CN109942815A - The polyimides compound resin and preparation method of a kind of low-k and application - Google Patents
The polyimides compound resin and preparation method of a kind of low-k and application Download PDFInfo
- Publication number
- CN109942815A CN109942815A CN201910214286.6A CN201910214286A CN109942815A CN 109942815 A CN109942815 A CN 109942815A CN 201910214286 A CN201910214286 A CN 201910214286A CN 109942815 A CN109942815 A CN 109942815A
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- China
- Prior art keywords
- residue
- bis
- benzene
- amino
- phenyl
- Prior art date
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 163
- 239000011347 resin Substances 0.000 title claims abstract description 156
- 229920005989 resin Polymers 0.000 title claims abstract description 156
- 150000001875 compounds Chemical class 0.000 title claims abstract description 138
- 239000004642 Polyimide Substances 0.000 title claims abstract description 132
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- -1 poly methylene Polymers 0.000 claims abstract description 139
- WDWDWGRYHDPSDS-UHFFFAOYSA-N methanimine Chemical compound N=C WDWDWGRYHDPSDS-UHFFFAOYSA-N 0.000 claims abstract description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000009719 polyimide resin Substances 0.000 claims abstract description 37
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 19
- 239000013039 cover film Substances 0.000 claims abstract description 18
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 107
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 claims description 70
- 239000002243 precursor Substances 0.000 claims description 63
- 239000010408 film Substances 0.000 claims description 57
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 52
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 50
- 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 45
- 239000000203 mixture Substances 0.000 claims description 40
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 33
- 239000004305 biphenyl Substances 0.000 claims description 32
- 235000010290 biphenyl Nutrition 0.000 claims description 32
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 30
- 150000001412 amines Chemical class 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 239000011889 copper foil Substances 0.000 claims description 20
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 18
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 16
- 206010034960 Photophobia Diseases 0.000 claims description 16
- 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 claims description 16
- 208000013469 light sensitivity Diseases 0.000 claims description 16
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 16
- 238000009413 insulation Methods 0.000 claims description 15
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 15
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 14
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- SDXUIOOHCIQXRP-UHFFFAOYSA-N 1,2,4,5-tetrafluorobenzene Chemical compound FC1=CC(F)=C(F)C=C1F SDXUIOOHCIQXRP-UHFFFAOYSA-N 0.000 claims description 12
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 12
- 238000013007 heat curing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000002798 polar solvent Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000001294 propane Substances 0.000 claims description 10
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 claims description 9
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 9
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 claims description 9
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 9
- KECOIASOKMSRFT-UHFFFAOYSA-N 2-amino-4-(3-amino-4-hydroxyphenyl)sulfonylphenol Chemical class C1=C(O)C(N)=CC(S(=O)(=O)C=2C=C(N)C(O)=CC=2)=C1 KECOIASOKMSRFT-UHFFFAOYSA-N 0.000 claims description 8
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 claims description 8
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims description 8
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 claims description 8
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 8
- 241000790917 Dioxys <bee> Species 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229940113088 dimethylacetamide Drugs 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 claims description 8
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 claims description 8
- 229940054441 o-phthalaldehyde Drugs 0.000 claims description 8
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 claims description 8
- 150000003457 sulfones Chemical group 0.000 claims description 8
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- UWQPDVZUOZVCBH-UHFFFAOYSA-N 2-diazonio-4-oxo-3h-naphthalen-1-olate Chemical class C1=CC=C2C(=O)C(=[N+]=[N-])CC(=O)C2=C1 UWQPDVZUOZVCBH-UHFFFAOYSA-N 0.000 claims description 6
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical group C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 6
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical group O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 claims description 5
- ZIPLKLQPLOWLTM-UHFFFAOYSA-N naphthalene-2,3-dicarbaldehyde Chemical compound C1=CC=C2C=C(C=O)C(C=O)=CC2=C1 ZIPLKLQPLOWLTM-UHFFFAOYSA-N 0.000 claims description 5
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims description 4
- FGRBYDKOBBBPOI-UHFFFAOYSA-N 10,10-dioxo-2-[4-(N-phenylanilino)phenyl]thioxanthen-9-one Chemical compound O=C1c2ccccc2S(=O)(=O)c2ccc(cc12)-c1ccc(cc1)N(c1ccccc1)c1ccccc1 FGRBYDKOBBBPOI-UHFFFAOYSA-N 0.000 claims description 4
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- ZJKAAVFEXXJDQW-UHFFFAOYSA-N 4-[4-[2-[4-[4-amino-2-(trifluoromethyl)phenoxy]phenyl]propan-2-yl]phenoxy]-3-(trifluoromethyl)aniline Chemical compound C=1C=C(OC=2C(=CC(N)=CC=2)C(F)(F)F)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1C(F)(F)F ZJKAAVFEXXJDQW-UHFFFAOYSA-N 0.000 claims description 4
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 4
- 229940100630 metacresol Drugs 0.000 claims description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 4
- IOUVQFAYPGDXFG-UHFFFAOYSA-N 4-[4-[2-[4-(3,4-dicarboxyphenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=C(C(C(O)=O)=CC=3)C(O)=O)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 IOUVQFAYPGDXFG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 2
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 claims 2
- MUNGMRPYTCHBFX-UHFFFAOYSA-N 1,5-diphenylpentane-1,3,5-trione Chemical compound C=1C=CC=CC=1C(=O)CC(=O)CC(=O)C1=CC=CC=C1 MUNGMRPYTCHBFX-UHFFFAOYSA-N 0.000 claims 2
- JRHNUZCXXOTJCA-UHFFFAOYSA-N 1-fluoropropane Chemical compound CCCF JRHNUZCXXOTJCA-UHFFFAOYSA-N 0.000 claims 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical group C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 2
- 125000006159 dianhydride group Chemical group 0.000 claims 2
- VGGRCVDNFAQIKO-UHFFFAOYSA-N formic anhydride Chemical compound O=COC=O VGGRCVDNFAQIKO-UHFFFAOYSA-N 0.000 claims 2
- 150000002576 ketones Chemical class 0.000 claims 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims 1
- XTEBLARUAVEBRF-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)aniline Chemical compound NC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 XTEBLARUAVEBRF-UHFFFAOYSA-N 0.000 claims 1
- 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 claims 1
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical class C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 claims 1
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 claims 1
- YKUPYLMLOKXQEN-UHFFFAOYSA-N C(C=1C(C(=O)O)=CC=CC1)(=O)O.[O] Chemical compound C(C=1C(C(=O)O)=CC=CC1)(=O)O.[O] YKUPYLMLOKXQEN-UHFFFAOYSA-N 0.000 claims 1
- 239000012954 diazonium Substances 0.000 claims 1
- ADXCEOBGDCQCKM-UHFFFAOYSA-N quinoline-2,3-dione Chemical class C1=CC=CC2=NC(=O)C(=O)C=C21 ADXCEOBGDCQCKM-UHFFFAOYSA-N 0.000 claims 1
- 239000011342 resin composition Substances 0.000 claims 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 12
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- 239000011521 glass Substances 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 239000004952 Polyamide Substances 0.000 description 11
- 229920002647 polyamide Polymers 0.000 description 11
- 239000000758 substrate Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 229920006259 thermoplastic polyimide Polymers 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 150000003949 imides Chemical group 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000008054 signal transmission Effects 0.000 description 3
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 2
- ALLIZEAXNXSFGD-UHFFFAOYSA-N 1-methyl-2-phenylbenzene Chemical group CC1=CC=CC=C1C1=CC=CC=C1 ALLIZEAXNXSFGD-UHFFFAOYSA-N 0.000 description 2
- ZMLHBBXPXZXTSP-UHFFFAOYSA-N 2-fluoropropane Chemical compound C[C](C)F ZMLHBBXPXZXTSP-UHFFFAOYSA-N 0.000 description 2
- VIUDTWATMPPKEL-UHFFFAOYSA-N 3-(trifluoromethyl)aniline Chemical class NC1=CC=CC(C(F)(F)F)=C1 VIUDTWATMPPKEL-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VWKLTFVCMNVHTI-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C1(=CC=CC=C1)C1=CC=CC=C1 Chemical compound N=NC=NN.N=NC=NN.C1(=CC=CC=C1)C1=CC=CC=C1 VWKLTFVCMNVHTI-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- URQUNWYOBNUYJQ-UHFFFAOYSA-N diazonaphthoquinone Chemical compound C1=CC=C2C(=O)C(=[N]=[N])C=CC2=C1 URQUNWYOBNUYJQ-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000000879 imine group Chemical group 0.000 description 2
- WMPJPAMWRAOQSU-UHFFFAOYSA-N naphthalene-1,2-dicarbaldehyde Chemical compound C1=CC=CC2=C(C=O)C(C=O)=CC=C21 WMPJPAMWRAOQSU-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 1
- SNLFYGIUTYKKOE-UHFFFAOYSA-N 4-n,4-n-bis(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 SNLFYGIUTYKKOE-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses the polyimides compound resin and preparation method of a kind of low-k and applications, are made of by way of copolymerization is blended polyimide resin unit with poly methylene imine resin unit；Reticular structure is formed in copolymer structure, increases strand gap.By the introducing of poly methylene imine resin, the dipole moment of polyimide molecule chain is reduced；Meanwhile fluorochemical monomer is used when polymerization, the common dielectric constant for reducing polyimides compound resin.Polyimide molecule segment flexible is designed by monomeric species, carry out the poly methylene imine molecular chain of balanced high degree of rigidity, the rigid-flexible of molecule segment in final polyimides compound resin is set to reach a preferable equalization point, not only guarantee that polyimides compound resin has preferable mechanical performance, also guarantee that polyimides compound resin has controllable thermal linear expansion coefficient, makes polyimides compound resin have good application prospect in flexibility coat copper plate, photosensitive cover film, route panel products.
Description
Technical field
The present invention relates to a kind of preparation technical fields of polyimides compound resin, and in particular to it is a kind of by polyimides with
The polyimides compound resin that copolymerization obtains is blended in poly methylene imine, the characteristic with low-k, in high-frequency high-speed route, electricity
Sub- Material Field has good application.Polyimides compound resin and corresponding flexibility coat copper plate of the invention is suitable for high frequency
Transmission flexible print wiring board, the insulating substrate of high-frequency electron device, high fidelity signals transmission, all kinds of electric equipment products
In.
Background technique
Polyimide resin is a kind of high performance engineering plastics, because of its intrinsic heat resistance, heatproof oxidation performance energy, is changed
Learn stability and excellent mechanical property, cold-resistant thermal shock, long-term use temperature range is from -50 DEG C to 250 DEG C, in industrial products
In be widely used.Polyimides has excellent insulation performance, and mechanical performance is high, and processability is strong, in electronic product, especially
In consumer high-end electronic product, such as mobile phone, tablet computer, camera product, have a wide range of applications.
Current electronic product constantly high-endization, mobile phone will also release the type of 5G signal transmission, the base station of 5G signal
To start to build, this proposes requirements at the higher level to the wiring board inside electronic product: on the one hand, insulating materials needs to have on wiring board
There are lower dielectric constant and dielectric loss, guarantee that 5G signal is undistorted in transmission process, guarantees wiring board under 5G mode
Work is not generated heat；On the other hand, the copper conductor on 5G semaphore request internal circuit board has better efficiency of transmission, due to electric current
Skin effect cause electric current conduction to be carried out on copper conductor and insulating basement membrane layer contact surface, therefore copper conductor and insulating substrate
Between roughness it is as low as possible, reduce signal transmission rate reduce and energy loss.Current board substrate, with epoxy
Based on resin, acrylic resin and polyimide resin, the dielectric constant of polyimide resin is 3.3-3.4, and dielectric loss is about
It is 0.007, is the material of the requirement of the closest 5G signal transmission of performance in these materials.Even so, polyimide resin
Dielectric constant or higher, transmission loss, distortion and route when 5G signal being caused to transmit are generated heat.
In general, the method for reducing the dielectric constant of polyimide resin, Ke Yiyou: pore-creating in film, fluororesin are mixed
Miscellaneous modification, modified, the fluorochemical monomer modification of aliphatic monomer etc..Pore-creating will cause the reduction of film mechanical performance in film, can also make
It is reduced at insulation performance, increasing electrical breakdown may；The hole made requires aperture submicron order or 100nm hereinafter, being difficult to control
Obtain the film of such small-bore, even aperture distribution.The doping vario-property of fluororesin, the dielectric that film is reduced by being blended are normal
Number；But the compatibility of fluororesin and polyimide resin is very poor, is easy to appear and mutually separates, mechanical performance is caused to significantly reduce.
Aliphatic monomer is modified, cuts off the charge transfer effect of polyimide molecule chain, can reduce dielectric constant；But aliphatic chain
It introduces, unavoidably heat resistance is caused to reduce；Although heat labile molecule segment can be dispelled by preparatory high-temperature process to mention
High subsequent heat resistance, but the mechanical performance that will cause final Kapton in this way reduces, it is also possible to it causes empty in film
Hole reduces the breakdown voltage of film.The dielectric constant of polyimides can be significantly reduced in the modification of fluorochemical monomer, passes through fluorine
The strong electron-withdrawing ability of atom reduces the dipole moment of molecule segment, passes through the repulsive interaction of fluoro-containing group and other molecule segments
Increase the gap of molecule interchain, above two ability makes fluorinated polyimide have lower dielectric constant.Even if but
In this way, the dielectric constant of polyimide resin be not yet it is very low, there is the space that further decreases；More it is essential that containing
Fluorine monomer generally is flexible unit, and the reduction of molecule chain rigidity is caused after introducing, and heat resistance can be reduced with dimensional stability, simultaneously
It causes molecule segment degree of orientation in the face of film to reduce, causes the increase of thermal expansion coefficient, application difficult in assist side.
Poly methylene imine is the height-oriented high molecular material of molecule chain, while having very strong rigid structure.It is tied
The major defect of structure is because molecule chain rigidity is too strong, caused by the longitudinal mechanical performance with transverse direction of film mismatch completely.One
As for, the poly methylene imine film being prepared using coating/melting extrusion method, strand is height-oriented in longitudinal direction,
It is longitudinal that there is excellent mechanical performance, and laterally there is film embrittlement, form threadiness division.But poly methylene imine molecular
On chain, it is made of imine group, rather than imide ring；There is no carbonyls, therefore have lower dipole moment, dielectric constant phase
To reduction.If the polyimides of itself and flexible structure is copolymerized, the mechanical performance after forming a film can be improved, can also reduce
The dielectric constant of polyimides.
The branched structure of polyimide resin brings steric hindrance when can accumulate/wind to strand, increase strand
Between spacing, cause the appearance in strand gap indirectly.Not only size is small in these gaps, but also is evenly distributed in the structure,
While not influencing the mechanical performance of polyimide resin, the same function in hole/gap being artificially introduced is played, to dielectric
The reduction of constant provides contribution.After branched structure forms two-dimensional reticular structure, improve poly methylene imine molecular chain in one direction
On it is height-oriented so that lateral mechanical performance is improved, avoid the occurrence of the division of transverse fiber shape.
For these reasons, the invention proposes the polyimides that a kind of polyimides and poly methylene imine homogeneous interpolymer obtain
Compound resin, by the introducing of poly methylene imine unit, to reduce the dielectric constant of polyimides compound resin；It is chained with branch
Structure not only increases molecule interchain voids, further decreases dielectric constant, can also improve the mechanicalness of the poly methylene imine resin of introducing
Can, guarantee that the mechanical performance of polyimides compound resin in all directions reaches the requirement of industrialization product.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to a kind of compound tree of the polyimides for providing low-k
Rouge and preparation method and application.By introducing poly methylene imine unit in polyimide resin, reduce the average dipole of strand
Square reduces the dielectric constant of resin；By introducing branched structure, not only increases strand gap, further decreases dielectric constant,
Also it can improve strand arranging situation of the poly methylene imine unit on laterally and longitudinally two different directions, guarantee all directions all
With certain mechanical performance.The introducing of fluoro-containing group not only brings the effect for reducing dielectric constant, but also makes polyimides point
Sub- chain flexibility increases；Polyimide flex molecule chain element interlinks with poly methylene imine high rigidity molecule chain element, makes point
The flexibility/stiffness of subchain has taken into account processing performance and mechanical performance, thermal linear expansion coefficient in a suitable range
Energy.Such polyimides compound resin with low-k property, will be widely used in electronic information field.
The purpose of the present invention is achieved through the following technical solutions: a kind of compound tree of the polyimides of low-k
Rouge, which is characterized in that the shape that the compound resin passes through copolymerization link by polyimide resin unit and poly methylene imine resin unit
Formula composition；Copolymer forms reticular structure, the general formula that the compound resin has the following structure, and each unit is uniformly mixed copolymerization:
Wherein, Ar1 is by the residue of pyromellitic acid anhydride, the residue of 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides, 4,4'-
The residue of (hexafluoro isopropyl) double O-phthalic acid dianhydrides, 1,4- difluoro pyromellitic acid anhydride residue, 2,2- it is bis- [4- (3,
4- di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride residue, 2,3,3', residue, the 3,3' of 4'- bibenzene tetracarboxylic dianhydride, 4,
The residue of residue, the 3,3' of 4'- diphenyl ether tetraformic dianhydride, 4,4'- benzophenone tetracarboxylic dianhydride, 4,4 '-are to benzene dioxy pair
The residue of phthalic anhydride, the residue of Bisphenol A Type Diether Dianhydride, the residue of 1,2,3,4- cyclobutane tetracarboxylic dianhydride, 2,3,
Bis- (the trifluoromethyl) -2,3,5,6- benzene tertacarbonic acids of residue, 1,4- of bis- (trifluoromethyl) the xanthene dianhydrides of 6,7- tetracarboxylic -9,9-
One or more of residue of bis- (3,4- dicarboxyl trifluoro-benzene oxygroup) the tetrafluoro benzene dianhydrides of residue, the 1,4- of dianhydride is by arbitrarily matching
It is formed than mixing；
Ar2 is by the residue of terephthalaldehyde, the residue of o-phthalaldehyde, the residue of m-terephthal aldehyde, 4,4- biphenyl diformazan
One or more of the residue of aldehyde, the residue of 2,3- naphthalene dicarbaldehyde, residue of 2,3,5,6- tetrafluorobenzene are pressed any
Proportion mixing composition；
B1 is by the residue of p-phenylenediamine, the residue of m-phenylene diamine (MPD), the residue of benzidine, 4,4'- diamino -2,2'- two
The residue of methyl biphenyl, the residue of 4,4'- diamino -3,3'- dimethyl diphenyl, 2,2'- bis- (trifluoromethyl) benzidine
Residue, bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 2,2- the bis- [4- (2- trifluoromethyl -4- aminobenzenes of residue, 2,2-
Oxygroup) phenyl] propane bis- (4- aminophenyl) hexafluoropropane of residue, 2,2- the bis- [4- (4- amino-benzene oxygen) of residue, 2,2-
Phenyl] hexafluoropropane bis- [4- (3- amino-benzene oxygen) phenyl] hexafluoropropane of residue, 2,2- residue, 4,4'- diamino two
The residue of phenylate, the residue of 3,4'- diaminodiphenyl ether, the residue of 4,4'- diaminobenzophenone, 4,4'- diamino hexichol
The residue of methylmethane, the residue of 4,4'- diaminobenzene sulfone, bis- (3- amino-4-hydroxylphenyl) sulfones bis- (the 3- ammonia of residue, 1,3-
Phenoxyl) benzene bis- (4- amino-benzene oxygen) benzene of residue, 1,3- bis- (4- amino-benzene oxygen) biphenyl of residue, 4,4'- it is residual
It is the residue of bis- [4- (4- amino-benzene oxygen) phenyl] propane of residue, the 2,2- of bis- (3- amino-benzene oxygen) biphenyl of base, 4,4'-, double
One or more of residue of [4- (3- amino-benzene oxygen) phenyl] sulfone is by any proportion mixing composition；
B2 by the residue of 1,3,5- triaminobenzene, the residue of three (2- amino-ethyl) amine, three (4- aminophenyl) amine it is residual
One or more of base, residue of 1,3,5- tri- (4- aminophenyl) benzene are formed by the mixing of any proportion；
M1, m2, n1 are natural number, and n2 is even number, 0.5≤m1/ (m1+m2) < 1,0.8≤n1/ (n1+n2) < 1,20≤(m1
+ m2+n1+n2)≤400, (n1+1.5*n2)=(m1+m2).
Further, the Ar1 in the general formula includes the residue of pyromellitic acid anhydride, 3,3', 4,4'- bibenzene tetracarboxylics
The residue of dianhydride, the residue of the double O-phthalic acid dianhydrides of 4,4'- (hexafluoro isopropyl), 1,4- difluoro pyromellitic acid anhydride it is residual
One or both of the residue of bis- [4- (3, the 4- di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydrides of base, 2,2-, and they
Total amount accounts for the 50-100% of the moles total number of Ar1；
Ar2 in the general formula includes the residue of the residue of 4,4- diphenyl-dimethanal, 2,3,5,6- tetrafluorobenzene,
And their total amount accounts for the 50-100% of the moles total number of Ar2；
B1 in the general formula includes the residue of p-phenylenediamine, the residue of 4,4'- diamino -2,2'- dimethyl diphenyl, 2,
Residue, the 2,2- of bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of the residue, 2,2'- of 2'- bis- (trifluoromethyl) benzidine
Appointing in the residue of bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of residue, the 2,2- of bis- (4- aminophenyl) hexafluoropropane
Meaning is one or two kinds of, and their total amount accounts for the 50-100% of the moles total number of B1；
B2 in the general formula includes the residue of 1,3,5- tri- (4- aminophenyl) benzene, and its total amount accounts for the moles total number of B2
50-100%.
Further, the Ar1 in the general formula include Isosorbide-5-Nitrae-difluoro pyromellitic acid anhydride residue, 2,2- it is bis- [4- (3,
4- di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride one or both of residue, and their total amount accounts for mole of Ar1
The 80-100% of total amount；
B1 in the general formula includes the residue of 4,4'- diamino -2,2'- dimethyl diphenyl, 2,2'- bis- (trifluoromethyl)
Any one in the residue of bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of residue, the 2,2- of benzidine or two
Kind, and their total amount accounts for the 80-100% of the moles total number of B1；
A kind of preparation method of the polyimides compound resin of low-k, comprising the following steps:
(1) it prepares the precursor solution of polyimides compound resin: in a nitrogen atmosphere, a rubbing while stirring in a reservoir
That diamine compounds and b moles of three aminated compounds are dissolved in intensive polar solvent, obtain solution, diamine compounds and triamine
The mass percent summation of class compound in the solution is 5%-13%；Then d moles of diformazan aldehyde compound is added, in nitrogen
The temperature that solution is controlled under atmosphere is 0-50 DEG C, reacts 4-24h；C moles of tetracarboxylic acid dianhydride is added in three times into solution later
Class compound, each additional amount account for 60%, 30%, the 10% of tetracarboxylic acid dianhydride class compound total weight respectively；Continue in nitrogen
4-48h is reacted under atmosphere, solution temperature controls the precursor solution that polyimides compound resin is obtained after 0-50 DEG C, reaction；Its
In, 0.5≤c/ (c+d) < 1,0.8≤a/ (a+b) < 1,20≤(a+b+c+d)≤400, (c+d): (a+1.5*b)=(0.95
~1.05): 1；
Wherein, tetracarboxylic acid dianhydride class compound is by pyromellitic acid anhydride, 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides, 4,
Bis- [4- (the 3,4- dicarboxyl benzene of the double O-phthalic acid dianhydrides of 4'- (hexafluoro isopropyl), 1,4- difluoro pyromellitic acid anhydride, 2,2-
Oxygroup) phenyl] hexafluoropropane dianhydride, 2,3,3', 4'- bibenzene tetracarboxylic dianhydride, 3,3', 4,4'- diphenyl ether tetraformic dianhydride, 3,
3', 4,4'- benzophenone tetracarboxylic dianhydride, 4,4 '-to benzene dioxy double phthalic anhydride, Bisphenol A Type Diether Dianhydride, 1,2,3,
4- cyclobutane tetracarboxylic dianhydride, bis- (trifluoromethyl) the xanthene dianhydrides of 2,3,6,7- tetracarboxylic -9,9-, the bis- (fluoroforms of 1,4-
Base) -2,3,5,6- benzene tertacarbonic acid dianhydride, one or more of bis- (3,4- dicarboxyl trifluoro-benzene oxygroup) tetrafluoro benzene dianhydrides of 1,4-
It mixes and forms by any proportion；
Diformazan aldehyde compound is by terephthalaldehyde, o-phthalaldehyde, m-terephthal aldehyde, 4,4- diphenyl-dimethanal, 2,3-
One or more of naphthalene dicarbaldehyde, 2,3,5,6- tetrafluorobenzene are by any proportion mixing composition；
Diamine compounds by p-phenylenediamine, m-phenylene diamine (MPD), benzidine, 4,4'- diamino -2,2'- dimethyl diphenyl,
4,4'- diamino -3,3'- dimethyl diphenyl, 2,2'- bis- (trifluoromethyl) benzidine, bis- (the 3- amino-4-hydroxies of 2,2-
Phenyl) hexafluoropropane, bis- [4- (2- trifluoromethyl-4-aminophenoxyl) phenyl] propane of 2,2-, 2,2- bis- (4- aminophenyls)
Bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of hexafluoropropane, 2,2-, bis- [4- (3- amino-benzene oxygen) phenyl] six of 2,2-
Fluoro-propane, 4,4'- diaminodiphenyl ether, 3,4'- diaminodiphenyl ether, 4,4'- diaminobenzophenone, 4,4'- diamino two
Phenylmethane, 4,4'- diaminobenzene sulfone, bis- (3- amino-4-hydroxylphenyl) sulfones, 1,3- bis- (3- amino-benzene oxygen) benzene, 1,3-
Bis- (4- amino-benzene oxygen) biphenyl of bis- (4- amino-benzene oxygen) benzene, 4,4'-, bis- (3- amino-benzene oxygen) biphenyl of 4,4'-, 2,2- are bis-
One or more of [4- (4- amino-benzene oxygen) phenyl] propane, bis- [4- (3- amino-benzene oxygen) phenyl] sulfones press any proportion
Mixing composition；
Three aminated compounds are by 1,3,5- triaminobenzene, three (2- amino-ethyl) amine, three (4- aminophenyl) amine, 1,3,5-
One or more of three (4- aminophenyl) benzene are by any proportion mixing composition；
The intensive polar solvent is by DMAC N,N' dimethyl acetamide (DMAc), N,N-dimethylformamide (DMF), N- methyl pyrrole
One of pyrrolidone (NMP), metacresol are a variety of according to any proportion mixing composition；
(2) precursor solution of the polyimides compound resin of step (1) preparation is coated on carrier, makes polyamides after drying
The film thickness of imines compound resin is 10-30 μm；Then it volatilizees at 80-150 DEG C, so that intensive polar solvent content is in 15-
Between 25wt%, the precursor photopolymer layer of polyimides compound resin is obtained；
(3) it is coated with the carrier of the precursor photopolymer layer of polyimides compound resin, in nitrogen atmosphere, in 280-350
Heat cure is carried out at a temperature of DEG C；The precursor photopolymer layer of polyimides compound resin is cured to form insulation film base；
(4) it by the insulation film base in step (3), is taken off from carrier surface by water-boiling method, obtains low-k
Polyimides compound resin.
Further, the tetracarboxylic acid dianhydride class compound includes pyromellitic acid anhydride, 3,3', 4,4'- biphenyl tetracarboxylics
Acid dianhydride, the double O-phthalic acid dianhydrides of 4,4'- (hexafluoro isopropyl), 1,4- difluoro pyromellitic acid anhydride, 2,2- it is bis- [4- (3,
4- di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride one or two, and their total amount accounts for tetracarboxylic acid dianhydride class compound
Moles total number 50-100%；The diformazan aldehyde compound includes 4,4- diphenyl-dimethanal, 2,3,5,6- tetrafluoro to benzene
The one or two of dicarbaldehyde, and their total amount accounts for the 50-100% of the moles total number of diformazan aldehyde compound；Described two
Aminated compounds includes p-phenylenediamine, 4,4'- diamino -2,2'- dimethyl diphenyl, (trifluoromethyl) diamino of 2,2'- bis- connection
Bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of benzene, 2,2'-, bis- (4- aminophenyl) hexafluoropropane of 2,2-, the bis- [4- (4- of 2,2-
Amino-benzene oxygen) phenyl] any one or two kinds in hexafluoropropane, and their total amount accounts for the mole total of diamine compounds
The 50-100% of amount；Three aminated compounds include 1,3,5- tri- (4- aminophenyl) benzene, and its total amount accounts for three amines
Close the 50-100% of the moles total number of object.
Further, the tetracarboxylic acid dianhydride class compound includes Isosorbide-5-Nitrae-difluoro pyromellitic acid anhydride, the bis- [4- of 2,2-
One or both of (3,4- di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride, and their total amount accounts for tetracarboxylic acid dianhydride class
The 80-100% of the moles total number of compound；The diamine compounds include 4,4'- diamino -2,2'- dimethyl diphenyl,
Bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of 2,2'- bis- (trifluoromethyl) benzidines, 2,2-, and their total amount
Account for the 80-100% of the moles total number of tetracarboxylic acid dianhydride class compound.
A kind of application of the polyimides compound resin of above-mentioned low-k, using the polyimides of the low-k
Compound resin prepares single-face flexibility copper-clad board, and the single-face flexibility copper-clad board includes one layer of copper foil layer and on copper foil layer
Polyimide layer, the polyimide layer can be made of the polyimides compound resin of one layer of low-k, can also be by a variety of low
The multilayered structure that the polyimides compound resin of dielectric constant is formed is formed；The thickness of the copper foil layer is no more than 105 μm, institute
Polyimides compound resin layer is stated with a thickness of 5-35 μm.
A kind of application of the polyimides compound resin of above-mentioned low-k, using the polyimides of the low-k
Compound resin prepares double side flexible copper coated board, the double side flexible copper coated board include two layers of copper foil layer and be located at two layers of copper foil layer it
Between polyimide layer, which can be made of the polyimides compound resin of one layer of low-k, can also be by more
The multilayered structure that the polyimides compound resin of kind low-k is formed is formed；The thickness of the copper foil layer is no more than 105 μ
M, the polyimides compound resin layer is with a thickness of 10-70 μm.
A kind of positive light sensitivity cover film, it by polyimides compound resin precursor solution and diazo naphthoquinone class emulsion
It is mixed to get；Weight percent of the diazo naphthoquinone class emulsion in positive light sensitivity cover film is 10-40%；Positive light sensitivity
The thicknesses of layers of cover film is 5-50um；The front body structure formula of polyimides compound resin is as shown in the following general formula:
Wherein, Ar1 is by the residue of pyromellitic acid anhydride, the residue of 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides, 4,4'-
The residue of (hexafluoro isopropyl) double O-phthalic acid dianhydrides, 1,4- difluoro pyromellitic acid anhydride residue, 2,2- it is bis- [4- (3,
4- di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride residue, 2,3,3', residue, the 3,3' of 4'- bibenzene tetracarboxylic dianhydride, 4,
The residue of residue, the 3,3' of 4'- diphenyl ether tetraformic dianhydride, 4,4'- benzophenone tetracarboxylic dianhydride, 4,4 '-are to benzene dioxy pair
The residue of phthalic anhydride, the residue of Bisphenol A Type Diether Dianhydride, the residue of 1,2,3,4- cyclobutane tetracarboxylic dianhydride, 2,3,
Bis- (the trifluoromethyl) -2,3,5,6- benzene tertacarbonic acids of residue, 1,4- of bis- (trifluoromethyl) the xanthene dianhydrides of 6,7- tetracarboxylic -9,9-
One or more of residue of bis- (3,4- dicarboxyl trifluoro-benzene oxygroup) the tetrafluoro benzene dianhydrides of residue, the 1,4- of dianhydride is by arbitrarily matching
It is formed than mixing；
Ar2 is by the residue of terephthalaldehyde, the residue of o-phthalaldehyde, the residue of m-terephthal aldehyde, 4,4- biphenyl diformazan
One or more of the residue of aldehyde, the residue of 2,3- naphthalene dicarbaldehyde, residue of 2,3,5,6- tetrafluorobenzene are pressed any
Proportion mixing composition；
B1 is by the residue of p-phenylenediamine, the residue of m-phenylene diamine (MPD), the residue of benzidine, 4,4'- diamino -2,2'- two
The residue of methyl biphenyl, the residue of 4,4'- diamino -3,3'- dimethyl diphenyl, 2,2'- bis- (trifluoromethyl) benzidine
Residue, bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 2,2- the bis- [4- (2- trifluoromethyl -4- aminobenzenes of residue, 2,2-
Oxygroup) phenyl] propane bis- (4- aminophenyl) hexafluoropropane of residue, 2,2- the bis- [4- (4- amino-benzene oxygen) of residue, 2,2-
Phenyl] hexafluoropropane bis- [4- (3- amino-benzene oxygen) phenyl] hexafluoropropane of residue, 2,2- residue, 4,4'- diamino two
The residue of phenylate, the residue of 3,4'- diaminodiphenyl ether, the residue of 4,4'- diaminobenzophenone, 4,4'- diamino hexichol
The residue of methylmethane, the residue of 4,4'- diaminobenzene sulfone, bis- (3- amino-4-hydroxylphenyl) sulfones bis- (the 3- ammonia of residue, 1,3-
Phenoxyl) benzene bis- (4- amino-benzene oxygen) benzene of residue, 1,3- bis- (4- amino-benzene oxygen) biphenyl of residue, 4,4'- it is residual
It is the residue of bis- [4- (4- amino-benzene oxygen) phenyl] propane of residue, the 2,2- of bis- (3- amino-benzene oxygen) biphenyl of base, 4,4'-, double
One or more of residue of [4- (3- amino-benzene oxygen) phenyl] sulfone is by any proportion mixing composition；
B2 by the residue of 1,3,5- triaminobenzene, the residue of three (2- amino-ethyl) amine, three (4- aminophenyl) amine it is residual
One or more of base, residue of 1,3,5- tri- (4- aminophenyl) benzene are formed by the mixing of any proportion；
M1, m2, n1 are natural number, and n2 is even number, 0.5≤m1/ (m1+m2) < 1,0.8≤n1/ (n1+n2) < 1,20≤(m1
+ m2+n1+n2)≤400, (n1+1.5*n2)=(m1+m2).
A kind of preparation method of above-mentioned positive light sensitivity cover film, comprising the following steps:
(1) it prepares the precursor solution of polyimides compound resin: in a nitrogen atmosphere, a rubbing while stirring in a reservoir
That diamine compounds and b moles of three aminated compounds are dissolved in intensive polar solvent, obtain solution, diamine compounds and triamine
The mass percent summation of class compound in the solution is 5%-13%；Then d moles of diformazan aldehyde compound is added, in nitrogen
The temperature that solution is controlled under atmosphere is 0-50 DEG C, reacts 4-24h；C moles of tetracarboxylic acid dianhydride is added in three times into solution later
Class compound, each additional amount account for 60%, 30%, the 10% of tetracarboxylic acid dianhydride class compound total weight respectively；Continue in nitrogen
4-48h is reacted under atmosphere, solution temperature controls the precursor solution that polyimides compound resin is obtained after 0-50 DEG C, reaction；Its
In, 0.5≤c/ (c+d) < 1,0.8≤a/ (a+b) < 1,20≤(a+b+c+d)≤400, (c+d): (a+1.5*b)=(0.95
~1.05): 1；
Wherein, tetracarboxylic acid dianhydride class compound is by pyromellitic acid anhydride, 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides, 4,
Bis- [4- (the 3,4- dicarboxyl benzene of the double O-phthalic acid dianhydrides of 4'- (hexafluoro isopropyl), 1,4- difluoro pyromellitic acid anhydride, 2,2-
Oxygroup) phenyl] hexafluoropropane dianhydride, 2,3,3', 4'- bibenzene tetracarboxylic dianhydride, 3,3', 4,4'- diphenyl ether tetraformic dianhydride, 3,
3', 4,4'- benzophenone tetracarboxylic dianhydride, 4,4 '-to benzene dioxy double phthalic anhydride, Bisphenol A Type Diether Dianhydride, 1,2,3,
4- cyclobutane tetracarboxylic dianhydride, bis- (trifluoromethyl) the xanthene dianhydrides of 2,3,6,7- tetracarboxylic -9,9-, the bis- (fluoroforms of 1,4-
Base) -2,3,5,6- benzene tertacarbonic acid dianhydride, one or more of bis- (3,4- dicarboxyl trifluoro-benzene oxygroup) tetrafluoro benzene dianhydrides of 1,4-
It mixes and forms by any proportion；
Diformazan aldehyde compound is by terephthalaldehyde, o-phthalaldehyde, m-terephthal aldehyde, 4,4- diphenyl-dimethanal, 2,3-
One or more of naphthalene dicarbaldehyde, 2,3,5,6- tetrafluorobenzene are by any proportion mixing composition；
Diamine compounds by p-phenylenediamine, m-phenylene diamine (MPD), benzidine, 4,4'- diamino -2,2'- dimethyl diphenyl,
4,4'- diamino -3,3'- dimethyl diphenyl, 2,2'- bis- (trifluoromethyl) benzidine, bis- (the 3- amino-4-hydroxies of 2,2-
Phenyl) hexafluoropropane, bis- [4- (2- trifluoromethyl-4-aminophenoxyl) phenyl] propane of 2,2-, 2,2- bis- (4- aminophenyls)
Bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of hexafluoropropane, 2,2-, bis- [4- (3- amino-benzene oxygen) phenyl] six of 2,2-
Fluoro-propane, 4,4'- diaminodiphenyl ether, 3,4'- diaminodiphenyl ether, 4,4'- diaminobenzophenone, 4,4'- diamino two
Phenylmethane, 4,4'- diaminobenzene sulfone, bis- (3- amino-4-hydroxylphenyl) sulfones, 1,3- bis- (3- amino-benzene oxygen) benzene, 1,3-
Bis- (4- amino-benzene oxygen) biphenyl of bis- (4- amino-benzene oxygen) benzene, 4,4'-, bis- (3- amino-benzene oxygen) biphenyl of 4,4'-, 2,2- are bis-
One or more of [4- (4- amino-benzene oxygen) phenyl] propane, bis- [4- (3- amino-benzene oxygen) phenyl] sulfones press any proportion
Mixing composition；
Three aminated compounds are by 1,3,5- triaminobenzene, three (2- amino-ethyl) amine, three (4- aminophenyl) amine, 1,3,5-
One or more of three (4- aminophenyl) benzene are by any proportion mixing composition；
The intensive polar solvent is by DMAC N,N' dimethyl acetamide (DMAc), N,N-dimethylformamide (DMF), N- methyl pyrrole
One of pyrrolidone (NMP), metacresol are a variety of according to any proportion mixing composition；
(2) in the precursor solution of the polyimides compound resin of step (1) preparation, diazo naphthoquinone class emulsion is added,
Make weight percent 10-40% of the diazo naphthoquinone class emulsion in final positive light sensitivity cover film；After addition, in nitrogen
The temperature that solution is controlled under atmosphere is 0-50 DEG C, continues to stir 4-24h, obtains photosensitive mixture solution；
(3) be film-made: the photosensitive mixture solution that step (2) is obtained is coated on carrier, makes photosensitive mixture after drying
Film thickness be 5-50 μm；Then it volatilizees at 60-90 DEG C, so that intensive polar solvent content between 2~15wt%, obtains photosensitive
Mixture film, as positive light sensitivity cover film.
Beneficial effects of the present invention are as follows:
1. polyimide resin unit of the invention, using fluorochemical monomer, the dielectric for not only reducing polyimide resin is normal
Number, also improves polyimide molecule chain flexibility.
2. poly methylene imine resin unit and polyimide resin unit are copolymerized, the flexible molecule chain of polyimides can change
The high rigidity of kind poly methylene imine molecular chain, makes the rigidity of polymer molecular chain in the reasonable scope.On the one hand guarantee strand
Ability is aligned, the thermal linear expansion coefficient of polyimide resin is reduced；On the other hand adjustment poly methylene imine molecular chain is rigid
Flexibility improves mechanical performance and processing performance.
3. poly methylene imine resin unit is made of imine group, compared to five yuan imide rings, there is lower dipole moment.
The introducing of poly methylene imine unit reduces the dipole moment of polyimide molecule chain, reduces the dielectric constant of polyimide resin.
4. the strand of pair polyimides compound resin optimizes, Triamine monomer, the strand being branched are introduced；
The mechanical performance that all directions are equalized after collateralization, avoids transverse fiberization caused by the high rigidity of poly methylene imine unit point
It splits；Collateralization also increases molecule interchain voids, further decreases dielectric constant to a certain extent.
5. being copolymerized by poly methylene imine unit and polyimides unit, while reducing dielectric constant, ensure that preferable
Mechanical performance can regulate and control thermal linear expansion coefficient.In flexible copper-clad plate material, have more preferably in 5G wiring board art
Application.
Specific embodiment
Representative embodiment specifically describes the contents of the present invention below, but these embodiments are not used in limitation this paper institute
Belong to the range of invention.
Dummy suffix notation used in embodiment is expressed as follows:
PMDA: pyromellitic acid anhydride；
BPDA:3,3', 4,4'- biphenyltetracarboxylic dianhydride；
The double O-phthalic acid dianhydrides of 6FDA:4,4'- (hexafluoro isopropyl)；
PF2DA:1,4- difluoro pyromellitic acid anhydride；
Bis- [4- (3,4- di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydrides of BFDA:2,2-；
TPAL: terephthalaldehyde；
BDAL:4,4- diphenyl-dimethanal；
NDAL:2,3- naphthalene dicarbaldehyde；
TF-TPAL:2,3,5,6- tetrafluorobenzene；
P-PDA: p-phenylenediamine；
M-TB:4,4'- diamino -2,2'- dimethyl diphenyl, tolidine；
TFMB:2,2'- bis- (trifluoromethyl) benzidine；
Bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 6FAP:2,2-；
Bis- (4- aminophenyl) hexafluoropropane of 6FDAM:2,2-；
Bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of 4-BDAF:2,2-；
TAB:1,3,5- triaminobenzene；
TAPA: three (4- aminophenyl) amine；
TAPB:1,3,5- tri- (4- aminophenyl) benzene；
NMP:N- methyl pyrrolidone；
DNQ: diazo naphthoquinone.
[embodiment 1-20]
[polyimides compound resin A-T] according in table 1 raw material input amount and following experimental procedures be prepared:
In a nitrogen atmosphere, in the three-necked flask of 100mL, while stirring by quantitative diamine compounds shown in table 1
It is dissolved in 40g NMP with three aminated compounds, makes the mass percent summation 5%-13% of aminated compounds.It is added later
Quantitative diformazan aldehyde compound shown in table 1, the temperature for controlling solution in a nitrogen atmosphere is 0-50 DEG C, reacts 4-24h.Later
Quantitative tetracarboxylic acid dianhydride class compound, each additional amount shown in table 1 is added in three times into solution and accounts for total weight respectively
60%, 30%, 10%；4-48h is reacted in continuation in a nitrogen atmosphere, and solution temperature is controlled at 0-50 DEG C.Finally obtain polyamides Asia
The precursor solution of amine compound resin.
Using coating machine, on a glass by the precursor solution coating of polyimides compound resin, and make polyamides after drying
The film thickness of imines compound resin is about 10-30um.Volatilize certain time at 80-150 DEG C, so that solvent content is in 15%-
Between 25%, the precursor photopolymer layer of polyimides compound resin is obtained.
It is coated with the glass plate of polyimides compound resin precursor photopolymer layer, in nitrogen atmosphere, at 280-350 DEG C
At a temperature of carry out heat cure；The precursor photopolymer layer of polyimides compound resin is cured to form polyimides compound resin layer, shape
At insulation film base.
Insulation film base is taken off from glass plate by water-boiling method, so that the polyimides for obtaining low-k is multiple
Resin film A-T.
[comparative example 21-22]
[polyimide resin U-V] as a comparison is according to the raw material input amount and the preparation of following experimental procedures in table 1
It obtains:
In a nitrogen atmosphere, in the three-necked flask of 100mL, while stirring by quantitative diamine compounds shown in table 1
It is dissolved in 40g NMP, makes the mass percent 5%-8% of aminated compounds.1 institute of table is added in three times into solution later
The quantitative tetracarboxylic acid dianhydride class compound shown, each additional amount account for 60%, 30%, the 10% of total weight respectively；In nitrogen atmosphere
Lower reaction 48h, solution temperature are controlled at 25 DEG C.Finally obtain the precursor solution of polyimide resin.
Using coating machine, on a glass by the precursor solution coating of polyimide resin, and make polyimides after drying
The film thickness of resin is about 10-30um.Volatilize 10min at 150 DEG C, so that solvent content between 15%-25%, obtains polyamides
The precursor photopolymer layer of imide resin.
Be coated with the glass plate of polyimide resin precursor photopolymer layer, in nitrogen atmosphere, 280 DEG C at a temperature of into
Row heat cure；The precursor photopolymer layer of polyimide resin is cured to form polyimide resin layer, forms insulation film base.
Insulation film base is taken off from glass plate by water-boiling method, to obtain Kapton U-V.
[comparative example 23]
[polyimides compound resin W] as a comparison is according to the raw material input amount and following experimental procedure systems in table 1
It is standby to obtain:
In a nitrogen atmosphere, in the three-necked flask of 100mL, while stirring by 0.74g p-PDA shown in table 1 and
3.28g TFMB is dissolved in 40g NMP, makes the mass percent summation 8% of diamine compounds.It is added shown in table 1 later
1.43g BDAL, in a nitrogen atmosphere control solution temperature be 0 DEG C, react 4h.Table 1 is added in three times into solution later
Shown in 4.55g 6FDA, each additional amount accounts for 60%, 30%, the 10% of total weight respectively；Continuation is reacted in a nitrogen atmosphere
36h, solution temperature are controlled at 0 DEG C.Finally obtain the precursor solution of polyimides compound resin.
Using coating machine, on a glass by the precursor solution coating of polyimides compound resin, and make polyamides after drying
The film thickness of imines compound resin is about 10-30um.Volatilize 15min at 120 DEG C, so that solvent content obtains polyamides 20%
The precursor photopolymer layer of imines compound resin.
It is coated with the glass plate of polyimides compound resin precursor photopolymer layer, in nitrogen atmosphere, in 350 DEG C of temperature
Lower carry out heat cure；The precursor photopolymer layer of polyimides compound resin is cured to form polyimides compound resin layer, is formed exhausted
Edge film ground layer.
Insulation film base is taken off from glass plate by water-boiling method, to obtain polyimides compound resin film W.
[comparative example 24]
[poly methylene imine resin X] according in table 1 raw material input amount and following experimental procedures be prepared:
In a nitrogen atmosphere, in the three-necked flask of 100mL, while stirring by 1.14g p-PDA shown in table 1 and
3.34g m-TB is dissolved in 40g NMP, makes the mass percent summation 9% of aminated compounds.It is added shown in table 1 later
5.52g BDAL, the temperature for controlling solution in a nitrogen atmosphere is 20 DEG C, reacts 20h.Before finally obtaining poly methylene imine resin
Liquid solution.
Using coating machine, on a glass by the precursor solution coating of poly methylene imine resin, and make poly methylene imine after drying
The film thickness of resin is about 10-30um.Volatilize 30min at 80 DEG C, so that solvent content obtains poly methylene imine resin 25%
Precursor photopolymer layer.
Be coated with the glass plate of poly methylene imine resin precursor photopolymer layer, in nitrogen atmosphere, 280 DEG C at a temperature of into
Row heat cure；The precursor photopolymer layer of poly methylene imine resin is cured to form poly methylene imine resin layer, forms insulation film base.
Insulation film base is taken off from glass plate by water-boiling method, to obtain poly methylene imine resin film X.
[comparative example 25]
[poly methylene imine resin Y] according in table 1 raw material input amount and following experimental procedures be prepared:
In a nitrogen atmosphere, in the three-necked flask of 100mL, while stirring by 3.99g m-TB and 1.07g shown in table 1
TAPB is dissolved in 40g NMP, makes the mass percent summation 10% of aminated compounds.4.94g shown in table 1 is added later
BDAL, the temperature for controlling solution in a nitrogen atmosphere is 45 DEG C, and reaction is for 24 hours.Finally obtain the precursor solution of poly methylene imine resin.
Using coating machine, on a glass by the precursor solution coating of poly methylene imine resin, and make poly methylene imine after drying
The film thickness of resin is about 10-30um.Volatilize 15min at 100 DEG C, so that solvent content obtains poly methylene imine resin 22%
Precursor photopolymer layer.
Be coated with the glass plate of poly methylene imine resin precursor photopolymer layer, in nitrogen atmosphere, 320 DEG C at a temperature of into
Row heat cure；The precursor photopolymer layer of poly methylene imine resin is cured to form poly methylene imine resin layer, forms insulation film base.
Insulation film base is taken off from glass plate by water-boiling method, to obtain final poly methylene imine resin film
Y。
Table 1: the raw material additional amount in embodiment and comparative example
By the performance comparison of embodiment and comparative example, the polyimides to illustrate low-k of the present invention is compound
Resin dielectric constant, mechanical performance, in terms of advantage.
To polyimide resin U-V, the polyamides of the polyimides compound resin A-T and comparative example 21-25 of embodiment 1-20
Imines compound resin W, poly methylene imine resin X-Y, are tested for the property, specific test condition and method are as follows:
Dielectric constant and dielectric loss are tested on the broad temperature, broadband impedance analyzer of German NOV DEG C of ONTROL, are surveyed
Frequency is tried from 100Hz to 1GHz.
Tensile strength and elongation at break, referring to IPC-TM-650 2.4.18B method, are surveyed on universal testing machine
Examination.
Thermal expansion coefficient is tested on the Q400TMA test equipment in TA company, the U.S..
It is as shown in table 2 below to test obtained film performance.
The performance comparison for the resin film that table 2 embodiment 1-20 and comparative example 21-25 is obtained
As can be known from Table 2, after poly methylene imine resin to be blended to copolymerization with polyimide resin, dielectric constant has the present invention
Apparent reduction: the dielectric constant of conventional polyimide resin (U-V sample) is 3.3-3.4；After copolymerization is blended in poly methylene imine,
The dielectric constant of polyimides compound resin be reduced to 3 hereinafter, some even to 2.5.It is total that this has benefited from poly methylene imine resin
After poly-, the dipole moment of strand is reduced；Also have benefited from the use of fluorochemical monomer.
In addition, poly methylene imine molecular chain rigidity is too strong, poly methylene imine resin W-X as a comparison case, although available
Part film, but film is very easy to cracking, and the case where will appear directive fibrosis；Three amines are added in formula
After compound, the mechanical performance after film forming makes moderate progress, the poly methylene imine modified resin Y of available tensile strength 110MPa.
Moreover, result it also seen that, the CTE of poly methylene imine modified resin Y also very little, this also has benefited from the high rigidity of its strand.Poly-
Three amine compound monomers are added in acid imide compound resin, also play the effect for improving molecule chain rigidity, avoid polyamides sub-
Products application requirement is not achieved in the mechanical performance of polyimide resin.
The addition of three aminated compounds can also reduce the dielectric constant of polyimides compound resin to a certain extent.Such as
Three amine compound monomer additive amount higher polyimides compound resin H, P, Q, S, dielectric constant substantially 2.5 or
2.5 following.Although also there is the collective effect of fluorochemical monomer Yu poly methylene imine resin, these compound resin dielectric constants are all
Significantly lower than other samples, it may be said that bright three aminated compounds, which still has a reduction of dielectric constant, obviously to be contributed.
The specific embodiment for preparing single-face flexibility copper-clad board is as follows:
(1) precursor solution is prepared.The precursor solution of polyimides compound resin is prepared according to embodiment 1-20；
(2) precursor solution for the polyimides compound resin for obtaining step (1), is coated uniformly on the copper of 12-105um thickness
Above foil, and the film thickness of polyimides compound resin after drying is made to be about 5-35um.It is put into 80-150 DEG C of baking oven, keeps certain
Time, volatilization removes solvent, so that solvent content between 15%-25%, obtains the precursor dry film of polyimides compound resin
Layer.By above-mentioned copper foil sample, it is put into 280-350 DEG C of high temperature nitrogen baking oven, heat cure is carried out with certain temperature program, is prepared into
The flexibility coat copper plate substrate of polyimides compound resin layer is coated on to copper foil.
It can be coated with a kind of polyimides compound resin in step (2), on copper foil, it is sub- that a variety of polyamides can also be coated with
Polyimide resin is to improve other performances of flexibility coat copper plate.It is compound in the first polyimides when being coated with a variety of polyimide resins
After the completion of the precursor solution coating and solvent volatilization of resin, that is, it is coated with the precursor solution of upper second of polyimides compound resin,
Carry out solvent volatilization.Listed condition optimizes in solvent volatilization condition optional step (2).After the completion of solvent volatilization, by sample
Product are put into 280-350 DEG C of high temperature nitrogen baking oven, carry out heat cure with certain temperature program, by the first with second or its
The precursor dry film of his more kinds of polyimides compound resins, while heat cure is carried out, it obtains being coated with a variety of polyimides on copper foil
The flexibility coat copper plate substrate of compound resin layer.
The specific embodiment for preparing double side flexible copper coated board is as follows:
(1) precursor solution is prepared, which includes following sub-step；
(1.1) precursor solution of polyimides compound resin is prepared according to embodiment 1-20；
(1.2) precursor solution of thermoplastic polyimide resin is prepared: in a nitrogen atmosphere, by the bis- (3- of 1, the 3- of 1.00g
Amino-benzene oxygen) bis- (4- amino-benzene oxygen) benzene of 1,3- of benzene and 3.99g are added in the nmp solvent of 40g, and stirring is to completely molten
Solution；The BPDA of 5.02g is added in three batches later, is subsequently agitated for about for 24 hours；The precursor that thermoplastic polyimide resin is prepared is molten
Liquid；
(2) can solderless substrate preparation.The precursor solution for the polyimides compound resin that step (1.1) is obtained, uniformly
Above copper foil coated in 12-105um thickness, and the film thickness of polyimides compound resin after drying is made to be about 5-35um.It is put into 80-
150 DEG C of baking oven keeps certain time, and volatilization removes solvent, so that solvent content between 15%-25%, obtains polyamides Asia
The precursor photopolymer layer of amine compound resin.Then, on the precursor dry film of polyimides compound resin, continue application step (1.2)
The precursor solution of obtained thermoplastic polyimide resin, and the film thickness of thermoplastic polyimide resin after drying is made to be about 0.5-
3um.It being put into 80-150 DEG C of baking oven, keeps certain time, volatilization removes solvent, so that solvent content is between 15%-25%,
Form the precursor photopolymer layer of thermoplastic polyimide resin.By above-mentioned copper foil sample, it is put into 280-350 DEG C of high temperature nitrogen baking oven,
Heat cure is carried out with certain temperature program, is prepared on copper foil and is coated with polyimides compound resin layer and thermoplasticity polyamides Asia
Amine resin layer can solderless substrate.
(3) the pressing preparation of double side flexible copper coated board.Solderless substrate obtained in 2 pieces of steps (2) is taken, symmetrical to be bonded, heat
Plastic polyimide resin layer contacts with each other；350 DEG C at a temperature of, under the pressure condition of 20Mpa, be laminated 10min, obtain double
Face flexibility coat copper plate.
In step (3), other than being symmetrically bonded 2 pieces of identical solderless substrates, it can also take in 1 piece of step (2)
Obtained solderless substrate and copper foil is carried out to patch, and thermoplastic polyimide resin layer contacts with each other with another 1 block of copper foil and is bonded；?
At a temperature of 350 DEG C, under the pressure condition of 20Mpa, it is laminated 10min, obtains double side flexible copper coated board.
The specific embodiment for preparing positive light sensitivity cover film is as follows:
(1) precursor solution for preparing polyimides compound resin prepares polyimides compound resin according to embodiment 1-20
Precursor solution；
(2) in the precursor solution of the polyimides compound resin of step (1) preparation, diazo naphthoquinone DNQ is added, makes DNQ
Weight percent in final positive light sensitivity cover film is 10-40%；After addition, the temperature of solution is controlled in a nitrogen atmosphere
Degree is 0-50 DEG C, continues to stir 4-24h；
(3) the photosensitive mixture solution that step (2) obtains is filmed: solution is coated in glass plate or other loads
On body, making the film thickness of photosensitive mixture after drying is about 5-50um；Then volatilize certain time at 60-90 DEG C, so that solvent
Content obtains photosensitive mixture film, as positive light sensitivity cover film between 2%-15%.
The positive light sensitivity cover film that step (3) is obtained carries out figure under the light irradiation of certain wavelength by film
Case exposure.Later, develop 2-20min in the tetramethylammonium hydroxide aqueous solution that weight percent is 0.1%.It is preferred that suitable expose
Light energy, time for exposure and developing time so that not removed thoroughly by the area development that film is covered, but are covered by film
The region of lid protection is completely retained, the pattern envisioned.Later, by above-mentioned covering membrane sample, it is put into 280-350 DEG C of height
Warm nitrogen oven carries out heat cure with certain temperature program, obtains the patterning cover film product of the field PCB/FPC needs.
Above embodiments, there is no the contents to polyimides compound resin of the invention to do any limitation with formula,
The ginseng used when there is no to the preparation for carrying out single-face flexibility copper-clad board and double side flexible copper coated board with polyimides compound resin
Said conditions do any limitation, according to the technical essence of the invention trickle amendment made to the above embodiment, equivalent change
Change and modify, all of which are still within the scope of the technical scheme of the invention.
Above-described embodiment is merely a preferred embodiment of the present invention, and cannot be limited the scope of protection of the present invention with this.Ability
The variation and replacement for any unsubstantiality that the technical staff in domain is done on the basis of the present invention belong to required by the present invention
Protection range.
Claims (10)
1. a kind of polyimides compound resin of low-k, which is characterized in that the compound resin is by polyimide resin list
Member and poly methylene imine resin unit are formed by way of copolymerization link；Copolymer forms reticular structure, the compound resin tool
Just like the general formula of flowering structure, each unit is uniformly mixed copolymerization:
Wherein, Ar1 is by the residue of pyromellitic acid anhydride, the residue of 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides, 4,4'- (hexafluoro
Isopropyl) residues of double O-phthalic acid dianhydrides, 1,4- difluoro pyromellitic acid anhydride bis- [4- (the 3,4- dicarboxyls of residue, 2,2-
Phenoxyl) phenyl] hexafluoropropane dianhydride residue, 2,3,3', residue, the 3,3' of 4'- bibenzene tetracarboxylic dianhydride, 4,4'- bis-
The residue of residue, the 3,3' of phenylate tetracarboxylic acid dianhydride, 4,4'- benzophenone tetracarboxylic dianhydride, 4,4 '-adjacent benzene two double to benzene dioxy
The residue of formic anhydride, the residue of Bisphenol A Type Diether Dianhydride, 1,2,3,4- cyclobutane tetracarboxylic dianhydride residue, 2,3,6,7- tetra-
Bis- (the trifluoromethyl) -2,3,5,6- benzene tertacarbonic acid's dianhydrides of residue, 1,4- of bis- (trifluoromethyl) the xanthene dianhydrides of carboxyl -9,9-
One or more of residue of bis- (3,4- dicarboxyl trifluoro-benzene oxygroup) the tetrafluoro benzene dianhydrides of residue, 1,4- is mixed by any proportion
Composition；
Ar2 is by the residue of terephthalaldehyde, the residue of o-phthalaldehyde, the residue of m-terephthal aldehyde, 4,4- diphenyl-dimethanal
One or more of residue, the residue of 2,3- naphthalene dicarbaldehyde, residue of 2,3,5,6- tetrafluorobenzene press any proportion
Mixing composition；
B1 is by the residue of p-phenylenediamine, the residue of m-phenylene diamine (MPD), the residue of benzidine, 4,4'- diamino -2,2'- dimethyl
The residue of biphenyl, the residue of 4,4'- diamino -3,3'- dimethyl diphenyl, 2,2'- bis- (trifluoromethyl) benzidine it is residual
Bis- [the 4- (2- trifluoromethyl-4-aminophenoxyl) of residue, 2,2- of bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of base, 2,2-
Phenyl] propane bis- (4- aminophenyl) hexafluoropropane of residue, 2,2- residue, 2,2- bis- [4- (4- amino-benzene oxygen) phenyl]
The residues of bis- [4- (3- amino-benzene oxygen) phenyl] hexafluoropropane of residue, the 2,2- of hexafluoropropane, 4,4'- diaminodiphenyl ether
Residue, the residue of 3,4'- diaminodiphenyl ether, the residue of 4,4'- diaminobenzophenone, 4,4'- diaminodiphenyl-methane
Residue, the residue of 4,4'- diaminobenzene sulfone, bis- (3- amino-4-hydroxylphenyl) sulfones bis- (the 3- aminobenzene oxygen of residue, 1,3-
Base) benzene bis- (4- amino-benzene oxygen) benzene of residue, 1,3- bis- (4- amino-benzene oxygen) biphenyl of residue, 4,4'- residue, 4,
Residue, the bis- [4- (3- of bis- [4- (4- amino-benzene oxygen) phenyl] propane of residue, the 2,2- of bis- (3- amino-benzene oxygen) biphenyl of 4'-
Amino-benzene oxygen) phenyl] one or more of the residue of sulfone forms by the mixing of any proportion；
B2 by the residue of 1,3,5- triaminobenzene, the residue of three (2- amino-ethyl) amine, the residue of three (4- aminophenyl) amine, 1,
One or more of residue of 3,5- tri- (4- aminophenyl) benzene is by any proportion mixing composition；
M1, m2, n1 are natural number, and n2 is even number, 0.5≤m1/ (m1+m2) < 1,0.8≤n1/ (n1+n2) < 1,20≤(m1+m2+
N1+n2)≤400, (n1+1.5*n2)=(m1+m2).
2. the polyimides compound resin of low-k as described in claim 1, which is characterized in that in the general formula
Ar1 includes the residue of pyromellitic acid anhydride, 3,3', residue, the 4,4'- (hexafluoro isopropyl) of 4,4'- bibenzene tetracarboxylic dianhydride
Bis- [4- (the 3,4- dicarboxyl benzene oxygen of residue, 2,2- of the residues of double O-phthalic acid dianhydrides, 1,4- difluoro pyromellitic acid anhydride
Base) phenyl] hexafluoropropane dianhydride one or both of residue, and their total amount accounts for the 50- of the moles total number of Ar1
100%；
Ar2 in the general formula includes the residue of the residue of 4,4- diphenyl-dimethanal, 2,3,5,6- tetrafluorobenzene, and it
Total amount account for Ar2 moles total number 50-100%；
B1 in the general formula includes residue, the 2,2'- of the residue of p-phenylenediamine, 4,4'- diamino -2,2'- dimethyl diphenyl
Residue, the 2,2- of bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of the residue, 2,2'- of two (trifluoromethyl) benzidines are bis-
It is any in the residue of bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of the residue, 2,2- of (4- aminophenyl) hexafluoropropane
One or two, and their total amount accounts for the 50-100% of the moles total number of B1；
B2 in the general formula includes the residue of 1,3,5- tri- (4- aminophenyl) benzene, and its total amount accounts for the moles total number of B2
50-100%.
3. the polyimides compound resin of low-k as claimed in claim 2, which is characterized in that in the general formula
Ar1 includes the residue of 1,4- difluoro pyromellitic acid anhydride, bis- [4- (3,4- di carboxyl phenyloxy) phenyl] hexafluoropropane of 2,2-
One or both of residue of dianhydride, and their total amount accounts for the 80-100% of the moles total number of Ar1；
B1 in the general formula includes the residue of 4,4'- diamino -2,2'- dimethyl diphenyl, 2,2'- bis- (trifluoromethyl) diamino
Any one in the residue of bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of residue, 2, the 2- of base biphenyl or two kinds, and
Their total amount accounts for the 80-100% of the moles total number of B1.
4. a kind of preparation method of the polyimides compound resin of low-k described in claim 1, which is characterized in that packet
Include following steps:
(1) precursor solution of polyimides compound resin is prepared: in a nitrogen atmosphere, in a reservoir while stirring by a moles two
Aminated compounds and b moles of three aminated compounds are dissolved in intensive polar solvent, obtain solution, diamine compounds and three amines
Closing the mass percent summation of object in the solution is 5%-13%；Then d moles of diformazan aldehyde compound is added, in nitrogen atmosphere
The temperature of lower control solution is 0-50 DEG C, reacts 4-24h；C moles of tetracarboxylic acid dianhydride class is added in three times into solution later
Object is closed, each additional amount accounts for 60%, 30%, the 10% of tetracarboxylic acid dianhydride class compound total weight respectively；Continue in nitrogen atmosphere
Lower reaction 4-48h, solution temperature control the precursor solution that polyimides compound resin is obtained after 0-50 DEG C, reaction；Wherein,
0.5≤c/ (c+d) < 1,0.8≤a/ (a+b) < 1,20≤(a+b+c+d)≤400, (c+d): (a+1.5*b)=(0.95~
1.05):1；
Wherein, tetracarboxylic acid dianhydride class compound is by pyromellitic acid anhydride, 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides, 4,4'- (six
Fluorine isopropyl) double O-phthalic acid dianhydrides, 1,4- difluoro pyromellitic acid anhydride, the bis- [4- (3,4- di carboxyl phenyloxy) of 2,2-
Phenyl] hexafluoropropane dianhydride, 2,3,3', 4'- bibenzene tetracarboxylic dianhydride, 3,3', 4,4'- diphenyl ether tetraformic dianhydride, 3,3', 4,
4'- benzophenone tetracarboxylic dianhydride, 4,4 '-are to benzene dioxy double phthalic anhydride, Bisphenol A Type Diether Dianhydride, 1,2,3,4- rings
Bis- (trifluoromethyl) the xanthene dianhydrides of butane tetracarboxylic acid dianhydride, 2,3,6,7- tetracarboxylic -9,9-, bis- (trifluoromethyl) -2 1,4-,
One or more of bis- (3,4- dicarboxyl trifluoro-benzene oxygroup) tetrafluoro benzene dianhydrides of 3,5,6- benzene tertacarbonic acid dianhydride, 1,4- are by any
Proportion mixing composition；
Diformazan aldehyde compound is by terephthalaldehyde, o-phthalaldehyde, m-terephthal aldehyde, 4,4- diphenyl-dimethanal, 2,3- naphthalene two
One or more of formaldehyde, 2,3,5,6- tetrafluorobenzene are by any proportion mixing composition；
Diamine compounds by p-phenylenediamine, m-phenylene diamine (MPD), benzidine, 4,4'- diamino -2,2'- dimethyl diphenyl, 4,
4'- diamino -3,3'- dimethyl diphenyl, 2,2'- bis- (trifluoromethyl) benzidine, bis- (the 3- amino-4-hydroxy benzene of 2,2-
Base) hexafluoropropane, bis- [4- (2- trifluoromethyl-4-aminophenoxyl) phenyl] propane of 2,2-, bis- (the 4- aminophenyls) six of 2,2-
Bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of fluoro-propane, 2,2-, bis- [4- (3- amino-benzene oxygen) phenyl] hexafluoros of 2,2-
Propane, 4,4'- diaminodiphenyl ether, 3,4'- diaminodiphenyl ether, 4,4'- diaminobenzophenone, 4,4'- diamino hexichol
Methylmethane, 4,4'- diaminobenzene sulfone, bis- (3- amino-4-hydroxylphenyl) sulfones, bis- (3- amino-benzene oxygen) benzene of 1,3-, 1,3- are bis-
Bis- (4- amino-benzene oxygen) biphenyl of (4- amino-benzene oxygen) benzene, 4,4'-, bis- (3- amino-benzene oxygen) biphenyl of 4,4'-, 2,2- are bis-
One or more of [4- (4- amino-benzene oxygen) phenyl] propane, bis- [4- (3- amino-benzene oxygen) phenyl] sulfones press any proportion
Mixing composition；
Three aminated compounds are by 1,3,5- triaminobenzene, three (2- amino-ethyl) amine, three (4- aminophenyl) amine, 1,3,5- tri-
One or more of (4- aminophenyl) benzene is by any proportion mixing composition；
The intensive polar solvent is by DMAC N,N' dimethyl acetamide (DMAc), N,N-dimethylformamide (DMF), N- crassitude
One of ketone (NMP), metacresol are a variety of according to any proportion mixing composition；
(2) precursor solution of the polyimides compound resin of step (1) preparation is coated on carrier, makes polyimides after drying
The film thickness of compound resin is 10-30 μm；Then volatilize at 80-150 DEG C so that intensive polar solvent content 15-25wt% it
Between, obtain the precursor photopolymer layer of polyimides compound resin；
(3) it is coated with the carrier of the precursor photopolymer layer of polyimides compound resin, in nitrogen atmosphere, at 280-350 DEG C
At a temperature of carry out heat cure；The precursor photopolymer layer of polyimides compound resin is cured to form insulation film base；
(4) it by the insulation film base in step (3), is taken off from carrier surface by water-boiling method, obtains the poly- of low-k
Acid imide compound resin.
5. the preparation method of the polyimides compound resin of low-k as claimed in claim 4, which is characterized in that described
Tetracarboxylic acid dianhydride class compound includes pyromellitic acid anhydride, 3,3', 4,4'- bibenzene tetracarboxylic dianhydride, 4,4'- (hexafluoro isopropyl
Base) double O-phthalic acid dianhydrides, 1,4- difluoro pyromellitic acid anhydride, 2,2- bis- [4- (3,4- di carboxyl phenyloxy) phenyl]
The one or two of hexafluoropropane dianhydride, and their total amount accounts for the 50- of the moles total number of tetracarboxylic acid dianhydride class compound
100%；The diformazan aldehyde compound includes 4,4- diphenyl-dimethanal, one kind of 2,3,5,6- tetrafluorobenzene or two
Kind, and their total amount accounts for the 50-100% of the moles total number of diformazan aldehyde compound；The diamine compounds include pair
Phenylenediamine, 4,4'- diamino -2,2'- dimethyl diphenyl, 2,2'- bis- (trifluoromethyl) benzidine, bis- (the 3- ammonia of 2,2'-
Base -4- hydroxy phenyl) hexafluoropropane, bis- (4- aminophenyl) hexafluoropropane of 2,2-, bis- [4- (4- amino-benzene oxygen) benzene of 2,2-
Base] any one or two kinds in hexafluoropropane, and their total amount accounts for the 50-100% of the moles total number of diamine compounds；
Three aminated compounds include 1,3,5- tri- (4- aminophenyl) benzene, and its total amount accounts for the moles total number of three aminated compounds
50-100%.
6. the preparation method of the polyimides compound resin of low-k as claimed in claim 4, which is characterized in that described
Tetracarboxylic acid dianhydride class compound include 1,4- difluoro pyromellitic acid anhydride, bis- [4- (3,4- di carboxyl phenyloxy) benzene of 2,2-
One or both of base] hexafluoropropane dianhydride, and their total amount accounts for the 80- of the moles total number of tetracarboxylic acid dianhydride class compound
100%；The diamine compounds include 4,4'- diamino -2,2'- dimethyl diphenyl, 2,2'- bis- (trifluoromethyl) diamino
Bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of base biphenyl, 2,2-, and their total amount accounts for tetracarboxylic acid dianhydride class compound
Moles total number 80-100%.
7. a kind of application of the polyimides compound resin of low-k described in claim 1, which is characterized in that application should
The polyimides compound resin of low-k prepares single-face flexibility copper-clad board, and the single-face flexibility copper-clad board includes one layer of copper foil
Layer and the polyimide layer on copper foil layer, the polyimide layer can be by the compound trees of polyimides of one layer of low-k
Rouge composition, can also be made of the multilayered structure that the polyimides compound resin of a variety of low-ks is formed；The copper foil layer
Thickness be no more than 105 μm, the polyimides compound resin layer is with a thickness of 5-35 μm.
8. a kind of application of the polyimides compound resin of low-k described in claim 1, which is characterized in that application should
The polyimides compound resin of low-k prepares double side flexible copper coated board, and the double side flexible copper coated board includes two layers of copper foil
Layer and the polyimide layer between two layers of copper foil layer, the polyimide layer can be answered by the polyimides of one layer of low-k
Resin composition, can also be made of the multilayered structure that the polyimides compound resin of a variety of low-ks is formed；The copper
The thickness of layers of foil is no more than 105 μm, and the polyimides compound resin layer is with a thickness of 10-70 μm.
9. a kind of positive light sensitivity cover film, which is characterized in that it by polyimides compound resin precursor solution and diazonium naphthalene
Quinones emulsion is mixed to get；Weight percent of the diazo naphthoquinone class emulsion in positive light sensitivity cover film is 10-40%；
The thicknesses of layers of positive light sensitivity cover film is 5-50um；The front body structure formula of polyimides compound resin such as the following general formula institute
Show:
Wherein, Ar1 is by the residue of pyromellitic acid anhydride, the residue of 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides, 4,4'- (hexafluoro
Isopropyl) residues of double O-phthalic acid dianhydrides, 1,4- difluoro pyromellitic acid anhydride bis- [4- (the 3,4- dicarboxyls of residue, 2,2-
Phenoxyl) phenyl] hexafluoropropane dianhydride residue, 2,3,3', residue, the 3,3' of 4'- bibenzene tetracarboxylic dianhydride, 4,4'- bis-
The residue of residue, the 3,3' of phenylate tetracarboxylic acid dianhydride, 4,4'- benzophenone tetracarboxylic dianhydride, 4,4 '-adjacent benzene two double to benzene dioxy
The residue of formic anhydride, the residue of Bisphenol A Type Diether Dianhydride, 1,2,3,4- cyclobutane tetracarboxylic dianhydride residue, 2,3,6,7- tetra-
Bis- (the trifluoromethyl) -2,3,5,6- benzene tertacarbonic acid's dianhydrides of residue, 1,4- of bis- (trifluoromethyl) the xanthene dianhydrides of carboxyl -9,9-
One or more of residue of bis- (3,4- dicarboxyl trifluoro-benzene oxygroup) the tetrafluoro benzene dianhydrides of residue, 1,4- is mixed by any proportion
Composition；
Ar2 is by the residue of terephthalaldehyde, the residue of o-phthalaldehyde, the residue of m-terephthal aldehyde, 4,4- diphenyl-dimethanal
One or more of residue, the residue of 2,3- naphthalene dicarbaldehyde, residue of 2,3,5,6- tetrafluorobenzene press any proportion
Mixing composition；
B1 is by the residue of p-phenylenediamine, the residue of m-phenylene diamine (MPD), the residue of benzidine, 4,4'- diamino -2,2'- dimethyl
The residue of biphenyl, the residue of 4,4'- diamino -3,3'- dimethyl diphenyl, 2,2'- bis- (trifluoromethyl) benzidine it is residual
Bis- [the 4- (2- trifluoromethyl-4-aminophenoxyl) of residue, 2,2- of bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of base, 2,2-
Phenyl] propane bis- (4- aminophenyl) hexafluoropropane of residue, 2,2- residue, 2,2- bis- [4- (4- amino-benzene oxygen) phenyl]
The residues of bis- [4- (3- amino-benzene oxygen) phenyl] hexafluoropropane of residue, the 2,2- of hexafluoropropane, 4,4'- diaminodiphenyl ether
Residue, the residue of 3,4'- diaminodiphenyl ether, the residue of 4,4'- diaminobenzophenone, 4,4'- diaminodiphenyl-methane
Residue, the residue of 4,4'- diaminobenzene sulfone, bis- (3- amino-4-hydroxylphenyl) sulfones bis- (the 3- aminobenzene oxygen of residue, 1,3-
Base) benzene bis- (4- amino-benzene oxygen) benzene of residue, 1,3- bis- (4- amino-benzene oxygen) biphenyl of residue, 4,4'- residue, 4,
Residue, the bis- [4- (3- of bis- [4- (4- amino-benzene oxygen) phenyl] propane of residue, the 2,2- of bis- (3- amino-benzene oxygen) biphenyl of 4'-
Amino-benzene oxygen) phenyl] one or more of the residue of sulfone forms by the mixing of any proportion；
B2 by the residue of 1,3,5- triaminobenzene, the residue of three (2- amino-ethyl) amine, the residue of three (4- aminophenyl) amine, 1,
One or more of residue of 3,5- tri- (4- aminophenyl) benzene is by any proportion mixing composition；
M1, m2, n1 are natural number, and n2 is even number, 0.5≤m1/ (m1+m2) < 1,0.8≤n1/ (n1+n2) < 1,20≤(m1+m2+
N1+n2)≤400, (n1+1.5*n2)=(m1+m2).
10. the preparation method of positive light sensitivity cover film described in a kind of claim 9, which comprises the following steps:
(1) precursor solution of polyimides compound resin is prepared: in a nitrogen atmosphere, in a reservoir while stirring by a moles two
Aminated compounds and b moles of three aminated compounds are dissolved in intensive polar solvent, obtain solution, diamine compounds and three amines
Closing the mass percent summation of object in the solution is 5%-13%；Then d moles of diformazan aldehyde compound is added, in nitrogen atmosphere
The temperature of lower control solution is 0-50 DEG C, reacts 4-24h；C moles of tetracarboxylic acid dianhydride class is added in three times into solution later
Object is closed, each additional amount accounts for 60%, 30%, the 10% of tetracarboxylic acid dianhydride class compound total weight respectively；Continue in nitrogen atmosphere
Lower reaction 4-48h, solution temperature control the precursor solution that polyimides compound resin is obtained after 0-50 DEG C, reaction；Wherein,
0.5≤c/ (c+d) < 1,0.8≤a/ (a+b) < 1,20≤(a+b+c+d)≤400, (c+d): (a+1.5*b)=(0.95~
1.05):1；
Wherein, tetracarboxylic acid dianhydride class compound is by pyromellitic acid anhydride, 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides, 4,4'- (six
Fluorine isopropyl) double O-phthalic acid dianhydrides, 1,4- difluoro pyromellitic acid anhydride, the bis- [4- (3,4- di carboxyl phenyloxy) of 2,2-
Phenyl] hexafluoropropane dianhydride, 2,3,3', 4'- bibenzene tetracarboxylic dianhydride, 3,3', 4,4'- diphenyl ether tetraformic dianhydride, 3,3', 4,
4'- benzophenone tetracarboxylic dianhydride, 4,4 '-are to benzene dioxy double phthalic anhydride, Bisphenol A Type Diether Dianhydride, 1,2,3,4- rings
Bis- (trifluoromethyl) the xanthene dianhydrides of butane tetracarboxylic acid dianhydride, 2,3,6,7- tetracarboxylic -9,9-, bis- (trifluoromethyl) -2 1,4-,
One or more of bis- (3,4- dicarboxyl trifluoro-benzene oxygroup) tetrafluoro benzene dianhydrides of 3,5,6- benzene tertacarbonic acid dianhydride, 1,4- are by any
Proportion mixing composition；
Diformazan aldehyde compound is by terephthalaldehyde, o-phthalaldehyde, m-terephthal aldehyde, 4,4- diphenyl-dimethanal, 2,3- naphthalene two
One or more of formaldehyde, 2,3,5,6- tetrafluorobenzene are by any proportion mixing composition；
Diamine compounds by p-phenylenediamine, m-phenylene diamine (MPD), benzidine, 4,4'- diamino -2,2'- dimethyl diphenyl, 4,
4'- diamino -3,3'- dimethyl diphenyl, 2,2'- bis- (trifluoromethyl) benzidine, bis- (the 3- amino-4-hydroxy benzene of 2,2-
Base) hexafluoropropane, bis- [4- (2- trifluoromethyl-4-aminophenoxyl) phenyl] propane of 2,2-, bis- (the 4- aminophenyls) six of 2,2-
Bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of fluoro-propane, 2,2-, bis- [4- (3- amino-benzene oxygen) phenyl] hexafluoros of 2,2-
Propane, 4,4'- diaminodiphenyl ether, 3,4'- diaminodiphenyl ether, 4,4'- diaminobenzophenone, 4,4'- diamino hexichol
Methylmethane, 4,4'- diaminobenzene sulfone, bis- (3- amino-4-hydroxylphenyl) sulfones, bis- (3- amino-benzene oxygen) benzene of 1,3-, 1,3- are bis-
Bis- (4- amino-benzene oxygen) biphenyl of (4- amino-benzene oxygen) benzene, 4,4'-, bis- (3- amino-benzene oxygen) biphenyl of 4,4'-, 2,2- are bis-
One or more of [4- (4- amino-benzene oxygen) phenyl] propane, bis- [4- (3- amino-benzene oxygen) phenyl] sulfones press any proportion
Mixing composition；
Three aminated compounds are by 1,3,5- triaminobenzene, three (2- amino-ethyl) amine, three (4- aminophenyl) amine, 1,3,5- tri-
One or more of (4- aminophenyl) benzene is by any proportion mixing composition；
The intensive polar solvent is by DMAC N,N' dimethyl acetamide (DMAc), N,N-dimethylformamide (DMF), N- crassitude
One of ketone (NMP), metacresol are a variety of according to any proportion mixing composition；
(2) in the precursor solution of the polyimides compound resin of step (1) preparation, diazo naphthoquinone class emulsion is added, makes weight
Weight percent of the quinoline quinones emulsion in final positive light sensitivity cover film is 10-40%；After addition, in nitrogen atmosphere
The temperature of lower control solution is 0-50 DEG C, continues to stir 4-24h, obtains photosensitive mixture solution；
(3) be film-made: the photosensitive mixture solution that step (2) is obtained is coated on carrier, makes the film of photosensitive mixture after drying
Thickness is 5-50 μm；Then it volatilizees at 60-90 DEG C, so that intensive polar solvent content between 2~15wt%, obtains photosensitive mixing
Object film, as positive light sensitivity cover film.
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| WO2021056790A1 (en) * | 2019-09-24 | 2021-04-01 | 武汉华星光电半导体显示技术有限公司 | Polyimide material, preparation method and application thereof |
| CN111138695A (en) * | 2019-12-24 | 2020-05-12 | 深圳先进电子材料国际创新研究院 | Polyimide film and preparation method thereof |
| CN113347783A (en) * | 2020-03-02 | 2021-09-03 | 广东生益科技股份有限公司 | Adhesive-free single-sided board, preparation method thereof and adhesive-free double-sided board comprising same |
| CN111876085A (en) * | 2020-07-10 | 2020-11-03 | 东莞东阳光科研发有限公司 | Composite bonding sheet, flexible metal laminated board and preparation method thereof |
| CN111876085B (en) * | 2020-07-10 | 2022-09-27 | 东莞东阳光科研发有限公司 | Composite bonding sheet, flexible metal laminated board and preparation method thereof |
| WO2022033364A1 (en) * | 2020-08-13 | 2022-02-17 | 无锡华睿芯材科技有限公司 | Photoresist and method for patterning imine material |
| CN111880371B (en) * | 2020-08-13 | 2022-05-03 | 常州华睿芯材科技有限公司 | Photoresist and method for patterning imine material |
| CN111880371A (en) * | 2020-08-13 | 2020-11-03 | 清华大学 | Photoresist and method for patterning imine material |
| CN113563585A (en) * | 2021-07-29 | 2021-10-29 | 上海八亿时空先进材料有限公司 | Polyimide and application thereof in metal laminated plate |
| CN113563585B (en) * | 2021-07-29 | 2022-06-17 | 上海八亿时空先进材料有限公司 | Polyimide and application thereof in metal laminated plate |
| CN114230791A (en) * | 2021-12-29 | 2022-03-25 | 山东华夏神舟新材料有限公司 | Intrinsic low-dielectric fluorine-containing polyimide film and preparation method thereof |
| CN114230791B (en) * | 2021-12-29 | 2023-10-24 | 山东华夏神舟新材料有限公司 | Intrinsic low-dielectric fluorine-containing polyimide film and preparation method thereof |
| CN114854012A (en) * | 2022-06-20 | 2022-08-05 | 杭州福斯特电子材料有限公司 | Polyimide resin, polyimide film, preparation method of polyimide film and copper clad plate |
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