CN116144023B - Polyimide, and preparation method and application thereof - Google Patents
Polyimide, and preparation method and application thereof Download PDFInfo
- Publication number
- CN116144023B CN116144023B CN202310326071.XA CN202310326071A CN116144023B CN 116144023 B CN116144023 B CN 116144023B CN 202310326071 A CN202310326071 A CN 202310326071A CN 116144023 B CN116144023 B CN 116144023B
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- Prior art keywords
- polyimide
- group
- methyl
- independently selected
- formula
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 219
- 239000004642 Polyimide Substances 0.000 title claims abstract description 207
- 238000002360 preparation method Methods 0.000 title abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 59
- 229920006259 thermoplastic polyimide Polymers 0.000 claims description 101
- -1 2-pentyl Chemical group 0.000 claims description 82
- 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 65
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 65
- 239000002131 composite material Substances 0.000 claims description 54
- 125000000217 alkyl group Chemical group 0.000 claims description 52
- 125000006413 ring segment Chemical group 0.000 claims description 51
- 229910052736 halogen Inorganic materials 0.000 claims description 43
- 150000002367 halogens Chemical class 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 36
- 125000003118 aryl group Chemical group 0.000 claims description 30
- 150000002148 esters Chemical class 0.000 claims description 26
- 150000004985 diamines Chemical class 0.000 claims description 24
- 125000001188 haloalkyl group Chemical group 0.000 claims description 24
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 17
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 12
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 12
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 11
- 125000004398 2-methyl-2-butyl group Chemical group CC(C)(CC)* 0.000 claims description 10
- 125000004918 2-methyl-2-pentyl group Chemical group CC(C)(CCC)* 0.000 claims description 10
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 claims description 10
- 125000004919 3-methyl-2-pentyl group Chemical group CC(C(C)*)CC 0.000 claims description 10
- 125000004921 3-methyl-3-pentyl group Chemical group CC(CC)(CC)* 0.000 claims description 10
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 claims description 10
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 10
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 10
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 10
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 238000007363 ring formation reaction Methods 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000003475 lamination Methods 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 70
- 239000011889 copper foil Substances 0.000 abstract description 59
- 238000002834 transmittance Methods 0.000 abstract description 13
- 230000009477 glass transition Effects 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 79
- 239000010408 film Substances 0.000 description 78
- 108010005491 trypsin carboxypeptidase peptide inhibitor Proteins 0.000 description 57
- 239000000243 solution Substances 0.000 description 52
- 238000006243 chemical reaction Methods 0.000 description 38
- 239000010949 copper Substances 0.000 description 36
- 238000003756 stirring Methods 0.000 description 31
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 27
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 22
- 238000000576 coating method Methods 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 17
- 239000000853 adhesive Substances 0.000 description 17
- 230000001070 adhesive effect Effects 0.000 description 17
- 238000003825 pressing Methods 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 229920005575 poly(amic acid) Polymers 0.000 description 16
- 239000002313 adhesive film Substances 0.000 description 14
- 125000002723 alicyclic group Chemical group 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 13
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 12
- 125000002993 cycloalkylene group Chemical group 0.000 description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 12
- 239000002270 dispersing agent Substances 0.000 description 12
- 125000000732 arylene group Chemical group 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 229920001169 thermoplastic Polymers 0.000 description 11
- 239000004416 thermosoftening plastic Substances 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003822 epoxy resin Substances 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000009719 polyimide resin Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- ZPSUIVIDQHHIFH-UHFFFAOYSA-N 3-(trifluoromethyl)-4-[2-(trifluoromethyl)phenyl]benzene-1,2-diamine Chemical group FC(F)(F)C1=C(N)C(N)=CC=C1C1=CC=CC=C1C(F)(F)F ZPSUIVIDQHHIFH-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 239000012024 dehydrating agents Substances 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 3
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 3
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical class NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 3
- 238000007429 general method Methods 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001408 amides Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000004979 cyclopentylene group Chemical group 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- 239000002355 dual-layer Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- BCGWQEUPMDMJNV-UHFFFAOYSA-N imipramine Chemical compound C1CC2=CC=CC=C2N(CCCN(C)C)C2=CC=CC=C21 BCGWQEUPMDMJNV-UHFFFAOYSA-N 0.000 description 2
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- SLGBZMMZGDRARJ-UHFFFAOYSA-N triphenylene Chemical compound C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 125000004922 2-methyl-3-pentyl group Chemical group CC(C)C(CC)* 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- 125000004917 3-methyl-2-butyl group Chemical group CC(C(C)*)C 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004653 anthracenylene group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 150000001717 carbocyclic compounds Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004976 cyclobutylene group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004977 cycloheptylene group Chemical group 0.000 description 1
- 125000003678 cyclohexadienyl group Chemical group C1(=CC=CCC1)* 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000005725 cyclohexenylene group Chemical group 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004980 cyclopropylene group Chemical group 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005067 haloformyl group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000005560 phenanthrenylene group Chemical group 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 125000006684 polyhaloalkyl group Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 125000004385 trihaloalkyl group Chemical group 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/036—Multilayers with layers of different types
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to polyimide, a preparation method and application thereof. The polyimide has a structure shown in a formula (1-1), realizes high heat resistance through constructing hydrogen bonds, has a glass transition temperature exceeding 350 ℃, has thermal expansion performance matched with copper foil, has high bonding strength with the copper foil, is a colorless material with high light transmittance and excellent dimensional stability, and is very suitable for copper-clad plates, in particular double-layer glue-free copper-clad plates.(1‑1)。
Description
Technical Field
The invention relates to the field of polymer synthesis, in particular to polyimide and a preparation method and application thereof.
Background
The PET-FCCL is a mature transparent FCCL product in the market, is mainly prepared by laminating PET serving as an insulating base film and an adhesive and a copper foil serving as a conductive layer, and is applied to antennas of various electronic equipment, automobile instruments, household appliances, electronic toys, computer auxiliary equipment and the like. The three-layer PET-FCCL is prepared by coating a layer of transparent adhesive on the surface of a PET film and then pressing the transparent adhesive with copper foil. PET-FCCL has excellent optical transmittance after etching, but because PET melting point is about 250 ℃, heat resistance is poor, and the PET-FCCL cannot be applied to Surface Mount Technology (SMT) process of Flexible Printed Circuit (FPC), and SMT welding temperature is generally above 260 ℃, so that the PET-FCCL is only suitable for low-temperature welding, and the application of PET in higher-order products is limited.
With the rapid development of polymers, flexible transparent Polyimide (PI) has been gaining attention, and PI films maintain high heat resistance and high bending properties of polyimide itself, and their high optical transmittance makes themThe application in many high and new technical fields is more extensive. For example, in a flexible OLED display, the transparent polyimide (CPI) will be an optically transparent film that is transparent to the flexible substrate, touch substrate, under-screen camera cover, cell phone cover, and so forth. In 2007, mitsubishi gas company of Japan announced that mass production of colorless transparent PI films was achieved with a production capacity of 5000 m 2 The product name is Neopulim, which is an enterprise for realizing the industrialized production of the transparent PI resin in the early world. In 2013, east-dupont introduced colorless PI films. In 2019, two companies, SKC and Kolon, developed CPI products, respectively, and the products thereof have been mass-produced. In 2019, the foldable mobile phone Galaxy Fold of samsung adopts a transparent polyimide cover plate with hardened surface of Sumitomo chemistry, and adopts transparent polyimide slurry of SKC as a touch substrate. In addition, the colorless transparent PI material can be applied to the aerospace field, and is particularly used as a substrate material of a solar cell array, an antenna reflection/collector material and the like, wherein the highest record of the efficiency of a small-area cell of the flexible PI substrate is 20.4%, and the highest record of the efficiency of a large-area component of the flexible PI substrate is 12%. In the field of fiber optic communications, colorless transparent PI materials are used to fabricate optical waveguides.
At present, polyimide is widely used as an insulating base film of a flexible printed circuit, and the flexible printed circuit is generally divided into a three-layer adhesive type flexible copper clad laminate and a two-layer adhesive-free flexible copper clad laminate.
The three-layer glue-type flexible copper-clad plate consists of copper foil, adhesive and polyimide film, and the traditional flexible copper-clad plate adopts yellow transparent polyimide film as a base material, and the FCCL can not be applied to colorless transparent flexible circuit boards due to the limitation of the color of the PI film. Therefore, colorless transparent polyimide must be used as a substrate for FCCL. In addition, the adhesive in the copper-clad plate mainly uses epoxy resin or acrylic resin, when the temperature is higher than 150 ℃, the peeling strength is greatly reduced due to the degradation of the adhesive, and when welding is performed on the flexible plate, the temperature is mostly higher than 300 ℃. In addition, the flexible copper clad laminate containing the adhesive can also have the problems of thick insulating layer, poor heat resistance and high thermal expansion coefficient. In addition, the three-layer adhesive flexible copper-clad plate has large size change rate influenced by temperature, poor size stability and poor chemical resistance.
The double-layer flexible copper clad laminate is free of adhesives and is composed of copper foil and polyimide film, so that the double-layer flexible copper clad laminate has better heat resistance, dimensional stability, flame retardance and chemical resistance, and particularly, the polyimide which can be applied to the glue-free copper clad laminate is required to be matched with the thermal expansion coefficient of the copper foil, has high enough bonding strength with the copper foil, and has long plagued related technicians how to develop polyimide meeting the requirements so as to be suitable for the double-layer glue-free flexible copper clad laminate.
Disclosure of Invention
Based on this, the present invention provides a polyimide having high optical transparency, a coefficient of thermal expansion matching that of the copper foil, and high adhesive strength with the copper foil.
A first aspect of the present invention provides a polyimide having a structure represented by formula (1-1):
(1-1);
wherein,,
x represents:
Q 1 、Q 2 Each independently selected from an aromatic group having 6 to 30 ring atoms, or a cycloalkyl group having 3 to 30 ring atoms;
m is selected from the group represented by formula (M-1) or (M-2);
(M-1)、/>(M-2);
each Y is independently selected from an aromatic group with a ring atom number of 6 to 30, an alicyclic group with a ring atom number of 6 to 30 or a C1-C20 aliphatic group;
a is selected from the group shown below:;
each R is 1 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen;
R 2 selected from single bonds or groups as shown below:
;
m and n are taken from 0.1 to 0.9, m+n=1, representing the linking site.
In one embodiment, Q 1 、Q 2 Each independently selected from phenyl or cyclohexyl.
In one embodiment, each Y is independently selected from the group shown below:
、/>、/>or->;
Each R is 3 And R is 5 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen; r is R 4 And R is 6 Each independently selected from a single bond or a group as shown below:
。
in one embodiment, each R 3 And R is 5 Independently selected from the group consisting of absent, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 fluoroalkyl, or halogen.
In one embodiment, each R 1 Independently selected from C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 fluoroalkyl or halogen.
A second aspect of the present invention provides a method for producing a polyimide as described above, comprising the steps of:
mixing diamine with a structure shown in a formula (I), dianhydride with a structure shown in a formula (II) and dianhydride with a structure shown in a formula (III) in a solvent, and carrying out polymerization reaction, dehydration and cyclization to prepare polyimide with a structure shown in a formula (1-1);
(I)、/>(II)、/>(III);
Q 1 、Q 2 each independently selected from an aromatic group having 6 to 30 ring atoms, or a cycloalkyl group having 3 to 30 ring atoms; m is selected from the group represented by formula (M-1) or (M-2);
(M-1)、/>(M-2);
each Y is independently selected from an aromatic group with a ring atom number of 6 to 30, an alicyclic group with a ring atom number of 6 to 30 or a C1-C20 aliphatic group;
a is selected from the group shown below:
;
each R is 1 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen;
R 2 Selected from single bonds or groups as shown below:
。
in one embodiment, the molar ratio of the dianhydride having the structure of formula (ii) to the dianhydride having the structure of formula (iii) is (10-90): (90-10);
the molar ratio of the total of the dianhydride having the structure of formula (II) and the dianhydride having the structure of formula (III) to the diamine having the structure of formula (I) is 100: (95-105).
In one embodiment, the polymerization reaction is performed at a temperature of 60 ℃ or lower for 0.1 to 30 hours.
In one embodiment, the diamine having the structure of formula (I) is selected from any one of the diamine compounds (I-1) to (I-4):
。
in one embodiment, the dianhydride having the structure of formula (II) is selected from the dianhydride compounds shown in any of the following (II-1) to (II-5):
。
in one embodiment, the dianhydride having the structure of formula (III) is selected from dianhydride compounds represented by any of the following (III-1) to (III-4):。
a third aspect of the present invention provides an optically transparent film comprising the polyimide as described above or a polyimide produced according to the process for producing a polyimide as described above.
A fourth aspect of the invention provides an OLED comprising an optically transparent film as described above.
A fifth aspect of the present invention provides a multilayer composite polyimide material having a structure comprising a first thermoplastic polyimide layer and a transparent polyimide layer in a stacked arrangement;
the first thermoplastic polyimide layer comprises a first thermoplastic polyimide and the transparent polyimide layer comprises a polyimide as described above or a polyimide prepared according to the preparation method as described above;
the structural unit of the first thermoplastic polyimide has a structure represented by formula (2-1):
(2-1);
wherein B is 1 An aromatic group having 6 to 30 ring atoms, an alicyclic group having 6 to 30 ring atoms, or a C1 to C20 aliphatic group;
Z 1 representation of;
Each R is 7 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen;
R 8 selected from single bonds or groups as shown below:
;
p is selected from any integer from 1 to 10.
In one embodiment, B 1 Representation of;
Each R is 9 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen;
R 10 a group selected from the group shown below:
;
q is selected from any integer from 1 to 10.
In one embodiment, each R 7 Independently selected from C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 fluoroalkyl or halogen.
In one embodiment, the thickness of the first thermoplastic polyimide layer is 0.5 μm to 20 μm and the thickness of the transparent polyimide layer is 50 μm to 100 μm. In one embodiment, the multilayer composite polyimide material further comprises a second thermoplastic polyimide layer disposed in a stack with the transparent polyimide layer in a direction away from the first thermoplastic polyimide layer;
the second thermoplastic polyimide layer comprises a second thermoplastic polyimide;
the structural unit of the second thermoplastic polyimide has a structure represented by formula (3-1):
(3-1);
wherein B is 2 An aromatic group having 6 to 30 ring atoms, an alicyclic group having 6 to 30 ring atoms, or a C1 to C20 aliphatic group;
Z 2 representation of;
Each R is 11 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen;
R 12 selected from single bonds or groups as shown below:
;
r is selected from any integer from 1 to 10.
In one embodiment, B 2 Representation of;
Each R is 13 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen;
R 14 a group selected from the group shown below:
;
s is selected from any integer from 1 to 10.
In one embodiment, each R 11 Independently selected from C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 fluoroalkyl or halogen.
In one embodiment, the second thermoplastic polyimide layer has a thickness of 0.5 μm to 20 μm.
A sixth aspect of the present invention provides an insulating base film comprising a multilayer composite polyimide material as described above.
A seventh aspect of the present invention provides a copper-clad laminate comprising the multilayer composite polyimide material as described above, or the insulating base film as described above.
An eighth aspect of the present invention provides a rigid printed circuit board comprising a multilayer composite polyimide material as described above, or an insulating base film as described above, or a copper-clad plate as described above.
A ninth aspect of the present invention provides a flexible printed circuit board comprising the multilayer composite polyimide material as described above, or the insulating base film as described above, or the copper-clad plate as described above.
The invention has the following beneficial effects: the polyimide shown in the formula (1-1) provided by the invention contains an amide structure, realizes high heat resistance by constructing hydrogen bonds, has a glass transition temperature of more than 350 ℃, has thermal expansion performance matched with copper foil, has high bonding strength with copper foil, is a colorless material with high light transmittance and excellent dimensional stability, and is very suitable for copper-clad plates, in particular double-layer glue-free copper-clad plates.
Further, the polyimide shown in the formula (1-1) and the thermoplastic polyimide shown in the formula (2-1) are compounded into the multi-layer composite polyimide material, so that the multi-layer composite polyimide material has excellent heat resistance, can be matched with the thermal expansion performance of the copper foil, has high bonding strength with the copper foil and good dimensional stability, and can be used for preparing the adhesive copper-clad plate, effectively reduce the thickness of the traditional adhesive copper-clad plate and solve the problems of layering, air bubbles and the like of the copper-clad plate in tin soldering treatment and high-temperature application.
In addition, the preparation method of the polyimide and the multilayer composite polyimide material provided by the invention has simple process and safety, and is suitable for large-scale production.
Drawings
FIG. 1 is a schematic diagram of a dual-layer composite polyimide material according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a three-layer composite polyimide material according to an embodiment of the present invention;
fig. 3 is a schematic structural view of a copper clad laminate according to an embodiment of the present invention;
fig. 4 is a schematic structural view of a copper clad laminate according to an embodiment of the present invention;
fig. 5 is an effect diagram of the coating film attached after the copper-clad plate in example 8 of the present invention is etched.
Description of the embodiments
The invention is further illustrated below in conjunction with the embodiments and examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Furthermore, it is to be understood that various changes and modifications may be made by one skilled in the art after reading the teachings of the invention, and such equivalents are intended to fall within the scope of the appended claims.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Terminology
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
the term "and/or", "and/or" as used herein includes a selection of any one of two or more of the listed items and also includes any and all combinations of the listed items, including any two or more of the listed items, or all combinations of the listed items. It should be noted that, when at least three items are connected by at least two conjunctions selected from the group consisting of "and/or", "and/or", it is to be understood that, in the present invention, the technical solutions certainly include technical solutions that all use "logical and" connection, and also certainly include technical solutions that all use "logical or" connection. For example, "a and/or B" includes three parallel schemes A, B and a+b. For another example, the technical schemes of "a, and/or B, and/or C, and/or D" include any one of A, B, C, D (i.e., the technical scheme of "logical or" connection), and also include any and all combinations of A, B, C, D, i.e., any two or three of A, B, C, D, and also include four combinations of A, B, C, D (i.e., the technical scheme of "logical and" connection).
In the present invention, "plural" means at least two, for example, two, three, etc., and "multi-layer" means at least two, for example, two, three, etc., unless specifically defined otherwise. In the description of the present invention, the meaning of "several" means at least one, such as one, two, etc., unless specifically defined otherwise.
All steps of the present invention may be performed sequentially or randomly unless otherwise specified. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further comprise step (c), meaning that step (c) may be added to the method in any order, e.g., the method may comprise steps (a), (b) and (c), steps (a), (c) and (b), steps (c), (a) and (b), etc.
In the present invention, "preferable", "preferred", "better", etc. are merely embodiments or examples for better effects, and it should be understood that the scope of the present invention is not limited thereto.
In the present invention, "further", "still further", "particularly" and the like are used for descriptive purposes to indicate differences in content but should not be construed as limiting the scope of the invention.
In the present invention, the terms "first", "second", "third", "fourth", "fifth", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying an importance or quantity of the indicated technical features. Also, "first," "second," "third," "fourth," "fifth," etc. are for non-exhaustive list of descriptive purposes only and are not to be construed as limiting the number of closed forms.
In the present invention, the technical features described in an open manner include a closed technical scheme composed of the listed features, and also include an open technical scheme including the listed features.
In the present invention, a numerical range (i.e., a numerical range) is referred to, and optional numerical distributions are considered to be continuous within the numerical range and include two numerical endpoints (i.e., a minimum value and a maximum value) of the numerical range and each numerical value between the two numerical endpoints unless otherwise specified. When a numerical range merely points to integers within the numerical range, both end integers of the numerical range are included, as well as each integer between the two ends, unless expressly stated otherwise. Further, when a plurality of range description features or characteristics are provided, these ranges may be combined. In other words, unless otherwise indicated, the ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
In the present invention, the number of atoms described by a numerical range includes both the end points of the integer of the numerical range and also includes each integer of the two end points. For example, "C1-C10 alkyl" represents an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms.
In the present invention,r is selected from single bond>Representation->。Represents the attachment site of the undefined substituent R to the benzene ring.
In the present invention, "×" indicates a ligation site.
In the present invention, "halogen" or "halo" means-F, -Cl, -Br or-I.
In the present invention, the term "alkyl" refers to a monovalent residue of a saturated hydrocarbon containing a primary (positive) carbon atom, or a secondary carbon atom, or a tertiary carbon atom, or a quaternary carbon atom, or a combination thereof, losing one hydrogen atom. The phrase containing the term, for example, "C1-C10 alkyl" refers to an alkyl group containing 1 to 10 carbon atoms, which may be, independently at each occurrence, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, or C10 alkyl. Suitable examples include, but are not limited to: methyl (Me, -CH) 3 ) Ethyl (Et, -CH) 2 CH 3 ) 1-propyl (n-Pr, n-propyl, -CH 2 CH 2 CH 3 ) 2-propyl (i-Pr, i-propyl, -CH (CH) 3 ) 2 ) 1-butyl (n-Bu, n-butyl, -CH) 2 CH 2 CH 2 CH 3 ) 2-methyl-1-propyl (i-Bu, i-butyl, -CH) 2 CH(CH 3 ) 2 ) 2-butyl (s-Bu, s-butyl, -CH (CH) 3 )CH 2 CH 3 ) 2-methyl-2-propyl (t-Bu, t-butyl, -C (CH) 3 ) 3 ) 1-pentyl (n-pentyl, -CH) 2 CH 2 CH 2 CH 2 CH 3 ) 2-pentyl (-CH (CH) 3 )CH 2 CH 2 CH 3 ) 3-pentyl (-CH (CH) 2 CH 3 ) 2 ) 2-methyl-2-butyl (-C (CH) 3 ) 2 CH 2 CH 3 ) 3-methyl-2-butyl (-CH (CH) 3 )CH(CH 3 ) 2 ) 3-methyl-1-butyl (-CH) 2 CH 2 CH(CH 3 ) 2 ) 2-methyl-1-butyl (-CH) 2 CH(CH 3 )CH 2 CH 3 ) 1-hexyl (-CH) 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2-hexyl (-CH (CH) 3 )CH 2 CH 2 CH 2 CH 3 ) 3-hexyl (-CH (CH) 2 CH 3 )(CH 2 CH 2 CH 3 ) 2-methyl-2-pentyl (-C (CH) 3 ) 2 CH 2 CH 2 CH 3 ) 3-methyl-2-pentyl (-CH (CH) 3 )CH(CH 3 )CH 2 CH 3 ) 4-methyl-2-pentyl (-CH (CH) 3 )CH 2 CH(CH 3 ) 2 ) 3-methyl-3-pentyl (-C (CH) 3 )(CH 2 CH 3 ) 2 ) 2-methyl-3-pentyl (-CH (CH) 2 CH 3 )CH(CH 3 ) 2 ) 2, 3-dimethyl-2-butyl (-C (CH) 3 ) 2 CH(CH 3 ) 2 ) 3, 3-dimethyl-2-butyl (-CH (CH) 3 )C(CH 3 ) 3 And octyl (- (CH) 2 ) 7 CH 3 )。
In the present invention, "haloalkyl" refers to an alkyl group substituted with one or more halogen (chlorine, fluorine, bromine or iodine) atoms. Polyhaloalkyl groups have the same or mixed types of halogen atoms. "perhaloalkyl" means that each hydrogen atom in the alkyl group is replaced with a halogen atom. A haloalkyl group "fully halogenated" with respect to a particular carbon atom means that all of the hydrogen atoms attached to that carbon atom are replaced with halogen atoms. Representative mono-, di-and tri-haloalkyl groups include: chloromethyl, chloroethyl, bromomethyl, bromoethyl, iodomethyl, iodoethyl, chloropropyl, bromopropyl, iodopropyl, 1-dichloromethyl, 1-dibromomethyl, 1-dichloropropyl, 1, 2-dibromopropyl, 2, 3-dibromopropyl, 1-chloro-2-bromoethyl, 2-chloro-3-bromopropyl, trifluoromethyl, trichloromethyl, and the like.
In the present invention, "cycloalkyl" refers to a non-aromatic hydrocarbon containing a ring carbon atom, and may be a monocyclic alkyl group, a spirocycloalkyl group, or a bridged cycloalkyl group. The phrase containing the term, for example, "C3-C10 cycloalkyl" refers to cycloalkyl groups containing 3-10 carbon atoms, which at each occurrence may be, independently of one another, C3 cycloalkyl, C4 cycloalkyl, C5 cycloalkyl, C6 cycloalkyl, C7 cycloalkyl, C8 cycloalkyl, C9 cycloalkyl or C10 cycloalkyl. Suitable examples include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. In addition, "cycloalkyl" may also contain one or more double bonds, and representative examples of cycloalkyl groups containing a double bond include cyclopentenyl, cyclohexenyl, cyclohexadienyl, and cyclobutenyl.
In the present invention, the "number of ring atoms" means the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below, unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the biphenyl ring is 12.
In the present invention, the term "aryl, aryl or aryl group" refers to a hydrocarbon group containing at least one aromatic ring, such as: benzene, naphthalene, anthracene, fluoranthene, phenanthrene, benzophenanthrene, perylene, naphthacene, pyrene, benzopyrene, acenaphthene, fluorene, biphenyl, terphenyl, and derivatives of the foregoing aryl groups.
In the present invention, the term "arylene" refers to an aromatic hydrocarbon group derived by removing two hydrogen atoms on the basis of an aromatic ring compound, which may be a monocyclic arylene group, or a condensed ring arylene group, or a polycyclic arylene group, at least one of which is an aromatic ring system for a polycyclic species. For example, "C6-C10 arylene" refers to arylene groups containing 6 to 10 carbon atoms, each occurrence of which may be, independently of the other, C6 arylene, C7 arylene, C8 arylene, C9 arylene, or C10 arylene. Suitable examples include, but are not limited to: phenylene, biphenylene, naphthylene, anthracenylene, phenanthrenylene, perylene, triphenylene and derivatives thereof.
In the present invention, the term "cycloalkylene" refers to a hydrocarbon group derived by removing two hydrogen atoms on the basis of a cycloalkyl group to form a center having two monovalent groups, and may be a monocycloalkylene group, or a spirocycloalkylene group, or a bridged cycloalkyl group. For example, "C3-C10 cycloalkylene" refers to cycloalkylene groups containing 3-9 carbon atoms, each occurrence of which may be, independently of the other, C3 cycloalkylene, C4 cycloalkylene, C5 cycloalkylene, C6 cycloalkylene, C7 cycloalkylene, C8 cycloalkylene, or C9 cycloalkylene. Suitable examples include, but are not limited to: cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene and cycloheptylene. In addition, the "cycloalkylene group" may also contain one or more double bonds, and representative examples of the cycloalkylene group containing double bonds include cyclopentylene group, cyclohexenylene group, cyclohexadienylene group, and cyclobutenylene group.
In the present invention, "substituted" means that a hydrogen atom in a substituted group is substituted by a substituent.
In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood that the defined group may be substituted with one or more substituents R selected from, but not limited to: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1 to 9C atoms, cycloalkyl containing 3 to 9C atoms, -NR' R ", silane, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate, thiocyanate, isothiocyanate, hydroxy, trifluoromethyl, which may be further substituted with substituents acceptable in the art; it will be appreciated that each of R 'and R' 'in-NR' R '' is independently selected from, but not limited to: H. deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1 to 9C atoms, cycloalkyl containing 3 to 9C atoms. The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or may vary within a predetermined temperature range. It should be appreciated that the constant temperature process described allows the temperature to fluctuate within the accuracy of the instrument control. Allows for fluctuations in a range such as + -5 deg.C, + -4 deg.C, + -3 deg.C, + -2 deg.C, + -1 deg.C.
In the present invention, the "double-layer composite polyimide material" means a composite polyimide material structure including a first thermoplastic polyimide layer and a transparent polyimide layer which are sequentially laminated. The three-layer composite polyimide material refers to a composite polyimide material structure comprising a first thermoplastic polyimide layer, a transparent polyimide layer and a second thermoplastic polyimide layer which are sequentially laminated.
The detailed description of the present invention is as follows:
the invention provides polyimide with high optical transparency, thermal expansion coefficient matched with copper foil and high bonding strength with copper foil.
The technical proposal is as follows:
a polyimide having a structure represented by the formula (1-1):
(1-1);
wherein,,
x represents:
Q 1 、Q 2 Each independently selected from an aromatic group having 6 to 30 ring atoms, or a cycloalkyl group having 3 to 30 ring atoms;
m is selected from the group represented by formula (M-1) or (M-2);
(M-1)、/>(M-2);
each Y is independently selected from an aromatic group with a ring atom number of 6 to 30, an alicyclic group with a ring atom number of 6 to 30 or a C1-C20 aliphatic group;
a is selected from the group shown below:
;
each R is 1 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen;
R 2 Selected from single bonds or groups as shown below:
;
m and n are taken from 0.1 to 0.9, m+n=1, representing the linking site.
The polyimide represented by the formula (1-1) provided by the invention contains an amide structure, realizes high heat resistance by constructing hydrogen bonds, has thermal expansion performance matched with copper foil, and has high bonding strength with copper foil, and is a colorless material with high light transmittance and excellent dimensional stability.
Through test, the light transmittance T% is more than or equal to 87 percent@360 nm-780 nm, and the glass transition temperature T g The heat decomposition temperature exceeding 350 ℃ and 5% of the heat decomposition temperature exceeding 500 ℃ are matched with the heat expansion of copper foil, the heat expansion coefficient CTE is 12 ppm/DEG C-20 ppm/DEG C, the transparent TCPI layer is well bonded, the bonding strength is greater than 1.2N/mm, the tensile strength is greater than 200MPa, the tensile modulus is greater than 4.0GPa, the elongation at break is greater than 30%, the excellent mechanical properties are shown, and the heat decomposition type copper-clad laminate is very suitable for copper-clad laminates, in particular double-layer non-adhesive copper-clad laminates.
In the present invention, a is selected from the group shown below:
;
each R is 1 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen.
Further, each R 1 Independently selected from C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 fluoroalkyl or halogen. Each R is 1 Are each independently selected from methyl (-CH) 3 ) Ethyl, 1-propyl, 2-propyl, 1-butyl, 2-methyl-1-propyl, 2-butyl, 2-methyl-2-propyl, 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-1-butyl, 2-methyl-1-butyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2, 3-dimethyl-2-butyl, 3-dimethyl-2-butyl, n-octyl, cyclohexyl, cyclooctyl, adamantyl, trifluoromethyl (-CF) 3 ) Or fluorine (-F). Further, each R 1 Are independently selected from-F, -CH 3 or-CF 3 。
In the present invention, Q 1 、Q 2 Each independently selected from an aromatic group having 6 to 30 ring atoms, or a cycloalkyl group having 3 to 30 ring atoms. The specific description is as follows:
in one embodiment, Q 1 、Q 2 Each independently selected from aromatic groups having 6 to 30 ring atoms, further Q 1 、Q 2 Each independently selected from aromatic groups having 6 to 20 ring atoms. Further, Q1, Q2 are each independently selected from phenyl, naphthyl, phenanthryl, anthracyl, biphenyl, or terphenyl.
In one embodiment, Q 1 、Q 2 Each independently selected from cycloalkyl groups having 3 to 30 ring atoms. Further, Q 1 、Q 2 Each independently selected from cycloalkyl groups having 6 to 20 ring atoms. Further, Q1, Q2 are each independently selected from cyclohexyl, cyclooctyl, or adamantyl.
In the present invention, each Y is independently selected from an aromatic group having 6 to 30 ring atoms, an alicyclic group having 6 to 30 ring atoms, or a C1 to C20 aliphatic group. The specific description is as follows:
in one embodiment, each Y is independently selected from unsubstituted, mono-or di-substituted aromatic groups having 6 to 30 ring atoms. Further, each Y is independently selected from unsubstituted, monosubstituted or disubstituted aromatic groups having 6 to 20 ring atoms. Further, each Y is independently selected from the group shown below:
or->;
Each R is 3 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen; r is R 4 Selected from single bonds or groups as shown below:
。
further, each R 3 Independently selected from C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 fluoroalkyl or halogen. Further, each R 3 Are each independently selected from methyl (-CH) 3 ) Ethyl, 1-propyl, 2-propyl, 1-butyl, 2-methyl-1-propyl, 2-butyl, 2-methyl-2-propyl, 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-1-butyl, 2-methyl-1-butyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2, 3-dimethyl-2-butyl, 3-dimethyl-2-butyl, n-octyl, cyclohexyl, cyclooctyl, adamantyl, trifluoromethyl (-CF) 3 ) Or fluorine (-F). Further, each R 3 Are independently selected from-F, -CH 3 or-CF 3 。
In one embodiment, each Y is independently selected from unsubstituted, mono-or di-substituted cycloaliphatic radicals having from 6 to 30 ring atoms. Further, each Y is independently selected from unsubstituted, mono-or di-substituted alicyclic groups having 6 to 20 ring atoms. Further, each Y is independently selected from the group shown below:
or->;
Each R is 5 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen;
R 6 selected from single bonds or groups as shown below:
。
further, each R 5 Independently selected from C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 fluoroalkyl or halogen. Further, each R 5 Are each independently selected from methyl (-CH) 3 ) Ethyl, 1-propyl, 2-propyl, 1-butyl, 2-methyl-1-propyl, 2-butyl, 2-methyl-2-propyl, 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-1-butyl, 2-methyl-1-butyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2, 3-dimethyl-2-butyl, 3-dimethyl-2-butyl, n-octyl, cyclohexyl, cyclooctyl, adamantyl, trifluoromethyl (-CF) 3 ) Or fluorine (-F). Further, each R 5 Are independently selected from-F, -CH 3 or-CF 3 。
In one embodiment, each Y is independently selected from C1-C20 aliphatic groups. Further, each Y is independently selected from C1-C10 aliphatic groups. Still further, each Y is independently selected from methylene or ethylene.
In the present invention, m and n are each taken from 0.1 to 0.9, and m+n is=1. It is understood that m includes, but is not limited to, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, and 0.9, and n includes, but is not limited to, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, and 0.1.
It is to be understood that the method for producing the polyimide according to the present invention is not particularly limited, and the polyimide may be synthesized by a known general method, for example, a method of producing a polyimide by a known general method of solution polymerization of a monomeric dianhydride and a monomeric diamine, a method of mixing a monomeric dianhydride and a monomeric diamine in an organic solvent, and a method of reacting the mixture may be easily carried out.
In one embodiment, the method for preparing polyimide as described in the above formula (1-1) comprises the steps of:
mixing diamine with a structure shown in a formula (I), dianhydride with a structure shown in a formula (II) and dianhydride with a structure shown in a formula (III) in a solvent, and carrying out polymerization reaction, dehydration and cyclization to prepare polyimide with a structure shown in a formula (1-1);
(I)、/>(II)、/>(III);
Q 1 、Q 2 Each independently selected from an aromatic group having 6 to 30 ring atoms, or a cycloalkyl group having 3 to 30 ring atoms;
m is selected from the group represented by formula (M-1) or (M-2);
(M-1)、/>(M-2);
each Y is independently selected from an aromatic group with a ring atom number of 6 to 30, an alicyclic group with a ring atom number of 6 to 30 or a C1-C20 aliphatic group;
a is selected from the group shown below:
;
each R is 1 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen;
R 2 selected from single bonds or groups as shown below:
。
it will be appreciated that Y, Q described in the polyimide preparation method 1 、Q 2 The definitions of M and A are the same as those described above for the polyimide having the structure represented by formula (1-1), and will not be repeated here.
In one embodiment, the diamine having the structure of formula (I) is selected from any one of the diamine compounds (I-1) to (I-4):
(I-1)、/>(I-2)、
(I-3)、/>(I-4)。
in one embodiment, the dianhydride having the structure of formula (II) is selected from any of the following compounds:
(X-2)、/>(X-3)。
further, the dianhydride having the structure of formula (X-2) is selected from the dianhydride compounds represented by any one of the following (II-1) to (II-5):
;
the dianhydride with the structure of the formula (X-3) is selected from dianhydride compounds shown in any of the following (II-3) to (II-5):
。
It is understood that the dianhydride compound represented by any one of the formulas (II-1) to (II-5) is obtained by condensation reaction of an amino group or a derivative thereof with a carboxyl group or a derivative thereof.
In one embodiment, the dianhydride having the structure of formula (III) is selected from dianhydride compounds represented by any of the following (III-1) to (III-4):
(III-1)、/>(III-2)、/>
(III-3)、/>(III-4)。
preferably, the dianhydride having the structure of formula (III) has a structure in which a plurality of aromatic rings are directly linearly linked, such as (III-2) or (III-4), which enables the polyimide to form a near-planar structure, facilitating the close packing of polyimide molecular chains, thereby reducing the free volume and the thermal expansion coefficient, while imparting excellent mechanical properties to the polyimide film.
It will be appreciated that the molecular weight of the polyamic acid and subsequent polyimide can be controlled by varying the molar ratio of the sum of all dianhydrides to the sum of all diamines in the polymerized monomer in the reaction.
In one embodiment, the molar ratio of the total of the dianhydride having the structure of formula (II) and the dianhydride having the structure of formula (III) to the diamine having the structure of formula (I) is 100: (95-105), preferably the molar ratio is close to 100:100, the molecular weight of the prepared polyamide acid and the subsequent polyimide is larger, and further, the molar ratio of the total amount of the dianhydride with the structure of the formula (II) and the dianhydride with the structure of the formula (III) to the diamine with the structure of the formula (I) is 100:100. Further, the molar ratio of the dianhydride having the structure of formula (II) to the dianhydride having the structure of formula (III) is (10-90): (90-10), wherein the molar total amount of the dianhydride having the structure of formula (II) and the dianhydride having the structure of formula (III) is 100.
The temperature conditions for the polymerization reaction in the present invention are not particularly limited, but are preferably 60℃or less, more preferably 0℃to 50 ℃. The reaction time may be arbitrarily set within a range of 10 minutes to 30 hours.
In one embodiment, the polymerization reaction is carried out at a temperature of 0-50 ℃ for 0.1-30 hours.
In one embodiment, the organic solvent is selected from the group consisting of N, N-dimethylacetamide, N-dimethylformamide, N-methyl-2-pyrrolidone, m-cresol, N-methylcaprolactam, sulfolane, dimethylsulfoxide (DMSO), cyclohexanone, hexamethylphosphoramide, and gamma-butyrolactone. That is, these solvents may be used singly or in combination of two or more. In addition, even a solvent in which polyamic acid is not dissolved may be added to the above solvent within the range where a homogeneous solution is obtained.
It is to be understood that in the present invention, diamine may be dissolved or dispersed in an organic solvent in a slurry form to prepare a diamine solution, and dianhydride may be added to the diamine solution. The tetracarboxylic dianhydride may be added in a solid state or may be dissolved or dispersed in an organic solvent in a slurry state.
Polyimide is produced from polyamic acid through dehydrative cyclic imidization, and the dehydrative cyclic imidization reaction is not particularly limited, and may be thermal imidization or chemical imidization. As in the case of the usual polyamic acid, imidization reaction can be performed by a method using a known dehydration reaction by heating or chemical cyclization. The imidization reaction of the amic acid to form an imide can be carried out by gradually increasing the temperature from 80℃to 400℃by heating.
Chemical cyclizing imidization is carried out by adding a chemical dehydrating agent to carry out a reaction for dehydrating and cyclizing amic acid to form imide. The dehydrating agent may be selected from acetic anhydride, benzoic anhydride. The catalysis can be carried out using organic bases such as pyridine or triethylamine. The reaction temperature can be-20-200 ℃. In this reaction, the polymerization solution of the polyamic acid may be used without change, or may be diluted. The polyimide-containing solution thus obtained may be used, or may be used by: the polymer is precipitated using a solvent such as methanol or ethanol and then isolated in the form of a powder, or the resulting powder is redissolved in a suitable solvent prior to use. The solvent for redissolution of the present invention is not particularly limited as long as the resulting polymer can be dissolved, such as a mixture of one or more selected from the group consisting of m-cresol, N-dimethylacetamide, N-dimethylformamide, N-methyl-2-pyrrolidone, cyclohexanone and γ -butyrolactone.
The invention also provides application of the polyimide, and the technical scheme is as follows:
1. an optically transparent film comprising a polyimide as described above or a polyimide produced according to the process for producing a polyimide as described above.
2. An OLED comprising an optically transparent film as described above.
3. A multilayer composite polyimide material has a structure including a first thermoplastic polyimide layer and a transparent polyimide layer arranged in a stack;
the first thermoplastic polyimide layer comprises a first thermoplastic polyimide (TCPI 1) and the transparent polyimide layer comprises a polyimide (CPI) as described above or a polyimide (CPI) prepared according to the preparation method as described above;
the structural unit of the first thermoplastic polyimide has a structure represented by formula (2-1):(2-1);
wherein B is 1 An aromatic group having 6 to 30 ring atoms, an alicyclic group having 6 to 30 ring atoms, or a C1 to C20 aliphatic group;
Z 1 representation of;
Each R is 7 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen;
R 8 selected from single bonds or groups as shown below:
;
p is selected from any integer from 1 to 10, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
The thermoplastic polyimide shown in the formula (2-1) is colorless thermoplastic transparent polyimide with the transmittance T% of more than or equal to 87 percent at 360 nm-780 nm, the glass transition temperature of 150 ℃ to 300 ℃ and the 5 percent thermal decomposition temperature of more than 340 ℃ and capable of being heated and melted.
The polyimide shown in the formula (1-1) and the thermoplastic polyimide shown in the formula (2-1) are compounded into the multi-layer composite polyimide material, so that the multi-layer composite polyimide material has excellent heat resistance, can be matched with the thermal expansion performance of copper foil, has high bonding strength with the copper foil and good dimensional stability, can be used for preparing a glue-type copper-clad plate, can effectively reduce the thickness of the traditional glue-type copper-clad plate, and solves the problems of layering, air bubbles and the like of the copper-clad plate in tin soldering treatment and high-temperature application.
In one embodiment, each R 7 Independently selected from C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 fluoroalkyl or halogen. Each R is 7 Are each independently selected from methyl (-CH) 3 ) Ethyl, 1-propyl, 2-propyl, 1-butyl, 2-methyl-1-propyl, 2-butyl, 2-methyl-2-propyl, 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-1-butyl, 2-methyl-1-butyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2, 3-dimethyl-2-butyl, 3-dimethyl-2-butyl, n-octyl, cyclohexyl, cyclooctyl, adamantyl, trifluoromethyl (-CF) 3 ) Or fluorine (-F). Further, each R 7 Are respectively and independently selected from-F, CH 3 or-CF 3 。
In the present invention, B 1 Selected from an aromatic group having 6 to 30 ring atoms, an alicyclic group having 6 to 30 ring atoms, or a C1 to C20 aliphatic group.
Further, B 1 Representation of;
Each R is 9 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen. Further, each R 9 Independently selected from C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 fluoroalkyl or halogen. Further, each R 9 Are each independently selected from methyl (-CH) 3 ) Ethyl, 1-propyl, 2-propyl, 1-butyl, 2-methyl-1-propyl, 2-butyl, 2-methyl-2-propyl, 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-1-butyl, 2-methyl-1-butyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2, 3-dimethyl-2-butyl, 3-dimethyl-2-butyl, n-octyl, cyclohexyl, cyclooctyl, adamantyl, trifluoromethyl (-CF) 3 ) Or fluorine (-F). Further, each R 9 Are independently selected from-F, -CH 3 or-CF 3 ;
R 10 A group selected from the group shown below:
;
q is selected from any integer from 1 to 10, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
The first thermoplastic polyimide can realize high bonding strength to the copper foil and the polyimide base film layer at the same time based on the performance characteristics of the aliphatic chain structure.
In one embodiment, the thickness of the first thermoplastic polyimide layer is 0.5 μm to 20 μm and the thickness of the transparent polyimide layer is 50 μm to 100 μm.
FIG. 1 is a schematic structural diagram of a dual-layer composite polyimide material according to one embodiment of the present invention, wherein 101 represents a first thermoplastic polyimide layer and 102 represents a transparent polyimide layer.
In one embodiment, the multilayer composite polyimide material further comprises a second thermoplastic polyimide layer (TCPI 2) disposed in a stack with the transparent polyimide layer (CPI) in a direction away from the first thermoplastic polyimide layer (TCPI 1);
the second thermoplastic polyimide layer comprises a second thermoplastic polyimide;
the structural unit of the second thermoplastic polyimide has a structure represented by formula (3-1):
(3-1);
wherein B is 2 An aromatic group having 6 to 30 ring atoms, an alicyclic group having 6 to 30 ring atoms, or a C1 to C20 aliphatic group;
Z 2 Representation of;
Each R is 11 Separately and independently from each otherSelected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen;
R 12 selected from single bonds or groups as shown below:
;
r is selected from any integer from 1 to 10, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
The thermoplastic polyimide shown in the formula (3-1) is colorless thermoplastic transparent polyimide with the transmittance T% of more than or equal to 87 percent at 360 nm-780 nm, the glass transition temperature of 150 ℃ to 300 ℃ and the 5 percent thermal decomposition temperature of more than 340 ℃ and capable of being heated and melted.
The multilayer composite polyimide material is designed into a sandwich type, and the structure of the multilayer composite polyimide material comprises a first thermoplastic polyimide layer, a transparent polyimide layer and a second thermoplastic polyimide layer which are laminated, so that the multilayer composite polyimide material has excellent heat resistance, can be matched with the thermal expansion performance of a copper foil, has high bonding strength with the copper foil and has good dimensional stability, and the multilayer composite polyimide material is used for preparing a glue type copper-clad plate, so that the thickness of the traditional glue type copper-clad plate can be effectively reduced, and the problems of layering, air bubbles and the like of the copper-clad plate in tin soldering treatment and high-temperature application are solved.
In one embodiment, each R 11 Independently selected from C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 fluoroalkyl or halogen. Further, each R 11 Are each independently selected from methyl (-CH) 3 ) Ethyl, 1-propyl, 2-propyl, 1-butyl, 2-methyl-1-propyl, 2-butyl, 2-methyl-2-propyl, 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-1-butyl, 2-methyl-1-butyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2, 3-dimethyl-2-butyl, 3-dimethyl-2-butyl, n-octyl, cyclohexyl, cyclooctyl, adamantyl, trifluoromethyl (-CF) 3 ) Or fluorine (-F). Further, each R 11 Are independently selected from-F, -CH 3 or-CF 3 。
In the present invention, B 2 Selected from an aromatic group having 6 to 30 ring atoms, an alicyclic group having 6 to 30 ring atoms, or a C1 to C20 aliphatic group.
Further, B 2 Representation of;
Each R is 13 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen. Further, each R 13 Independently selected from C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 fluoroalkyl or halogen. Further, each R 13 Are each independently selected from methyl (-CH) 3 ) Ethyl, 1-propyl, 2-propyl, 1-butyl, 2-methyl-1-propyl, 2-butyl, 2-methyl-2-propyl, 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-1-butyl, 2-methyl-1-butyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2, 3-dimethyl-2-butyl, 3-dimethyl-2-butyl, n-octyl, cyclohexyl, cyclooctyl, adamantyl, trifluoromethyl (-CF) 3 ) Or fluorine (-F). Further, each R 13 Are independently selected from-F, -CH 3 or-CF 3 ;
R 14 A group selected from the group shown below:
;
s is selected from any integer from 1 to 10, i.e. 1, 2,3, 4, 5, 6, 7, 8, 9 or 10.
In one embodiment, the second thermoplastic polyimide layer has a thickness of 0.5 μm to 20 μm.
It is understood that in a specific example, the thermoplastic polyimides represented by the formulas (2-1) and (3-1) are independent of each other and may be the same or different.
Also, in the present invention, the thermoplastic polyimide contained in the first thermoplastic polyimide layer and the second thermoplastic polyimide layer are independent of each other and may be the same or different.
Fig. 2 is a schematic structural diagram of a three-layer composite polyimide material according to an embodiment of the present invention, wherein 201 represents a first thermoplastic polyimide layer (TCPI 1), 202 represents a transparent polyimide layer (CPI), and 203 represents a second thermoplastic polyimide layer (TCPI 2).
In order to further improve the adhesion of the thermoplastic polyimide TCPI to copper and polyimide CPI, in the present invention, a silane coupling agent may be further contained in the thermoplastic polyimide layer (TCPI 1 layer and/or TCPI2 layer) to adjust the interfacial adhesion with the substrate. The silane coupling agent is an alkoxy silane group compound with reactivity, and the structural formula is as follows: X-Si (R) 1 )m-(OR 2 ) (3-m) Wherein X represents a hydrocarbyl substituent containing an amino group, an epoxy group, an acryloxy group, a mercapto group, R 1 Represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, R 2 Represents a hydrocarbon group having 1 to 10 carbon atoms, and m represents 0, 1 or 2. Specifically, N-2- (aminoethyl) -3-aminopropyl methyldimethoxy silane, N-2- (aminoethyl) -3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, 3-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl methyldimethoxy silane, 3-mercaptopropyl trimethoxy silane, 3-mercaptopropyl methyldimethoxy silane, 3-acryloxypropyl trimethoxy silane.
It is to be understood that the present invention is not particularly limited to the method for preparing the first thermoplastic polyimide TCPI1 represented by the above formula (2-1) or the second thermoplastic polyimide TCPI2 represented by the above formula (3-1), and can be synthesized by a known general method, for example, a one-step heating method or a two-step chemical method may be selected. The one-step heating method is to heat dicarboxylic anhydride and diamine with set molar ratio in an organic solvent to a temperature of 50-200 ℃ (preferably 100-180 ℃) to perform polycondensation reaction for about 0.1-12 hours (preferably 0.1-5 hours) in general, so as to obtain the thermoplastic polyimide TCPI. The two-step chemical method refers to a reaction for preparing polyamic acid by reacting monomeric dianhydride with monomeric diamine, and performing a reaction for dehydrating cyclization of amic acid to form imide by adding a chemical dehydrating agent, wherein the dehydrating agent can be selected from acetic anhydride and benzoic anhydride, and can be catalyzed by using organic base such as pyridine or triethylamine.
In the present invention, the organic solvent used for preparing the first thermoplastic polyimide and the second thermoplastic polyimide is an organic solvent in which the product is soluble and which can be heated to a desired temperature, such as aprotic polar solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, triethylene glycol dimethyl ether, etc.; ketone solvents such as cyclohexanone and butanone; phenolic solvents such as m-cresol, phenol, chlorophenol, etc.; aromatic solvents such as toluene and xylene. The organic solvent may be a combination of one or more of the above solvents. In the above reaction, a known reaction dehydrating agent or catalyst may be used. As the reaction catalyst, for example, tertiary amines such as triethylamine, dimethylaniline, pyridine, picoline, isoquinoline, and the like may be used, or two or more kinds may be used in combination. Examples of the dehydrating agent include acetic anhydride and benzoic anhydride, and two or more of them may be combined.
Preferably, the present invention prepares the first thermoplastic polyimide represented by formula (2-1) or the second thermoplastic polyimide represented by formula (31) according to a one-step heating method. The technical proposal is as follows:
a method for preparing a first thermoplastic polyimide as shown in formula (2-1), comprising the following steps:
mixing diamine with a structure shown in a formula (IV) and dianhydride with a structure shown in a formula (V) in a solvent, and carrying out polymerization reaction to obtain first thermoplastic polyimide with a structure shown in a formula (2-1);
(IV)、/>(V);
wherein B is 1 An aromatic group having 6 to 30 ring atoms, an alicyclic group having 6 to 30 ring atoms, or a C1 to C20 aliphatic group; z is Z 1 Representation of;
Each R is 7 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen;
R 8 selected from single bonds or groups as shown below:
;
p is selected from any integer from 1 to 10, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
Understandably, the first thermoplastic polyimide preparation method is described as B 1 、Z 1 、R 7 、R 8 And p are as defined above for the first thermoplastic polyimide having the structure represented by formula (2-1) with respect to the structural unit, and are not described in detail herein.
In one embodiment, the diamine having the structure of formula (IV) is selected from any one of the diamine compounds shown below:
、/>、/>、。
In one embodiment, the dianhydride having the structure of formula (V) is selected from the group consisting of the dianhydride compounds shown in any of the following:
、/>、
。
in one embodiment, the molar ratio (95-105) of the diamine having the structure of formula (IV) and the dianhydride having the structure of formula (V): 100.
in one embodiment, the polymerization reaction to prepare the first thermoplastic polyimide is carried out at a temperature of 50 ℃ to 200 ℃ for typically about 0.1h to 12h (preferably 0.1h to 5 h). Preferably, the polymerization reaction for preparing the first thermoplastic polyimide is carried out at 100-180 ℃ for 0.1-5 h.
A method for producing a second thermoplastic polyimide represented by the above formula (3-1), comprising the steps of:
mixing diamine with a structure shown in a formula (VI) and dianhydride with a structure shown in a formula (VII) in a solvent for polymerization reaction to prepare second thermoplastic polyimide with a structure shown in a formula (3-1);
(VI)、/>(VII);
wherein B is 2 An aromatic group having 6 to 30 ring atoms, an alicyclic group having 6 to 30 ring atoms, or a C1 to C20 aliphatic group;
Z 2 representation of;
Each R is 11 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen;
R 12 selected from single bonds or groups as shown below:
;
r is selected from any integer from 1 to 10, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
Understandably, the second thermoplastic polyimide preparation method is described as B 2 、Z 2 、R 11 、R 12 And r are as defined above for the second thermoplastic polyimide having the structure represented by formula (3-1) with respect to the structural unit, and are not described in detail herein.
In one embodiment, the diamine having the structure of formula (VI) is selected from any of the diamine compounds shown below:
、/>、/>、。
in one embodiment, the dianhydride having the structure of formula (VII) is selected from the group consisting of the dianhydride compounds shown in any of the following:
、/>、
。
in one embodiment, the molar ratio (95-105) of the diamine having the structure of formula (VI) and the dianhydride having the structure of formula (VII): 100.
in one embodiment, the polymerization reaction to prepare the second thermoplastic polyimide is carried out at a temperature of 50 ℃ to 200 ℃ for typically about 0.1h to 12h (preferably 0.1h to 5 h). Preferably, the polymerization reaction for preparing the second thermoplastic polyimide is carried out at 100-180 ℃ for 0.1-5 h.
The invention also provides a preparation method of the multilayer composite polyimide material, and the multilayer composite polyimide material is formed by compounding two polyimide with different properties, and optionally, the multilayer composite polyimide material with a two-layer or three-layer laminated composite structure is manufactured by a tape casting coating process, and is preferably in a film form.
The technical proposal is as follows:
(1) The preparation method of the double-layer composite polyimide material comprises the following steps:
1) Preparing polyimide;
2) Preparing a first thermoplastic transparent polyimide to obtain a corresponding first thermoplastic transparent polyimide solution with the viscosity meeting the requirement;
3) A first thermoplastic transparent polyimide solution is coated on one side of the polyimide and baked.
(2) The preparation method of the three-layer composite polyimide material comprises the following steps:
1) Preparing polyimide;
2) Preparing a first thermoplastic transparent polyimide to obtain a corresponding first thermoplastic transparent polyimide solution with the viscosity meeting the requirement;
3) Preparing a second thermoplastic transparent polyimide to obtain a corresponding second thermoplastic transparent polyimide solution with the viscosity meeting the requirement;
4) And coating a first thermoplastic transparent polyimide solution on one side of the polyimide, coating a second thermoplastic transparent polyimide solution on the other side of the polyimide, and drying.
Thermoplastic polyimide TCPI solution is coated on one side or two sides of the polyimide CPI film, and the dry film thickness of the coating TCPI is 0.5-50 mu m, preferably 1-20 mu m. The heating and drying temperature and duration are not particularly limited as long as the solvent is removed, and for example, the temperature may be selected to be 100 ℃ to 150 ℃ and the drying time may be 5min to 60min.
The multilayer composite polyimide material (composite film) formed by coating and baking can be used as an insulating adhesive material for transparent circuit boards, such as rigid Printed Circuit Boards (PCBs), flexible printed circuit boards (FPCs), and multilayer circuit boards thereof. Specifically:
the invention also provides an insulating base film comprising the multilayer composite polyimide material as described above.
The invention also provides a copper-clad plate which comprises the multilayer composite polyimide material or the insulating base film.
In one embodiment, the copper foil in the copper-clad plate is distributed on one side of the multilayer composite polyimide material. Further, the multi-layer composite polyimide material is a double-layer composite polyimide material, and the structural schematic diagram of the copper-clad plate can be seen in fig. 3, wherein 301 represents a copper foil, 302 represents a first thermoplastic polyimide layer (TCPI 1), and 303 represents a transparent polyimide layer (CPI).
In one embodiment, the copper foil in the copper-clad plate is distributed on two sides of the multi-layer composite polyimide material, the multi-layer composite polyimide material is a three-layer composite polyimide material, and the structural schematic diagram of the copper-clad plate can be seen in fig. 4, wherein 401 and 405 each represent copper foil, 402 represents a first thermoplastic polyimide layer (TCPI 1), 403 represents a transparent polyimide layer (CPI), and 404 represents a second thermoplastic polyimide layer (TCPI 2).
The invention also provides a preparation method of the copper-clad plate, which comprises the following steps:
copper foils are pressed on one side or two sides of the multilayer composite polyimide material, and a single-sided or double-sided glue-free copper-clad plate is correspondingly formed.
In one embodiment, the pressing temperature is 180-300 ℃.
The invention also provides a rigid printed circuit board which comprises the multilayer composite polyimide material, the insulating base film or the copper-clad plate.
The invention also provides a flexible printed circuit board which comprises the multilayer composite polyimide material, the insulating base film or the copper-clad plate.
The following are specific examples.
The starting materials and reagents referred to in the following specific examples may be obtained commercially or may be prepared by known means by those skilled in the art.
The test method of the invention is as follows:
(1) coefficient of Thermal Expansion (CTE): and (3) adopting a TMA Q400 type static Thermal Mechanical Analyzer (TMA) to characterize thermal dimensional change behavior of the polyimide film, testing under a nitrogen atmosphere, wherein the temperature interval is 50-300 ℃, the fixed load is 0.05N, the heating rate is 5 ℃/min, and heating the sample to 300 ℃ to eliminate residual stress before testing.
(2) Optical transmittance: the average light transmittance of the Shimadzu UV-2550 ultraviolet visible spectrum tester at the wavelength of 360-780 nm.
(3) Glass transition temperature (Tg): the polyimide film was tested by DSC Perkin-Elmer DSC-7 with nitrogen and a heating rate of 10deg.C/min.
(4) Thermal weight loss Temperature (TGA): the polyimide film is tested by TGA Perkin-Elemer TGA-2, nitrogen is used, the temperature is 50-700 ℃, and the heating rate is 10 ℃/min.
(5) Mechanical property test: tensile Strength (σ) of polyimide film using an Universal tester model INSTRON-1121 m ) Tensile modulus (E t ) And elongation at breakε b ) Testing at a stretching rate of 5 mm min -1 Each film test sample was not less than five, and the average was taken as the final test result.
And (3) testing a copper-clad plate:
peel strength: a TA-630 peel strength tester (CECO) was used, in accordance with the IPC-TM650 standard.
Solder-resistant: solder pot, according to IPC-TM650 2.4.13 standard.
;
The synthesis of the above compounds is described in CN112625017a.
Example 1
The embodiment provides polyimide and a preparation method thereof, thermoplastic polyimide and a preparation method thereof, and a copper-clad plate and a preparation method thereof. The method comprises the following steps:
2,2' -bis (trifluoromethyl) diaminobiphenyl is added to a reaction vessel (3.2023 g,0.01 mol), dimethylacetamide (35.8 g), and the temperature was controlled at 25℃and dissolved by stirring. The dianhydride T1 compound is added in portions(1.0117 g, 0.003mol) and 3,3', 4' -biphenyltetracarboxylic dianhydride +.>(2.0595 g, 0.0075mol) was polymerized under nitrogen atmosphere for 24 hours to form a transparent polyamic acid solution. Acetic anhydride (8.6 g) and triethylamine (3.2 g) were added to the polymerization system, and the reaction was continued for 12 hours. The reaction mixture was slowly poured into ethanol to precipitate a white fine-wire-like precipitate, which was filtered off and dried to obtain a transparent polyimide resin. The resin was dissolved in dimethylacetamide to form a 20% mass fraction solution, coated on a glass plate, and placed in an oven heated to 250 ℃ to form a transparent polyimide CPI film.
1, 4-Cyclohexanedimethylamine is added into the reaction vessel(0.2844 g,0.002 mol), 2' -bis (trifluoromethyl) diaminobiphenyl->(2.5618g,0.008mol)Dimethylformamide (15.7 g) and cyclohexanone (17.1 g) were dissolved by stirring. 3,4,3',4' -biphenyltetracarboxylic dianhydride (2.9422 g,0.01 mol) was added thereto, and the temperature was raised to 170℃to react with 7. 7 h, thereby obtaining a thermoplastic polyimide solution TCPI. Adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (0.2540 g) and a dispersing agent BYK-333 (0.0063 g) into the polyimide solution system, mechanically stirring uniformly, coating on two sides of a polyimide CPI base film, heating at 130 ℃ for 10min, attaching copper foils with corresponding sizes on two sides of the adhesive film, placing into a quick press, preheating at 180 ℃ for 20s, and pressing for 120s under 10 MPa; and (3) placing the mixture in a baking oven at 200+/-10 ℃ for baking for 60min to obtain the sample Cu/TCPI/CPI/TCPI/Cu, wherein the thickness is 85 mu m. Wherein the thickness of the copper foil is 12.5 μm, the thickness of CPI film is 50 μm, and the thickness of TCPI film is 5 μm.
Example 2
The embodiment provides polyimide and a preparation method thereof, thermoplastic polyimide and a preparation method thereof, and a copper-clad plate and a preparation method thereof. The method comprises the following steps:
2,2' -bis (trifluoromethyl) diaminobiphenyl is added to a reaction vessel(3.2023 g,0.01 mol), N-methyl-2-pyrrolidone (25.8 g), and controlling the temperature to be not more than 30 ℃, stirring and dissolving. The dianhydride T1 compound is added in portions>(3.0352 g,0.009 mol) and pyromellitic dianhydride +.>(0.2181 g,0.001 mol) was polymerized in a nitrogen atmosphere for 15 hours to form a transparent polyamic acid solution, which was coated on a glass plate, and then placed in an oven, and heated from 50℃to 300℃in a gradient to form a transparent polyimide CPI film.
1, 3-Cyclohexanediamine is added into the reaction vessel(0.1422g,0.001 mol), 2' -bis (trifluoromethyl) diaminobiphenyl->(2.8820 g,0.009 mol), N-methyl-2-pyrrolidone (16.8 g) and toluene (19.18 g) were dissolved by stirring. 4,4' -oxydiphthalic anhydride is added>(3.1021 g,0.01 mol) and heated to 160℃for 10 hours to obtain a thermoplastic polyimide solution TCPI. Adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (0.3247 g) and a dispersing agent BYK-333 (0.0055 g) into the polyimide solution system, mechanically stirring uniformly, coating on two sides of a polyimide CPI base film, heating at 150 ℃ for 5min, attaching copper foils with corresponding sizes on two sides of the adhesive film, placing into a quick press, preheating at 200 ℃ for 20 s, and pressing for 240s under 12 MPa; and (3) placing the mixture in a baking oven at 220+/-10 ℃ for baking for 30min to obtain the sample Cu/TCPI/CPI/TCPI/Cu, wherein the thickness is 115 mu m. Wherein, the thickness of the copper foil is 12.5 μm, the thickness of the CPI film is 85 μm, and the thickness of the TCPI film is 2.5 μm.
Example 3
The embodiment provides polyimide and a preparation method thereof, thermoplastic polyimide and a preparation method thereof, and a copper-clad plate and a preparation method thereof. The method comprises the following steps:
1, 4-cyclohexanediamine is added into a reaction vessel(1.1419 g,0.01 mol) and sulfolane (25.8 g), and the mixture was dissolved by stirring at a temperature of 0 ℃. The dianhydride T2 compound is added in portions>(2.4453 g, 0.0075mol) and hexafluorodianhydride +.>(1.3327 g, 0.003mol) was polymerized in a nitrogen atmosphere for 9 hours to form a transparent polyamic acid solution, which was applied to a glass plate, placed in an oven, and gradually raisedThe temperature was heated from 25℃to 280℃to form a transparent polyimide CPI film.
1, 4-Cyclohexanedimethylamine is added into the reaction vessel(0.2844 g,0.002 mol), 2' -bis (trifluoromethyl) diaminobiphenyl->(2.5618 g,0.008 mol), dimethylformamide (19.2 g) and xylene (25.5 g) were dissolved by stirring. Adding bisphenol A type diether dianhydride(5.2049 g,0.01 mol) was heated to 150℃and reacted for 12 hours to obtain a thermoplastic polyimide solution TCPI. Adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (0.2114 g) and a dispersing agent BYK-333 (0.0059 g) into the polyimide solution system, mechanically stirring uniformly, coating the polyimide solution on two sides of a polyimide CPI base film, heating at 100 ℃ for 15min, attaching copper foils with corresponding sizes on two sides of the adhesive film, placing the adhesive film into a quick press, preheating at 180 ℃ for 10s, and pressing for 300s under 10 MPa; and (3) placing the mixture in a baking oven at 170+/-10 ℃ for baking for 60min to obtain the sample Cu/TCPI/CPI/TCPI/Cu, wherein the thickness is 140 mu m. Wherein, the thickness of the copper foil is 12.5 μm, the thickness of the CPI film is 95 μm, and the thickness of the TCPI film is 10 μm.
Example 4
The embodiment provides polyimide and a preparation method thereof, thermoplastic polyimide and a preparation method thereof, and a copper-clad plate and a preparation method thereof. The method comprises the following steps: 2, 2-bis (4-aminophenyl) hexafluoropropane is added to a reaction vessel(3.3426 g,0.01 mol) and dimethylacetamide (35.8 g), and the temperature is controlled at 15 ℃, and the mixture is stirred and dissolved. The dianhydride T3 compound is added in portions>(2.2818g,0.005 mol) and 3,3', 4' -biphenyltetracarboxylic dianhydride +.>(1.4711 g,0.005 mol) was polymerized in a nitrogen atmosphere to form a transparent polyamic acid solution of 9. 9 h. Acetic anhydride (5.10 g) and triethylamine (2.8 g) were added to the polymerization system, and the reaction was continued for 24. 24 h. The reaction mixture was slowly poured into ethanol to precipitate a white fine-wire-like precipitate, which was filtered off and dried to obtain a transparent polyimide resin. The resin was dissolved in dimethylacetamide to form a 20% mass fraction solution, coated on a glass plate, and placed in an oven heated to 300 ℃ to form a transparent polyimide CPI film.
Adding hydrogenated biphenyldiamine into a reaction vessel(0.9816 g,0.005 mol), 2' -bis (trifluoromethyl) diaminobiphenyl->(1.6011 g,0.005 mol), dimethylformamide (19.2 g), and cyclohexanone (25.5 g) were dissolved by stirring. Adding bisphenol A type diether dianhydride- >(4.1639 g,0.008 mol) and 3,3', 4' -biphenyltetracarboxylic dianhydride +.>(0.5884 g, 0.002mol), acetic anhydride (10.9 g) and triethylamine (4.8 g) were added to the polymerization system and the reaction was continued for 24 hours. The reaction mixture was slowly poured into ethanol to precipitate a white fine-wire-like precipitate, which was filtered off and dried to obtain a thermoplastic polyimide resin. This resin was dissolved in dimethylacetamide to obtain a thermoplastic polyimide solution TCPI. Adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (0.2734 g) and dispersant BYK-333 (0.0072 g) into the polyimide solution system, mechanically stirring, coating on two sides of polyimide CPI base film, heating at 125deg.C for 3min, attaching copper foil with corresponding size on two sides of the adhesive film, and placing into a quick press for 1Preheating at 80 ℃ for 10s, and pressing for 180s under 15 MPa; and (3) placing the mixture in an oven at 190+/-10 ℃ for baking for 45min to obtain the sample Cu/TCPI/CPI/TCPI/Cu, wherein the thickness is 130 mu m. Wherein, the thickness of the copper foil is 12.5 μm, the thickness of the CPI film is 65 μm, and the thickness of the TCPI film is 20 μm.
Example 5
The embodiment provides polyimide and a preparation method thereof, thermoplastic polyimide and a preparation method thereof, and a copper-clad plate and a preparation method thereof. The method comprises the following steps:
2,2' -bis (trifluoromethyl) diaminobiphenyl is added to a reaction vessel(3.2023 g,0.01 mol), dimethylacetamide (29.8 g), and the temperature was controlled to 5℃and dissolved by stirring. The dianhydride T3 compound is added in portions(3.6508 g,0.008 mol) and pyromellitic dianhydride +.>(0.4362 g, 0.002mol) was polymerized under nitrogen atmosphere for 15 hours to form a transparent polyamic acid solution. Acetic anhydride (11.5 g) and triethylamine (4.8 g) were added to the polymerization system, and the reaction was continued for 12 hours. The reaction mixture was slowly poured into ethanol to precipitate a white fine-wire-like precipitate, which was filtered off and dried to obtain a transparent polyimide resin. The resin was dissolved in dimethylacetamide to form a 20% mass fraction solution, which was coated on a glass plate and placed in an oven heated to 250 c to form a transparent polyimide CPI film. Pramine 1075 (0.5370 g,0.001 mol), 2' -bis (trifluoromethyl) diaminobiphenyl were added to the reaction vessel(2.8820 g,0.009 mol) and dimethyl sulfoxide (39.8 g) were dissolved with stirring. 4,4' -oxydiphthalic anhydride is added>(3.1021g,0.01mol),25℃Acetic anhydride (10.2 g) and pyridine (3.8 g) were added to the polymerization system for 24 hours, and the reaction was continued for 24 hours. The reaction mixture was slowly poured into ethanol to precipitate a white fine-wire-like precipitate, which was filtered off and dried to obtain a thermoplastic polyimide resin. This resin was dissolved in dimethylacetamide to obtain polyimide solution TCPI. Adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (0.2715 g) and a dispersing agent BYK-333 (0.0039 g) into the polyimide solution system, mechanically stirring uniformly, coating the polyimide solution on two sides of a polyimide CPI base film, heating at 150 ℃ for 5min, attaching copper foils with corresponding sizes on two sides of the adhesive film, placing the adhesive film into a quick press, preheating for 10s at 180 ℃, and pressing for 180s under 12 MPa; and (3) placing the mixture in a baking oven at 200+/-10 ℃ for baking for 60min to obtain the sample Cu/TCPI/CPI/TCPI/Cu, wherein the thickness is 79 mu m. Wherein, the thickness of the copper foil is 12.5 μm, the thickness of the CPI film is 50 μm, and the thickness of the TCPI film is 2 μm.
Example 6
The embodiment provides polyimide and a preparation method thereof, thermoplastic polyimide and a preparation method thereof, and a copper-clad plate and a preparation method thereof. The method comprises the following steps:
2,2' -bis (trifluoromethyl) diaminobiphenyl is added to a reaction vessel(3.2023 g,0.01 mol), N-methyl-2-pyrrolidone (25.8 g), and the temperature was controlled at 5℃and dissolved by stirring. The dianhydride T4 compound is added in portions(2.3120 g,0.005 mol) and pyromellitic dianhydride ∈ ->(1.0906 g,0.005 mol) was polymerized in a nitrogen atmosphere for 20 hours to form a transparent polyamic acid solution, which was coated on a glass plate, and placed in an oven, and heated from 20℃to 270℃in a gradient to form a transparent polyimide CPI film.
Pramine 1075 (0.2685 g,0.0005 mol), 2' -bis (trifluoromethyl) was added to the reaction vesselDiaminodiphenyl(3.0421 g,0.0095 mol) and N-methyl-2-pyrrolidone (35.5 g) were dissolved by stirring. Adding bisphenol A type diether dianhydride->(5.2049 g,0.01 mol), 11. 11 h was reacted at 50℃and acetic anhydride (10.2 g) and pyridine (3.8 g) were added to the polymerization system to continue the reaction for 24 hours. The reaction mixture was slowly poured into ethanol to precipitate a white fine-wire-like precipitate, which was filtered off and dried to obtain a thermoplastic polyimide resin. This resin was dissolved in N-methyl-2-pyrrolidone to obtain a thermoplastic polyimide solution TCPI. Adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (0.3725 g) and a dispersing agent BYK-333 (0.0045 g) into the polyimide solution system, mechanically stirring uniformly, coating on two sides of a polyimide CPI base film, heating at 110 ℃ for 10min, attaching copper foils with corresponding sizes on two sides of the adhesive film, placing into a quick press, preheating at 180 ℃ for 10s, and pressing for 240s under 10 MPa; and (3) placing the mixture in a baking oven at 210+/-10 ℃ for baking for 60min to obtain the sample Cu/TCPI/CPI/TCPI/Cu, wherein the thickness is 107 mu m. Wherein, the thickness of the copper foil is 12.5 μm, the CPI film is 70 μm, and the TCPI film is 6 μm.
Example 7
The embodiment provides polyimide and a preparation method thereof, thermoplastic polyimide and a preparation method thereof, and a copper-clad plate and a preparation method thereof. The method comprises the following steps:
adding hydrogenated biphenyldiamine into a reaction vessel(1.9633 g,0.01 mol), N-methyl-2-pyrrolidone (32.9 g), and the temperature was controlled at 40℃and the mixture was dissolved by stirring. The dianhydride T1 compound is added in portions>(2.6979 g,0.008 mol) and 2,3,6, 7-naphthalene tetracarboxylic dianhydride +.>(0.5363 g, 0.002mol) was polymerized in a nitrogen atmosphere for 8 hours to form a transparent polyamic acid solution, which was applied to a glass plate, and then placed in an oven, and heated from 50℃to 300℃with a gradient to form a transparent polyimide CPI film.
1, 3-Cyclohexanediamine is added into the reaction vessel(0.3556 g,0.0025 mol), 2' -bis (trifluoromethyl) diaminobiphenyl +.>(2.4017 g,0.0075 mol), N-methyl-2-pyrrolidone (17.8 g) and phenol (19.5 g) were dissolved by stirring. 4,4' -oxydiphthalic anhydride is added>(3.1021 g,0.01 mol) and heated to 180 ℃ for 5h to obtain a thermoplastic polyimide solution TCPI. Adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (0.3847 g) and a dispersing agent BYK-333 (0.0045 g) into the thermoplastic polyimide solution system, mechanically stirring uniformly, coating on two sides of a polyimide CPI base film, heating at 115 ℃ for 8min, attaching copper foils with corresponding sizes on two sides of the adhesive film, placing into a quick press, preheating at 190 ℃ for 20s, and pressing for 300s under 12 MPa; and (3) placing the mixture in a baking oven at 200+/-10 ℃ for baking for 60min to obtain the sample Cu/TCPI/CPI/TCPI/Cu, wherein the thickness is 92 mu m. Wherein, the thickness of the copper foil is 12.5 μm, the thickness of the CPI film is 50 μm, and the thickness of the TCPI film is 8.5 μm.
Example 8
The embodiment provides polyimide and a preparation method thereof, thermoplastic polyimide and a preparation method thereof, and a copper-clad plate and a preparation method thereof. The method comprises the following steps:
2,2' -bis (trifluoromethyl) diaminobiphenyl is added to a reaction vessel(3.2023 g,0.01 mol) N-methylAnd (3) base-2-pyrrolidone (25.8 g), controlling the temperature to be not more than 30 ℃, and stirring and dissolving. The dianhydride T1 compound is added in portions>(3.0352 g,0.009 mol) and pyromellitic dianhydride +.>(0.2181 g,0.001 mol) was polymerized in a nitrogen atmosphere for 15 hours to form a transparent polyamic acid solution, which was coated on a glass plate, and then placed in an oven, and heated from 50℃to 300℃in a gradient to form a transparent polyimide CPI film.
1, 3-Cyclohexanediamine is added into the reaction vessel(0.1422 g,0.001 mol), 2' -bis (trifluoromethyl) diaminobiphenyl->(2.8820 g,0.009 mol), N-methyl-2-pyrrolidone (16.8 g) and toluene (19.18 g) were dissolved by stirring. 4,4' -oxydiphthalic anhydride is added>(3.1021 g,0.01 mol) and reacted at 160℃for 10 h to obtain a thermoplastic polyimide solution TCPI. Adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (0.3247 g) and a dispersing agent BYK-333 (0.0055 g) into the polyimide solution system, mechanically stirring uniformly, coating on one side of a polyimide CPI base film, heating at 150 ℃ for 5min, attaching copper foil with corresponding size on the surface of the adhesive film, placing into a quick press, preheating at 200 ℃ for 20s, and pressing for 240s under 12 MPa; and (3) placing the mixture in a baking oven at 220+/-10 ℃ for baking for 30min to obtain a sample Cu/TCPI/CPI with the thickness of 145 mu m. Wherein, the thickness of the copper foil is 12.5 μm, the thickness of the CPI film is 100 μm, and the thickness of the TCPI film is 10 μm.
Comparative example 1
The comparative example provides a polyester and a preparation method thereof, and a copper-clad plate and a preparation method thereof. The method comprises the following steps:
2,2' -bis [4- (4-aminophenoxyphenyl) was added to the epoxy resin GA-240 (10.5 g) system]Propane(10.9 g), 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (0.856 g) and a dispersing agent BYK-333 (0.0214 g), mechanically stirring uniformly, coating on two sides of a polyethylene terephthalate PET base film, heating at 150 ℃ for 5min, attaching copper foils with corresponding sizes on two sides of the adhesive film, placing into a quick press, preheating at 180 ℃ for 10s, and pressing for 180s under 12 MPa; and (3) placing the mixture in a baking oven at 200+/-10 ℃ for baking for 60min to obtain the sample Cu/epoxy resin/PET/epoxy resin/Cu, wherein the thickness is 140 mu m. Wherein the thickness of the copper foil is 12.5 μm, the thickness of the PET film is 75 μm, and the thickness of the epoxy resin film is 20 μm.
Comparative example 2
The comparative example provides a polyester and a preparation method thereof, and a copper-clad plate and a preparation method thereof. The method comprises the following steps:
addition of nadic anhydride to epoxy resin GA-240 (10.5 g) System(14.28 g), 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (0.9912 g) and a dispersing agent BYK-333 (0.0247 g), mechanically stirring uniformly, coating on two sides of a polyethylene terephthalate PET base film, heating at 125 ℃ for 10min, attaching copper foils with corresponding sizes on two sides of the adhesive film, placing into a quick press, preheating at 180 ℃ for 10s, and pressing for 120s under 10 MPa; and (3) placing the mixture in a baking oven at 170+/-10 ℃ for baking for 60min to obtain the sample Cu/epoxy resin/PET/epoxy resin/Cu, wherein the thickness is 165 mu m. Wherein the thickness of the copper foil is 12.5 μm, the thickness of the PET film is 100 μm, and the thickness of the epoxy resin film is 20 μm.
Comparative example 3
The comparative example provides polyimide and a preparation method thereof, thermoplastic polyimide and a preparation method thereof, and a copper-clad plate and a preparation method thereof. The method comprises the following steps:
reverse directionAdding 2,2' -di (trifluoromethyl) diaminobiphenyl into a reaction vessel(3.2023 g,0.01 mol), dimethylacetamide (35.8 g), and the temperature was controlled at 25℃and dissolved by stirring. Adding hexafluorodianhydride in batches(4.4424 g,001 mol) was polymerized under nitrogen atmosphere for 24 hours to form a transparent polyamic acid solution. Acetic anhydride (8.6 g) and triethylamine (3.2 g) were added to the polymerization system, and the reaction was continued for 12 hours. The reaction mixture was slowly poured into ethanol to precipitate a white fine-wire-like precipitate, which was filtered off and dried to obtain a transparent polyimide resin. The resin was dissolved in dimethylacetamide to form a 20% mass fraction solution, coated on a glass plate, and placed in an oven heated to 250 ℃ to form a transparent polyimide CPI film.
1, 4-Cyclohexanedimethylamine is added into the reaction vessel(0.2844g,0.002 mol), 2' -bis (trifluoromethyl) diaminobiphenyl +.>(2.5618 g,0.008 mol), dimethylformamide (15.7 g) and cyclohexanone (17.1 g) were dissolved by stirring. 3,4,3',4' -biphenyltetracarboxylic dianhydride (2.9422 g,0.01 mol) was added thereto, and the temperature was raised to 170℃for 7 hours to obtain a thermoplastic polyimide solution TCPI. Adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (0.2540 g) and a dispersing agent BYK-333 (0.0063 g) into the polyimide solution system, mechanically stirring uniformly, coating on two sides of a polyimide CPI base film, heating at 130 ℃ for 10 min, attaching copper foils with corresponding sizes on two sides of the adhesive film, placing into a quick press, preheating at 180 ℃ for 20s, and pressing for 120s under 10 MPa; and (3) placing the mixture in a baking oven at 200+/-10 ℃ for baking for 60min to obtain the sample Cu/TCPI/CPI/TCPI/Cu, wherein the thickness is 85 mu m. Wherein, the thickness of the copper foil is 12.5 μm, the thickness of the CPI film is 50 μm, and the thickness of the TCPI film is 5 μm.
Comparative example 4
The comparative example provides polyimide and a preparation method thereof, thermoplastic polyimide and a preparation method thereof, and a copper-clad plate and a preparation method thereof. The method comprises the following steps: adding hydrogenated biphenyldiamine into a reaction vessel(1.9633 g,0.01 mol), N-methyl-2-pyrrolidone (32.9 g), and the temperature was controlled at 40℃and the mixture was dissolved by stirring. Addition of BTDA in portions(2.5778 g,0.008 mol) and 2,3,6, 7-naphthalene tetracarboxylic dianhydride +.>(0.5363 g, 0.002mol) was polymerized in a nitrogen atmosphere for 8 hours to form a transparent polyamic acid solution, which was applied to a glass plate, and then placed in an oven, and heated from 50℃to 300℃with a gradient to form a transparent polyimide CPI film.
1, 3-Cyclohexanediamine is added into the reaction vessel(0.3556 g,0.0025 mol), 2' -bis (trifluoromethyl) diaminobiphenyl +.>(2.4017 g,0.0075 mol), N-methyl-2-pyrrolidone (17.8 g) and phenol (19.5 g) were dissolved by stirring. 4,4' -oxydiphthalic anhydride is added>(3.1021 g,0.01 mol) and heated to 180 ℃ for 5h to obtain a thermoplastic polyimide solution TCPI. Adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (0.3847 g) and dispersant BYK-333 (0.0045 g) into the thermoplastic polyimide solution system, mechanically stirring, coating on two sides of polyimide CPI base film, heating at 115deg.C for 8min, attaching copper foil with corresponding size on two sides of the adhesive film, and placing into a quick press Preheating at 190 ℃ for 20s, and pressing for 300s under the pressure of 12 MPa; and (3) placing the mixture in a baking oven at 200+/-10 ℃ for baking for 60min to obtain the sample Cu/TCPI/CPI/TCPI/Cu, wherein the thickness is 92 mu m. Wherein, the thickness of the copper foil is 12.5 μm, the thickness of the CPI film is 50 μm, and the thickness of the TCPI film is 8.5 μm.
1. The results of the characterization of the properties of the transparent polyimide are shown in Table 1 below: TABLE 1
As can be seen from table 1, TCPI containing alkyl fatty chains exhibits high light transmittance while having good thermoplasticity. The colorless transparent polyimide base films of examples 1 to 8 having the structure represented by the formula (1-1) had higher glass transition temperature (Tg) than comparative example 3 and comparative example 4>350 c), and lower Coefficient of Thermal Expansion (CTE)<16ppm K -1 )。
2. The results of the thermoplastic polyimide performance characterization are shown in Table 2 below:
TABLE 2
3. The characterization results of the performance of the copper-clad plates prepared in each example and comparative example are shown in the following table 3:
TABLE 3 Table 3
As can be seen from Table 3, the CPI-FCCL prepared in examples 1 to 8 has a solder resistance temperature higher (> 340 ℃) than PET-FCCL, meets the process temperature requirements, and has a peel strength higher than 1.2N/mm. Examples 1 to 8 use the colorless transparent polyimide having the structure represented by the formula (1-1) of the present invention to have a better compounding effect with the thermoplastic polyimide and a higher peel strength than comparative example 3 and comparative example 4.
4. Light transmission test of laminating covering film after copper-clad plate etching
Taking the Cu/TCPI/CPI copper-clad plate in example 8 as an example, the following operations are performed:
(1) The copper foil in the Cu/TCPI/CPI is partially protected by using an adhesive tape, then is soaked in an aqueous solution of a prepared PCB copper plate corrosive agent (the mass ratio is commercial corrosive agent/water=1/10), the unprotected copper foil can be completely dissolved, the protected copper foil can be reserved, and after etching is finished, the patterned FCCL can be obtained by drying.
(2) And (3) another part of CPI film is taken, a layer of transparent adhesive TCPI is coated on the surface of the CPI film, and the CPI film is dried and then is attached to release paper to obtain the transparent covering film.
(3) Pressing the transparent covering film on the etched adhesive surface of the patterned FCCL, preheating for 20s at the pressing temperature of 200 ℃, and pressing for 240s at the pressure of 12 MPa; and placing in an oven at 220+/-10 ℃ for baking for 30min.
The visible light transmittance of the CPI film attached to the copper foil is slightly reduced due to the increased surface roughness of the copper foil during etching, but the cover film is attached after etching, the roughness of the copper foil surface is leveled, and the visible light transmittance is restored, thereby obtaining the transparent FCCL shown in fig. 5.
The technical features of the above-described embodiments and examples may be combined in any suitable manner, and for brevity of description, all of the possible combinations of the technical features of the above-described embodiments and examples are not described, however, as long as there is no contradiction between the combinations of the technical features, they should be considered to be within the scope described in the present specification.
The above examples merely represent a few embodiments of the present invention and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Further, it is understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the above teachings, and equivalents thereof are intended to fall within the scope of the present invention. It should also be understood that, based on the technical solutions provided by the present invention, those skilled in the art obtain technical solutions through logical analysis, reasoning or limited experiments, all of which are within the scope of protection of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.
Claims (23)
1. A polyimide having a structure represented by the formula (1-1):
;
wherein,,
x represents:
Q 1 、Q 2 Each independently selected from phenyl or cyclohexyl;
m is selected from the group represented by formula (M-1) or (M-2);
(M-1)、/>(M-2);
Each Y is independently selected from the group shown below:
、/>、/>or->;
Each Y 1 Each independently selected from the group shown below:
or->;
Each R is 3 And R is 5 Each independently selected from the group consisting of absent, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 fluoroalkyl, ester, or halogen;
R 4 and R is 6 Each independently selected from a single bond or a group as shown below:
;
a is selected from the group shown below:
;
each R is 1 Each independently selected from the group consisting of absent, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 fluoroalkyl, ester, or halogen;
R 2 selected from single bonds or groups as shown below:
;
m is taken from 0.3 to 0.9, m+n=1,representing the ligation site.
2. The polyimide according to claim 1, wherein each R 3 And R is 5 Are each independently selected from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-methyl-1-propyl, 2-butyl, 2-fluviographMethyl-2-propyl, 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-1-butyl, 2-methyl-1-butyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2, 3-dimethyl-2-butyl, 3-dimethyl-2-butyl, n-octyl, cyclohexyl, cyclooctyl, adamantyl, trifluoromethyl or fluorine.
3. The polyimide according to claim 1, wherein each R 3 And R is 5 Are independently selected from-F, -CH 3 or-CF 3 。
4. A polyimide according to any one of claims 1 to 3, wherein each R 1 Each independently selected from methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-methyl-1-propyl, 2-butyl, 2-methyl-2-propyl, 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-1-butyl, 2-methyl-1-butyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2, 3-dimethyl-2-butyl, 3-dimethyl-2-butyl, n-octyl, cyclohexyl, cyclooctyl, adamantyl, trifluoromethyl or fluorine.
5. A polyimide according to any one of claims 1 to 3, wherein each R 1 Are independently selected from-F, -CH 3 or-CF 3 。
6. A method for producing the polyimide according to any one of claims 1 to 5, comprising the steps of:
mixing diamine with a structure shown in a formula (I), dianhydride with a structure shown in a formula (II) and dianhydride with a structure shown in a formula (III) in a solvent, and carrying out polymerization reaction, dehydration and cyclization to prepare polyimide with a structure shown in a formula (1-1);
(I)、/>(II)、/>(III);
Q 1 、Q 2 Each independently selected from an aromatic group having 6 to 30 ring atoms, or a cycloalkyl group having 3 to 30 ring atoms;
m is selected from the group represented by formula (M-1) or (M-2);
(M-1)、/>(M-2);
each Y is independently selected from the group shown below:
、/>、/>or->;
Each Y 1 Each independently selected from the group shown below:
or->;
Each R is 3 And R is 5 Each independently selected from the group consisting of absent, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 fluoroalkyl, ester, or halogen;
R 4 and R is 6 Each independently selected from a single bond or a group as shown below:
;
a is selected from the group shown below:
;
each R is 1 Each independently selected from the group consisting of absent, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 fluoroalkyl, ester, or halogen;
R 2 selected from single bonds or groups as shown below:
。
7. the method for producing a polyimide according to claim 6, wherein the molar ratio of the dianhydride having the structure of formula (II) to the dianhydride having the structure of formula (III) is (30 to 90): (70-10);
the molar ratio of the total of the dianhydride having the structure of formula (II) and the dianhydride having the structure of formula (III) to the diamine having the structure of formula (I) is 100: (95-105).
8. The method according to claim 6, wherein the polymerization reaction is carried out at a temperature of 60 ℃ or lower for 0.1 to 30 hours.
9. The method for producing a polyimide according to any one of claims 6 to 8, wherein the diamine having the structure of formula (I) is selected from diamine compounds represented by any one of the following (I-1) to (I-4):
(I-1)、/>(I-2)、
(I-3)、/>(I-4)。
10. the method for producing a polyimide according to any one of claims 6 to 8, wherein the dianhydride having a structure of formula (II) is selected from dianhydride compounds represented by any one of the following (II-1) to (II-5):
(II-1)、/>(II-2)、
(II-3)、
(II-4)、
(II-5)。
11. the method for producing a polyimide according to any one of claims 6 to 8, wherein the dianhydride having a structure of formula (III) is selected from dianhydride compounds represented by any one of the following (III-1) to (III-4):
(III-1)、/>(III-2)、
(III-3)、/>(III-4)。
12. an optically transparent film comprising the polyimide according to any one of claims 1 to 5 or the polyimide produced by the production method according to any one of claims 6 to 11.
13. An OLED comprising the optically transparent film of claim 12.
14. The multilayer composite polyimide material is characterized by comprising a first thermoplastic polyimide layer and a transparent polyimide layer which are arranged in a lamination manner;
the first thermoplastic polyimide layer comprises a first thermoplastic polyimide, and the transparent polyimide layer comprises the polyimide of any one of claims 1 to 5 or a polyimide produced according to the production method of any one of claims 6 to 11;
The structural unit of the first thermoplastic polyimide has a structure represented by formula (2-1):
(2-1);
wherein B is 1 Representation of;
Each R is 9 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen;
R 10 a group selected from the group shown below:
;
q is selected from any integer from 1 to 10;
Z 1 representation of;
Each R is 7 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen;
R 8 selected from single bonds or groups as shown below:
。
15. the multilayer composite polyimide material according to claim 14, wherein each R 7 Independently selected from C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 fluoroalkyl or halogen.
16. The multilayer composite polyimide material according to any one of claims 14 to 15, wherein the thickness of the first thermoplastic polyimide layer is 0.5 to 20 μm and the thickness of the transparent polyimide layer is 50 to 100 μm.
17. The multilayer composite of any of claims 14 to 15, further comprising a second thermoplastic polyimide layer disposed in a stack with the transparent polyimide layer in a direction away from the first thermoplastic polyimide layer;
The second thermoplastic polyimide layer comprises a second thermoplastic polyimide;
the structural unit of the second thermoplastic polyimide has a structure represented by formula (3-1):
(3-1);
wherein B is 2 Representation of;
Each R is 13 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen;
R 14 a group selected from the group shown below:
;
s is selected from any integer from 1 to 10;
Z 2 representation of;
Each R is 11 Each independently selected from the group consisting of absent, chain alkyl, cycloalkyl, haloalkyl, ester, or halogen;
R 12 selected from single bonds or groups as shown below:
。
18. the multilayer composite polyimide material according to claim 17, wherein each R 11 Independently selected from C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 fluoroalkyl or halogen.
19. The multilayer composite of claim 17, wherein the second thermoplastic polyimide layer has a thickness of 0.5 μιη to 20 μιη.
20. An insulating base film comprising the multilayer composite polyimide material of any one of claims 14 to 19.
21. A copper-clad plate comprising the multilayer composite polyimide material according to any one of claims 14 to 19, or the insulating base film according to claim 20.
22. A rigid printed circuit board comprising the multilayer composite polyimide material of any one of claims 14 to 19, or the insulating base film of claim 20, or the copper-clad laminate of claim 21.
23. A flexible printed circuit board comprising the multilayer composite polyimide material of any one of claims 14 to 19, or the insulating base film of claim 20, or the copper-clad laminate of claim 21.
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