JP5735287B2 - Multilayer polyimide film and flexible metal foil-clad laminate using the same - Google Patents
Multilayer polyimide film and flexible metal foil-clad laminate using the same Download PDFInfo
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- JP5735287B2 JP5735287B2 JP2011005114A JP2011005114A JP5735287B2 JP 5735287 B2 JP5735287 B2 JP 5735287B2 JP 2011005114 A JP2011005114 A JP 2011005114A JP 2011005114 A JP2011005114 A JP 2011005114A JP 5735287 B2 JP5735287 B2 JP 5735287B2
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- JP
- Japan
- Prior art keywords
- thermoplastic polyimide
- multilayer
- polyimide film
- dianhydride
- thermoplastic
- 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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- 229920001721 polyimide Polymers 0.000 title claims description 79
- 229910052751 metal Inorganic materials 0.000 title claims description 57
- 239000002184 metal Substances 0.000 title claims description 57
- 229920006259 thermoplastic polyimide Polymers 0.000 claims description 131
- 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 53
- 239000002253 acid Substances 0.000 claims description 37
- 239000000126 substance Substances 0.000 claims description 26
- 150000004985 diamines Chemical class 0.000 claims description 24
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical group C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 23
- 239000011888 foil Substances 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000012024 dehydrating agents Substances 0.000 claims description 16
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 15
- 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 10
- 238000003825 pressing Methods 0.000 claims description 2
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 73
- 229920005575 poly(amic acid) Polymers 0.000 description 69
- 238000000034 method Methods 0.000 description 67
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 60
- 239000010408 film Substances 0.000 description 40
- 239000000463 material Substances 0.000 description 39
- 238000010030 laminating Methods 0.000 description 36
- 230000015572 biosynthetic process Effects 0.000 description 32
- 238000003786 synthesis reaction Methods 0.000 description 31
- 230000001681 protective effect Effects 0.000 description 30
- 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 description 26
- 238000010438 heat treatment Methods 0.000 description 25
- -1 4,4'-diaminodiphenyl N-methylamine Chemical compound 0.000 description 19
- 239000000945 filler Substances 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 16
- 229920001169 thermoplastic Polymers 0.000 description 16
- 239000004416 thermosoftening plastic Substances 0.000 description 16
- 239000000178 monomer Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 14
- 229910000679 solder Inorganic materials 0.000 description 13
- 125000003118 aryl group Chemical group 0.000 description 12
- 238000004804 winding Methods 0.000 description 12
- 239000004642 Polyimide Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 150000004984 aromatic diamines Chemical class 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000003475 lamination Methods 0.000 description 8
- 239000002798 polar solvent Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 239000002648 laminated material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 6
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 108010025899 gelatin film Proteins 0.000 description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 238000001029 thermal curing Methods 0.000 description 4
- 238000009823 thermal lamination Methods 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000002313 adhesive film Substances 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 125000006159 dianhydride group Chemical group 0.000 description 3
- 238000006358 imidation reaction Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-UHFFFAOYSA-N 0.000 description 1
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- TYKLCAKICHXQNE-UHFFFAOYSA-N 3-[(2,3-dicarboxyphenyl)methyl]phthalic acid Chemical compound OC(=O)C1=CC=CC(CC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O TYKLCAKICHXQNE-UHFFFAOYSA-N 0.000 description 1
- UCFMKTNJZCYBBJ-UHFFFAOYSA-N 3-[1-(2,3-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)C1=CC=CC(C(O)=O)=C1C(O)=O UCFMKTNJZCYBBJ-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 1
- IJJNNSUCZDJDLP-UHFFFAOYSA-N 4-[1-(3,4-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 IJJNNSUCZDJDLP-UHFFFAOYSA-N 0.000 description 1
- GEYAGBVEAJGCFB-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 GEYAGBVEAJGCFB-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- JLRGJRBPOGGCBT-UHFFFAOYSA-N Tolbutamide Chemical compound CCCCNC(=O)NS(=O)(=O)C1=CC=C(C)C=C1 JLRGJRBPOGGCBT-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 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
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- GZORJAFFPJJJQU-UHFFFAOYSA-N n,n-dimethylacetamide;1-methylpyrrolidin-2-one Chemical compound CN(C)C(C)=O.CN1CCCC1=O GZORJAFFPJJJQU-UHFFFAOYSA-N 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
本発明は、フレキシブルプリント配線板に好適に使用できる多層ポリイミドフィルム及びフレキシブル金属箔張積層板に関する。 The present invention relates to a multilayer polyimide film and a flexible metal foil-clad laminate that can be suitably used for flexible printed wiring boards.
近年、エレクトロニクス製品の軽量化、小型化、高密度化にともない、各種プリント基板の需要が伸びているが、中でも、フレキシブル積層板(フレキシブルプリント配線板(FPC)等とも称する)の需要が特に伸びている。フレキシブル積層板は、ポリイミドフィルム等の絶縁性フィルム上に金属層からなる回路が形成された構造を有している。 In recent years, the demand for various printed circuit boards has increased along with the reduction in weight, size and density of electronic products. In particular, the demand for flexible laminates (also referred to as flexible printed circuit boards (FPCs), etc.) has increased. ing. The flexible laminate has a structure in which a circuit made of a metal layer is formed on an insulating film such as a polyimide film.
上記フレキシブルプリント配線板の元になるフレキシブル金属箔張積層板は、一般に、各種絶縁材料により形成され、柔軟性を有する絶縁性フィルムを基板とし、この基板の表面に、各種接着材料を介して金属箔を加熱・圧着することにより貼り合わせる方法により製造される。上記絶縁性フィルムとしては、ポリイミドフィルム等が好ましく用いられる。上記接着材料としては、エポキシ系、アクリル系等の熱硬化性接着剤が一般的に用いられている。 The flexible metal foil-clad laminate that is the basis of the flexible printed wiring board is generally formed of various insulating materials, and a flexible insulating film is used as a substrate, and the surface of the substrate is metalized with various adhesive materials. Manufactured by a method of laminating foil by heating and pressure bonding. A polyimide film or the like is preferably used as the insulating film. As the adhesive material, epoxy-based, acrylic-based thermosetting adhesives are generally used.
熱硬化性接着剤は、比較的低温での接着が可能であるという利点があるが、耐熱性、屈曲性、電気的信頼性といった要求特性が厳しくなるに従い、熱硬化性接着剤を用いた三層FPCでは対応が困難になると考えられる。このため、絶縁性フィルムに直接金属層を設けたり、接着層に熱可塑性ポリイミドを使用した二層FPCが提案されている。この二層FPCは、三層FPCよりも優れた特性を有し、今後需要が伸びていくと期待される。 Thermosetting adhesives have the advantage that they can be bonded at relatively low temperatures. However, as the required properties such as heat resistance, flexibility, and electrical reliability become stricter, three types of thermosetting adhesives are used. It is considered difficult to cope with the layer FPC. For this reason, a two-layer FPC has been proposed in which a metal layer is directly provided on an insulating film or a thermoplastic polyimide is used for an adhesive layer. This two-layer FPC has characteristics superior to those of the three-layer FPC, and demand is expected to increase in the future.
しかし、ポリイミドは、吸湿率が高いため、半田加工時に、膨れが発生することがあった。これに対し、半田耐熱性300℃をクリアできる金属箔積層体が提案されているが、積極的に吸湿させた状態では、半田加工時に膨れが発生し、問題となることがあった(例えば、特許文献1〜2参照。)。 However, since polyimide has a high moisture absorption rate, swelling may occur during solder processing. On the other hand, a metal foil laminate capable of clearing solder heat resistance of 300 ° C. has been proposed, but in a state where moisture is actively absorbed, swelling occurs during solder processing, which may be a problem (for example, (See Patent Documents 1 and 2.)
また、積極的に吸湿させた状態で、半田加工時に膨れが発生しないフレキシブル金属箔張積層板が提案されているが、別途製造したポリイミドオリゴマーをポリアミド酸に混合し、加熱処理して接着層を形成しており、生産性が問題となることがあった(例えば、特許文献3参照。)。 In addition, a flexible metal foil-clad laminate that has been actively absorbed and does not generate blisters during soldering has been proposed. A polyimide oligomer produced separately is mixed with polyamic acid and heat-treated to form an adhesive layer. As a result, productivity may be a problem (for example, see Patent Document 3).
本発明は、上記の課題に鑑みてなされたものであって、その目的は、銅箔の引き剥がし強度が良好で、かつ積極的に吸湿させた状態でも半田加工時に膨れが発生せず、生産性の良い多層ポリイミドフィルム及びフレキシブル金属箔張積層板を提供することにある。 The present invention has been made in view of the above-mentioned problems, and its purpose is that the copper foil has a good peel strength and does not swell at the time of soldering even in a state where moisture is actively absorbed and produced. An object of the present invention is to provide a multilayer polyimide film and a flexible metal foil-clad laminate having good properties.
本発明者らは、上記の課題に鑑み鋭意検討した結果、本発明に至った。 As a result of intensive studies in view of the above problems, the present inventors have reached the present invention.
すなわち本発明は、非熱可塑性ポリイミドを含む非熱可塑性ポリイミド層の少なくとも一方に熱可塑性ポリイミドを含む熱可塑性ポリイミド層を有する多層ポリイミドフィルムであって、上記熱可塑性ポリイミドを構成する酸二無水物が3,3´,4,4´−ビフェニルテトラカルボン酸二無水物とピロメリット酸二無水物を必須成分とし、3,3´,4,4´−ビフェニルテトラカルボン酸二無水物とピロメリット酸二無水物のモル比が、5/95〜30/70であり、かつ上記熱可塑性ポリイミドを構成するジアミンが2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパンを必須成分とし、上記非熱可塑性ポリイミドを構成する酸二無水物がピロメリット酸二無水物を必須成分とし、かつ上記非熱可塑性ポリイミドを構成するジアミンが2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパンを必須成分とすることを特徴とする多層ポリイミドフィルムに関する。 That is, the present invention is a multilayer polyimide film having a thermoplastic polyimide layer containing a thermoplastic polyimide on at least one of the non-thermoplastic polyimide layers containing a non-thermoplastic polyimide, and the acid dianhydride constituting the thermoplastic polyimide is 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are essential components, and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic acid The dianhydride molar ratio is 5/95 to 30/70, and the diamine constituting the thermoplastic polyimide has 2,2-bis [4- (4-aminophenoxy) phenyl] propane as an essential component, The acid dianhydride composing the non-thermoplastic polyimide contains pyromellitic dianhydride as an essential component, and the dither composing the non-thermoplastic polyimide. The present invention relates to a multilayer polyimide film characterized in that min contains 2,2-bis [4- (4-aminophenoxy) phenyl] propane as an essential component.
上記多層ポリイミドフィルムは、上記多層ポリイミドフィルムの少なくとも非熱可塑性ポリイミド層に、イミド化触媒及び化学脱水剤を投入し、イミド化させたものであることが好ましい。 It is preferable that the multilayer polyimide film is obtained by imidizing an imidization catalyst and a chemical dehydrating agent into at least the non-thermoplastic polyimide layer of the multilayer polyimide film.
また、上記多層ポリイミドフィルムが多層共押出によって製造されていることが好ましい。 Moreover, it is preferable that the said multilayer polyimide film is manufactured by multilayer coextrusion.
また、上記多層ポリイミドフィルムは、非熱可塑性ポリイミド層の両面に熱可塑性ポリイミド層を有する構造であることが好ましい。 Moreover, it is preferable that the said multilayer polyimide film is a structure which has a thermoplastic polyimide layer on both surfaces of a non-thermoplastic polyimide layer.
また、上記多層ポリイミドフィルムは、上記多層ポリイミドフィルムの非熱可塑性ポリイミド層のみに、イミド化触媒及び化学脱水剤を投入し、イミド化させたものであることが好ましい。 Moreover, it is preferable that the said multilayer polyimide film is imidized by throwing an imidation catalyst and a chemical dehydrating agent only into the non-thermoplastic polyimide layer of the said multilayer polyimide film.
また、本発明は、上記多層ポリイミドフィルムと金属箔を、1対の熱ロールで加熱圧着させることにより得られることを特徴とするフレキシブル金属箔張積層板に関する。 The present invention also relates to a flexible metal foil-clad laminate obtained by heat-pressing the multilayer polyimide film and the metal foil with a pair of hot rolls.
本発明により、銅箔の引き剥がし強度が良好で、かつ積極的に吸湿させた状態でも半田加工時に膨れが発生せず、生産性の良いフレキシブル金属箔張積層板を提供することができる。 According to the present invention, it is possible to provide a flexible metal foil-clad laminate having good productivity, which has good peeling strength of copper foil and does not swell during soldering even in a state where moisture is actively absorbed.
本発明の実施の一形態について、以下に説明する。 One embodiment of the present invention will be described below.
本発明は、非熱可塑性ポリイミドを含む非熱可塑性ポリイミド層の少なくとも一方に熱可塑性ポリイミドを含む熱可塑性ポリイミド層を有する多層ポリイミドフィルムであって、上記熱可塑性ポリイミドを構成する酸二無水物が3,3´,4,4´−ビフェニルテトラカルボン酸二無水物とピロメリット酸二無水物を必須成分とし、3,3´,4,4´−ビフェニルテトラカルボン酸二無水物とピロメリット酸二無水物のモル比が、5/95〜30/70であり、かつ上記熱可塑性ポリイミドを構成するジアミンが2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパンを必須成分とし、非熱可塑性ポリイミドを構成する酸二無水物がピロメリット酸二無水物を必須成分とし、かつ上記非熱可塑性ポリイミドを構成するジアミンが2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパンを必須成分とすることを特徴とする多層ポリイミドフィルムに関する。 The present invention is a multilayer polyimide film having a thermoplastic polyimide layer containing a thermoplastic polyimide on at least one of the non-thermoplastic polyimide layers containing a non-thermoplastic polyimide, wherein the acid dianhydride constituting the thermoplastic polyimide is 3 , 3 ', 4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are essential components, and 3,3', 4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride The molar ratio of the anhydride is 5/95 to 30/70, and the diamine constituting the thermoplastic polyimide has 2,2-bis [4- (4-aminophenoxy) phenyl] propane as an essential component, The acid dianhydride constituting the thermoplastic polyimide contains pyromellitic dianhydride as an essential component, and the diamine constituting the non-thermoplastic polyimide is 2,2 The present invention relates to a multilayer polyimide film comprising bis [4- (4-aminophenoxy) phenyl] propane as an essential component.
本発明における非熱可塑性ポリイミドとは、一般に加熱しても軟化、接着性を示さないポリイミドをいう。本発明では、フィルムの状態で380℃、2分間加熱を行い、シワが入ったり伸びたりせず、形状を保持しているポリイミド、若しくは実質的にガラス転移温度を有しないポリイミドをいう。 The non-thermoplastic polyimide in the present invention generally means a polyimide that does not soften or show adhesiveness even when heated. In the present invention, it refers to a polyimide which is heated at 380 ° C. for 2 minutes in the state of a film and does not wrinkle or stretch and maintains its shape, or a polyimide having substantially no glass transition temperature.
また、熱可塑性ポリイミドとは、一般的にDSC(示差走査熱量測定)で、ガラス転移温度を有するポリイミドをいう。本発明での熱可塑性ポリイミドは、前記ガラス転移温度が、150℃〜350℃であるものをいう。 The thermoplastic polyimide generally means a polyimide having a glass transition temperature by DSC (differential scanning calorimetry). The thermoplastic polyimide in the present invention refers to one having a glass transition temperature of 150 ° C to 350 ° C.
多層ポリイミドフィルムの非熱可塑性ポリイミド層中の非熱可塑性ポリイミド及び熱可塑性ポリイミド層中の熱可塑性ポリイミドの原料として用いる芳香族酸二無水物はピロメリット酸二無水物を必須成分として用いる。ピロメリット酸二無水物以外の酸二無水物としては、特に限定されないが、2,3,6,7−ナフタレンテトラカルボン酸二無水物、3,3´,4,4´−ビフェニルテトラカルボン酸二無水物、1,2,5,6−ナフタレンテトラカルボン酸二無水物、2,2´,3,3´−ビフェニルテトラカルボン酸二無水物、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物、2,2−ビス(3,4−ジカルボキシフェニル)プロパン二無水物、3,4,9,10−ペリレンテトラカルボン酸二無水物、1,1−ビス(2,3−ジカルボキシフェニル)エタン二無水物、1,1−ビス(3,4−ジカルボキシフェニル)エタン二無水物、ビス(2,3−ジカルボキシフェニル)メタン二無水物、オキシジフタル酸二無水物、ビス(3,4−ジカルボキシフェニル)スルホン二無水物、p−フェニレンビス(トリメリット酸モノエステル酸無水物)、エチレンビス(トリメリット酸モノエステル酸無水物)、ビスフェノールAビス(トリメリット酸モノエステル酸無水物)及びそれらの誘導体を含み、これらを単独で、または任意の割合で混合した混合物を好ましく用いることができる。 The aromatic acid dianhydride used as a raw material for the non-thermoplastic polyimide in the non-thermoplastic polyimide layer of the multilayer polyimide film and the thermoplastic polyimide in the thermoplastic polyimide layer uses pyromellitic dianhydride as an essential component. The acid dianhydride other than pyromellitic dianhydride is not particularly limited, but 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid Dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetra Carboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,1-bis (2,3 -Dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, oxydiphthalic dianhydride, Screw (3,4 Dicarboxyphenyl) sulfone dianhydride, p-phenylenebis (trimellitic acid monoester acid anhydride), ethylene bis (trimellitic acid monoester acid anhydride), bisphenol A bis (trimellitic acid monoester acid anhydride) And their derivatives, and a mixture of these alone or in an arbitrary ratio can be preferably used.
中でも、非熱可塑性ポリイミドを構成する酸二無水物であって、ピロメリット酸二無水物以外の酸二無水物としては、3,3´,4,4´−ビフェニルテトラカルボン酸二無水物、及び3,3´,4,4´−ベンゾフェノンテトラカルボン酸二無水物からなる群より選ばれる少なくとも1種の酸二無水物であることが好ましく、製造時の溶媒溶解性の面で、3,3´,4,4´−ベンゾフェノンテトラカルボン酸二無水物がさらに好ましい。 Among them, acid dianhydrides constituting non-thermoplastic polyimides, and acid dianhydrides other than pyromellitic dianhydride include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, And at least one acid dianhydride selected from the group consisting of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and in terms of solvent solubility during production, More preferred is 3 ', 4,4'-benzophenone tetracarboxylic dianhydride.
また、熱可塑性ポリイミドを構成する酸二無水物としては、3,3´,4,4´−ビフェニルテトラカルボン酸二無水物とピロメリット酸二無水物を必須成分として用いる。混合比は、モル比として、5/95〜30/70を用いる。5/95よりも、3,3´,4,4´−ビフェニルテトラカルボン酸二無水物が少ない場合、熱可塑性ポリイミド層の熱可塑性が低くなり、銅箔の引き剥がし強度が低くなる。また、30/70よりも、3,3´,4,4´−ビフェニルテトラカルボン酸二無水物が多い場合、吸湿時の半田耐熱性が低くなる。引き剥がし強度は、10N/cm以上が好ましく、吸湿時の半田耐熱性は、280℃以上が好ましい。3,3´,4,4´−ビフェニルテトラカルボン酸二無水物とピロメリット酸二無水物の混合比は、5/95〜30/70であるが、5/95〜25/75が吸湿時の半田耐熱性の面でさらに好ましく、5/95〜20/80が特に好ましい。 As acid dianhydrides constituting the thermoplastic polyimide, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are used as essential components. The mixing ratio is 5/95 to 30/70 as the molar ratio. When the amount of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is less than 5/95, the thermoplastic polyimide layer has low thermoplasticity and the copper foil peel strength is low. In addition, when 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is more than 30/70, solder heat resistance during moisture absorption is lowered. The peel strength is preferably 10 N / cm or more, and the solder heat resistance during moisture absorption is preferably 280 ° C. or more. The mixing ratio of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride is 5 / 95-30 / 70, but 5 / 95-25 / 75 is moisture absorption In view of solder heat resistance, 5/95 to 20/80 is particularly preferable.
熱可塑性ポリイミドを構成する酸二無水物としては、3,3´,4,4´−ビフェニルテトラカルボン酸二無水物とピロメリット酸二無水物以外に、前記酸二無水物を併用して用いることができ、酸二無水物の合計モル数の10%を上限に用いることができる。 As the acid dianhydride constituting the thermoplastic polyimide, in addition to 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride, the acid dianhydride is used in combination. 10% of the total number of moles of acid dianhydride can be used as the upper limit.
多層ポリイミドフィルムの非熱可塑性ポリイミド層中の非熱可塑性ポリイミド及び熱可塑性ポリイミド層中の熱可塑性ポリイミドの原料として用いる芳香族ジアミンは2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパンを必須成分として用いる。2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパン以外のジアミンとしては、特に限定されないが、4,4´−ジアミノジフェニルエーテル、3,4´−ジアミノジフェニルエーテル、1,3−ビス(4−アミノフェノキシ)ベンゼン、1,4−ビス(4−アミノフェノキシ)ベンゼン、p−フェニレンジアミン、4,4´−ジアミノジフェニルプロパン、4,4´−ジアミノジフェニルメタン、ベンジジン、3,3’−ジクロロベンジジン、4,4´−ジアミノジフェニルスルフィド、3,3´−ジアミノジフェニルスルホン、4,4´−ジアミノジフェニルスルホン、4,4´−ジアミノジフェニルエーテル、3,3´−ジアミノジフェニルエーテル、3,4´−ジアミノジフェニルエーテル、1,5−ジアミノナフタレン、4,4´−ジアミノジフェニルジエチルシラン、4,4’−ジアミノジフェニルシラン、4,4´−ジアミノジフェニルエチルホスフィンオキシド、4,4´−ジアミノジフェニルN−メチルアミン、4,4´−ジアミノジフェニル N−フェニルアミン、1,4−ジアミノベンゼン(p−フェニレンジアミン)、1,3−ジアミノベンゼン、1,2−ジアミノベンゼン、及びそれらの誘導体などが挙げられ、これらを単独で、または任意の割合で混合した混合物を好ましく用いることができる。 The aromatic diamine used as a raw material for the non-thermoplastic polyimide in the non-thermoplastic polyimide layer of the multilayer polyimide film and the thermoplastic polyimide in the thermoplastic polyimide layer is 2,2-bis [4- (4-aminophenoxy) phenyl] propane Is used as an essential component. The diamine other than 2,2-bis [4- (4-aminophenoxy) phenyl] propane is not particularly limited, but 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 1,3-bis ( 4-Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, benzidine, 3,3'-dichloro Benzidine, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′- Diaminodiphenyl ether, 1,5-diaminonaphthalene, 4,4 '-Diaminodiphenyldiethylsilane, 4,4'-diaminodiphenylsilane, 4,4'-diaminodiphenylethylphosphine oxide, 4,4'-diaminodiphenyl N-methylamine, 4,4'-diaminodiphenyl N-phenylamine 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene, 1,2-diaminobenzene, and derivatives thereof, and the like, or a mixture in which these are mixed alone or in an arbitrary ratio Can be preferably used.
中でも、非熱可塑性ポリイミドを構成する2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパン以外のジアミン単量体としては、p−フェニレンジアミン、4,4´−ジアミノジフェニルエーテルを用いることは、線膨張係数及び強度の制御の面で好ましい。 Among them, as diamine monomers other than 2,2-bis [4- (4-aminophenoxy) phenyl] propane constituting non-thermoplastic polyimide, p-phenylenediamine and 4,4′-diaminodiphenyl ether are used. Is preferable in terms of controlling the linear expansion coefficient and strength.
なお、非熱可塑性ポリイミド中において熱可塑性ブロック成分を含むこと、すなわち、非熱可塑性ポリイミド層になるポリアミド酸が、分子中に熱可塑性ブロック成分を有する非熱可塑性ポリイミドの前駆体であるポリアミド酸であることは、非熱可塑性ポリイミド層と熱可塑性ポリイミド層との密着性を向上させることができる点で好ましい。 It should be noted that the non-thermoplastic polyimide contains a thermoplastic block component, that is, the polyamic acid that becomes the non-thermoplastic polyimide layer is a polyamic acid that is a precursor of the non-thermoplastic polyimide having a thermoplastic block component in the molecule. A certain thing is preferable at the point which can improve the adhesiveness of a non-thermoplastic polyimide layer and a thermoplastic polyimide layer.
また、熱可塑性ポリイミドを構成する2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパン以外のジアミン単量体としては、4,4´−ジアミノジフェニルエーテルを用いることが、耐熱性向上の面で好ましい。 In addition, as a diamine monomer other than 2,2-bis [4- (4-aminophenoxy) phenyl] propane constituting the thermoplastic polyimide, it is possible to use 4,4′-diaminodiphenyl ether to improve heat resistance. In terms of surface.
多層ポリイミドフィルムの製造方法としては、例えば、(1)予め製造しておいた非熱可塑性ポリイミドフィルムに、熱可塑性ポリアミド酸溶液を塗布・乾燥した後、150℃以上の高温で加熱して多層ポリイミドフィルムを製造する方法、(2)多層共押出により、同時に多層ポリアミド酸をドラム、エンドレスベルト等の支持体に塗布・乾燥した後、ゲルフィルムを支持体から剥がし、150℃以上の高温で加熱して多層ポリイミドフィルムを製造する方法がある。中でも、生産性の面で、多層共押出により、多層ポリイミドフィルムを製造することが好ましい。また、吸湿半田耐熱性の面でも、多層共押出により、多層ポリイミドフィルムを製造することが好ましい。これは、明確では無いが、非熱可塑性ポリイミド層のポリアミド酸と熱可塑性ポリイミド層のポリアミド酸が同時に押出されることで、界面で双方のポリアミド酸が少なからず混合し、非熱可塑性ポリイミド層と熱可塑性ポリイミド層の一体性が向上するためと推定している。 As a method for producing a multilayer polyimide film, for example, (1) a non-thermoplastic polyimide film produced in advance is coated and dried with a thermoplastic polyamic acid solution and then heated at a high temperature of 150 ° C. or more to obtain a multilayer polyimide film. (2) The multilayer polyamic acid is simultaneously coated and dried on a support such as a drum or an endless belt by multilayer coextrusion, and then the gel film is peeled off from the support and heated at a high temperature of 150 ° C. or higher. There is a method of manufacturing a multilayer polyimide film. Among these, in terms of productivity, it is preferable to produce a multilayer polyimide film by multilayer coextrusion. In terms of heat-absorbing solder heat resistance, it is preferable to produce a multilayer polyimide film by multilayer coextrusion. This is not clear, but the polyamic acid of the non-thermoplastic polyimide layer and the polyamic acid of the thermoplastic polyimide layer are extruded at the same time. It is presumed that the integrity of the thermoplastic polyimide layer is improved.
非熱可塑性ポリイミド層と熱可塑性ポリイミド層の一体性を向上させるためには、熱可塑性ポリイミドを構成する酸二無水物単量体及びジアミン単量体の合計モル数の60%以上が、非熱可塑性ポリイミドを構成する酸二無水物単量体とジアミン単量体であることが好ましい。具体的な算出方法について記載する。熱可塑性ポリイミドで用いられる酸二無水物及びジアミンの総モル数を基準にし、非熱可塑性ポリイミドで用いられている酸二無水物及びジアミンと同じものを使用している、熱可塑性ポリイミドで用いられる酸二無水物及びジアミンの割合を算出する。算出する方法は、まず、熱可塑性ポリイミドで用いる酸二無水物及びジアミンの総モル数を算出する(総モル数)。次に、熱可塑性ポリイミドを構成する酸二無水物及びジアミンであって、非熱可塑性ポリイミドで用いる酸二無水物及びジアミンと同じ種類の酸二無水物及びジアミンの合計モル数を算出する(同種モル数)。最後に、(同種モル数)/(総モル数)で、熱可塑性ポリイミドで用いられる酸二無水物及びジアミンの総モルを基準にし、非熱可塑性ポリイミドで用いられている酸二無水物及びジアミンと同じ種類のものを使用している、熱可塑性ポリイミドで用いられる酸二無水物及びジアミンの割合を算出する。熱可塑性ポリイミドを構成する酸二無水物単量体とジアミン単量体の合計モル数の60%以上が、非熱可塑性ポリイミドを構成する酸二無水物単量体とジアミン単量体であるということは、熱可塑性ポリイミドを構成する酸二無水物単量体とジアミン単量体のそれぞれ少なくとも1種の単量体が非熱可塑性ポリイミドを構成する酸二無水物単量体とジアミン単量体と同じということである。上記比率は、70%以上が好ましく、80%以上がさらに好ましい。また、比率の上限は、熱可塑性ポリイミドの熱可塑性を発現させ、高いピール強度を実現させるため、99%以下が好ましく、98%以下がさらに好ましい。 In order to improve the integrity of the non-thermoplastic polyimide layer and the thermoplastic polyimide layer, 60% or more of the total number of moles of acid dianhydride monomer and diamine monomer constituting the thermoplastic polyimide is It is preferable that they are the acid dianhydride monomer and diamine monomer which comprise a plastic polyimide. A specific calculation method will be described. Used in thermoplastic polyimide, which uses the same acid dianhydride and diamine used in non-thermoplastic polyimide, based on the total number of moles of acid dianhydride and diamine used in thermoplastic polyimide The ratio of acid dianhydride and diamine is calculated. First, the total number of moles of acid dianhydride and diamine used in the thermoplastic polyimide is calculated (total number of moles). Next, the acid dianhydride and diamine constituting the thermoplastic polyimide, and the total number of moles of the acid dianhydride and diamine of the same type as the acid dianhydride and diamine used in the non-thermoplastic polyimide is calculated (same kind Moles). Finally, (same mole number) / (total mole number), based on the total moles of acid dianhydride and diamine used in thermoplastic polyimide, acid dianhydride and diamine used in non-thermoplastic polyimide The ratio of the acid dianhydride and diamine used in thermoplastic polyimide is calculated using the same type of More than 60% of the total number of moles of acid dianhydride monomer and diamine monomer constituting the thermoplastic polyimide is said to be acid dianhydride monomer and diamine monomer constituting the non-thermoplastic polyimide. This means that at least one monomer of an acid dianhydride monomer and a diamine monomer constituting the thermoplastic polyimide each constitutes a non-thermoplastic polyimide. Is the same. The ratio is preferably 70% or more, and more preferably 80% or more. In addition, the upper limit of the ratio is preferably 99% or less, and more preferably 98% or less, in order to develop the thermoplasticity of the thermoplastic polyimide and realize high peel strength.
特に、多層共押出で多層ポリイミドフィルムを製造する場合、高温加熱すると、非熱可塑性ポリイミド層から発生した溶剤や水等が熱可塑性ポリイミド層を通過する。しかし、非熱可塑性ポリイミド層から溶剤や水等の排出する速度が、溶剤や水等が熱可塑性ポリイミド層を通過する速度よりも極端に速い場合、非熱可塑性ポリイミド層と熱可塑性ポリイミド層の間に、溶剤、水等が溜まり、層の間で剥がれる又は白濁(白色化)することがあった。また、非熱可塑性ポリイミド層のイミド化速度が熱可塑性ポリイミド層よりも極端に速いと、非熱可塑性ポリイミド層と熱可塑性ポリイミド層の密着性が低下し、層の間で剥がれる又は白濁(白色化)することがあった。非熱可塑性ポリイミド層と熱可塑性ポリイミド層に用いる酸二無水物とジアミンが、同じものである割合が高いほど、熱可塑性ポリイミド層は、非熱可塑性ポリイミド層から排出された溶剤や水等が同程度に排出されやすく、また、同様の構造であるため、熱可塑性ポリイミド層と非熱可塑性ポリイミド層との密着性が向上する面で好ましい。 In particular, when a multilayer polyimide film is produced by multilayer coextrusion, when heated at a high temperature, the solvent, water, etc. generated from the non-thermoplastic polyimide layer pass through the thermoplastic polyimide layer. However, when the speed at which the solvent, water, etc. are discharged from the non-thermoplastic polyimide layer is extremely faster than the speed at which the solvent, water, etc. passes through the thermoplastic polyimide layer, the gap between the non-thermoplastic polyimide layer and the thermoplastic polyimide layer In addition, a solvent, water, and the like may accumulate, and may peel off or become cloudy (whiten) between layers. Also, if the imidization rate of the non-thermoplastic polyimide layer is extremely faster than that of the thermoplastic polyimide layer, the adhesion between the non-thermoplastic polyimide layer and the thermoplastic polyimide layer is reduced, and the layers are separated or become cloudy (whitened) ) The higher the ratio of the acid dianhydride and diamine used in the non-thermoplastic polyimide layer and the thermoplastic polyimide layer is, the higher the ratio of the solvent and water discharged from the non-thermoplastic polyimide layer is. Since it is easy to discharge | emit to the extent and it is the same structure, it is preferable at the surface which the adhesiveness of a thermoplastic polyimide layer and a non-thermoplastic polyimide layer improves.
また、多層ポリイミドフィルムの反りを抑制するため、非熱可塑性ポリイミド層の両面が熱可塑性ポリイミド層であることが好ましい。非熱可塑性ポリイミド層の片面のみ熱可塑性ポリイミド層を形成した場合、熱可塑性ポリイミド層のイミド化反応を進行させた場合、非対称構造となるため、フィルムが反ってしまうことがあった。非熱可塑性ポリイミド層の両面の熱可塑性ポリイミド層の厚みは、1〜15μmが好ましく、両面の厚みの差は、厚い熱可塑性ポリイミド層の厚みを基準にし、もう一方の厚みが40%以上、100%以下であれば、フィルム形状として問題は無い。 Moreover, in order to suppress the curvature of a multilayer polyimide film, it is preferable that both surfaces of a non-thermoplastic polyimide layer are thermoplastic polyimide layers. When a thermoplastic polyimide layer is formed on only one surface of the non-thermoplastic polyimide layer, when the imidization reaction of the thermoplastic polyimide layer is advanced, the film may be warped because of an asymmetric structure. The thickness of the thermoplastic polyimide layer on both sides of the non-thermoplastic polyimide layer is preferably 1 to 15 μm, and the difference in thickness on both sides is based on the thickness of the thick thermoplastic polyimide layer, and the other thickness is 40% or more, 100 If it is% or less, there is no problem as a film shape.
多層ポリイミドフィルムの非熱可塑性ポリイミド層と熱可塑性ポリイミド層の厚み比率は、多層ポリイミドフィルムの線膨張係数を制御する面で55/45〜95/5が好ましい。この比率は、非熱可塑性ポリイミド層と熱可塑性ポリイミド層が複数層になっても、それぞれの総厚みの比率であり、熱可塑性ポリイミド層の層数が多くなっても、非熱可塑性ポリイミド層の厚みを超えないことが好ましい。 The thickness ratio of the non-thermoplastic polyimide layer and the thermoplastic polyimide layer of the multilayer polyimide film is preferably 55/45 to 95/5 in terms of controlling the linear expansion coefficient of the multilayer polyimide film. This ratio is a ratio of the total thickness of each of the non-thermoplastic polyimide layer and the thermoplastic polyimide layer, and even if the number of the thermoplastic polyimide layers is increased, the non-thermoplastic polyimide layer It is preferable not to exceed the thickness.
本発明においてポリアミド酸を合成するための好ましい溶媒は、ポリアミド酸を溶解する溶媒であればいかなるものも用いることができるが、アミド系溶媒、すなわちN,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N−メチル−2−ピロリドンなどを例示することができる。中でも、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミドを特に好ましく用いることができる。 As the preferred solvent for synthesizing the polyamic acid in the present invention, any solvent can be used as long as it dissolves the polyamic acid, but amide solvents, that is, N, N-dimethylformamide, N, N-dimethylacetamide N-methyl-2-pyrrolidone and the like can be exemplified. Of these, N, N-dimethylformamide and N, N-dimethylacetamide can be particularly preferably used.
本発明において非熱可塑性ポリアミド酸の重合にはいかなるモノマーの添加方法を用いても良い。代表的な重合方法として、次のような方法が挙げられる。すなわち、
1)芳香族ジアミンを有機極性溶媒中に溶解し、これと実質的に等モルの芳香族テトラカルボン酸二無水物を反応させて重合する方法、
2)芳香族テトラカルボン酸二無水物とこれに対し過小モル量の芳香族ジアミン化合物とを有機極性溶媒中で反応させ、両末端に酸無水物基を有するプレポリマーを得る。続いて、全工程において芳香族テトラカルボン酸二無水物と芳香族ジアミン化合物が実質的に等モルとなるように芳香族ジアミン化合物を用いて重合させる方法、
3)芳香族テトラカルボン酸二無水物とこれに対し過剰モル量の芳香族ジアミン化合物とを有機極性溶媒中で反応させ、両末端にアミノ基を有するプレポリマーを得る。続いてここに芳香族ジアミン化合物を追加添加後、全工程において芳香族テトラカルボン酸二無水物と芳香族ジアミン化合物が実質的に等モルとなるように芳香族テトラカルボン酸二無水物を用いて重合する方法、
4)芳香族テトラカルボン酸二無水物を有機極性溶媒中に溶解および/または分散させた後、実質的に等モルとなるように芳香族ジアミン化合物を用いて重合させる方法、
5)実質的に等モルの芳香族テトラカルボン酸二無水物と芳香族ジアミンの混合物を有機極性溶媒中で反応させて重合する方法、
などのような方法である。これらの方法を単独で用いても良いし、部分的に組み合わせて用いることもできる。
In the present invention, any monomer addition method may be used for the polymerization of the non-thermoplastic polyamic acid. As typical polymerization methods, the following methods may be mentioned. That is,
1) A method in which an aromatic diamine is dissolved in an organic polar solvent, and this is reacted with a substantially equimolar aromatic tetracarboxylic dianhydride for polymerization.
2) An aromatic tetracarboxylic dianhydride is reacted with a small molar amount of an aromatic diamine compound in an organic polar solvent to obtain a prepolymer having acid anhydride groups at both ends. Subsequently, a method of polymerizing with an aromatic diamine compound so that the aromatic tetracarboxylic dianhydride and the aromatic diamine compound are substantially equimolar in all steps,
3) An aromatic tetracarboxylic dianhydride and an excess molar amount of the aromatic diamine compound are reacted in an organic polar solvent to obtain a prepolymer having amino groups at both ends. Subsequently, after adding an aromatic diamine compound here, using the aromatic tetracarboxylic dianhydride so that the aromatic tetracarboxylic dianhydride and the aromatic diamine compound are substantially equimolar in all steps. How to polymerize,
4) A method in which an aromatic tetracarboxylic dianhydride is dissolved and / or dispersed in an organic polar solvent and then polymerized using an aromatic diamine compound so as to be substantially equimolar,
5) A method of polymerizing by reacting a mixture of substantially equimolar aromatic tetracarboxylic dianhydride and aromatic diamine in an organic polar solvent,
And so on. These methods may be used singly or in combination.
中でも、非熱可塑性ポリアミド酸は、下記の工程(a)〜(c):
(a)芳香族酸二無水物と、これに対し過剰モル量の芳香族ジアミンとを有機極性溶媒中で反応させ、両末端にアミノ基を有するプレポリマーを得る、
(b)続いて、ここに芳香族ジアミンを追加添加する、
(c)更に、全工程における芳香族酸二無水物と芳香族ジアミンが実質的に等モルとなるように芳香族酸二無水物を添加して重合する、
を経ることによって得られることが好ましい。
Among these, non-thermoplastic polyamic acid is used in the following steps (a) to (c):
(A) reacting an aromatic dianhydride with an excess molar amount of aromatic diamine in an organic polar solvent to obtain a prepolymer having amino groups at both ends;
(B) Subsequently, an aromatic diamine is additionally added thereto.
(C) Furthermore, the aromatic acid dianhydride is added and polymerized so that the aromatic dianhydride and the aromatic diamine are substantially equimolar in all steps.
It is preferable to obtain by going through.
前記方法で得られたポリアミド酸が、イミド化され、多層ポリイミドフィルムが得られる。 The polyamic acid obtained by the above method is imidized to obtain a multilayer polyimide film.
熱可塑性ポリイミドの製造に用いる熱可塑性ポリアミド酸溶液の製造方法は、(a)芳香族酸二無水物と、これに対して過剰モル量の芳香族ジアミンとを有機極性中で反応させ、両末端にアミノ基を有するプレポリマーを得る工程、(b)続いて、全工程における芳香族酸二無水物と芳香族ジアミンの比が、決めた比になるように、芳香族酸二無水物を添加して重合することが好ましい。(b)で、芳香族酸二無水物を添加する方法として、粉末を投入する方法、予め酸二無水物を有機極性溶媒に溶解した酸溶液を投入する方法等があるが、反応が均一に進行しやすい面で、酸溶液を投入する方法が好ましい。 A method for producing a thermoplastic polyamic acid solution used for producing a thermoplastic polyimide comprises: (a) reacting an aromatic acid dianhydride with an excess molar amount of an aromatic diamine in an organic polarity to both ends, (B) Subsequently, the aromatic acid dianhydride is added so that the ratio of the aromatic dianhydride to the aromatic diamine in all the steps becomes a predetermined ratio. It is preferable to perform polymerization. In (b), there are a method of adding an aromatic acid dianhydride, a method of adding a powder, a method of adding an acid solution in which an acid dianhydride is dissolved in an organic polar solvent in advance, and the reaction is uniform. In view of easy progress, a method of adding an acid solution is preferable.
熱可塑性ポリイミドの製造に用いる熱可塑性ポリアミド酸溶液は、複数のポリアミド酸溶液を混合して製造することができるが、オリゴマー成分を単離して、再度溶液にする工程を含むと、生産性の面で好ましくない。 The thermoplastic polyamic acid solution used for the production of the thermoplastic polyimide can be produced by mixing a plurality of polyamic acid solutions. However, if a process of isolating the oligomer component and making it into a solution again is included, the productivity side It is not preferable.
非熱可塑性ポリアミド酸および熱可塑性ポリアミド酸の重合時の固形成分濃度は、10〜30重量%であることが好ましい。固形成分濃度は、重合速度、重合粘度で決めることができる。重合粘度は、熱可塑性ポリイミドのポリアミド酸溶液を、支持体フィルムに塗工する場合、又は非熱可塑性ポリイミドと共押出する場合に合わせて設定することができるが、塗工する場合、例えば、固形成分濃度14重量%において重合粘度は100poise以下であることが好ましい。また、共押出する場合、例えば、固形成分濃度14重量%において重合粘度が100poise〜1200poiseであることが好ましい。前記で説明した芳香族酸二無水物と芳香族ジアミンは、多層ポリイミドフィルムの特性及び生産性を考慮し、順番を変更して用いることができる。 The solid component concentration during polymerization of the non-thermoplastic polyamic acid and the thermoplastic polyamic acid is preferably 10 to 30% by weight. The solid component concentration can be determined by the polymerization rate and the polymerization viscosity. The polymerization viscosity can be set according to the case where the polyamic acid solution of thermoplastic polyimide is applied to the support film, or when it is coextruded with non-thermoplastic polyimide. The polymerization viscosity is preferably 100 poise or less at a component concentration of 14% by weight. In the case of coextrusion, for example, the polymerization viscosity is preferably 100 poise to 1200 poise at a solid component concentration of 14% by weight. The aromatic dianhydride and aromatic diamine described above can be used by changing the order in consideration of the properties and productivity of the multilayer polyimide film.
また、非熱可塑性ポリアミド酸および熱可塑性ポリアミド酸には、摺動性、熱伝導性、導電性、耐コロナ性等のフィルムの諸特性を改善する目的でフィラーを添加することもできる。フィラーとしては特に制限されないが、好ましい例としてはシリカ、酸化チタン、アルミナ、窒化珪素、窒化ホウ素、リン酸水素カルシウム、リン酸カルシウム、雲母などが挙げられる。ただし、多層ポリイミドフィルムの製造方法として、(1)予め製造しておいた非熱可塑性ポリイミドフィルムに、熱可塑性ポリアミド酸溶液を塗布・乾燥して多層ポリイミドフィルムを製造する方法を得る場合、非熱可塑性ポリイミドフィルムおよび多層ポリイミドフィルムの諸物性を改善する目的で、非熱可塑性ポリアミド酸および熱可塑性ポリアミド酸にフィラーを添加することが好ましく、(2)多層共押出により、多層ポリイミドフィルムを得る場合、多層ポリイミドフィルムの諸物性を改善する目的で、熱可塑性ポリアミド酸のみにフィラーを添加することが工程を簡便にできる点で好ましい。 In addition, a filler can be added to the non-thermoplastic polyamic acid and the thermoplastic polyamic acid for the purpose of improving various characteristics of the film such as slidability, thermal conductivity, conductivity, and corona resistance. The filler is not particularly limited, and preferred examples include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica and the like. However, as a method for producing a multilayer polyimide film, (1) in the case of obtaining a method for producing a multilayer polyimide film by applying and drying a thermoplastic polyamic acid solution on a previously produced non-thermoplastic polyimide film, For the purpose of improving various physical properties of the plastic polyimide film and the multilayer polyimide film, it is preferable to add a filler to the non-thermoplastic polyamic acid and the thermoplastic polyamic acid. (2) When obtaining a multilayer polyimide film by multilayer coextrusion, For the purpose of improving various physical properties of the multilayer polyimide film, it is preferable that a filler is added only to the thermoplastic polyamic acid because the process can be simplified.
フィラーの粒子径は改質すべきフィルム特性と添加するフィラーの種類によって決定されるため、特に限定されるものではないが、フィルムの摺動性改善のために添加する場合、粒子径は0.1〜10μm、好ましくは0.1〜5μmである。粒子径がこの範囲を下回ると摺動性改善の効果が発現しにくく、この範囲を上回ると高精細な配線パターンを作成し難くなる傾向にある。またさらにこの場合、フィラーの分散状態も重要であり、20μm以上のフィラーの凝集物が50個/m2以下、好ましくは40個/m2以下にするのが好ましい。20μm以上のフィラー凝集物がこの範囲よりも多いと、高精細配線パターンを作成したときにフレキシブルプリント基板そのものの絶縁信頼性を落とす傾向にある。 The particle size of the filler is not particularly limited because it is determined depending on the film characteristics to be modified and the type of filler to be added, but when added for improving the slidability of the film, the particle size is 0.1. Is 10 μm, preferably 0.1 to 5 μm. If the particle diameter is below this range, the effect of improving the slidability is hardly exhibited, and if it exceeds this range, it tends to be difficult to produce a high-definition wiring pattern. Further, in this case, the dispersion state of the filler is also important, and it is preferable that the aggregate of fillers of 20 μm or more is 50 pieces / m 2 or less, preferably 40 pieces / m 2 or less. When there are more filler aggregates of 20 μm or more than this range, the insulation reliability of the flexible printed circuit board tends to be lowered when a high-definition wiring pattern is formed.
フィラーの添加は、例えば、
(1)重合前または途中に重合反応液に添加する方法
(2)重合完了後、3本ロールなどを用いてフィラーを混錬する方法
(3)フィラーを含む分散液を用意し、これをポリアミド酸有機溶媒溶液に混合する方法
(4)ビーズミル等により分散する方法
などいかなる方法を用いてもよいが、フィラーを含む分散液をポリアミド酸溶液に混合する方法、特に製膜直前に混合する方法が、製造ラインのフィラーによる汚染が最も少なくてすむため、好ましい。
Addition of the filler is, for example,
(1) A method of adding to a polymerization reaction solution before or during polymerization (2) A method of kneading fillers using three rolls after the completion of polymerization (3) A dispersion containing fillers is prepared, and this is added to polyamide Method of mixing with acid organic solvent solution (4) Any method such as a method of dispersing by bead mill or the like may be used, but a method of mixing a dispersion containing filler with a polyamic acid solution, particularly a method of mixing just before film formation It is preferable because the contamination by the filler in the production line is minimized.
フィラーを含む分散液を用意する場合、ポリアミド酸の重合溶媒と同じ溶媒を用いるのが好ましい。また、フィラーを良好に分散させ、また分散状態を安定化させるために、分散剤、増粘剤等をフィルム物性に影響を及ぼさない範囲内で用いることもできる。 When preparing a dispersion containing a filler, it is preferable to use the same solvent as the polymerization solvent for the polyamic acid. Moreover, in order to disperse | distribute a filler favorably and stabilize a dispersion state, a dispersing agent, a thickener, etc. can also be used in the range which does not affect a film physical property.
ポリイミドは、ポリイミドの前駆体、即ちポリアミド酸からの脱水転化反応により得られ、当該転化反応を行う方法としては、熱によってのみ行う熱キュア法と、化学脱水剤を使用する化学キュア法の2法が最も広く知られている。しかしながら、生産性に優れていることから、化学キュア法の採用がより好ましい。また、熱キュア法と化学キュア法共に、イミド化触媒を用いることがイミド化反応を早く進行させる面で好ましい。 Polyimide is obtained by a dehydration conversion reaction from a polyimide precursor, that is, a polyamic acid. As a method for performing the conversion reaction, there are two methods of a thermal curing method using only heat and a chemical curing method using a chemical dehydrating agent. Is the most widely known. However, since it is excellent in productivity, it is more preferable to employ a chemical curing method. Moreover, it is preferable to use an imidization catalyst in both the thermal curing method and the chemical curing method in terms of advancing the imidization reaction quickly.
化学脱水剤とは、ポリアミド酸に対する脱水閉環剤であり、その主成分として、脂肪族酸無水物、芳香族酸無水物、N,N′−ジアルキルカルボジイミド、低級脂肪族ハロゲン化物、ハロゲン化低級脂肪族酸無水物、アリールスルホン酸ジハロゲン化物、チオニルハロゲン化物またはそれら2種以上の混合物を好ましく用いることができる。その中でも特に、脂肪族酸無水物及び芳香族酸無水物が良好に作用する。また、イミド化触媒とはポリアミド酸に対する脱水閉環作用を促進する効果を有する成分であるが、例えば、脂肪族3級アミン、芳香族3級アミン、複素環式3級アミンを用いることができる。そのうち、イミダゾ−ル、ベンズイミダゾ−ル、イソキノリン、キノリン、またはβ−ピコリンなどの含窒素複素環化合物であることが好ましい。さらに、化学脱水剤及びイミド化触媒からなる溶液中に、有機極性溶媒を導入することも適宜選択されうる。 The chemical dehydrating agent is a dehydrating ring-closing agent for polyamic acid, and the main components thereof are aliphatic acid anhydride, aromatic acid anhydride, N, N'-dialkylcarbodiimide, lower aliphatic halide, halogenated lower fat. An aromatic acid anhydride, an aryl sulfonic acid dihalide, a thionyl halide, or a mixture of two or more thereof can be preferably used. Of these, aliphatic acid anhydrides and aromatic acid anhydrides work particularly well. The imidation catalyst is a component having an effect of promoting the dehydration ring closure action on the polyamic acid. For example, an aliphatic tertiary amine, an aromatic tertiary amine, or a heterocyclic tertiary amine can be used. Of these, nitrogen-containing heterocyclic compounds such as imidazole, benzimidazole, isoquinoline, quinoline, or β-picoline are preferred. Furthermore, introduction of an organic polar solvent into a solution composed of a chemical dehydrating agent and an imidization catalyst can be appropriately selected.
多層ポリイミドフィルムの製造方法として、(1)予め製造しておいた非熱可塑性ポリイミドフィルムに、熱可塑性ポリアミド酸溶液を塗布・乾燥した後、150℃以上の高温で加熱して多層ポリイミドフィルムを製造する方法がある。非熱可塑性ポリイミドフィルムを製造する際、熱キュア法、化学キュア法どちらを選択して良いが、生産性の面で化学キュア法を選択する方が良い。予め製造した非熱可塑性ポリイミドフィルムの表面に、熱可塑性ポリアミド酸溶液を塗布・乾燥した後、150℃以上の高温で加熱して多層ポリイミドフィルムを製造する際、熱キュア法、化学キュア法どちらを選択して良いが、生産性の面で化学キュア法を選択する方が良く、設備投資の面で熱キュア法を選択する方が良い。 As a method for producing a multilayer polyimide film, (1) a thermoplastic polyimide acid solution is applied to a previously produced non-thermoplastic polyimide film, dried, and then heated at a high temperature of 150 ° C. or higher to produce a multilayer polyimide film. There is a way to do it. When producing a non-thermoplastic polyimide film, either a thermal cure method or a chemical cure method may be selected, but it is better to select a chemical cure method in terms of productivity. After applying and drying a thermoplastic polyamic acid solution on the surface of a pre-manufactured non-thermoplastic polyimide film, when heating it at a high temperature of 150 ° C or higher to produce a multilayer polyimide film, either thermal curing method or chemical curing method is used. It is better to select the chemical curing method in terms of productivity, and it is better to select the thermal curing method in terms of capital investment.
また、多層ポリイミドフィルムの製造方法として、(2)多層共押出により、同時に多層ポリアミド酸をドラム、エンドレスベルト等の支持体に塗布・乾燥した後、ゲルフィルムを支持体から剥がし、150℃以上の高温で加熱して多層ポリイミドフィルムを製造する方法がある。非熱可塑性ポリイミド層のポリアミド酸に、イミド化触媒及び/または化学脱水剤を用いても良いが、生産性の面でイミド化触媒及び化学脱水剤を用いる方が良い。また、熱可塑性ポリイミド層のポリアミド酸に、イミド化触媒及び/または化学脱水剤を用いても良い。ただし、コストの面を考慮すると、非熱可塑性ポリイミド層のみに、イミド化触媒及び化学脱水剤を投入し、イミド化させることが好ましい。 In addition, as a method for producing a multilayer polyimide film, (2) after multilayer polyamic acid is simultaneously applied and dried on a support such as a drum or an endless belt by multilayer coextrusion, the gel film is peeled off from the support, There is a method for producing a multilayer polyimide film by heating at a high temperature. Although an imidization catalyst and / or a chemical dehydrating agent may be used for the polyamic acid of the non-thermoplastic polyimide layer, it is better to use an imidization catalyst and a chemical dehydrating agent in terms of productivity. Moreover, you may use an imidation catalyst and / or a chemical dehydrating agent for the polyamic acid of a thermoplastic polyimide layer. However, in view of cost, it is preferable to imidize the non-thermoplastic polyimide layer by introducing an imidization catalyst and a chemical dehydrating agent only.
前記の通り、イミド化法として、熱キュア法と化学キュア法があるが、本発明では、熱キュア法は化学脱水剤を用いず、化学キュア法は化学脱水剤を用いるイミド化法である。双方、イミド化触媒を用い、イミド化反応を促進することができる。 As described above, the imidization method includes a thermal cure method and a chemical cure method. In the present invention, the thermal cure method does not use a chemical dehydrating agent, and the chemical cure method is an imidization method using a chemical dehydrating agent. Both can use an imidization catalyst to promote the imidization reaction.
化学脱水剤の含有量は、化学脱水剤及びイミド化触媒を含有せしめる溶液に含まれるポリアミド酸中のアミド酸ユニット1モルに対して、0.5〜4.0モルが好ましく、1.0〜3.0モル、さらには、支持体から剥がす際のゲルフィルムの強度と支持体からの剥れ性のバランスを取れる点で1.2〜2.5モルが特に好ましい。 The content of the chemical dehydrating agent is preferably 0.5 to 4.0 mol with respect to 1 mol of the amic acid unit in the polyamic acid contained in the solution containing the chemical dehydrating agent and the imidization catalyst, and 1.0 to 3.0 mol, and more preferably 1.2 to 2.5 mol in terms of balancing the strength of the gel film when peeled from the support and the peelability from the support.
同様の理由で、イミド化触媒の含有量は、化学脱水剤及びイミド化触媒を含有せしめる溶液に含まれるポリアミド酸中のアミド酸ユニット1モルに対して、0.05〜2.0モルが好ましく、0.05〜1.0モル、さらには0.3〜0.8モルが特に好ましい
イミド化時間に関しては、実質的にイミド化および乾燥が完結するに十分な時間を取ればよく、一義的に限定されるものではないが、一般的には、化学キュア法を採用する場合、1〜600秒程度、熱キュア法を採用する場合、60〜1800秒の範囲で適宜設定される。
For the same reason, the content of the imidization catalyst is preferably 0.05 to 2.0 mol with respect to 1 mol of the amic acid unit in the polyamic acid contained in the solution containing the chemical dehydrating agent and the imidization catalyst. 0.05 to 1.0 mol, particularly 0.3 to 0.8 mol is particularly preferable. With regard to the imidization time, it is sufficient to take a sufficient time to complete imidization and drying. In general, the time is set appropriately in the range of about 1 to 600 seconds when the chemical cure method is employed, and 60 to 1800 seconds when the thermal cure method is employed.
イミド化する際にかける張力としては、1kg/m〜15kg/mの範囲内とすることが好ましく、5kg/m〜10kg/mの範囲内とすることが特に好ましい。張力が上記範囲より小さい場合、フィルム搬送時にたるみや蛇行が生じ、巻取り時にシワが入ったり、均一に巻き取れない等の問題が生じる可能性がある。逆に上記範囲よりも大きい場合、強い張力がかかった状態で高温加熱されるため、金属箔張積層板用基材を用いて作製される金属箔張積層板の寸法特性が悪化することがある。 The tension applied during imidization is preferably in the range of 1 kg / m to 15 kg / m, and particularly preferably in the range of 5 kg / m to 10 kg / m. If the tension is smaller than the above range, sagging or meandering may occur during film conveyance, which may cause problems such as wrinkling during winding or inability to uniformly wind. On the other hand, when it is larger than the above range, the metal foil-clad laminate produced using the metal foil-clad laminate substrate may deteriorate in dimensional characteristics because it is heated at a high temperature with a strong tension applied. .
以下に、多層共押出により多層ポリイミドフィルムの製造方法について述べる。多層共押出とは、ポリアミド酸溶液を二層以上の多層ダイへ同時に供給し、前記ダイの吐出口から少なくとも二層以上の薄膜状体として支持体上に押出す工程を含むフィルムの製造方法である。多層ポリイミドフィルムは加熱処理時の反りを軽減させるため、三層構造が好ましい。 Below, the manufacturing method of a multilayer polyimide film by multilayer coextrusion is described. Multi-layer coextrusion is a method for producing a film including a step of simultaneously feeding a polyamic acid solution to two or more multilayer dies and extruding the thin film-like body of at least two layers from a discharge port of the die onto a support. is there. The multilayer polyimide film preferably has a three-layer structure in order to reduce warpage during heat treatment.
一般的に用いられる方法について説明すると、二層以上の多層ダイから押出された前記の溶液を、平滑な支持体上に連続的に押し出し、次いで、前記支持体上の多層の薄膜状体の溶媒の少なくとも一部を揮散せしめることで、自己支持性を有する多層膜を得る。支持体上の塗膜を最高温度が100〜200℃で加熱することが好ましい。 To describe a generally used method, the solution extruded from two or more multilayer dies is continuously extruded onto a smooth support, and then a multilayer thin film solvent on the support. A multilayer film having self-supporting properties is obtained by volatilizing at least a part of the film. It is preferable to heat the coating film on the support at a maximum temperature of 100 to 200 ° C.
さらに、当該多層膜を前記支持体上から剥離し、最後に、当該多層膜を高温(250−600℃)で充分に加熱処理することによって、溶媒を実質的に除去すると共にイミド化を進行させることで多層ポリイミドフィルムを得ることができる。支持体から引き剥がした多層膜は、ポリアミド酸からポリイミドへの硬化の中間段階にあり、自己支持性を有し、式(1)
(A−B)×100/B・・・・(1)
式(1)中
A,Bは以下のものを表す。
A:多層膜の重量
B:多層膜を450℃で20分間加熱した後の重量
から算出される揮発分含量は5〜200重量%の範囲、好ましくは10〜100重量%、より好ましくは30〜80重量%の範囲にある。この範囲のフィルムを用いることが好適であり、この範囲内では、焼成過程でフィルム破断、乾燥ムラによるフィルムの色調ムラ、特性ばらつき等の不具合が起こりにくい。また、接着層の熔融流動性を改善する目的で、意図的にイミド化率を低くする及び/又は溶媒を残留させてもよい。
Further, the multilayer film is peeled from the support, and finally the multilayer film is sufficiently heated at a high temperature (250-600 ° C.) to substantially remove the solvent and advance imidization. Thus, a multilayer polyimide film can be obtained. The multilayer film peeled off from the support is in the intermediate stage of curing from polyamic acid to polyimide and has a self-supporting property.
(AB) × 100 / B (1)
In formula (1), A and B represent the following.
A: Weight of the multilayer film B: The volatile content calculated from the weight after heating the multilayer film at 450 ° C. for 20 minutes is in the range of 5 to 200% by weight, preferably 10 to 100% by weight, more preferably 30 to 30%. It is in the range of 80% by weight. It is preferable to use a film in this range. Within this range, problems such as film breakage, uneven color tone of the film due to uneven drying, and characteristic variations are less likely to occur during the baking process. Further, for the purpose of improving the melt fluidity of the adhesive layer, the imidization rate may be intentionally lowered and / or the solvent may be left.
本発明において、支持体とは、多層ダイから押出された多層液膜を、その上に流延するためのもので、当該支持体上で多層液膜を加熱乾燥せしめ、自己支持性を付与するものである。該支持体の形状は特に問わないが、接着フィルムの生産性を考慮すると、ドラム状若しくはベルト状であることが好ましい。また、該支持体の材質も特に問わず、金属、プラスチック、ガラス、磁器などが挙げられ、好ましくは金属であり、更に好ましくは耐腐食性に優れるSUS材である。また、Cr、Ni、Snなどの金属メッキをしても良い。 In the present invention, a support is for casting a multilayer liquid film extruded from a multilayer die onto the support. The multilayer liquid film is heated and dried on the support to provide self-supporting properties. Is. The shape of the support is not particularly limited, but in consideration of the productivity of the adhesive film, it is preferably a drum shape or a belt shape. The material of the support is not particularly limited, and examples thereof include metal, plastic, glass, porcelain, etc., preferably metal, and more preferably SUS material having excellent corrosion resistance. Further, metal plating such as Cr, Ni, Sn may be performed.
上記の多層ダイとしては各種構造のものが使用できるが、例えば複数層用フィルム作成用のTダイス等が使用できる。また、従来既知のあらゆる構造のものを好適に使用可能であるが、特に好適に使用可能なものとして、フィードブロックTダイやマルチマニホールドTダイが例示される。 As the above-mentioned multilayer die, those having various structures can be used. For example, a T die for forming a multilayer film can be used. In addition, any conventionally known structure can be suitably used, and feed block T dies and multi-manifold T dies are exemplified as particularly suitable ones.
本発明にかかるフレキシブル金属箔張積層板の製造方法について説明すると、以下の通りであるが、これに限定されるものでない。 The production method of the flexible metal foil-clad laminate according to the present invention will be described as follows, but is not limited thereto.
本発明にかかるフレキシブル金属箔張積層板の製造方法は、上記多層ポリイミドフィルムに金属箔を貼り合わせる工程を含むことが好ましい。フレキシブル金属積層板で用いられる銅箔は、厚みは1〜25μmを用いることができ、圧延銅箔、電解銅箔のどちらを用いても良い。 It is preferable that the manufacturing method of the flexible metal foil clad laminated board concerning this invention includes the process of bonding metal foil to the said multilayer polyimide film. The copper foil used in the flexible metal laminate may have a thickness of 1 to 25 μm, and either a rolled copper foil or an electrolytic copper foil may be used.
多層ポリイミドフィルムと金属箔の貼り合わせ方法としては、例えば、一対以上の金属ロールを有する熱ロールラミネート装置、またはダブルベルトプレス(DBP)による連続処理を用いることができる。中でも、装置構成が単純であり保守コストの面で有利であるという点から、一対以上の金属ロールを有する熱ロールラミネート装置を用いることが好ましい。 As a method for laminating the multilayer polyimide film and the metal foil, for example, a hot roll laminating apparatus having a pair of metal rolls or a continuous process using a double belt press (DBP) can be used. Among these, it is preferable to use a hot roll laminating apparatus having a pair of metal rolls because the apparatus configuration is simple and advantageous in terms of maintenance cost.
ここでいう「一対以上の金属ロールを有する熱ロールラミネート装置」とは、材料を加熱加圧するための金属ロールを有している装置であればよく、その具体的な装置構成は特に限定されるものではない。 The “heat roll laminating apparatus having a pair of metal rolls” herein may be an apparatus having a metal roll for heating and pressurizing a material, and the specific apparatus configuration is particularly limited. It is not a thing.
なお、多層ポリイミドフィルムと金属箔とを熱ラミネートにより貼り合わせる工程を、以下、「熱ラミネート工程」と称する。 The process of bonding the multilayer polyimide film and the metal foil together by thermal lamination is hereinafter referred to as “thermal lamination process”.
上記熱ラミネートを実施する手段(以下、「熱ラミネート手段」ともいう)の具体的な構成は特に限定されるものではないが、得られる積層板の外観を良好なものとするために、加圧面と金属箔との間に保護材料を配置することが好ましい。 The specific configuration of the means for carrying out the thermal laminating (hereinafter also referred to as “thermal laminating means”) is not particularly limited, but in order to improve the appearance of the resulting laminate, the pressure surface It is preferable to arrange a protective material between the metal foil and the metal foil.
上記保護材料としては、熱ラミネート工程の加熱温度に耐えうる材料、例えば、非熱可塑性ポリイミドフィルム等の耐熱性プラスチック、銅箔、アルミニウム箔、SUS箔等の金属箔等が挙げられる。中でも、耐熱性、再使用性等のバランスが優れる点から、非熱可塑性ポリイミドフィルム、もしくは、ガラス転移温度(Tg)がラミネート温度よりも50℃以上高い熱可塑性ポリイミドからなるフィルムが好ましく用いられる。熱可塑性ポリイミドを使用する場合、上記の条件を満たすものを選択することによって、熱可塑性ポリイミドのロールへの付着を防ぐことができる。 Examples of the protective material include materials that can withstand the heating temperature in the heat laminating process, for example, heat-resistant plastics such as non-thermoplastic polyimide films, metal foils such as copper foil, aluminum foil, and SUS foil. Among these, a non-thermoplastic polyimide film or a film made of a thermoplastic polyimide having a glass transition temperature (Tg) higher by 50 ° C. or more than the laminating temperature is preferably used from the viewpoint of excellent balance of heat resistance, reusability and the like. When using thermoplastic polyimide, adhesion of the thermoplastic polyimide to the roll can be prevented by selecting one that satisfies the above conditions.
また、保護材料の厚みが薄いと、ラミネート時の緩衝並びに保護の役目を十分に果たさなくなるため、非熱可塑性ポリイミドフィルムの厚みは75μm以上であることが好ましい。 In addition, if the thickness of the protective material is thin, the role of buffering and protection at the time of lamination will not be sufficiently fulfilled, so the thickness of the non-thermoplastic polyimide film is preferably 75 μm or more.
また、この保護材料は、必ずしも1層である必要はなく、異なる特性を有する2層以上の多層構造でもよい。 Further, the protective material does not necessarily have to be a single layer, and may have a multilayer structure of two or more layers having different characteristics.
また、ラミネート温度が高温の場合、保護材料をそのままラミネートに用いると、急激な熱膨張により、得られるフレキシブル金属箔張積層板の外観や寸法安定性が充分でない場合がある。従って、ラミネート前に、保護材料に予備加熱を施すことが好ましい。このように、保護材料の予備加熱を行った後、ラミネートする場合、保護材料の熱膨張が終了しているため、フレキシブル金属箔張積層板の外観や寸法特性に影響を与えることが抑制される。 When the laminate temperature is high, if the protective material is used as it is for the laminate, the appearance and dimensional stability of the resulting flexible metal foil-clad laminate may not be sufficient due to rapid thermal expansion. Therefore, it is preferable to preheat the protective material before lamination. As described above, when the protective material is preheated and then laminated, since the thermal expansion of the protective material is finished, the appearance and dimensional characteristics of the flexible metal foil-clad laminate are suppressed from being affected. .
予備加熱の手段としては、保護材料を加熱ロールに抱かせるなどして接触させる方法が挙げられる。接触時間としては、1秒間以上が好ましく、3秒間以上がさらに好ましい。接触時間が上記よりも短い場合、保護材料の熱膨張が終了しないままラミネートが行われるため、ラミネート時に保護材料の急激な熱膨張が起こり、得られるフレキシブル金属箔張積層板の外観や寸法特性が悪化することがある。保護材料を加熱ロールに抱かせる距離については、特に限定されず、加熱ロールの径と上記接触時間から適宜調整すればよい。 Examples of the preheating means include a method of bringing a protective material into contact with a heating roll. The contact time is preferably 1 second or longer, and more preferably 3 seconds or longer. When the contact time is shorter than the above, since the lamination is performed without completing the thermal expansion of the protective material, the thermal expansion of the protective material occurs during the lamination, and the appearance and dimensional characteristics of the resulting flexible metal foil-clad laminate are May get worse. The distance at which the protective material is held on the heating roll is not particularly limited, and may be appropriately adjusted from the diameter of the heating roll and the contact time.
上記熱ラミネート手段における被積層材料の加熱方式は、特に限定されるものではなく、例えば、熱循環方式、熱風加熱方式、誘導加熱方式等、所定の温度で加熱しうる従来公知の方式を採用した加熱手段を用いることができる。同様に、上記熱ラミネート手段における被積層材料の加圧方式も、特に限定されるものではなく、例えば、油圧方式、空気圧方式、ギャップ間圧力方式等、所定の圧力を加えることができる従来公知の方式を採用した加圧手段を用いることができる。 The heating method of the material to be laminated in the heat laminating means is not particularly limited, and a conventionally known method capable of heating at a predetermined temperature, such as a heat circulation method, a hot air heating method, an induction heating method, etc., is adopted. A heating means can be used. Similarly, the method for pressurizing the material to be laminated in the thermal laminating means is not particularly limited, and is a conventionally known method capable of applying a predetermined pressure such as a hydraulic method, a pneumatic method, a gap pressure method, or the like. A pressurizing means adopting the method can be used.
上記熱ラミネート工程における加熱温度、すなわちラミネート温度は、多層ポリイミドフィルムの熱可塑性ポリイミド層に含まれる熱可塑性ポリイミドのガラス転移温度(Tg)+50℃以上の温度であることが好ましく、多層ポリイミドフィルム熱可塑性ポリイミド層に含まれる熱可塑性ポリイミドのTg+100℃以上がより好ましい。Tg+50℃以上の温度であれば、多層ポリイミドフィルムと金属箔とを良好に熱ラミネートすることができる。また、Tg+100℃以上であれば、ラミネート速度を上昇させてその生産性をより向上させることができる。 The heating temperature in the thermal laminating step, that is, the laminating temperature, is preferably a glass transition temperature (Tg) of the thermoplastic polyimide contained in the thermoplastic polyimide layer of the multilayer polyimide film + 50 ° C. or higher, and the multilayer polyimide film thermoplasticity Tg + 100 ° C. or higher of the thermoplastic polyimide contained in the polyimide layer is more preferable. If it is Tg + 50 degreeC or more temperature, a multilayer polyimide film and metal foil can be heat-laminated favorably. Moreover, if it is Tg + 100 degreeC or more, the lamination speed | rate can be raised and the productivity can be improved more.
特に、本発明の多層ポリイミドフィルムのコアとして使用しているポリイミドフィルムは、ラミネートを行った場合に、熱応力の緩和が有効に作用するように設計することが好ましく、これにより、寸法安定性に優れたフレキシブル金属箔張積層板が、生産性良く得られる。 In particular, it is preferable that the polyimide film used as the core of the multilayer polyimide film of the present invention is designed so that relaxation of thermal stress acts effectively when laminating, thereby improving dimensional stability. An excellent flexible metal foil-clad laminate can be obtained with high productivity.
加熱ロールへの接触時間は、0.1秒間以上が好ましく、より好ましくは0.2秒間以上、0.5秒間以上が特に好ましい。接触時間が上記範囲より短い場合、緩和効果が十分に発生しない場合がある。接触時間の上限は、5秒間以下が好ましい。5秒間よりも長く接触させても緩和効果が、より大きくなるわけではなく、ラミネート速度の低下やラインの取り回しに制約が生じるため好ましくない。 The contact time with the heating roll is preferably 0.1 seconds or more, more preferably 0.2 seconds or more, and particularly preferably 0.5 seconds or more. When the contact time is shorter than the above range, the relaxation effect may not be sufficiently generated. The upper limit of the contact time is preferably 5 seconds or less. Even if the contact is made for longer than 5 seconds, the relaxation effect is not increased, and it is not preferable because a decrease in the laminating speed and restrictions on the line handling occur.
また、ラミネート後に加熱ロールに接触させて徐冷を行ったとしても、依然としてフレキシブル金属箔張積層板と室温との差は大きく、また、残留歪みを緩和しきれていない場合もある。そのため、加熱ロールに接触させて徐冷した後のフレキシブル金属箔張積層板は、保護材料を配したままの状態で、後加熱工程を行うことが好ましい。この際の張力は、1〜10N/cmの範囲とすることが好ましい。また、後加熱の雰囲気温度は(徐冷した後のフレキシブル金属箔張積層板の温度−200℃)〜(ラミネート温度+100℃)の範囲とすることが好ましい。 Moreover, even if it is brought into contact with a heating roll after lamination and subjected to slow cooling, the difference between the flexible metal foil-clad laminate and room temperature is still large, and the residual strain may not be alleviated. Therefore, it is preferable that the flexible metal foil-clad laminate after being brought into contact with the heating roll and gradually cooled is subjected to a post-heating step with the protective material still disposed. The tension at this time is preferably in the range of 1 to 10 N / cm. Moreover, it is preferable to make the atmospheric temperature of post-heating into the range of (The temperature of the flexible metal foil tension laminated board after slow cooling -200 degreeC)-(Lamination temperature +100 degreeC).
ここでいう「雰囲気温度」とは、フレキシブル金属箔張積層板の両面に密着させている保護材料の外表面温度をいう。実際のフレキシブル金属箔張積層板の温度は、保護材料の厚みによって多少変化するが、保護材料表面の温度を上記範囲内にすれば、後加熱の効果を発現させることが可能である。保護材料の外表面温度測定は、熱電対や温度計などを用いて行うことができる。 The “atmosphere temperature” here refers to the outer surface temperature of the protective material in close contact with both surfaces of the flexible metal foil-clad laminate. The actual temperature of the flexible metal foil-clad laminate varies somewhat depending on the thickness of the protective material, but if the temperature of the surface of the protective material is within the above range, the effect of post-heating can be exhibited. The outer surface temperature of the protective material can be measured using a thermocouple or a thermometer.
上記熱ラミネート工程におけるラミネート速度は、0.5m/分以上であることが好ましく、1.0m/分以上であることがより好ましい。0.5m/分以上であれば、十分な熱ラミネートが可能になり、さらに、1.0m/分以上であれば、生産性をより一層向上することができる。 The laminating speed in the thermal laminating step is preferably 0.5 m / min or more, and more preferably 1.0 m / min or more. If it is 0.5 m / min or more, sufficient thermal lamination is possible, and if it is 1.0 m / min or more, productivity can be further improved.
上記熱ラミネート工程における圧力、すなわちラミネート圧力は、高ければ高いほどラミネート温度を低く、かつラミネート速度を速くすることができる利点があるが、一般に、ラミネート圧力が高すぎると、得られる積層板の寸法変化が悪化する傾向がある。逆に、ラミネート圧力が低すぎると、得られる積層板の金属箔の接着強度が低くなる。そのため、ラミネート圧力は、49〜490N/cm(5〜50kgf/cm)の範囲内であることが好ましく、98〜294N/cm(10〜30kgf/cm)の範囲内であることがより好ましい。この範囲内であれば、ラミネート温度、ラミネート速度、およびラミネート圧力の三条件を良好なものにすることができ、生産性をより一層向上することができる。 The higher the pressure in the thermal laminating process, that is, the laminating pressure, there is an advantage that the laminating temperature can be lowered and the laminating speed can be increased. However, in general, when the laminating pressure is too high, the dimensions of the obtained laminate are obtained. Changes tend to get worse. On the other hand, when the lamination pressure is too low, the adhesive strength of the metal foil of the resulting laminate is reduced. Therefore, the laminating pressure is preferably in the range of 49 to 490 N / cm (5 to 50 kgf / cm), and more preferably in the range of 98 to 294 N / cm (10 to 30 kgf / cm). Within this range, the three conditions of laminating temperature, laminating speed, and laminating pressure can be improved, and productivity can be further improved.
上記ラミネート工程における接着フィルム張力は、0.01〜4N/cmの範囲内であることが好ましく、0.02〜2.5N/cmの範囲内であることがより好ましく、0.05〜1.5N/cmの範囲内であることが特に好ましい。張力が上記範囲を下回ると、ラミネートの搬送時に、たるみや蛇行が生じ、均一に加熱ロールに送り込まれないために、外観の良好なフレキシブル金属箔張積層板を得ることが困難となることがある。逆に、上記範囲を上回ると、接着層のTgと貯蔵弾性率の制御では緩和できないほど張力の影響が強くなり、寸法安定性が劣ることがある。 The adhesive film tension in the laminating step is preferably in the range of 0.01 to 4 N / cm, more preferably in the range of 0.02 to 2.5 N / cm, and 0.05 to 1. A range of 5 N / cm is particularly preferable. If the tension is below the above range, sagging or meandering occurs during the conveyance of the laminate, and it is difficult to obtain a flexible metal foil-clad laminate with good appearance because it is not uniformly fed into the heating roll. . On the other hand, if it exceeds the above range, the influence of tension becomes so strong that it cannot be relaxed by controlling the Tg and storage modulus of the adhesive layer, and the dimensional stability may be inferior.
本発明にかかるフレキシブル金属箔張積層板を得るためには、連続的に被積層材料を加熱しながら圧着する熱ラミネート装置を用いることが好ましい。さらに、この熱ラミネート装置では、熱ラミネート手段の前段に、被積層材料を繰り出す被積層材料繰出手段を設けてもよいし、熱ラミネート手段の後段に、被積層材料を巻き取る被積層材料巻取手段を設けてもよい。これらの手段を設けることで、上記熱ラミネート装置の生産性をより一層向上させることができる。 In order to obtain the flexible metal foil-clad laminate according to the present invention, it is preferable to use a thermal laminating apparatus that continuously press-bonds the material to be laminated while heating. Further, in this thermal laminating apparatus, a laminated material feeding means for feeding the laminated material may be provided before the thermal laminating means, or a laminated material winding for winding the laminated material is taken after the thermal laminating means. Means may be provided. By providing these means, the productivity of the thermal laminating apparatus can be further improved.
上記被積層材料繰出手段および被積層材料巻取手段の具体的な構成は特に限定されるものではなく、例えば、接着フィルムや金属箔、あるいは得られる積層板を巻き取ることのできる公知のロール状巻取機等を挙げることができる。 The specific configuration of the laminated material feeding means and the laminated material winding means is not particularly limited. For example, a known roll shape capable of winding an adhesive film, a metal foil, or a laminated sheet to be obtained. A winder etc. can be mentioned.
さらに、保護材料を巻き取ったり繰り出したりする保護材料巻取手段や保護材料繰出手段を設けると、より好ましい。これら保護材料巻取手段・保護材料繰出手段を備えていれば、熱ラミネート工程で、一度使用された保護材料を巻き取って繰り出し側に再度設置することで、保護材料を再使用することができる。 Furthermore, it is more preferable to provide a protective material winding means and a protective material feeding means for winding and feeding the protective material. If these protective material take-up means and protective material feeding means are provided, the protective material can be reused by winding the protective material once used in the thermal laminating step and installing it again on the pay-out side. .
また、保護材料を巻き取る際に、保護材料の両端部を揃えるために、端部位置検出手段および巻取位置修正手段を設けてもよい。これによって、精度よく保護材料の端部を揃えて巻き取ることができるので、再使用の効率を高めることができる。なお、これら保護材料巻取手段、保護材料繰出手段、端部位置検出手段および巻取位置修正手段の具体的な構成は特に限定されるものではなく、従来公知の各種装置を用いることができる。 Further, when winding up the protective material, end position detecting means and winding position correcting means may be provided in order to align both ends of the protective material. As a result, the end portions of the protective material can be aligned and wound with high accuracy, so that the efficiency of reuse can be increased. The specific configurations of the protective material winding means, the protective material feeding means, the end position detecting means, and the winding position correcting means are not particularly limited, and various conventionally known devices can be used.
本発明にかかるフレキシブル金属箔張積層板は、本発明の多層ポリイミドフィルムに金属箔を貼り合わせて得られるものであればよいが、フレキシブル金属箔張積層板の多層ポリイミドフィルムと金属箔の引き剥がし強度は、FPCで使用する際、銅箔が多層ポリイミドフィルムから剥がれない点で、10N/cm以上が好ましい。 The flexible metal foil-clad laminate according to the present invention may be obtained by laminating a metal foil to the multilayer polyimide film of the present invention. The strength is preferably 10 N / cm or more in that the copper foil does not peel from the multilayer polyimide film when used in FPC.
本発明にかかるフレキシブル金属箔張積層板の半田耐熱性は、常態測定では320℃以上が好ましく、330℃以上がさらに好ましく、340℃以上が特に好ましい。また、吸湿後測定では、280℃以上が好ましく、290℃以上がさらに好ましく、300℃以上が特に好ましい。 The solder heat resistance of the flexible metal foil-clad laminate according to the present invention is preferably 320 ° C. or higher, more preferably 330 ° C. or higher, and particularly preferably 340 ° C. or higher in the normal state measurement. Moreover, in the measurement after moisture absorption, 280 degreeC or more is preferable, 290 degreeC or more is more preferable, 300 degreeC or more is especially preferable.
以下、実施例により本発明を具体的に説明するが、本発明はこれら実施例のみに限定されるものではない。なお、合成例、実施例及び比較例における多層ポリイミドフィルムと金属箔の引き剥がし強度および半田耐熱性の評価法は次の通りである。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these Examples. In addition, the evaluation method of the peeling strength of a multilayer polyimide film and metal foil and solder heat resistance in a synthesis example, an Example, and a comparative example is as follows.
(金属箔張積層板の作製方法)
多層ポリイミドフィルムの両面に18μmの圧延銅箔(BHY−22B−T;日鉱金属製)、さらにその両側に保護材料(アピカル125NPI;カネカ製)を配して、熱ロールラミネート機を用いて、ラミネート温度380℃、ラミネート圧力294N/cm(30kgf/cm)、ラミネート速度1.0m/分の条件で連続的に熱ラミネートを行い、フレキシブル金属箔張積層板を作製した。
(Method for producing metal foil-clad laminate)
Laminated copper film with 18 μm rolled copper foil (BHY-22B-T; manufactured by Nikko Metal) on both sides of the multilayer polyimide film, and protective material (Apical 125 NPI; manufactured by Kaneka) on both sides. Thermal lamination was performed continuously under the conditions of a temperature of 380 ° C., a laminating pressure of 294 N / cm (30 kgf / cm), and a laminating speed of 1.0 m / min to produce a flexible metal foil-clad laminate.
(金属箔の引き剥がし強度)
JIS C6471の「6.5 引きはがし強さ」に従って、サンプルを作製し、5mm幅の金属箔部分を、180度の剥離角度、50mm/分の条件で剥離し、その荷重を測定した。
(Stripping strength of metal foil)
A sample was prepared according to “6.5 Peel Strength” of JIS C6471, and a 5 mm wide metal foil part was peeled off at a peeling angle of 180 degrees and 50 mm / min, and the load was measured.
(半田耐熱性評価)
IPC−TM−650 No.2.4.13に準拠して測定した。常態測定は、試験片を23℃/55%RHで24時間調整した後、250℃〜350℃を10℃刻みに加熱した半田浴を用い、30秒フロートさせて評価した。吸湿後測定は、85℃/85%RHで24時間調整した後、加熱した半田浴を用い、10秒フロートで評価した。いずれも膨れが発生しなかった最高温度を評価値とした。
(Solder heat resistance evaluation)
IPC-TM-650 No. Measured according to 2.4.13. The normal state measurement was performed by adjusting the test piece at 23 ° C./55% RH for 24 hours, and then using a solder bath heated from 250 ° C. to 350 ° C. in increments of 10 ° C. to float for 30 seconds for evaluation. The measurement after moisture absorption was adjusted at 85 ° C./85% RH for 24 hours, and then evaluated using a heated solder bath with a 10-second float. In each case, the maximum temperature at which no blistering occurred was taken as the evaluation value.
以下に、合成例で用いるモノマーおよび溶剤の略称を示す。
DMF:N,N−ジメチルホルムアミド
BAPP:2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパン
ODA:4,4´−ジアミノジフェニルエーテル
PDA:p−フェニレンジアミン
BPDA:3,3´,4,4´−ビフェニルテトラカルボン酸二無水物
BTDA:3,3´,4,4´−ベンゾフェノンテトラカルボン酸二無水物
PMDA:ピロメリット酸二無水物
以下に、ポリアミド酸溶液の合成例を示す。
The abbreviations of monomers and solvents used in the synthesis examples are shown below.
DMF: N, N-dimethylformamide BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane ODA: 4,4′-diaminodiphenyl ether PDA: p-phenylenediamine BPDA: 3, 3 ′, 4 , 4'-biphenyltetracarboxylic dianhydride BTDA: 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride PMDA: pyromellitic dianhydride The synthesis example of a polyamic acid solution is shown below.
(合成例1:非熱可塑性ポリイミド層のポリアミド酸溶液)
10℃に冷却したDMF(1173.5g)に、BAPP(57.3g:0.140mol)、ODA(18.6g:0.093mol)、を溶解した。ここに、BTDA(30.0g:0.093mol)、PMDA(25.4g:0.116mol)を添加して、30分間均一攪拌し、プレポリマーを得た。
この溶液にPDA(25.2g:0.232mol)を溶解した後、PMDA(46.4g:0.213mol)を溶解し、別途調製してあったPMDAの7.2重量%DMF溶液を注意深く115.1g(PMDA:0.038mol)添加し、粘度が2500poise程度に達したところで添加を止めた。1時間撹拌を行って、23℃での回転粘度が2600ポイズのポリアミド酸溶液を得た。総使用量を表1にまとめた。
(Synthesis Example 1: Polyamic acid solution of non-thermoplastic polyimide layer)
BAPP (57.3 g: 0.140 mol) and ODA (18.6 g: 0.093 mol) were dissolved in DMF (1173.5 g) cooled to 10 ° C. BTDA (30.0 g: 0.093 mol) and PMDA (25.4 g: 0.116 mol) were added thereto, and the mixture was stirred uniformly for 30 minutes to obtain a prepolymer.
After PDA (25.2 g: 0.232 mol) was dissolved in this solution, PMDA (46.4 g: 0.213 mol) was dissolved, and a 7.2 wt% DMF solution of PMDA prepared separately was carefully 115. 0.1 g (PMDA: 0.038 mol) was added, and the addition was stopped when the viscosity reached about 2500 poise. Stirring was performed for 1 hour to obtain a polyamic acid solution having a rotational viscosity at 23 ° C. of 2600 poise. The total amount used is summarized in Table 1.
(合成例A)
N,N−ジメチルホルムアミド(DMF)843.4gに、BAPP(118.6g:0.289mol)を溶解した。10℃に冷却した後、PMDA(58.2g:0.267mol)を添加し、プレポリマーを得た。
その後、別途調製してあったPMDAの7重量%DMF溶液62.3g(PMDA:0.020mol)を注意深く添加し、粘度が23℃において800poiseのポリアミド酸溶液を得た。その後、DMFを加え、固形成分濃度14重量%のポリアミド酸溶液を得た。総使用量を表1にまとめた。
(Synthesis Example A)
BAPP (118.6 g: 0.289 mol) was dissolved in 843.4 g of N, N-dimethylformamide (DMF). After cooling to 10 ° C., PMDA (58.2 g: 0.267 mol) was added to obtain a prepolymer.
Thereafter, 62.3 g (PMDA: 0.020 mol) of a 7 wt% DMF solution of PMDA, which was separately prepared, was carefully added to obtain a polyamic acid solution having a viscosity of 800 poise at 23 ° C. Thereafter, DMF was added to obtain a polyamic acid solution having a solid component concentration of 14% by weight. The total amount used is summarized in Table 1.
(合成例B)
N,N−ジメチルホルムアミド(DMF)843.4gに、BAPP(118.6g:0.289mol)を溶解した。10℃に冷却した後、BPDA(4.12g:0.014molを添加し、溶解させた。その後、PMDA(55.2g:0.253mol)を添加し、プレポリマーを得た。
その後、別途調製してあったPMDAの7重量%DMF溶液62.3g(PMDA:0.020mol)を注意深く添加し、粘度が23℃において800poiseのポリアミド酸溶液を得た。その後、DMFを加え、固形成分濃度14重量%のポリアミド酸溶液を得た。総使用量を表1にまとめた。
(Synthesis Example B)
BAPP (118.6 g: 0.289 mol) was dissolved in 843.4 g of N, N-dimethylformamide (DMF). After cooling to 10 ° C., BPDA (4.12 g: 0.014 mol) was added and dissolved. After that, PMDA (55.2 g: 0.253 mol) was added to obtain a prepolymer.
Thereafter, 62.3 g (PMDA: 0.020 mol) of a 7 wt% DMF solution of PMDA, which was separately prepared, was carefully added to obtain a polyamic acid solution having a viscosity of 800 poise at 23 ° C. Thereafter, DMF was added to obtain a polyamic acid solution having a solid component concentration of 14% by weight. The total amount used is summarized in Table 1.
(合成例C)
N,N−ジメチルホルムアミド(DMF)843.4gに、BAPP(118.6g:0.289mol)を溶解した。10℃に冷却した後、BPDA(12.7g:0.043molを添加し、溶解させた。その後、PMDA(48.9g:0.224mol)を添加し、プレポリマーを得た。
その後、別途調製してあったPMDAの7重量%DMF溶液62.3g(PMDA:0.020mol)を注意深く添加し、粘度が23℃において800poiseのポリアミド酸溶液を得た。その後、DMFを加え、固形成分濃度14重量%のポリアミド酸溶液を得た。総使用量を表1にまとめた。
(Synthesis Example C)
BAPP (118.6 g: 0.289 mol) was dissolved in 843.4 g of N, N-dimethylformamide (DMF). After cooling to 10 ° C., BPDA (12.7 g: 0.043 mol) was added and dissolved. After that, PMDA (48.9 g: 0.224 mol) was added to obtain a prepolymer.
Thereafter, 62.3 g (PMDA: 0.020 mol) of a 7 wt% DMF solution of PMDA, which was separately prepared, was carefully added to obtain a polyamic acid solution having a viscosity of 800 poise at 23 ° C. Thereafter, DMF was added to obtain a polyamic acid solution having a solid component concentration of 14% by weight. The total amount used is summarized in Table 1.
(合成例D)
N,N−ジメチルホルムアミド(DMF)843.4gに、BAPP(118.6g:0.289mol)を溶解した。10℃に冷却した後、BPDA(17.1g:0.058molを添加し、溶解させた。その後、PMDA(45.6g:0.209mol)を添加し、プレポリマーを得た。
その後、別途調製してあったPMDAの7重量%DMF溶液62.3g(PMDA:0.020mol)を注意深く添加し、粘度が23℃において800poiseのポリアミド酸溶液を得た。その後、DMFを加え、固形成分濃度14重量%のポリアミド酸溶液を得た。総使用量を表1にまとめた。
(Synthesis Example D)
BAPP (118.6 g: 0.289 mol) was dissolved in 843.4 g of N, N-dimethylformamide (DMF). After cooling to 10 ° C., BPDA (17.1 g: 0.058 mol) was added and dissolved. After that, PMDA (45.6 g: 0.209 mol) was added to obtain a prepolymer.
Thereafter, 62.3 g (PMDA: 0.020 mol) of a 7 wt% DMF solution of PMDA, which was separately prepared, was carefully added to obtain a polyamic acid solution having a viscosity of 800 poise at 23 ° C. Thereafter, DMF was added to obtain a polyamic acid solution having a solid component concentration of 14% by weight. The total amount used is summarized in Table 1.
(合成例E)
N,N−ジメチルホルムアミド(DMF)843.4gに、BAPP(118.6g:0.289mol)を溶解した。10℃に冷却した後、BPDA(21.5g:0.073molを添加し、溶解させた。その後、PMDA(42.3g:0.194mol)を添加し、プレポリマーを得た。
その後、別途調製してあったPMDAの7重量%DMF溶液62.3g(PMDA:0.020mol)を注意深く添加し、粘度が23℃において800poiseのポリアミド酸溶液を得た。その後、DMFを加え、固形成分濃度14重量%のポリアミド酸溶液を得た。総使用量を表1にまとめた。
(Synthesis Example E)
BAPP (118.6 g: 0.289 mol) was dissolved in 843.4 g of N, N-dimethylformamide (DMF). After cooling to 10 ° C., BPDA (21.5 g: 0.073 mol was added and dissolved. After that, PMDA (42.3 g: 0.194 mol) was added to obtain a prepolymer.
Thereafter, 62.3 g (PMDA: 0.020 mol) of a 7 wt% DMF solution of PMDA, which was separately prepared, was carefully added to obtain a polyamic acid solution having a viscosity of 800 poise at 23 ° C. Thereafter, DMF was added to obtain a polyamic acid solution having a solid component concentration of 14% by weight. The total amount used is summarized in Table 1.
(合成例F)
N,N−ジメチルホルムアミド(DMF)843.4gに、BAPP(118.6g:0.289mol)を溶解した。10℃に冷却した後、BPDA(25.6g:0.087molを添加し、溶解させた。その後、PMDA(39.3g:0.180mol)を添加し、プレポリマーを得た。
その後、別途調製してあったPMDAの7重量%DMF溶液62.3g(PMDA:0.020mol)を注意深く添加し、粘度が23℃において800poiseのポリアミド酸溶液を得た。その後、DMFを加え、固形成分濃度14重量%のポリアミド酸溶液を得た。総使用量を表1にまとめた。
(Synthesis Example F)
BAPP (118.6 g: 0.289 mol) was dissolved in 843.4 g of N, N-dimethylformamide (DMF). After cooling to 10 ° C., BPDA (25.6 g: 0.087 mol) was added and dissolved. After that, PMDA (39.3 g: 0.180 mol) was added to obtain a prepolymer.
Thereafter, 62.3 g (PMDA: 0.020 mol) of a 7 wt% DMF solution of PMDA, which was separately prepared, was carefully added to obtain a polyamic acid solution having a viscosity of 800 poise at 23 ° C. Thereafter, DMF was added to obtain a polyamic acid solution having a solid component concentration of 14% by weight. The total amount used is summarized in Table 1.
(合成例G)
N,N−ジメチルホルムアミド(DMF)843.4gに、BAPP(118.6g:0.289mol)を溶解した。10℃に冷却した後、BPDA(42.4g:0.144molを添加し、溶解させた。その後、PMDA(26.8g:0.123mol)を添加し、プレポリマーを得た。
その後、別途調製してあったPMDAの7重量%DMF溶液62.3g(PMDA:0.020mol)を注意深く添加し、粘度が23℃において800poiseのポリアミド酸溶液を得た。その後、DMFを加え、固形成分濃度14重量%のポリアミド酸溶液を得た。総使用量を表1にまとめた。
(Synthesis Example G)
BAPP (118.6 g: 0.289 mol) was dissolved in 843.4 g of N, N-dimethylformamide (DMF). After cooling to 10 ° C., BPDA (42.4 g: 0.144 mol) was added and dissolved. PMDA (26.8 g: 0.123 mol) was then added to obtain a prepolymer.
Thereafter, 62.3 g (PMDA: 0.020 mol) of a 7 wt% DMF solution of PMDA, which was separately prepared, was carefully added to obtain a polyamic acid solution having a viscosity of 800 poise at 23 ° C. Thereafter, DMF was added to obtain a polyamic acid solution having a solid component concentration of 14% by weight. The total amount used is summarized in Table 1.
(合成例H)
N,N−ジメチルホルムアミド(DMF)843.4gに、BAPP(118.6g:0.289mol)を溶解した。20℃に冷却した後、BPDA(78.5g:0.267molを添加し、溶解させ、プレポリマーを得た。
その後、BPDA(5.9g:0.020mol)を粉で注意深く添加し、粘度が23℃において800poiseのポリアミド酸溶液を得た。その後、DMFを加え、固形成分濃度14重量%のポリアミド酸溶液を得た。総使用量を表1にまとめた。
(Synthesis Example H)
BAPP (118.6 g: 0.289 mol) was dissolved in 843.4 g of N, N-dimethylformamide (DMF). After cooling to 20 ° C., BPDA (78.5 g: 0.267 mol was added and dissolved to obtain a prepolymer.
Thereafter, BPDA (5.9 g: 0.020 mol) was carefully added as a powder to obtain a polyamic acid solution having a viscosity of 800 poise at 23 ° C. Thereafter, DMF was added to obtain a polyamic acid solution having a solid component concentration of 14% by weight. The total amount used is summarized in Table 1.
(実施例1)
合成例1で得られたポリアミド酸溶液に、ポリアミド酸溶液100gに対して、イソキノリン/無水酢酸/DMF(重量比:7.3g/25.6g/67.1g)からなるイミド化触媒及び化学脱水剤を50g添加して、0℃以下の温度で攪拌、脱泡した。また、合成例Bで得られたポリアミド酸溶液も脱泡し、0℃以下で冷却した。
リップ幅200mmのマルチマニホールド式の3層共押出多層ダイを用い、合成例Bで得られたポリアミド酸溶液/合成例1で得られたポリアミド酸溶液/合成例Bで得られたポリアミド酸溶液の順の3層構造でアルミ箔上に押出し流延した。次いで、この多層膜を150℃×100秒で加熱した後、自己支持性を有するゲルフィルムを引き剥がして、金属枠に固定し、250℃×40秒、300℃×60秒、350℃×60秒、370℃×30秒で乾燥・イミド化し、熱可塑性ポリイミド層/非熱可塑性ポリイミド層/熱可塑性ポリイミド層の厚みが、4μm/17μm/4μmの多層ポリイミドフィルムを得た。
多層ポリイミドフィルムを用い金属箔張積層板を作製した後、金属箔の引き剥がし強度の測定、および半田耐熱性の評価を行った。結果は表2にまとめた。
Example 1
Imidization catalyst and chemical dehydration composed of isoquinoline / acetic anhydride / DMF (weight ratio: 7.3 g / 25.6 g / 67.1 g) with respect to 100 g of the polyamic acid solution in the polyamic acid solution obtained in Synthesis Example 1. 50 g of the agent was added, and the mixture was stirred and degassed at a temperature of 0 ° C. or lower. The polyamic acid solution obtained in Synthesis Example B was also degassed and cooled at 0 ° C. or lower.
Using a multi-manifold type three-layer coextrusion multilayer die having a lip width of 200 mm, the polyamic acid solution obtained in Synthesis Example B / the polyamic acid solution obtained in Synthesis Example 1 / the polyamic acid solution obtained in Synthesis Example B It was extruded and cast on an aluminum foil with a three-layer structure in order. Next, after heating this multilayer film at 150 ° C. × 100 seconds, the gel film having self-supporting properties is peeled off and fixed to a metal frame, 250 ° C. × 40 seconds, 300 ° C. × 60 seconds, 350 ° C. × 60 Second, 370 ° C. × 30 seconds, and imidized to obtain a multilayer polyimide film having a thermoplastic polyimide layer / non-thermoplastic polyimide layer / thermoplastic polyimide layer thickness of 4 μm / 17 μm / 4 μm.
After producing a metal foil-clad laminate using a multilayer polyimide film, the peel strength of the metal foil was measured and the solder heat resistance was evaluated. The results are summarized in Table 2.
(実施例2)
合成例Bで得られたポリアミド酸溶液を合成例Cに変更する以外は、実施例1と同様に実施した。結果は表2にまとめた。
(Example 2)
The same procedure as in Example 1 was performed except that the polyamic acid solution obtained in Synthesis Example B was changed to Synthesis Example C. The results are summarized in Table 2.
(実施例3)
合成例Bで得られたポリアミド酸溶液を合成例Dに変更する以外は、実施例1と同様に実施した。結果は表2にまとめた。
(Example 3)
The same procedure as in Example 1 was performed except that the polyamic acid solution obtained in Synthesis Example B was changed to Synthesis Example D. The results are summarized in Table 2.
(実施例4)
合成例Bで得られたポリアミド酸溶液を合成例Eに変更する以外は、実施例1と同様に実施した。結果は表2にまとめた。
Example 4
The same procedure as in Example 1 was performed except that the polyamic acid solution obtained in Synthesis Example B was changed to Synthesis Example E. The results are summarized in Table 2.
(実施例5)
合成例Bで得られたポリアミド酸溶液を合成例Fに変更する以外は、実施例1と同様に実施した。結果は表2にまとめた。
(Example 5)
The same procedure as in Example 1 was performed except that the polyamic acid solution obtained in Synthesis Example B was changed to Synthesis Example F. The results are summarized in Table 2.
(比較例1)
合成例Bで得られたポリアミド酸溶液を合成例Aに変更する以外は、実施例1と同様に実施した。結果は表2にまとめた。
(Comparative Example 1)
The same procedure as in Example 1 was performed except that the polyamic acid solution obtained in Synthesis Example B was changed to Synthesis Example A. The results are summarized in Table 2.
(比較例2)
合成例Bで得られたポリアミド酸溶液を合成例Gに変更する以外は、実施例1と同様に実施した。結果は表2にまとめた。
(Comparative Example 2)
The same procedure as in Example 1 was performed except that the polyamic acid solution obtained in Synthesis Example B was changed to Synthesis Example G. The results are summarized in Table 2.
(比較例3)
合成例Bで得られたポリアミド酸溶液を合成例Hに変更する以外は、実施例1と同様に実施した。結果は表2にまとめた。
(Comparative Example 3)
The same procedure as in Example 1 was performed except that the polyamic acid solution obtained in Synthesis Example B was changed to Synthesis Example H. The results are summarized in Table 2.
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