CN116693911A - Composite film and method for producing same - Google Patents
Composite film and method for producing same Download PDFInfo
- Publication number
- CN116693911A CN116693911A CN202310298001.8A CN202310298001A CN116693911A CN 116693911 A CN116693911 A CN 116693911A CN 202310298001 A CN202310298001 A CN 202310298001A CN 116693911 A CN116693911 A CN 116693911A
- Authority
- CN
- China
- Prior art keywords
- polyimide varnish
- layer
- varnish layer
- composite membrane
- polyimide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title description 2
- 229920001721 polyimide Polymers 0.000 claims abstract description 224
- 239000004642 Polyimide Substances 0.000 claims abstract description 205
- 239000002966 varnish Substances 0.000 claims abstract description 181
- 239000012528 membrane Substances 0.000 claims abstract description 30
- 230000003746 surface roughness Effects 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000010410 layer Substances 0.000 claims description 278
- -1 styrene-ethylene-butylene-styrene Chemical class 0.000 claims description 43
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- 150000004985 diamines Chemical class 0.000 claims description 35
- 239000000178 monomer Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 27
- 239000012790 adhesive layer Substances 0.000 claims description 26
- 239000011256 inorganic filler Substances 0.000 claims description 23
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 21
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 239000004962 Polyamide-imide Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229920002312 polyamide-imide Polymers 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 11
- 239000000049 pigment Substances 0.000 claims description 11
- 150000008064 anhydrides Chemical class 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
- 239000012948 isocyanate Substances 0.000 claims description 9
- 150000002513 isocyanates Chemical class 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000003063 flame retardant Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 8
- 239000001023 inorganic pigment Substances 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- 229910052582 BN Inorganic materials 0.000 claims description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 6
- 239000005083 Zinc sulfide Substances 0.000 claims description 6
- 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 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 6
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 6
- OAXARSVKYJPDPA-UHFFFAOYSA-N tert-butyl 4-prop-2-ynylpiperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(CC#C)CC1 OAXARSVKYJPDPA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 6
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000012860 organic pigment Substances 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 4
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 229920006378 biaxially oriented polypropylene Polymers 0.000 claims description 4
- 239000011127 biaxially oriented polypropylene Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 4
- 229920000052 poly(p-xylylene) Polymers 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 229920002379 silicone rubber Polymers 0.000 claims description 4
- 239000004945 silicone rubber Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 4
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 claims description 3
- FMJUDUJLTNVWCH-UHFFFAOYSA-N 2-ethoxy-3-(4-hydroxyphenyl)propanoic acid Chemical compound CCOC(C(O)=O)CC1=CC=C(O)C=C1 FMJUDUJLTNVWCH-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 3
- ZWQOXRDNGHWDBS-UHFFFAOYSA-N 4-(2-phenylphenoxy)aniline Chemical group C1=CC(N)=CC=C1OC1=CC=CC=C1C1=CC=CC=C1 ZWQOXRDNGHWDBS-UHFFFAOYSA-N 0.000 claims description 3
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 claims description 3
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 claims description 3
- SSDBTLHMCVFQMS-UHFFFAOYSA-N 4-[4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 SSDBTLHMCVFQMS-UHFFFAOYSA-N 0.000 claims description 3
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 claims description 3
- PJCCVNKHRXIAHZ-UHFFFAOYSA-N 4-[4-[[4-(4-aminophenoxy)phenyl]methyl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1CC(C=C1)=CC=C1OC1=CC=C(N)C=C1 PJCCVNKHRXIAHZ-UHFFFAOYSA-N 0.000 claims description 3
- UNAJNYASXFIDJJ-UHFFFAOYSA-N C1=CC(=C(C2=C1C(=O)OC2=O)CCC3=C(C=CC4=C3C(=O)OC4=O)C(=O)O)C(=O)O Chemical compound C1=CC(=C(C2=C1C(=O)OC2=O)CCC3=C(C=CC4=C3C(=O)OC4=O)C(=O)O)C(=O)O UNAJNYASXFIDJJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 3
- 239000004809 Teflon Substances 0.000 claims description 3
- 229920006362 Teflon® Polymers 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004056 anthraquinones Chemical class 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- LSDYQEILXDCDTR-UHFFFAOYSA-N bis[4-(4-aminophenoxy)phenyl]methanone Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 LSDYQEILXDCDTR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 claims description 3
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 claims description 3
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 3
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920006132 styrene block copolymer Polymers 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 239000001052 yellow pigment Substances 0.000 claims description 3
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 claims description 3
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 1
- 150000001639 boron compounds Chemical class 0.000 claims 1
- 229910017464 nitrogen compound Inorganic materials 0.000 claims 1
- 150000002830 nitrogen compounds Chemical class 0.000 claims 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims 1
- 239000010408 film Substances 0.000 description 61
- 230000000052 comparative effect Effects 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000013039 cover film Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000012787 coverlay film Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011143 downstream manufacturing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920006332 epoxy adhesive Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- UCRIXEWTILHNCG-UHFFFAOYSA-N 1-ethyl-2h-pyridine Chemical compound CCN1CC=CC=C1 UCRIXEWTILHNCG-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- ZPSUIVIDQHHIFH-UHFFFAOYSA-N 3-(trifluoromethyl)-4-[2-(trifluoromethyl)phenyl]benzene-1,2-diamine Chemical group FC(F)(F)C1=C(N)C(N)=CC=C1C1=CC=CC=C1C(F)(F)F ZPSUIVIDQHHIFH-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000003351 stiffener Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/50—Adhesives in the form of films or foils characterised by a primer layer between the carrier and the adhesive
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
- C09J2479/083—Presence of polyamine or polyimide polyimide in the primer coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
- C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a composite membrane and a preparation method thereof. The composite film includes: a carrier layer; a first polyimide varnish layer formed on the carrier layer; and a second polyimide varnish layer formed on the first polyimide varnish layer; wherein the surface roughness of the carrier layer on the side contacting the first polyimide varnish layer is 0.001 to 10 μm, and the surface roughness of the first polyimide varnish layer on the side contacting the carrier layer is 0.001 to 10 μm.
Description
Technical Field
The invention belongs to the technical field of covering films, and particularly relates to a composite film comprising a carrier layer and a plurality of polyimide layers.
Background
Along with the development of miniaturization and high functionalization of electronic products, a polyimide film with high functionality plays an important role in electronic materials. Polyimide (PI) is a material with a wide application temperature range and excellent heat and chemical resistance, mechanical properties, electrical properties, and the like, so that Polyimide films can be used in the electronic fields such as LCD liquid crystal display industry, IC semiconductor industry, and flexible circuit board industry, for example, in cover films, PI reinforcing plates, inks, EMI (Electromagnetic Interference) shielding film products.
However, polyimide films have a bottleneck in thin design, and are difficult to conform to the trend of further thinning and thinning of electronic products. Specifically, when the thickness of polyimide film is reduced to 5-7.5 μm, the basic technical indexes such as mechanical strength, processing operability, bending property and the like start to fail to meet the requirements of industry specifications, and the process yield is low. In addition, in the trend of thinning, even with the modified biaxial stretching method, the polyimide film produced generally has an elongation of only 40 to 90%, whereas for colored polyimide films, the elongation is generally lower than 60% or even lower than 40%. In addition, the requirements of high-current scenes, high signal transmission quantity and other high-thickness step differences, and high-folding scenes such as folding screens, mechanical arms and the like which need a large number of bending parts also appear at present, so that the performance of the film material is required to be further improved.
In order to solve the bottleneck of the polyimide thin film and the colored film applied to high density assembly, high level difference and high bending, an improved technology is known in which a polyimide film obtained by a stretching method is replaced with a polyimide varnish type insulating layer matched with a carrier or a release film. Although the improved technology has the advantages of improving the performances of various insulating layers and processing operation, the insulating layers are colored by adding more powder when the polyimide varnish type insulating layers are used as the covering films, so that the mechanical performance is still insufficient, the polyimide varnish type insulating layers need to depend on release films used as carriers, and the release agents contain more organic silicon and deviate from the trend of undesirable organic silicon residues of downstream PCB factories, and the reliability of the electroplating process is easily reduced due to the organic silicon residues.
For these problems, there is a need for a polyimide composite film and a cover film that meet the demands of thin design, have dimensional stability, good bendability, high mechanical properties, and are easy to process.
Disclosure of Invention
The invention mainly solves the technical problem of providing a composite membrane and a preparation method thereof.
In order to solve the technical problems, the invention adopts a technical scheme that: providing a composite film comprising a support layer having a surface roughness of 0.001 to 10 μm;
at least one first polyimide varnish layer formed on the carrier layer, wherein the first polyimide varnish layer in contact with the carrier layer has a surface roughness matching the carrier layer of 0.001 to 10 μm;
and a second polyimide varnish layer formed on the first polyimide varnish layer, wherein the second polyimide varnish layer comprises a copolymer formed by polymerizing a plurality of monomers, and the monomers comprise diamine and anhydride.
Further, the thickness of the carrier layer is 12.5 to 250 μm, and the total thickness of the first polyimide varnish layer and the second polyimide varnish layer is 1 to 150 μm.
Further, the first polyimide varnish layer includes a resin including at least one selected from the group consisting of polyimide-based resins and polyamideimides, and the resin is 50 to 98wt% based on the total weight of the first polyimide varnish layer.
Further, the resin further includes at least one selected from the group consisting of epoxy resin, acrylic resin, urethane resin, silicone rubber resin, parylene resin, bismaleimide resin and styrene-ethylene-butylene-styrene block copolymer.
Further, the first polyimide varnish layer and/or the carrier layer further comprises an inorganic filler, the particle size of the inorganic filler is 10-20000 nm, and the inorganic filler is 0-50wt% based on the total weight of the first polyimide varnish layer or the carrier layer.
Further, the inorganic filler is at least one selected from the group consisting of calcium sulfate, carbon black, silica, titanium dioxide, zinc sulfide, zirconium oxide, calcium carbonate, silicon carbide, boron nitride, aluminum oxide, talc, aluminum nitride, glass powder, quartz powder, and clay.
Further, the first polyimide varnish layer further includes a pigment, and the pigment is 0 to 50wt% based on the total weight of the first polyimide varnish layer.
Further, the pigment is an inorganic pigment or an organic pigment, the inorganic pigment is at least one selected from the group consisting of cadmium red, cadmium lemon yellow, cadmium orange, titanium dioxide, carbon black, black iron oxide and black complex, and the organic pigment is at least one selected from the group consisting of aniline black, perylene black, anthraquinone black, benzidine yellow pigment, phthalocyanine blue and phthalocyanine green.
Further, the diamine comprises a silicon diamine and a second type of diamine different from the silicon diamine, and the silicon diamine is 20 to 85 mole percent based on the total moles of the diamine.
Further, the second diamine is at least one selected from the group consisting of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), 2' -bis (trifluoromethyl) diaminobiphenyl (TFMB), 2-bis (4-aminophenyl) hexafluoropropane, 4' -diaminodiphenyl ether, bis [4- (3-aminophenoxy) phenyl ] sulfonamide, bis [4- (4-aminophenoxy) phenyl ] sulfonamide, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl ] methane, 4' -bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] diethyl ether, bis [4- (4-aminophenoxy) phenyl ] ketone, 1, 3-bis (4-aminophenoxy) benzene, and 1, 4-bis (4-aminophenoxy) benzene.
Further, the silicon diamine is selected from at least one of the compounds represented by the following formulas 1 to 3:
wherein n is 1 to 150.
Further, the acid anhydride is at least one selected from the group consisting of hexafluorodianhydride (6 FDA), bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 1, 2-ethylenebis [1, 3-dihydro-1, 3-dioxoisobenzofuran-5-carboxylate ], 3', 4' -benzophenone tetracarboxylic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, benzene tetracarboxylic dianhydride, trimellitic anhydride (TMA) and cis-aconitic anhydride.
Further, the molar ratio of the diamine to the anhydride is from 1:0.9 to 1:1.1.
Further, the monomer further comprises isocyanate selected from at least one of 4,4' -diphenylmethane diisocyanate (MDI), 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, naphthalene-1, 5-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and lysine diisocyanate.
Still further, the molar ratio of the diamine to the isocyanate is from 1:1.0 to 1:1.5.
Further, the copolymer is formed by polymerizing a plurality of monomers in the presence of the tertiary amine catalyst, wherein the tertiary amine catalyst is at least one selected from the group consisting of triethylamine (Et 3N), isoquinoline, pyridine, N-ethylpiperidine and benzimidazole.
Further, the tertiary amine catalyst is 0 to 3wt% based on the total weight of the material from which the polymerization reaction is performed.
Further, the second polyimide varnish layer has an elongation of 30% or more.
Further, the first polyimide varnish layer further comprises an additive, wherein the additive is at least one selected from the group consisting of a curing agent, a catalyst, a surfactant and a flame retardant, wherein the additive is 0 to 20wt% based on the total weight of the first polyimide varnish layer, and the flame retardant is at least one selected from the group consisting of silicon dioxide, titanium dioxide, aluminum hydroxide, aluminum oxide, carbon black, calcium carbonate, teflon, zinc sulfide, zirconium oxide, silicon carbide, boron nitride, talcum powder, aluminum nitride, glass powder, quartz powder, clay, a halogen-containing compound, a phosphorus-based compound, a nitrogen-based compound and a boron-based compound.
Further, the carrier layer comprises at least one selected from the group consisting of polypropylene, biaxially oriented polypropylene, polyethylene terephthalate, polyimide, polyphenylene sulfide, polyethylene naphthalate, polyurethane and polyamide.
Further, the composite film further comprises: an adhesive layer formed on the polyimide varnish layer at the outermost side of the composite film;
and a release layer formed on the adhesive layer.
The invention also provides a method of preparing a composite membrane comprising: coating a first polyimide varnish layer on the carrier layer; curing the first polyimide varnish layer; coating a second polyimide varnish layer on the first polyimide varnish layer; and curing the second polyimide varnish layer.
In addition, the invention also provides a method for preparing the composite film, which comprises the following steps: coating a first polyimide varnish layer on the carrier layer; drying the first polyimide varnish layer; coating a second polyimide varnish layer on the first polyimide varnish layer; drying the second polyimide varnish layer; and curing the first polyimide varnish layer and the second polyimide varnish layer together.
Further, the curing is performed at a temperature of 50 to 180 ℃.
Further, the method further comprises the steps of: forming an adhesive layer on the cured outermost polyimide varnish layer by a coating method or a transfer method; and attaching a release layer on the adhesive layer.
The invention has the beneficial effects that:
1. the invention can easily separate the carrier layer from the first polyimide layer in application under the condition that the carrier layer does not use a release agent by matching the surface energy and the surface roughness of the carrier layer and the first polyimide layer; moreover, the high surface energy of the first polyimide layer makes the first polyimide layer easy to attach and adhere, and no additional surface treatment processes such as corona and the like are needed;
2. the invention reduces the powder addition amount in the composite polyimide film, so that the overall mechanical properties are improved;
3. compared with a tape casting method, the method has the advantages that the polyimide varnish is coated on the carrier layer, the cost is lower, films with wide range of thickness can be produced, and the prepared films have better dimensional stability without stress residues in stretching in the process; in addition, no additional film is needed in the downstream process to avoid tearing the film, so that the operation and the processing are easier;
4. The composite film forms a plurality of polyimide layers in a multi-layer coating mode, is easy to consider various characteristics and can be matched with the processing requirements of downstream processes;
5. the pigment proportion in the polyimide layer can be regulated and controlled, and polyimide films with various colors, such as Amber (Amber), matt black (matt black), white (white color) and the like, can be produced according to various requirements;
6. the composite film of the invention can further improve mechanical properties by adding other resins or additives, and particularly, the silicon diamine is used for partially replacing other diamines, so that the total elongation can be basically 40%, 60% can be broken through, and even the maximum elongation can be more than 260%.
Drawings
FIG. 1 is a schematic structural view of one embodiment of a composite membrane of the present invention;
FIG. 2 is a schematic view of another embodiment of the composite membrane of the present invention;
the drawings are as follows:
100 composite film
101 Carrier layer
1021 first polyimide varnish layer
1022 second polyimide varnish layer
1023 first polyimide varnish layer
200 composite film
201 Carrier layer
2021 first polyimide varnish layer
2022 second polyimide varnish layer
203 adhesive layer
204, releasing layer.
Detailed Description
The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings so that the advantages and features of the present invention can be more easily understood by those skilled in the art, thereby making clear and defining the scope of the present invention.
Examples: a composite membrane comprising: a support layer having a surface roughness of 0.001 to 10 μm; at least one first polyimide varnish layer formed on the carrier layer, wherein the first polyimide varnish layer in contact with the carrier layer has a surface roughness matching the carrier layer of 0.001 to 10 μm; and a second polyimide varnish layer formed on the first polyimide varnish layer, wherein the second polyimide varnish layer comprises a copolymer formed by polymerizing a plurality of monomers, and the monomers comprise diamine and anhydride.
In a specific embodiment of the invention, the surface roughness of the support layer is 0.001 to 10 μm, 0.001 to 5 μm, 0.01 to 5, 0.01 to 3 μm, 0.05 to 2 μm, 0.05 to 1.5 μm or 0.05 to 2 μm. The surface roughness is, for example, 0.001, 0.0025, 0.005, 0.008, 0.01, 0.02, 0.030, 0.040, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 3, 3.5, 4, 4.5, 5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 or 10 μm. By controlling the surface roughness of the carrier layer so that the carrier layer can be separated from the first polyimide varnish layer described later, the downstream or terminal operability is improved.
In particular embodiments of the present invention, the surface roughness of the first polyimide varnish layer in contact with the carrier layer is 0.001 to 10 μm, 0.001 to 5 μm, 0.01 to 5, 0.01 to 3 μm, 0.05 to 2 μm, 0.05 to 1.5 μm, or 0.05 to 2 μm, such as, but not limited to, 0.001, 0.0025, 0.005, 0.008, 0.01, 0.02, 0.030, 0.040, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.1, 2.2, 2.3, 2.4, 2.5, 3, 3.5, 4, 3.5, 4.7, 5, 5.8, 5.5, 5.9, 5.5, 5.8, 5.5, 10.5, 5, or 10.8. By controlling the surface roughness of the first polyimide varnish layer to facilitate separation of the first polyimide varnish layer from the carrier layer, downstream or terminal operability is improved.
In a specific embodiment of the present invention, when the first polyimide varnish layer is a plurality of layers, the surface roughness of the first polyimide varnish layer in contact with the carrier layer is greater than the surface roughness of the other first polyimide varnish layers not in contact with the carrier layer. In a specific embodiment, when the first polyimide varnish layer is a plurality of layers, only the surface roughness of the first polyimide varnish layer contacted by the carrier layer is controlled to match the surface roughness matched to the carrier layer.
In particular embodiments of the invention, the thickness of the support layer may be 12.5 to 250 μm, 12.5 to 30 μm, 30 to 50 μm, 50 to 100 μm, 100 to 150 μm, 150 to 200 μm, or 200 to 250 μm, such as, but not limited to 12.5, 15, 20, 25, 30, 35, 45, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, or 250 μm.
In particular embodiments of the present invention, the total thickness of the first and second polyimide varnish layers is 1 to 150 μm, 1 to 100 μm, 1 to 75 μm, 1 to 50 μm, 3 to 45 μm, or 5 to 35 μm, while the thickness of the first and second polyimide varnish layers may each be 1 to 50 μm, 1 to 30 μm, or 1 to 10 μm, the layer thicknesses and total thicknesses being, for example, but not limited to, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, or 150 μm.
In a specific embodiment of the present invention, the carrier layer includes at least one selected from the group consisting of polypropylene, biaxially oriented polypropylene, polyethylene terephthalate, polyimide, polyphenylene sulfide, polyethylene naphthalate, polyurethane, and polyamide.
In particular embodiments of the invention, the support layer further comprises an inorganic filler having a particle size of 10nm to 20 μm, and the inorganic filler is 0 to 50wt%, 0 to 20wt%, 0 to 10wt%, or 2 to 10wt%, such as, but not limited to, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50wt%, based on the total weight of the support layer. In a specific embodiment, the inorganic filler is at least one selected from the group consisting of calcium sulfate, carbon black, silica, titanium dioxide, zinc sulfide, zirconium oxide, calcium carbonate, silicon carbide, boron nitride, aluminum oxide, talc, aluminum nitride, glass powder, quartz powder, and clay. The surface roughness of the carrier layer can be controlled by the type and content of the inorganic filler, and the color of the carrier layer can be adjusted by the type and content of the inorganic filler instead of the natural color, so that the product has better product appearance.
In a specific embodiment of the present invention, the first polyimide varnish layer may also include the inorganic filler, and the particle size, content and type of the inorganic filler may be defined by the range defined by the inorganic filler included in the carrier layer, so that no further description is given here. In particular embodiments, the inorganic filler is silica, which may be present in an amount of 5wt%. In another embodiment, when the first polyimide varnish layer is a multilayer, only the first polyimide varnish layer in contact with the carrier layer includes the inorganic filler, and the other first polyimide varnish layers do not include the inorganic filler to maintain preferable mechanical properties. In the invention, the surface roughness of the first polyimide varnish layer can be controlled by the type and content of the inorganic filler.
In particular embodiments of the present invention, the first polyimide varnish layer may include a resin including at least one selected from the group consisting of polyimide-based resins and polyamideimides, and the resin may be contained in an amount of 50 to 98wt%, 50 to 90wt%, 60 to 90wt%, or 70 to 90wt%, for example, but not limited to, 50, 55, 60, 65, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 95, 98wt%, based on the total weight of the first polyimide varnish layer. In a specific embodiment, the resin includes at least one selected from the group consisting of polyimide-based resins and polyamideimides. In another embodiment, the resin includes at least one selected from the group consisting of an epoxy resin, an acrylic resin, a urethane resin, a silicone rubber resin, a parylene resin, a bismaleimide resin, and a styrene-ethylene-butylene-styrene block copolymer in addition to at least one selected from the group consisting of polyimide resins and polyamideimides. In another embodiment, the resin is a polyamideimide resin of the structure of formula (I)
Wherein n is 25 to 35, and the content of the resin may be 80 to 95wt%.
In particular embodiments of the present invention, the first polyimide varnish layer further includes a pigment to modulate the color of the first polyimide varnish layer, and the pigment is present in an amount of 0 to 50wt%, 0 to 30wt%, 5 to 30wt%, or 10 to 30wt%, such as, but not limited to, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 35, 40, 45, 50wt%, based on the total weight of the first polyimide varnish layer. In a specific embodiment, the pigment is selected from at least one inorganic pigment selected from the group consisting of cadmium red, cadmium lemon yellow, cadmium orange, titanium dioxide, carbon black, black iron oxide, and black complexes; or at least one organic pigment selected from the group consisting of aniline black, perylene black, anthraquinone black, biphenyl amine yellow pigments, phthalocyanine blue and phthalocyanine green. In another embodiment, the pigment is carbon black and may be present in an amount of 10wt%.
In a specific embodiment of the present invention, the first polyimide varnish layer further includes an additive, where the additive is at least one selected from the group consisting of a curing agent, a catalyst, a surfactant, and a flame retardant. In particular embodiments, the additive is present in an amount of 0 to 20wt%, 0 to 10wt%, or 1 to 10wt%, and the additive is present in an amount of 0 to 10wt%, or 1 to 10wt%, based on the total weight of the first polyimide varnish layer, the total additive and the ingredients are present in amounts such as, but not limited to, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 15, 20wt%. In another embodiment, the flame retardant is at least one selected from the group consisting of silica, titania, aluminum hydroxide, alumina, carbon black, calcium carbonate, teflon, zinc sulfide, zirconia, silicon carbide, boron nitride, talc, aluminum nitride, glass powder, quartz powder, clay, halogen-containing compound, phosphorus-based compound, nitrogen-based compound, and boron-based compound. In another embodiment, the additives are 4,4' -diaminodiphenyl sulfone curing agent and Clariant company The OP 935 flame retardant may be present in an amount of 5wt% in total.
In a specific embodiment of the invention, the pencil hardness of the first polyimide varnish layer is 2H to 6H, and the pencil hardness can be regulated and controlled by adding inorganic filler.
In a specific embodiment of the present invention, when the first polyimide varnish layer is a plurality of layers, each of the first polyimide varnish layers is independent and may be the same or different.
In a specific embodiment of the present invention, the second polyimide varnish layer includes a copolymer formed by polymerizing a plurality of monomers, wherein the monomers include diamine and anhydride. In particular embodiments, the diamine comprises a silicon diamine and a second type of diamine different from the silicon diamine, and the silicon diamine is 20 mole% to 85 mole% or 30 mole% to 85 mole%, such as, but not limited to, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 mole%, based on the total moles of the diamine. In the invention, the adjustment of the proportion between the silicon diamine and all the diamines has an important effect on the extensibility of the resin after the second polyimide varnish layer is cured.
In specific embodiments, the second class of diamine monomers is selected from at least one of the group consisting of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), 2' -bis (trifluoromethyl) diaminobiphenyl (TFMB), 2-bis (4-aminophenyl) hexafluoropropane, 4' -diaminodiphenyl ether, bis [4- (3-aminophenoxy) phenyl ] sulfonamide, bis [4- (4-aminophenoxy) phenyl ] sulfonamide, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl ] methane, 4' -bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] diethyl ether, bis [4- (4-aminophenoxy) phenyl ] ketone, 1, 3-bis (4-aminophenoxy) benzene, and 1, 4-bis (4-aminophenoxy) benzene.
In a specific embodiment, the silicon diamine is selected from at least one of the compounds represented by the following formulas (1) to (3),
wherein n is 1 to 150.
In a specific embodiment, the silicon diamine is KF-8012 (molecular weight: 4400) from the company Xinyue chemical industry, and the diamine is 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP) or 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFMB).
In specific embodiments, the anhydride is selected from at least one of the group consisting of hexafluorodianhydride (6 FDA), bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 1, 2-ethylenebis [1, 3-dihydro-1, 3-dioxoisobenzofuran-5-carboxylate ], 3', 4' -benzophenone tetracarboxylic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, benzene tetracarboxylic dianhydride, trimellitic anhydride (TMA), and cis-aconitic anhydride. In another embodiment, the anhydride is trimellitic anhydride (TMA), hexafluorodianhydride (6 FDA), bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, or a combination thereof. In another embodiment, the molar ratio of the diamine to the anhydride is between 1:0.9 and 1:1.1.
In a specific embodiment, the monomer used to form the copolymer further comprises an isocyanate selected from at least one of the group consisting of 4,4' -diphenylmethane diisocyanate (MDI), 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, naphthalene-1, 5-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and lysine diisocyanate. In another embodiment, the isocyanate is 4,4' -diphenylmethane diisocyanate (MDI). In another embodiment, the molar ratio of the diamine to the isocyanate is between 1:1.0 and 1:1.5.
In a specific embodiment, the copolymer is formed by polymerizing a plurality of the monomers in the presence of the tertiary amine catalyst selected from at least one of the group consisting of triethylamine (Et 3N), isoquinoline, pyridine, N-ethylpiperidine, benzimidazole, and the like. In another embodiment, the tertiary amine catalyst is triethylamine or N-ethylpiperidine. In another embodiment, the tertiary amine catalyst is 0 to 3wt% based on the total weight of the material from which the polymerization reaction is performed.
In specific embodiments, the polymerization is performed in the presence of a solvent selected from at least one of the group consisting of N-methylpyrrolidone (NMP), γ -butyrolactone, cyclohexanone, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, pyridine, cyclohexane, dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, 1, 2-dichloroethane, trichloroethylene, triethylamine, 4-methyl-2-pentanone, toluene, xylene. In particular embodiments, the solvent is N-methylpyrrolidone (NMP), toluene, or a combination thereof.
In a specific embodiment of the present invention, the elongation of the second polyimide varnish layer is 30% or more, 60% or more, 80% or more, or even 100% or more. The invention can improve the extensibility of the whole composite film by matching the second polyimide varnish layer which is regulated and controlled by components and has high extensibility in the first polyimide varnish layer which is regulated and controlled by components and has the performances of color, high hardness, high tensile strength, low reverse elasticity, high flame retardance and the like, and can maintain the mechanical properties such as hardness, tensile strength, elastic modulus and the like, color, flame retardance, heat resistance and chemical resistance which meet the requirements, and the invention has excellent dimensional stability by adopting a film-making method that polyimide varnish is coated on a carrier layer and cured.
The first and second polyimide varnish layers of the present invention may be cured once or multiple times, for example, after one of the layers is applied, or after one of the layers is applied, the layer is dried, the other layer is applied and dried, and then the two layers are cured together. The invention can solve the problem that micropores appear on the surface in the coating process by a mode of coating varnish type resin in multiple layers and curing.
In a specific embodiment of the present invention, the composite film further includes an adhesive layer, so that it can be used as a cover film. The adhesive layer is formed on the polyimide varnish layer at the outermost side of the composite film. In a specific embodiment, the adhesive layer is at least one selected from the group consisting of epoxy resins, acrylic resins, urethane resins, silicone rubber resins, parylene resins, bismaleimide resins, styrene-ethylene/butylene-styrene block copolymers, polyimide resins, and polyamideimides.
In particular embodiments, the thickness of the adhesive layer may be 3 to 25 μm, 4 to 22 μm, 7 to 20 μm, or 12 to 18 μm, such as, but not limited to, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 μm.
In particular embodiments of the present invention, the composite film further includes a release layer formed on the adhesive layer to facilitate storage and protection of the adhesive layer, to prevent contaminants from adhering to the adhesive layer or to prevent the adhesive layer from adhering to undesired objects before the composite film is not used. In a specific embodiment, the release layer is at least one selected from the group consisting of polypropylene, biaxially oriented polypropylene, and polyethylene terephthalate. In another embodiment, the release layer is a release film or release paper.
A second aspect of the present invention provides a method of preparing a composite membrane comprising: coating a first polyimide varnish layer on the surface of the carrier layer; curing the first polyimide varnish layer; coating a second polyimide varnish layer on the first polyimide varnish layer; and curing the second polyimide varnish layer.
The third aspect of the present invention also provides a method of preparing a composite film, comprising: coating a first polyimide varnish layer on the surface of the carrier layer; drying the first polyimide varnish layer; coating a second polyimide varnish layer on the first polyimide varnish layer; drying the second polyimide varnish layer; and curing the first polyimide varnish layer and the second polyimide varnish layer together.
In a specific embodiment of the present invention, the curing is performed at a low temperature of 50 to 180 ℃.
In a specific embodiment of the present invention, the method for preparing a composite film further includes: forming an adhesive layer on the cured outermost polyimide varnish layer by a coating method or a transfer printing method; and attaching a release layer to the adhesive layer, thereby preparing a composite film suitable for being used as a covering film.
The invention adopts a plurality of polyimide varnish layers, and obtains polyimide varnish layers with different performances by selecting and adding different resins and additives, after the layers are matched with each other, the mechanical strength can be effectively improved, and the elongation percentage of more than 100% can be breakthrough achieved, thereby solving the technical bottleneck that the existing polyimide film on the market generally only has low elongation percentage due to the thickness of less than 8 mu m.
As shown in fig. 1, in the structure of one embodiment of the composite film of the present invention, the composite film 100 includes: a carrier layer 101; and a first polyimide varnish layer 1021, a second polyimide varnish layer 1022, and another first polyimide varnish layer 1023 sequentially laminated on the carrier layer 101. In this embodiment, the first polyimide varnish layer is two layers, and the second polyimide varnish layer 1022 is laminated between the two first polyimide varnish layers. However, in other embodiments, the first polyimide varnish layer may be more than two layers, wherein one first polyimide varnish layer is laminated on the carrier layer, and the second polyimide varnish layer may be laminated between any two first polyimide varnish layers, or on the first polyimide varnish layer to be located at the outermost side of the composite film.
As shown in fig. 2, another embodiment of the composite film of the present invention is constructed, and the composite film may be used as a cover film. The composite film 200 in this embodiment includes: a carrier layer 201; a first polyimide varnish layer 2021 formed on the carrier layer 201; a second polyimide varnish layer 2022 formed on the first polyimide varnish layer 2021; an adhesive layer 203 formed on the second polyimide varnish layer 2022 such that the second polyimide varnish layer 2022 is located between the first polyimide varnish layer 2021 and the adhesive layer 203; and a release layer 204 formed on the adhesive layer 203 such that the adhesive layer 203 is located between the second polyimide varnish layer 2022 and the release layer 204. Similarly, although the first polyimide varnish layer is one layer in the present embodiment, in other embodiments, the first polyimide varnish layer may be more than one layer, wherein one first polyimide varnish layer is laminated on the carrier layer, and the second polyimide varnish layer may be laminated between any two first polyimide varnish layers, or may be laminated on the outermost side of the entire first polyimide varnish layer, and the adhesive layer may be laminated on the first or second polyimide varnish layers, and the release layer may be further laminated on the adhesive layer.
By increasing the number of layers of the first polyimide varnish layer in the composite film of fig. 1 and 2, the overall mechanical strength of the composite film can be improved.
The following examples illustrate embodiments of the present invention in further detail, but are not intended to limit the invention.
Examples 1-1 to 1-7: preparation of highly extensible second polyimide varnish layer (polyamideimide)
Diamine monomer BAPP and silicon diamine monomer (KF-8012, molecular weight 4400 of Xinyue chemical industry Co.) are added into N-methyl pyrrolidone (NMP) solvent, nitrogen is introduced into the solvent and stirred and dissolved at 80 ℃, then acid anhydride monomer TMA is added into the solvent, and copolymerization reaction is carried out for 1 hour at 80 ℃. Then, after toluene was added, the temperature was raised to 170℃to distill off water, and finally, the temperature was raised to 190℃to distill off toluene. After cooling to room temperature, isocyanate monomer MDI and tertiary amine monomer Et3N are added, and the temperature is raised to 120 ℃ to react for 3 hours, thus completing the soluble polyamide imide solution.
As shown in tables 1.1 and 1.2, the diamine/silamine molar ratio, tensile strength elongation and elastic modulus of the highly extensible second polyimide varnish layers of examples 1-1 to 1-7 are described. The tensile strength, elastic modulus and elongation are measured by using an electronic universal tensile machine according to IPC-TM-650.2.4.19 standard.
TABLE 1.1
TABLE 1.2
As shown in tables 1.1 and 1.2, the high-extensibility second polyimide layers prepared in examples 1-1 to 1-7 have significantly higher extensibility than the polyimide varnish layer of comparative example 1-1 without adding the diamine monomer, especially when the mole ratio of the diamine monomer of the second type to the diamine monomer of the second type is 60:40 to 15:85, because the composition ratio of the diamine monomer of the second type in the formulation is different.
Examples 1-8 to 1-14: preparation of highly extensible second polyimide varnish layer (polyamideimide)
Diamine monomer TFMB and silicon diamine monomer (KF-8012, molecular weight 4400 of Xinyue chemical industry Co.) are added into NMP solvent, nitrogen is introduced and stirred and dissolved at 80 ℃, then anhydride monomer 6FDA and bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride (B1317) are added, and copolymerization reaction is carried out at 80 ℃ for 1 hour. Then, the acid anhydride monomers 6FDA and B1317 were added in equal proportions, the addition amount being 5% of the addition amount. Heating to 150 ℃, adding tertiary amine monomer N-ethylpyridine, heating to 190 ℃ and reacting for 4 hours to finish the soluble polyamide-imide solution.
As shown in tables 2.1 and 2.2, the diamine/silamine molar ratio, tensile strength elongation and elastic modulus of the highly extensible second polyimide varnish layers in examples 1 to 8 to 1 to 14 are described. The tensile strength, elastic modulus and elongation are measured by using an electronic universal tensile machine according to IPC-TM-650.2.4.19 standard.
TABLE 2.1
TABLE 2.2
As shown in tables 2.1 and 2.2, the high-extensibility second polyimide varnish layers obtained in examples 1-8 to 1-14 change the polymerization of the molecular bond structure according to the composition ratio of the second diamine monomer and the silicon diamine monomer in the formulation, and especially when the molar ratio of the second diamine monomer to the silicon diamine monomer is 80:20 to 15:85, the second polyimide varnish layer containing the copolymer has significantly higher extensibility compared with the polyimide varnish layer without adding the silicon diamine monomer in comparative examples 1-2.
Examples A1 to A6 preparation of composite films of different gauges
Specific components were added to prepare the first polyimide varnish layers and carrier layers of examples 2-1 to 2-16, as shown in table 3.1, and their surface roughness (Rz) and release force were tested. As also shown in table 3.2, the impact of laminating the first and second polyimide varnish layers to form composite films of different specifications on mechanical properties and dimensional stability in practical use (i.e., carrier removed) is described for the examples, as well as for the comparative examples and other commercial products. The dimensional stability was measured using a two-dimensional coordinate measuring machine and according to the IPC-TM-650.2.2.4C specification.
TABLE 3.1
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TABLE 3.2
In examples 2-1 to 2-16 of Table 3.1, examples A1 to A6, B5 and B6 of Table 3.2, the polyamideimide resin used for the first polyimide varnish layer has the following structural formula, wherein n is 25 to 35:
in examples A1 to A6, B5 and B6 of Table 3.2, the curing agent used for the first polyimide varnish layer was 4,4' diaminodiphenyl sulfone, and the flame retardant was Clariant, model:OP 935, inorganic filler silica, inorganic pigment carbon black, and solvent cyclohexanone. In addition, in examples A1 to A6, the first polyimide varnish layer was used with a resin weight percentage of 80%, an inorganic filler weight percentage of 5%, an inorganic pigment weight percentage of 10%, and a total weight percentage of the curing agent, the catalyst, and the surfactant of 5%.
The highly extensible second polyimide varnish layers in examples A1 to A6 were used in examples 3, 5 and 7 in table 1.1, and in examples 9, 11 and 13 in table 2.1, respectively; whereas the second polyimide varnish layers of comparative examples B5 and B6 were used in comparative examples 1 and 2, respectively. On the other hand, only one polyimide layer was contained in comparative examples B1 to B4, wherein the polyimide layers of comparative examples B1 and B2 were made of a polyimide film HB-N of Shenzhen Ruihai Co., and the polyimide layers of comparative examples B3 and B4 were made of a black polyimide film Kapton of DuPont Co. The comparative examples B1 and B2 are similar gauge cover films using monoaxially stretched films on the market, and the comparative examples B3 and B4 are similar gauge cover films using biaxially stretched films on the market.
As can be seen from the results in table 3, the examples A1 to A6 show that the combination of the first polyimide varnish layer and the high-extensibility second polyimide varnish layer has excellent performance in various aspects such as tensile strength, extensibility, elastic modulus, dimensional stability, etc., so that the overall performance meets the industry requirement, and various characteristics (particularly extensibility) can be adjusted and changed by adjusting and controlling the formulation; in contrast, comparative examples B3 to B6 are commercially available coverlay films subjected to a stretching process, which are inferior in dimensional stability of the finished product, and in particular, comparative examples B1 and B2 are polyimide films produced by a casting method without biaxial stretching, which do not contain the highly-extensible second polyimide varnish layer of the present invention, which show the worst dimensional stability of the finished product.
Example 4 preparation of composite films of different gauges
As shown in Table 4, the effects of the composite films of the examples of the present invention, comparative examples and other commercially available products of different specifications on mechanical properties and dimensional stability in practical use (i.e., carrier removed) are described. Wherein, the breakdown voltage is measured by using a breakdown voltage analyzer according to ASTM D149; the thermal shock test (wicking) was measured using a lead-free solder oven and was performed in accordance with the IPC-TM-650.2.6.8 specification; the 1oz loop circuit filling is to etch a single-sided copper foil substrate into a loop circuit with a line width of 50/50 microns, and press the circuit according to a fast-press parameter (180 ℃ x 20kg x 60 sec); the test sample wafer has good insulating layer appearance, can be fully attached to the circuit, has no copper leakage and layering phenomenon, and is regarded as the judgment of the filling property of the circuit.
TABLE 4 Table 4
In table 4, examples C1 to C3 are composite films (cover films) obtained by adding an epoxy adhesive layer (available from Arisawa, AU) to the composite films (including the first and second polyimide varnish layers) of examples A2, A3, A6 of table 3, and comparative examples D1 and D2 are commercially available polyimide films of comparative examples B2 and B4 of table 3, and the same epoxy adhesive was blended to prepare a composite film (cover film).
As shown in Table 4, the tensile strength, elongation, elastic modulus and dimensional stability of examples C1 to C3 are excellent, the overall performance meets the industry requirements, and the elongation is significantly improved, and the elongation of the finished product is 134% to 277%. Meanwhile, the cover films of examples C1 to C3 still have the same insulation and heat resistance as those of the commercially available polyimide films, and can pass thermal shock test by dip soldering and soldering. The comparative example D1 was observed to be a polyimide film produced by casting method without biaxial extension, which did not contain the highly-extensible second polyimide varnish layer of the present invention, and as a result, showed that the dimensional stability of the final product was the worst; in contrast, the coating film obtained by using the commercially available polyimide film in comparative example D2 showed no remarkable effect in terms of elongation.
In summary, the present invention provides a polyimide composite film with a carrier layer, which can be used as an insulating resin film in a coverlay film, PI stiffener, ink, EMI shielding film, and the like. The composite film provided by the invention comprises a carrier layer and a composite polyimide varnish layer, wherein the composite polyimide varnish layer also comprises a first polyimide varnish layer and a second polyimide varnish layer with high extensibility through regulating and controlling a formula, so that the composite film has high flame retardance, insulating surface glossiness, color adjustability, high shielding property, high dimensional stability, high extensibility and other mechanical properties, high surface hardness, and is particularly suitable for being used in super-density assembly lines, high bending scenes and wireless charging applications. On the other hand, the invention also solves the difficulty that the existing stretching method is difficult to achieve the ultrathin film with single specification under the condition of colorization (such as black). Besides the above properties, the invention also changes the surface roughness and surface energy by regulating the powder content and the proportion and/or the surface treatment in the formulation of the polyimide varnish layer and/or the carrier layer, so that the better release force between the polyimide varnish layer and the carrier layer can eliminate the problem of organosilicon transfer without using a release agent, and the cost of the adopted method and the adopted process is lower than that of the prior release layer.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the present invention and the accompanying drawings, or direct or indirect application in other related technical fields, are included in the scope of the present invention.
Claims (25)
1. A composite membrane, characterized in that: comprising
A support layer having a surface roughness of 0.001 to 10 μm;
at least one first polyimide varnish layer formed on the carrier layer, wherein the first polyimide varnish layer in contact with the carrier layer has a surface roughness matching the carrier layer of 0.001 to 10 μm;
and a second polyimide varnish layer formed on the first polyimide varnish layer, wherein the second polyimide varnish layer comprises a copolymer formed by polymerizing a plurality of monomers, and the monomers comprise diamine and anhydride.
2. A composite membrane according to claim 1, wherein: the thickness of the carrier layer is 12.5 to 250 μm, and the total thickness of the first polyimide varnish layer and the second polyimide varnish layer is 1 to 150 μm.
3. A composite membrane according to claim 1, wherein: the first polyimide varnish layer includes a resin including at least one selected from the group consisting of polyimide-based resins and polyamideimides, and the resin is 50 to 98wt% based on the total weight of the first polyimide varnish layer.
4. A composite membrane according to claim 3, wherein: the resin further includes at least one selected from the group consisting of epoxy resin, acrylic resin, urethane resin, silicone rubber resin, parylene resin, bismaleimide resin, and styrene-ethylene-butylene-styrene block copolymer.
5. A composite membrane according to claim 1, wherein: the first polyimide varnish layer and/or the carrier layer further comprises an inorganic filler, the particle size of the inorganic filler is 10-20000 nm, and the inorganic filler is 0-50wt% based on the total weight of the first polyimide varnish layer or the carrier layer.
6. A composite membrane according to claim 5, wherein: the inorganic filler is at least one selected from the group consisting of calcium sulfate, carbon black, silicon dioxide, titanium dioxide, zinc sulfide, zirconium oxide, calcium carbonate, silicon carbide, boron nitride, aluminum oxide, talcum powder, aluminum nitride, glass powder, quartz powder and clay.
7. A composite membrane according to claim 1, wherein: the first polyimide varnish layer further includes a pigment, and the pigment is 0 to 50wt% based on the total weight of the first polyimide varnish layer.
8. A composite membrane according to claim 7, wherein: the pigment is an inorganic pigment or an organic pigment, the inorganic pigment is at least one selected from the group consisting of cadmium red, cadmium lemon yellow, cadmium orange, titanium dioxide, carbon black, black iron oxide and black complex, and the organic pigment is at least one selected from the group consisting of aniline black, perylene black, anthraquinone black, biphenyl amine yellow pigment, phthalocyanine blue and phthalocyanine green.
9. A composite membrane according to claim 1, wherein: the diamine comprises a silicon diamine and a second type of diamine different from the silicon diamine, and the silicon diamine is 20 to 85 mole percent based on the total moles of the diamine.
10. A composite membrane according to claim 9, wherein: the second diamine is selected from at least one of the group consisting of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2' -bis (trifluoromethyl) diaminobiphenyl, 2-bis (4-aminophenyl) hexafluoropropane, 4' -diaminodiphenyl ether, bis [4- (3-aminophenoxy) phenyl ] sulfonamide, bis [4- (4-aminophenoxy) phenyl ] sulfonamide, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl ] methane, 4' -bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] diethyl ether, bis [4- (4-aminophenoxy) phenyl ] ketone, 1, 3-bis (4-aminophenoxy) benzene, and 1, 4-bis (4-aminophenoxy) benzene.
11. A composite membrane according to claim 9, wherein: the silicon diamine is selected from at least one of the compounds represented by the following formulas 1 to 3:
wherein n is 1 to 150.
12. A composite membrane according to claim 1, wherein: the acid anhydride is at least one selected from the group consisting of hexafluorodianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 1, 2-ethylenebis [1, 3-dihydro-1, 3-dioxoisobenzofuran-5-carboxylate ], 3', 4' -benzophenone tetracarboxylic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, benzoic tetracarboxylic dianhydride, trimellitic anhydride and cis-aconitic anhydride.
13. A composite membrane according to claim 1, wherein: the molar ratio of the diamine to the anhydride is from 1:0.9 to 1:1.1.
14. A composite membrane according to claim 1, wherein: the monomer further comprises isocyanate, wherein the isocyanate is at least one selected from the group consisting of 4,4' -diphenylmethane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, naphthalene-1, 5-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and lysine diisocyanate.
15. A composite membrane according to claim 14, wherein: the molar ratio of the diamine to the isocyanate is from 1:1.0 to 1:1.5.
16. A composite membrane according to claim 1, wherein: the copolymer is formed by polymerizing a plurality of monomers in the presence of a tertiary amine catalyst, wherein the tertiary amine catalyst is at least one selected from the group consisting of triethylamine, isoquinoline, pyridine, N-ethylpiperidine and benzimidazole.
17. A composite membrane according to claim 1, wherein: the tertiary amine catalyst is 0 to 3wt% based on the total weight of the material from which the polymerization reaction is carried out.
18. A composite membrane according to claim 1, wherein: the elongation of the second polyimide varnish layer is more than 30%.
19. A composite membrane according to claim 1, wherein: the first polyimide varnish layer further comprises an additive, wherein the additive is at least one selected from the group consisting of a curing agent, a catalyst, a surfactant and a flame retardant, the additive is 0 to 20 weight percent based on the total weight of the first polyimide varnish layer, and the flame retardant is at least one selected from the group consisting of silicon dioxide, titanium dioxide, aluminum hydroxide, aluminum oxide, carbon black, calcium carbonate, teflon, zinc sulfide, zirconium oxide, silicon carbide, boron nitride, talcum powder, aluminum nitride, glass powder, quartz powder, clay, a halogen-containing compound, a phosphorus compound, a nitrogen compound and a boron compound.
20. A composite membrane according to claim 1, wherein: the carrier layer comprises at least one selected from the group consisting of polypropylene, biaxially oriented polypropylene, polyethylene terephthalate, polyimide, polyphenylene sulfide, polyethylene naphthalate, polyurethane and polyamide.
21. A composite membrane according to claim 1, wherein: further comprises:
an adhesive layer formed on the polyimide varnish layer at the outermost side of the composite film;
and a release layer formed on the adhesive layer.
22. A preparation method of a composite membrane is characterized by comprising the following steps: comprising the following steps:
coating the first polyimide varnish layer on the carrier layer;
curing the first polyimide varnish layer;
coating a second polyimide varnish layer on the first polyimide varnish layer;
and curing the second polyimide varnish layer.
23. A preparation method of a composite membrane is characterized by comprising the following steps: comprising the following steps:
coating the first polyimide varnish layer on the carrier layer;
drying the first polyimide varnish layer;
coating a second polyimide varnish layer on the first polyimide varnish layer;
Drying the second polyimide varnish layer; and
and curing the first polyimide varnish layer and the second polyimide varnish layer together.
24. A method of producing a composite film according to claim 22 or 23, wherein: the curing is carried out at a temperature of 50 to 180 ℃.
25. A method of producing a composite film according to claim 22 or 23, wherein:
further comprises: forming an adhesive layer on the cured outermost polyimide varnish layer by a coating method or a transfer method; and attaching a release layer on the adhesive layer.
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| Application Number | Priority Date | Filing Date | Title |
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| TW112100267 | 2023-01-04 | ||
| TW112100267 | 2023-01-04 |
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| CN116693911A true CN116693911A (en) | 2023-09-05 |
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| CN115558436A (en) * | 2022-10-18 | 2023-01-03 | 昆山雅森电子材料科技有限公司 | High-performance polyimide shielding film and preparation method thereof |
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Application publication date: 20230905 |