprolactone, epsilon-caprolactone, alpha-methyl-gamma-butyrolactone, a carbonate solvent such as ethylene carbonate, propylene carbonate, a glycol solvent such as triethylene glycol, a phenol solvent such as m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, acetophenone, 1, 3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide, and the like are preferably used. In addition, other general organic solvents, that is, phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, turpentine, mineral spirits, naphtha-based solvents, and the like may also be used. It should be noted that two or more solvents may be used in combination.
The logarithmic viscosity of the polyimide precursor is not particularly limited, but the logarithmic viscosity in an N, N-dimethylacetamide solution having a concentration of 0.5g/dL at 30℃is preferably 0.2dL/g or more, more preferably 0.3dL/g or more, particularly preferably 0.4dL/g or more. When the logarithmic viscosity is 0.2dL/g or more, the molecular weight of the polyimide precursor is high, and the obtained polyimide is excellent in mechanical strength and heat resistance.
The imidization ratio of the polyimide precursor can be used in a wide range of about 0% (5% or less) to about 100% (95% or more). The polyimide precursors (polyamic acid, polyamic acid ester, polyamic acid silyl ester) obtained by the above method have a low imidization rate. These are imidized by subjecting them to imidization treatment (thermal imidization, chemical imidization) in a solution, and the imidization ratio can be adjusted to a desired imidization ratio. For example, the polyimide precursor obtained by imidization can be obtained by stirring the polyamic acid solution at, for example, 80 to 230℃and preferably 120 to 200℃for, for example, 1 to 24 hours. When polyimide is soluble in a solvent, a polyimide obtained by precipitating polyimide by pouring the reaction mixture after imidization into a poor solvent, or a solution of a polyimide precursor (low imidization rate) (containing an imidization catalyst, a dehydrating agent if necessary) is poured onto a carrier substrate, for example, and heat-treated, dried, imidized (thermal imidization, chemical imidization), and the polyimide thus obtained is dissolved in a solvent, and can be used as a polyimide precursor for film production.
< Phosphorus Compound >
The phosphorus compound that can be used is a compound having at least 1 structure selected from P (=o) OH and P (=o) OR (where R is an alkyl group having 4 OR more carbon atoms) in the molecule. The phosphorus compound preferably does not have an aryl group directly bonded to the phosphorus atom P, and more preferably does not contain an aryl group in the molecule. The phosphorus compound can have 1 or 2 or more phosphorus atoms in the molecule.
In a preferred embodiment of the invention, the phosphorus compound contains only one phosphorus atom. The compound having one phosphorus atom includes a compound represented by the formula (P).
[ Chemical 22]
Wherein at least 1 group in R 1~R3 represents OH or an alkoxy group having 4 or more carbon atoms, and the remaining groups independently represent groups selected from OH, alkoxy, H and alkyl.
The alkoxy group having 4 or more carbon atoms is preferably an alkoxy group having 4 to 18 carbon atoms, more preferably an alkoxy group having 4 to 12 carbon atoms. They may be any of linear, branched, alicyclic, preferably linear alkoxy. The "alkoxy group having not limited to 4 or more carbon atoms" preferably includes an alkoxy group having 1 to 18 carbon atoms, and examples thereof include an alkoxy group having 1 to 3 carbon atoms other than the above-mentioned alkoxy group having 4 or more carbon atoms.
Examples of the alkyl group include an alkyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms. They may be any of linear, branched, alicyclic, preferably linear alkyl.
In the case where at least 1 group in R 1~R3 is OH, the remaining groups are not particularly limited, and are preferably selected from OH, alkoxy and alkyl. As the combination of R 1~R3 in this case, all of OH (phosphoric acid), 2 OH and 1 alkoxy (monoalkyl phosphate), 1 OH and 2 alkoxy (dialkyl phosphate), 2 OH and 1 alkyl (monoalkyl phosphonate), 1 OH and 2 alkyl (dialkyl phosphinate), 1 OH and 1 alkoxy and 1 alkyl (monoalkyl phosphinate) are mentioned.
In the case where at least 1 group in R 1~R3 is an alkoxy group having 4 or more carbon atoms, the remaining groups are not particularly limited, and are preferably selected from OH, alkoxy and alkyl groups. When OH is contained as R 1~R3, the above combination corresponds to the case where the number of carbon atoms of the alkoxy group is 4 or more. Examples of the combination of R 1~R3 selected from the group consisting of an alkoxy group and an alkyl group include an alkoxy group having 4 or more carbon atoms (trialkyl phosphate), an alkoxy group having 2 or more carbon atoms and 1 alkyl group (dialkyl monoalkyl phosphonate), an alkoxy group having 1 or more carbon atoms and 2 alkyl groups (monoalkyl dialkylphosphinate). When the phosphorus compound contains 2 or more alkoxy groups, they are preferably the same because they are easily available. Therefore, when "an alkoxy group having 4 or more carbon atoms" is required to be contained in the compound, 2 or more alkoxy groups are preferably the same "an alkoxy group having 4 or more carbon atoms".
Examples of the phosphorus compound having 2 or more phosphorus atoms include polyphosphoric acids such as diphosphoric acid, triphosphoric acid, cyclotriphosphoric acid, tetraphosphoric acid, and ester compounds thereof (partially or wholly esterified compounds). In the case of a fully esterified compound, at least a part, preferably all, of the alkoxy moiety of the ester is an alkoxy group having 4 or more carbon atoms. In the case of a partially esterified compound, the number of carbon atoms of the alkoxy moiety is not limited, and an alkoxy group having 4 or more carbon atoms is also preferable.
As the phosphorus compound containing 2 or more phosphorus atoms, a compound having a polyphosphate structure or an oligophosphate structure may be mentioned. Specifically, the compound represented by the general formula (PPE) is exemplified.
[ Chemical 23]
In the formula (PPE), R 1~R3 are independent from each other, more than 2R 2 are independent from each other and represent a group selected from OH, alkoxy, H and alkyl, and at least 1 group in R 1~R3 represents OH or alkoxy with more than 4 carbon atoms. R 4 represents a 2-valent hydrocarbon group. n is an integer of 0 or more.
The preferred group for R 1~R3 is the same as R 1~R3 shown for formula (P). Most preferably, all R 1~R3 represents an alkoxy group having 4 or more carbon atoms. R 4 is preferably a hydrocarbon group having 1 to 16 carbon atoms or less, more preferably 1 to 6 carbon atoms, and is preferably a linear or branched alkylene group. n is preferably 0 to 4, more preferably 0 to 2, and still more preferably 0.
In the present invention, the molecular weight of the phosphorus compound is preferably less than 400, and in particular, in the phosphorus compound represented by the formula (P) and the phosphorus compound represented by the formula (PPE), the molecular weight is preferably less than 400.
Specific examples of the phosphorus compound include phosphoric acid, methylphosphonic acid, ethylphosphonic acid, n-propylphosphonic acid, isopropylphosphonic acid, n-butylphosphonic acid, sec-butylphosphonic acid, isobutylphosphonic acid, tert-butylphosphonic acid, n-pentylphosphonic acid, isopentylphosphonic acid, neopentylphosphonic acid, n-hexylphosphonic acid, cyclohexylphosphonic acid, heptylphosphonic acid, n-octylphosphonic acid, nonylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid, phenylphosphonic acid, (4-hydroxyphenyl) phosphonic acid, methylenediphosphonic acid, 1, 2-ethylenediphosphonic acid, phthalenediphosphonic acid, m-xylylenediphosphonic acid, p-xylylenediphosphonic acid, dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, ethylbutylphosphinic acid, dipropylphosphinic acid, phenylphosphinic acid, diphenylphosphinic acid, methylphenylphosphinic acid, (2-carboxyethyl) phenylphosphinic acid, (2-ethylhexyl) phosphonic acid, mono-2-ethylhexyl phosphate, tributyl phosphate, n-ethylhexyl phosphate, tributyl phosphate, 2-diisobutylphosphate, and tributyl phosphate (2-diisobutylphosphate (=1 h). In the above compound, the alkyl group may be substituted with a structural isomer having the same number of carbon atoms, at least 1H in the alkyl group or the aryl group may be substituted with fluorine, and the substitution position in the aryl group is arbitrary. In addition, the phosphorus compound may be used alone or in combination of 2 or more.
In one embodiment of the present invention, the polyimide precursor composition is sometimes preferably different from the following composition: when the phosphorus compound is phosphoric acid or tributyl phosphate, the polyimide precursor is a polyimide precursor obtained from only norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2 "-norbornane-5, 5",6 "-tetracarboxylic dianhydride (CpODA), 4' -Diaminoanilide (DABAN), and p-phenylenediamine (PPD). In one embodiment of the invention, the polyimide precursor is also sometimes preferably selected from a combination of monomers other than the combination of CpODA, DABAN and PPD.
< Compounding of polyimide precursor composition >
The polyimide precursor composition used in the present invention comprises at least one polyimide precursor, at least one of the above-described phosphorus compounds, and a solvent.
The content of the phosphorus compound may be adjusted in consideration of the peel strength between the polyimide film and the substrate. In general, if too small, the peel strength is too large, and peeling becomes difficult; on the other hand, if the amount is too large, not only is waste, but also the peel strength becomes extremely small, and particularly, the color of the colorless transparent polyimide film becomes large (the yellow degree b * becomes large), and the polyimide film is sometimes unsuitable for transparent use.
The content of the phosphorus compound is preferably more than 0.001 mol%, more preferably 0.005 mol% or more, still more preferably 0.01 mol% or more, still more preferably 0.02 mol% or more, still more preferably 0.05 mol% or more, based on the total monomer units of the polyimide precursor (i.e., the recurring units of the formula (I) and the formula (I) are calculated as 2 mol%). In addition, it is usually less than 5 mol%, more preferably 4 mol% or less, still more preferably 3 mol% or less, and particularly preferably 2 mol% or less.
As the solvent, the above-described solvents described as solvents used in the preparation of polyimide precursors can be used. In general, the solvent used in the preparation of the polyimide precursor may be used as it is, that is, in the form of a polyimide precursor solution, but may be diluted or concentrated as needed. The phosphorus compound is dissolved and present in the polyimide precursor composition.
The viscosity (rotational viscosity) of the polyimide precursor of the present invention is not particularly limited, but the rotational viscosity measured using an E-type rotational viscometer at a temperature of 25℃and a shear rate of 20sec -1 is preferably 0.01 to 1000 Pa-sec, more preferably 0.1 to 100 Pa-sec. In addition, thixotropic properties may be imparted as needed. In the above range of viscosity, the film can be easily handled when coating or film formation is performed, shrinkage cavity is suppressed, and leveling property is excellent, so that a good film can be obtained.
The polyimide precursor composition of the present invention may contain, if necessary, a chemical imidizing agent (an acid anhydride such as acetic anhydride, an amine compound such as pyridine or isoquinoline), an antioxidant, an ultraviolet absorber, a filler (inorganic particles such as silica), a coupling agent such as a dye, a pigment or a silane coupling agent, a primer, a flame retardant, a defoaming agent, a leveling agent, a rheology control agent (flow aid), and the like.
As for the preparation of the polyimide precursor composition, the preparation can be performed by adding a phosphorus compound or a solution of a phosphorus compound to the polyimide precursor solution obtained by the above-described method and mixing. If the reaction is not affected, the tetracarboxylic acid component and the diamine component may be reacted in the presence of a phosphorus compound.
Production of polyimide/substrate laminate and flexible electronic device
The method for manufacturing a flexible electronic device of the present invention comprises: (a) A step of applying the polyimide precursor composition to a substrate; (b) A step of producing a laminate (polyimide/substrate laminate) in which a polyimide film is laminated on the substrate by heating the polyimide precursor on the substrate; (c) Forming at least 1 layer selected from a conductor layer and a semiconductor layer on the polyimide film of the laminate; and (d) peeling the base material from the polyimide film by an external force.
The polyimide precursor composition that can be used in the method of the present invention contains a polyimide precursor, a phosphorus compound, and a solvent. The phosphorus compound described in the above item of phosphorus compound can be used. The polyimide precursor may be any of the polyimide precursors described in the section of the polyimide precursor composition. The polyimide precursor described as a preferable material in the item of the polyimide precursor composition is also preferable in the method of the present invention, and is not particularly limited.
One embodiment of the method of the present invention does not include the following: in the step (a), a polyimide/base material laminate of the step (b) is produced by using a precursor composition containing phosphoric acid or tributyl phosphate as a phosphorus compound, a tetracarboxylic acid component consisting of CpODA, and a diamine component consisting of a mixture of DABAN and PPD as the polyimide precursor composition, and performing the step (b) under heating conditions at a maximum temperature of 410 ℃, preferably 410 ℃ or higher. Preferably, the following method is not included: in the step (a), as the polyimide precursor composition, "a precursor composition containing phosphoric acid or tributyl phosphate as a phosphorus compound, a tetracarboxylic acid component consisting of CpODA, and a diamine component consisting of a mixture of DABAN and PPD" is used.
First, in the step (a), a polyimide precursor solution (including an imide solution having a high imidization rate and further including a composition solution containing an additive as required) is poured onto a substrate, imidization and desolvation (mainly desolvation in the case of a polyimide solution) are performed by a heat treatment, whereby a polyimide film is formed, and a laminate of the substrate and the polyimide film (polyimide/substrate laminate) is obtained.
As the base material, a heat-resistant material is used, and for example, a plate-like or sheet-like base material such as a ceramic material (glass, alumina, or the like), a metal material (iron, stainless steel, copper, aluminum, or the like), a semiconductor material (silicon, a compound semiconductor, or the like), or a film or sheet-like base material such as a heat-resistant plastic material (polyimide, or the like) is used. In general, a flat and smooth plate-like glass substrate such as soda lime glass, borosilicate glass, alkali-free glass, or sapphire glass is usually preferable; a semiconductor (including a compound semiconductor) substrate such as silicon or GaAs, inP, gaN; metal substrates such as iron, stainless steel, copper, and aluminum. In particular, a flat, smooth and large-area glass substrate is being developed and is readily available, and is therefore preferred. These substrates may be formed with an inorganic thin film (for example, a silicon oxide film) or a resin thin film on the surface.
The thickness of the plate-like base material is not limited, but is, for example, 20 μm to 4mm, preferably 100 μm to 2mm, in view of ease of handling.
The method of casting the polyimide precursor solution on the substrate is not particularly limited, and examples thereof include conventionally known methods such as spin coating, screen printing, bar coating, and electrodeposition.
In the step (b), the polyimide precursor composition is heat-treated on the substrate and converted into a polyimide film, thereby obtaining a polyimide/substrate laminate. The heating treatment conditions are not particularly limited, and it is preferable to carry out the treatment at a maximum heating temperature, for example, 150 to 600 ℃, preferably 200 to 550 ℃, more preferably 250 to 500 ℃ after drying at a temperature range of 50 to 150 ℃. The heating conditions in the case of using the polyimide solution are not particularly limited, and the maximum heating temperature is, for example, 100 to 600 ℃, preferably 150 ℃ or higher, more preferably 200 ℃ or higher, and preferably 500 ℃ or lower, more preferably 450 ℃ or lower.
The thickness of the polyimide film is preferably 1 μm or more, more preferably 2 μm or more, and still more preferably 5 μm or more. If the thickness is less than 1 μm, the polyimide film may not maintain sufficient mechanical strength, and may not be completely stressed and broken when used as a flexible electronic device substrate, for example. The thickness of the polyimide film is preferably 100 μm or less, more preferably 50 μm or less, and still more preferably 20 μm or less. If the thickness of the polyimide film is increased, the thickness of the flexible device may be difficult to thin. In order to maintain sufficient resistance as a flexible device and further thin the polyimide film, the thickness of the polyimide film is preferably 2 to 50 μm.
In one embodiment, the polyimide film preferably has excellent optical characteristics such as 400nm transmittance, total light transmittance (average transmittance of 380nm to 780 nm), and yellowness b (YI). The 400nm light transmittance is preferably 50% or more, more preferably 70% or more, still more preferably 75% or more, most preferably 80% or more, the total light transmittance is preferably 84% or more, more preferably 85% or more, and the yellowness index b (YI) is preferably 0 to 5, more preferably 3 or less, as measured with a film having a thickness of 10 μm, respectively. In 400nm transmittance, total light transmittance and yellowness b (YI), preferably at least 1, more preferably at least 2, most preferably 3 are simultaneously satisfied with the preferred ranges.
In one embodiment, the polyimide film preferably has a thickness direction retardation (retardation) R th small. In addition, the addition of the phosphorus compound specified in the present invention to the polyimide precursor composition of the present invention does not substantially change R th of the resulting polyimide film. Therefore, in the present invention, the peel strength between the polyimide film and the substrate can be adjusted without affecting R th.
The polyimide film thus obtained is bonded to a base material such as a glass substrate and laminated. In order to enable easy mechanical peeling, the peel strength of the substrate and the polyimide film is preferably 0.8N/in (N/25.4 mm) or less, more preferably 0.6N/in or less, and still more preferably 0.4N/in or less, in the case of measurement according to JIS K6854-1, for example, in a stretching speed of 2 mm/min, 90℃peel test. On the other hand, the lower limit is preferably 0.01N/in or more. Peel strength is typically measured in air or in the atmosphere.
The polyimide film in the polyimide/base material laminate may have a2 nd layer such as a resin film or an inorganic film on the surface. That is, after forming a polyimide film on a base material, the 2 nd layer may be laminated to form a flexible electronic device substrate. It is preferable to have at least an inorganic film, and particularly preferable to function as a barrier layer for water vapor, oxygen (air), or the like. Examples of the water vapor barrier layer include an inorganic film containing an inorganic substance selected from the group consisting of a metal oxide, a metal nitride, and a metal oxynitride, such as silicon nitride (SiN x), silicon oxide (SiO x), silicon oxynitride (SiO xNy), aluminum oxide (Al 2O3), titanium oxide (TiO 2), and zirconium oxide (ZrO 2). Generally, as a film forming method of these thin films, a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method, a chemical vapor deposition method (chemical vapor deposition method) such as a plasma CVD method, a catalytic chemical vapor deposition method (Cat-CVD method), or the like is known. The layer 2 may be a plurality of layers.
In the present application, the peel strength can be reduced by containing the phosphorus compound in the polyimide precursor composition. Accordingly, the present application also discloses a method for reducing the peel strength of a laminate comprising a substrate and a polyimide film formed on the substrate, wherein the polyimide precursor composition for forming the polyimide film contains the phosphorus compound.
In the step (c), at least one layer selected from the conductor layer and the semiconductor layer is formed on the polyimide film (including the case where the 2 nd layer such as an inorganic film is laminated on the surface of the polyimide film) using the polyimide/base material laminate obtained in the step (b). These layers may be directly formed on the polyimide film (including the case where the 2 nd layer is laminated), or may be formed indirectly after other layers necessary for the device are laminated.
The conductor layer and/or the semiconductor layer the appropriate conductor layer and (inorganic, organic) semiconductor layer are selected according to the elements and circuits required for the target electronic device. In the step (c) of the present invention, when at least one of the conductor layer and the semiconductor layer is formed, it is preferable that at least one of the conductor layer and the semiconductor layer is formed on the polyimide film on which the inorganic film is formed.
The conductor layer and the semiconductor layer include both of the case of being formed on the entire surface of the polyimide film and the case of being formed on a part of the polyimide film. The present invention may be transferred to the step (d) immediately after the step (c), or may be transferred to the step (d) after forming at least one layer selected from the conductor layer and the semiconductor layer in the step (c) and then further forming the device structure.
In the case of manufacturing a TFT liquid crystal display device as a flexible device, for example, metal wirings, TFTs using amorphous silicon or polysilicon, transparent pixel electrodes, for example, are formed on a polyimide film having an inorganic film formed on the entire surface as needed. The TFT includes, for example, a semiconductor layer such as a gate metal layer or an amorphous silicon film, a gate insulating layer, a wiring connected to a pixel electrode, and the like. In addition, the structure required for the liquid crystal display can be further formed by a known method. In addition, a transparent electrode and a color filter may be formed on the polyimide film.
In the case of manufacturing an organic EL display, for example, a TFT may be formed as needed on a polyimide film in which an inorganic film is formed over the entire surface as needed, for example, in addition to a transparent electrode, a light-emitting layer, a hole-transporting layer, an electron-transporting layer, and the like.
The polyimide film preferred in the present invention is excellent in various properties such as heat resistance and toughness, and thus a method for forming a circuit, an element, and other structures required for a device is not particularly limited.
Next, in the step (d), the base material and the polyimide film are physically separated by an external force. By "by external force" is meant that a force is applied to separate the substrate from the polyimide film. For example, by a human hand or by a suitable tool, clamp, device, etc. When peeled, one or both of the base material and the polyimide film are bent, but the polyimide film is bent in a range where the conductor layer, the semiconductor layer, and other structures formed on the polyimide film are not damaged. For this purpose, the polyimide film can be peeled off by using a tool, a jig, a device, or the like as appropriate so that the radius of curvature at the time of bending is not reduced. Specifically, examples thereof include: (i) A method of peeling a polyimide film by inserting a tool such as a blade between a substrate and the polyimide film and moving the tool; (ii) A method of peeling off a film by pulling it up from a substrate (in this case, a tool such as a blade may be used); (iii) A method of bending a substrate and peeling the substrate while maintaining the flatness of the film as much as possible; etc. The stripping is preferably carried out in gas or vacuum, usually in air or in the atmosphere.
The device is completed by further forming or assembling a structure or a component required for the device in a (semi) product having the polyimide film after peeling the substrate as a substrate.
In a preferred embodiment of the present invention, the separation of the base material from the polyimide film is performed by a separation method using only an external force without performing laser irradiation.
In another embodiment of the present invention, the method of the present invention, that is, the method of the polyimide precursor containing the phosphorus compound can be applied as an auxiliary means when the peeling cannot be achieved only by the laser irradiation.
Accordingly, another aspect of the present invention relates to a method of manufacturing a flexible electronic device, having:
(a) A step of applying a polyimide precursor composition containing a polyimide precursor, a phosphorus compound having a P (=o) OH structure OR a P (=o) OR structure (wherein R is an alkyl group having 4 OR more carbon atoms), and a solvent to a substrate;
(b) A step of producing a laminate in which a polyimide film is laminated on the base material by heating the polyimide precursor on the base material;
(c) Forming at least 1 layer selected from a conductor layer and a semiconductor layer on the polyimide film of the laminate;
(e) A step of irradiating the laminate with laser light; and
(D) And peeling the base material from the polyimide film by an external force.
A further aspect of the present invention relates to a method capable of performing laser lift-off when laser irradiation lift-off is not possible. For reasons such as dependence on composition and insufficient output of laser light, when the polyimide precursor composition cannot be peeled even when laser irradiation is performed, laser peeling can be performed by using the polyimide precursor composition containing a phosphorus compound. That is, this embodiment relates to a method for manufacturing a flexible electronic device, which includes the steps of,
(A2) A step of applying a polyimide precursor composition containing a polyimide precursor and a solvent to a substrate;
(b2) A step of producing a laminate in which a polyimide film is laminated on the base material by heating the polyimide precursor on the base material;
(c2) Forming at least 1 layer selected from a conductor layer and a semiconductor layer on the polyimide film of the laminate; and
(E2) A step of irradiating the laminate with a laser beam,
The polyimide precursor composition is characterized by containing a phosphorus compound having a P (=O) OH structure OR a P (=O) OR structure (wherein R is an alkyl group having 4 OR more carbon atoms).
Examples
The present invention will be further described below with reference to examples and comparative examples. The present invention is not limited to the following examples.
< Evaluation of polyimide film >
[b*(YI)]
B * (=yi; yellowness) of a polyimide film having a film thickness of 10 μm and a square size of 3cm was measured according to ASTEM E313,313 standard using an ultraviolet-visible spectrophotometer/V-650 DS (manufactured by japan spectroscopy). The light source is D65, and the visual angle is 2 degrees.
[400Nm transmittance, total transmittance ]
The transmittance and total transmittance (average transmittance at wavelengths of 380nm to 780 nm) of a polyimide film having a film thickness of 10 μm and a square size of 5cm were measured at a wavelength of 400nm using an ultraviolet-visible spectrophotometer/V-650 DS (manufactured by Japan spectroscopy).
[ Peel Strength ]
The peel strength in the 90℃direction was measured using TENSILON RTA-500 manufactured by ORIENTEC company under the condition of a stretching speed of 2 mm/min.
[ Glass transition temperature (Tg) ]
A polyimide film having a film thickness of about 10 μm was cut into a long shape having a width of 4mm, and a test piece was produced, and the temperature was raised to 500℃under conditions of a chuck spacing of 15mm, a load of 2g and a heating rate of 20℃per minute using TMA/SS6100 (manufactured by SII Nanotechnology Co., ltd.). The glass transition temperature (Tg) was calculated from the inflection point of the obtained TMA curve.
[1% Weight loss temperature (Td 1%) ]
A polyimide film having a film thickness of about 10 μm was used as a test piece, and the temperature was increased from 25℃to 600℃in a nitrogen gas stream at a rate of 10℃per minute by using a calorimeter measurement apparatus (Q5000 IR) manufactured by TA INSTRUMENTS. From the weight curve obtained, a 1% weight loss temperature was determined.
The abbreviations of the compounds used in the following examples are as follows.
TFMB:4,4' -bis (trifluoromethyl) benzidine
ODA:4,4' -diaminodiphenyl ether
4,4' -DDS:4,4' -diaminodiphenyl sulfone
M-TD:2,2 '-dimethyl-4, 4' -diaminobiphenyl
BAFL:9, 9-bis (4-aminophenyl) fluorene
BAPB:4,4' -bis (4-aminophenoxy) biphenyl
6FDA:4,4' - (2, 2-hexafluoro-isopropenyl) diphthalic anhydride
PMDA-HS:1R,2S,4S, 5R-cyclohexane tetracarboxylic dianhydride
S-BPDA:3,3', 4' -biphenyltetracarboxylic dianhydride
BPADA:5,5' - ((propane 2-2-diylbis (1, 4-phenylene)) bis (oxy)) bis (isobenzofuran-1, 3-dione)
CpODA: norbornane-2-spiro-alpha-cyclopentanone-alpha' -spiro-2 "-norbornane-5, 5",6 "-tetracarboxylic dianhydride
CBDA: cyclobutane tetracarboxylic dianhydride
PPHT: n, N' - (1, 4-phenylene) bis (1, 3-dioxooctahydroisobenzofuran-5-carboxamide)
TABLE 1
TABLE 2
Synthesis example 1
A reaction vessel replaced with nitrogen was charged with 8.38g (26.2 mmol) of TFMB, and 80.03g of N-methyl-2-pyrrolidone, the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) of which was 20% by mass, was added thereto, and the mixture was stirred at room temperature for 30 minutes. To this solution was slowly added 6FDA 11.62g (26.2 mmol). Stirring at room temperature for 12 hours gave a polyimide precursor solution which was homogeneous and viscous.
Synthesis example 2
An ODA 8.02g (40.0 mmol) was charged into a nitrogen-substituted reaction vessel, and 83.04g of N, N-dimethylacetamide was added to the reaction vessel in an amount such that the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) became 17% by mass, and the mixture was stirred at room temperature for 30 minutes. To this solution was slowly added 8.98g (40.0 mmol) of PMDA-HS. Stirring at room temperature for 12 hours gave a polyimide precursor solution which was homogeneous and viscous.
Synthesis example 3
A nitrogen-substituted reaction vessel was charged with 6.68g (20.8 mmol) of TFMB, 59.99g of N-methyl-2-pyrrolidone in an amount of 20% by mass based on the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) was added, and the mixture was stirred at room temperature for 30 minutes. 6FDA 6.48g (14.6 mmol) and s-BPDA 1.85g (6.3 mmol) were slowly added to the solution. Stirring at room temperature for 12 hours gave a polyimide precursor solution which was homogeneous and viscous.
Synthesis example 4
A reaction vessel replaced with nitrogen was charged with 10.20g (31.9 mmol) of TFMB and 0.16g (0.6 mmol) of 4,4' -DDS, 80.02g of N, N-dimethylacetamide in an amount of 20% by mass based on the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) was added, and the mixture was stirred at room temperature for 30 minutes. To this solution, 0.17g (0.3 mmol) of BPADA and 9.47g (32.2 mmol) of s-BPDA were slowly added. Stirring at room temperature for 12 hours gave a polyimide precursor solution which was homogeneous and viscous.
Synthesis example 5
A nitrogen-substituted reaction vessel was charged with 10.93g (51.5 mmol) of m-TD, 78.01g of N-methyl-2-pyrrolidone in an amount of 22% by mass based on the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) was added, and the mixture was stirred at room temperature for 30 minutes. To this solution was slowly added CpODA 1.98.98 g (5.1 mmol) and CBDA 9.88g (46.3 mmol). Stirring at room temperature for 12 hours gave a polyimide precursor solution which was homogeneous and viscous.
Synthesis example 6
BAFL 13.55.55 g (38.9 mmol) of BAPB 33.44g (90.8 mmol) and 395.02g of N-methyl-2-pyrrolidone in an amount of 21 mass% based on the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) were charged in a reaction vessel replaced with nitrogen gas, and the mixture was stirred at room temperature for 30 minutes. To this solution was slowly added CpODA 12.46.46 g (32.4 mmol), PPHT 45.55g (97.2 mmol). Stirring at room temperature for 12 hours gave a polyimide precursor solution which was homogeneous and viscous.
Example 1
1.6Mg (0.017 mmol) of methylphosphonic acid and 0.56g of N-methyl-2-pyrrolidone were charged into a reaction vessel to obtain a homogeneous solution. To this solution, 30.17g of the polyamic acid solution obtained in Synthesis example 1 (total monomer amount in the polyamic acid solution: 15.8 mmol) was added, and the mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. The proportion of methylphosphonic acid relative to the total amount of polyimide monomers was calculated from the amount charged, and was 0.11mol%.
The polyamic acid solution was applied to a glass plate of a substrate by a spin coater, and the coated film was heated from 30℃to 350℃at a heating rate of 3℃per minute under a nitrogen atmosphere, and heat-treated at 350℃for 10 minutes, whereby a polyimide film having a thickness of 10 μm was formed on the glass plate. Regarding peel strength, a test specimen having a width of 1 inch (25.4 mm) was prepared from the obtained polyimide film/glass laminate and measured. In the tensile test, the obtained polyimide film/glass laminate was immersed in water, and then the polyimide film was peeled off from the glass plate, dried, cut into a predetermined size, and a test sample was prepared and the characteristics thereof were measured. In the following examples, tensile test samples were prepared and measured in the same manner. Regarding the optical characteristics, a polyimide film was mechanically peeled from a polyimide film/glass laminate, cut into a predetermined size, and a test sample was prepared and measured. In the following examples, a measurement sample was prepared in the same manner as the preparation of the tensile test sample for the comparative example having high peel strength and being mechanically unable to peel. The results are shown in the table.
Example 2
2.2Mg (0.023 mmol) of methylphosphonic acid and 0.53g of N-methyl-2-pyrrolidone were charged into a reaction vessel to obtain a homogeneous solution. To this solution, 30.00g of the polyamic acid solution obtained in Synthesis example 2 (the total monomer amount in the polyamic acid solution was 24.0 mmol) was added, and the mixture was stirred at room temperature for 12 hours, to obtain a uniform and viscous polyimide precursor solution. The proportion of methylphosphonic acid relative to the total amount of polyimide monomers was calculated from the amount charged, and was 0.10mol%.
The polyamic acid solution was applied to a glass plate of a substrate by a spin coater, and the coated film was heated from 30℃to 350℃at a heating rate of 3℃per minute under a nitrogen atmosphere, and heat-treated at 350℃for 10 minutes, whereby a polyimide film having a thickness of 10 μm was formed on the glass plate. The obtained film was peeled from the glass plate, and various characteristics were measured.
Example 3
1.6Mg (0.017 mmol) of methylphosphonic acid and 0.53g of N-methyl-2-pyrrolidone were charged into a reaction vessel to obtain a homogeneous solution. To this solution, 30.02g of the polyamic acid solution obtained in Synthesis example 3 (total monomer amount in the polyamic acid solution: 16.7 mmol) was added, and the mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. The proportion of methylphosphonic acid relative to the total amount of polyimide monomers was calculated from the amount charged, and was 0.10mol%.
The polyamic acid solution was applied to a glass plate of a substrate by a spin coater, and the coated film was heated from 30℃to 350℃at a heating rate of 3℃per minute under a nitrogen atmosphere, and heat-treated at 350℃for 10 minutes, whereby a polyimide film having a thickness of 10 μm was formed on the glass plate. The obtained film was peeled from the glass plate, and various characteristics were measured.
Example 4
29.99G (total monomer amount in the polyamic acid solution was 20.8 mmol) of the polyamic acid solution obtained in Synthesis example 4 was added to 1.9mg (0.020 mmol) of methylphosphonic acid, and stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. The proportion of methylphosphonic acid relative to the total amount of polyimide monomers was calculated from the amount charged, and was 0.10mol%.
The polyamic acid solution was applied to a glass plate of a substrate using a spin coater, and the coated film was heated from 30℃to 70℃at a heating rate of 2.5℃per minute under a nitrogen atmosphere, kept at 70℃for 20 minutes, then heated from 70℃to 120℃at a heating rate of 2.5℃per minute, kept at 120℃for 20 minutes, then heated from 120℃to 300℃at a heating rate of 4.6℃per minute, and heat-treated at 300℃for 5 minutes, to form a polyimide film having a thickness of 10. Mu.m on the glass plate. The obtained film was peeled from the glass plate, and various characteristics were measured.
Example 5
To 3.1mg (0.032 mmol) of methylphosphonic acid was added 30.03g of the polyamic acid solution obtained in Synthesis example 5 (the total monomer amount in the polyamic acid solution was 30.9 mmol), and the mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. The proportion of methylphosphonic acid relative to the total amount of polyimide monomers was calculated from the amount charged, and was 0.10mol%.
The polyamic acid solution was applied to a glass plate of a substrate by a spin coater, and the coated film was heated from 30℃to 80℃at a heating rate of 3℃per minute under a nitrogen atmosphere, kept at 80℃for 30 minutes, then heated from 80℃to 260℃at a heating rate of 3℃per minute, and heat-treated at 260℃for 10 minutes, whereby a polyimide film having a thickness of 10 μm was formed on the glass plate. The obtained film was peeled from the glass plate, and various characteristics were measured.
Example 6
1.9Mg (0.020 mmol) of methylphosphonic acid and 0.60g of N-methyl-2-pyrrolidone were charged into a reaction vessel to obtain a homogeneous solution. To this solution, 40.02g of the polyamic acid solution obtained in Synthesis example 6 (total monomer amount in the polyamic acid solution: 20.8 mmol) was added, and the mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. The proportion of methylphosphonic acid relative to the total amount of polyimide monomers was calculated from the amount charged, and was 0.10mol%.
The polyamic acid solution was applied to a glass plate of a substrate by a spin coater, and the coated film was heated from 30℃to 310℃at a heating rate of 5℃per minute under a nitrogen atmosphere, and heat-treated at 310℃for 20 minutes, whereby a polyimide film having a thickness of 10 μm was formed on the glass plate. The obtained film was peeled from the glass plate, and various characteristics were measured.
Comparative example 1
A polyimide film was formed in the same manner as in example 6 except that the polyamic acid solution obtained in synthesis example 6 was used as it is, and various characteristics were measured. However, in the peeling test, although the production of a test sample was attempted, the adhesion force between the glass plate and the polyimide film was large, and the film grip portion could not be produced, and measurement could not be performed.
Comparative example 2
10Mg (0.10 mmol) of methylphosphonic acid and 10.02g of N-methyl-2-pyrrolidone were charged into a reaction vessel to obtain a homogeneous solution. To 14.5mg of the solution was added 30.00g of the polyamic acid solution obtained in Synthesis example 6 (total monomer amount in the polyamic acid solution: 15.6 mmol), and the mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. The proportion of methylphosphonic acid relative to the total amount of polyimide monomers was calculated from the amount charged, and was 0.001mol%. A polyimide film was formed in the same manner as in example 6 except that the polyamic acid solution was used, and various characteristics were measured.
Example 7
10Mg (0.10 mmol) of methylphosphonic acid and 10.01g of N-methyl-2-pyrrolidone were charged into a reaction vessel to obtain a homogeneous solution. To 149.9mg of the solution was added 29.98g of the polyamic acid solution obtained in Synthesis example 6 (total monomer amount in the polyamic acid solution: 15.5 mmol), and the mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. The proportion of methylphosphonic acid relative to the total amount of polyimide monomers was calculated from the amount charged, and was 0.01mol%. A polyimide film was formed in the same manner as in example 6 except that the polyamic acid solution was used, and various characteristics were measured.
Example 8
49.9Mg (0.52 mmol) of methylphosphonic acid and 5.07g of N-methyl-2-pyrrolidone were charged into a reaction vessel to obtain a homogeneous solution. To 50.2mg of the solution was added 20.01g of the polyamic acid solution obtained in Synthesis example 6 (the total monomer amount in the polyamic acid solution was 10.4 mmol), and the mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. The proportion of methylphosphonic acid relative to the total amount of polyimide monomers was calculated from the amount charged, and was 0.05mol%. A polyimide film was formed in the same manner as in example 6 except that the polyamic acid solution was used, and various characteristics were measured.
Example 9
7.7Mg (0.080 mmol) of methylphosphonic acid and 0.52g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. To this solution, 30.14g of the polyamic acid solution obtained in Synthesis example 6 (total monomer amount in the polyamic acid solution: 15.6 mmol) was added, and the mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. The proportion of methylphosphonic acid relative to the total amount of polyimide monomers was calculated from the amount charged, and was 0.5mol%. A polyimide film was formed in the same manner as in example 6 except that the polyamic acid solution was used, and various characteristics were measured.
Example 10
12.0Mg (0.13 mmol) of methylphosphonic acid and 0.50g of N-methyl-2-pyrrolidone were charged into a reaction vessel to obtain a homogeneous solution. To this solution, 20.16g of the polyamic acid solution obtained in Synthesis example 6 (total monomer amount in the polyamic acid solution: 10.5 mmol) was added, and the mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. The proportion of methylphosphonic acid relative to the total amount of polyimide monomers was 1.2mol% calculated from the amount charged. A polyimide film was formed in the same manner as in example 6 except that the polyamic acid solution was used, and various characteristics were measured.
Comparative example 3
49.8Mg (0.52 mmol) of methylphosphonic acid and 0.50g of N-methyl-2-pyrrolidone were added to a reaction vessel, giving a homogeneous solution. To this solution, 20.03g of the polyamic acid solution obtained in Synthesis example 6 (total monomer amount in the polyamic acid solution: 10.4 mmol) was added, and the mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. The proportion of methylphosphonic acid relative to the total amount of polyimide monomers was 5.0mol% calculated from the amount charged. A polyimide film was formed in the same manner as in example 6 except that the polyamic acid solution was used, and various characteristics were measured. However, the peel strength between the glass plate and the polyimide film was too low, and the glass plate was naturally peeled off during the production of the peel test sample.
Example 11
2.4Mg (0.021 mmol) of phosphoric acid and 0.60g of N-methyl-2-pyrrolidone were charged into a reaction vessel to obtain a uniform solution. To this solution was added 43.29g of the polyamic acid solution obtained in Synthesis example 6 (total monomer amount in the polyamic acid solution was 22.4 mmol), and the mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. The proportion of phosphoric acid relative to the total amount of polyimide monomers was 0.09mol% calculated from the charged amount. A polyimide film was formed in the same manner as in example 6 except that the polyamic acid solution was used, and various characteristics were measured.
Example 12
9.2Mg (0.080 mmol) of phosphoric acid and 0.51g of N-methyl-2-pyrrolidone were charged into a reaction vessel to obtain a uniform solution. To this solution, 30.00g of the polyamic acid solution obtained in Synthesis example 6 (total monomer amount in the polyamic acid solution: 15.6 mmol) was added, and the mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. The proportion of phosphoric acid relative to the total amount of polyimide monomers was 0.51mol% calculated from the charged amount. A polyimide film was formed in the same manner as in example 6 except that the polyamic acid solution was used, and various characteristics were measured.
Example 13
12.2Mg (0.106 mmol) of phosphoric acid and 0.53g of N-methyl-2-pyrrolidone were charged into a reaction vessel to obtain a uniform solution. To this solution, 19.99g of the polyamic acid solution obtained in Synthesis example 6 (total monomer amount in the polyamic acid solution: 10.4 mmol) was added, and the mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. The proportion of phosphoric acid relative to the total amount of polyimide monomers was 1.0mol% calculated from the charged amount. A polyimide film was formed in the same manner as in example 6 except that the polyamic acid solution was used, and various characteristics were measured.
Example 14
Tributyl phosphate 4.5mg (0.017 mmol) and N-methyl-2-pyrrolidone 0.60g were added to the reaction vessel to give a homogeneous solution. To this solution, 35.96g of the polyamic acid solution obtained in Synthesis example 6 (total monomer amount in the polyamic acid solution: 18.6 mmol) was added, and the mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. The proportion of tributyl phosphate relative to the total polyimide monomer was 0.09mol% calculated from the charged amount. A polyimide film was formed in the same manner as in example 6 except that the polyamic acid solution was used, and various characteristics were measured.
Example 15
Tributyl phosphate 32.7mg (0.123 mmol) and N-methyl-2-pyrrolidone 0.50g were charged into the reaction vessel to obtain a uniform solution. To this solution, 20.06g of the polyamic acid solution obtained in Synthesis example 6 (total monomer amount in the polyamic acid solution: 10.4 mmol) was added, and the mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. The proportion of tributyl phosphate relative to the total polyimide monomer was 1.2mol% calculated from the charged amount. A polyimide film was formed in the same manner as in example 6 except that the polyamic acid solution was used, and various characteristics were measured.
Example 16
4.4Mg (0.0201 mmol) of diphenylphosphinic acid and 0.61g of N-methyl-2-pyrrolidone were charged into a reaction vessel to obtain a homogeneous solution. To this solution, 40.11g of the polyamic acid solution obtained in Synthesis example 6 (total monomer amount in the polyamic acid solution: 20.8 mmol) was added, and the mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. The proportion of diphenylphosphinic acid relative to the total amount of polyimide monomers was 0.10mol% as calculated from the charged amount. A polyimide film was formed in the same manner as in example 6 except that the polyamic acid solution was used, and various characteristics were measured.
Comparative example 4
Diethyl methylphosphonate 3.5mg (0.023 mmol) and N-methyl-2-pyrrolidone 0.61g were added to a reaction vessel to give a homogeneous solution. To this solution, 40.06g of the polyamic acid solution obtained in Synthesis example 6 (total monomer amount in the polyamic acid solution: 20.8 mmol) was added, and the mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution. The proportion of diethyl methylphosphonate relative to the total amount of polyimide monomers was calculated from the feed amount and found to be 0.11mol%. A polyimide film was formed in the same manner as in example 6 except that the polyamic acid solution was used, and various characteristics were measured.
Comparative example 5
Tributylphosphine oxide 4.6mg (0.021 mmol) and N-methyl-2-pyrrolidone 0.79g were added to a reaction vessel to obtain a uniform solution. To this solution, 39.97g of the polyamic acid solution obtained in Synthesis example 6 (total monomer amount in the polyamic acid solution: 20.7 mmol) was added, and the mixture was stirred at room temperature for 12 hours, to obtain a uniform and viscous polyimide precursor solution. The proportion of tributylphosphine oxide relative to the total amount of polyimide monomer was 0.10mol% calculated from the charged amount. A polyimide film was formed in the same manner as in example 6 except that the polyamic acid solution was used, and various characteristics were measured.
Comparative examples 6 to 9
A polyimide film was formed in the same manner as in example 6, except that the polyamic acid solutions obtained in synthesis examples 1 to 3 and 5 were used as they are, and various characteristics were measured.
The compositions of examples and comparative examples, b *, peeling properties, and 400nm transmittance of the obtained films are shown in tables 3 to 7, and the film properties of examples are further measured, and the results are shown in tables 8 to 10.
TABLE 3
The unit N/in is N/25.4mm.
TABLE 4
* ) Large: the peel strength was too high to prepare a test sample. The size is small: the peel strength was too low and the test specimens were peeled off naturally during the production.
TABLE 5
TABLE 6
TABLE 7
TABLE 8
Physical Properties | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
Tg(TMA)/℃ | 324 | 333 | 323 | 304 | 325 | 300 |
Td 1%/℃ | - | - | - | - | - | 413 |
Transmittance at 400 nm% | 85.9 | 84.3 | 81.9 | 60.5 | 88.7 | 85.8 |
Total light transmittance/%T (380-780 nm) | 90.6 | 89.6 | 89.6 | 85.5 | 90.1 | 88.5 |
In the table-no measurement is shown.
TABLE 9
Physical Properties | Example 7 | Example 8 | Example 9 | Example 10 |
Tg(TMA)/℃ | 301 | 299 | 302 | 311 |
Td 1%/℃ | - | - | - | - |
Transmittance at 400 nm% | 86.4 | 87.0 | 86.7 | 87.1 |
Total light transmittance/%T (380-780 nm) | 89.6 | 89.7 | 89.3 | 89.7 |
TABLE 10
Physical Properties | Example 11 | Example 12 | Example 13 | Example 14 | Example 15 | Example 16 |
Tg(TMA)/℃ | 302 | - | - | 301 | - | 300 |
Td 1%/℃ | 415 | - | - | 419 | 407 | 415 |
Transmittance at 400 nm% | 85.6 | 86.4 | 85.7 | 85.7 | 85.1 | 85.8 |
Total light transmittance/%T (380-780 nm) | 88.5 | 89.4 | 89.4 | 88.5 | - | 88.5 |
Industrial applicability
The present invention can be suitably used in the manufacture of flexible electronic devices, such as liquid crystal displays, organic EL displays, and display devices such as electronic papers, solar cells, and light receiving devices such as CMOS.
Claims (14)
1. A polyimide precursor composition comprising a polyimide precursor and a polyimide precursor, characterized by comprising:
a polyimide precursor;
A phosphorus compound in an amount exceeding 0.001 mol% and less than 5 mol% with respect to the total monomer units of the polyimide precursor, the phosphorus compound being selected from the group consisting of phosphoric acid, a monoalkyl phosphonate having 2 OH and 1 alkyl groups bonded to a phosphorus atom, a dialkyl phosphinate having 1 OH and 2 alkyl groups bonded to a phosphorus atom, an alkyl monoalkyl phosphinate having 1 OH and 1 alkoxy and 1 alkyl groups bonded to a phosphorus atom, a dialkyl monoalkyl phosphinate having 2 alkoxy groups having 4 or more carbon atoms and 1 alkyl group bonded to a phosphorus atom, and a monoalkyl dialkyl phosphinate having 1 alkoxy group having 4 or more carbon atoms and 2 alkyl groups bonded to a phosphorus atom; and
The solvent is used for the preparation of the aqueous solution,
Wherein the polyimide precursor composition satisfies the following condition (A),
(A) The polyimide precursor is not a polyimide precursor obtained from only 3,3', 4' -biphenyltetracarboxylic dianhydride and p-phenylenediamine.
2. The composition according to claim 1, wherein the content of the phosphorus compound is 0.01 mol% or more relative to the total monomer units of the polyimide precursor.
3. The composition of claim 1, wherein the phosphorus compound has a molecular weight of less than 400.
4. The composition of claim 1, wherein the polyimide precursor comprises a repeating unit selected from the group consisting of a structure represented by the following general formula (I) and a structure in which at least 1 amide structure in the general formula (I) is imidized,
[ Chemical 1]
In the general formula I, X 1 is a 4-valent aliphatic group or aromatic group, Y 1 is a 2-valent aliphatic group or aromatic group, and R 1 and R 2 are, independently of each other, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkylsilyl group having 3 to 9 carbon atoms.
5. The composition according to claim 4, wherein X 1 is a 4-valent group having an alicyclic structure and Y 1 is a 2-valent group having an alicyclic structure, and the content of the repeating unit represented by general formula (I) is 50 mol% or less based on the total repeating units.
6. The composition of claim 4, wherein X 1 in formula (I) is a 4-valent group having an aromatic ring and Y 1 is a 2-valent group having an aromatic ring.
7. The composition of claim 4, wherein X 1 in the general formula (I) is a 4-valent group having an alicyclic structure, and Y 1 is a 2-valent group having an aromatic ring.
8. The composition of claim 4, wherein X 1 in formula (I) is a 4-valent group having an aromatic ring and Y 1 is a 2-valent group having an alicyclic structure.
9. The composition according to claim 4, wherein X 1 in the general formula (I) is a repeating unit having a 4-valent group having an alicyclic structure, wherein X 1 is a 4-valent group having an alicyclic structure and Y 1 is a 2-valent group having an alicyclic structure, and the content of the repeating unit represented by the general formula (I) is 50 mol% or less with respect to the total repeating units, in an amount exceeding 60% of the total repeating units.
10. A method of manufacturing a flexible electronic device, comprising:
(a) A step of applying the polyimide precursor composition according to any one of claims 1 to 9 to a substrate;
(b) A step of producing a laminate in which a polyimide film is laminated on the base material by heating the polyimide precursor on the base material;
(c) Forming at least 1 layer selected from a conductor layer and a semiconductor layer on the polyimide film of the laminate; and
(D) And peeling the base material from the polyimide film by an external force.
11. The method of manufacturing according to claim 10, wherein the substrate is a glass plate.
12. The method according to claim 10 or 11, wherein laser irradiation is not performed in the step of peeling the substrate from the polyimide film.
13. A method for reducing peel strength of a laminate, which is a method for reducing peel strength between a polyimide film and a substrate of a laminate having the substrate and the polyimide film formed on the substrate, characterized by comprising the steps of,
The polyimide precursor composition for forming the polyimide film contains a phosphorus compound so as to be the polyimide precursor according to any one of claims 1 to 9.
14. The method of claim 13, wherein the substrate is a glass sheet.
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