JP4821411B2 - Polyimide film with heat-sealability only on one side, single-sided copper-clad laminate - Google Patents
Polyimide film with heat-sealability only on one side, single-sided copper-clad laminate Download PDFInfo
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- JP4821411B2 JP4821411B2 JP2006104041A JP2006104041A JP4821411B2 JP 4821411 B2 JP4821411 B2 JP 4821411B2 JP 2006104041 A JP2006104041 A JP 2006104041A JP 2006104041 A JP2006104041 A JP 2006104041A JP 4821411 B2 JP4821411 B2 JP 4821411B2
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- Prior art keywords
- heat
- layer
- polyimide
- film
- fusible
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- 229920001721 polyimide Polymers 0.000 title claims description 269
- 239000004642 Polyimide Substances 0.000 claims description 205
- 150000004985 diamines Chemical class 0.000 claims description 46
- 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 39
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 39
- 239000011888 foil Substances 0.000 claims description 33
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 20
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 17
- OMHOXRVODFQGCA-UHFFFAOYSA-N 4-[(4-amino-3,5-dimethylphenyl)methyl]-2,6-dimethylaniline Chemical compound CC1=C(N)C(C)=CC(CC=2C=C(C)C(N)=C(C)C=2)=C1 OMHOXRVODFQGCA-UHFFFAOYSA-N 0.000 claims description 7
- 239000010410 layer Substances 0.000 description 202
- 239000000243 solution Substances 0.000 description 60
- 239000010408 film Substances 0.000 description 55
- 239000002253 acid Substances 0.000 description 27
- 229920005575 poly(amic acid) Polymers 0.000 description 25
- 125000004432 carbon atom Chemical group C* 0.000 description 20
- 239000002243 precursor Substances 0.000 description 18
- -1 3-aminophenoxy Chemical group 0.000 description 17
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 14
- 239000000178 monomer Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 125000003545 alkoxy group Chemical group 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 238000005187 foaming Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000004927 fusion Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 3
- VILWHDNLOJCHNJ-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfanylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1SC1=CC=C(C(O)=O)C(C(O)=O)=C1 VILWHDNLOJCHNJ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 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 3
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 3
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 3
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000006159 dianhydride group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- YKNMIGJJXKBHJE-UHFFFAOYSA-N (3-aminophenyl)-(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC(N)=C1 YKNMIGJJXKBHJE-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 2
- FGWQCROGAHMWSU-UHFFFAOYSA-N 3-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC(N)=C1 FGWQCROGAHMWSU-UHFFFAOYSA-N 0.000 description 2
- DVXYMCJCMDTSQA-UHFFFAOYSA-N 3-[2-(3-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=CC(N)=CC=1C(C)(C)C1=CC=CC(N)=C1 DVXYMCJCMDTSQA-UHFFFAOYSA-N 0.000 description 2
- NYRFBMFAUFUULG-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=C(N)C=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=CC(N)=C1 NYRFBMFAUFUULG-UHFFFAOYSA-N 0.000 description 2
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 2
- IWXCYYWDGDDPAC-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)methyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C(C(O)=O)=C1 IWXCYYWDGDDPAC-UHFFFAOYSA-N 0.000 description 2
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-UHFFFAOYSA-N 0.000 description 2
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 229920001646 UPILEX Polymers 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000006358 imidation reaction Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
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- 239000010409 thin film Substances 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-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
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 1
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 1
- OJSPYCPPVCMEBS-UHFFFAOYSA-N 2,8-dimethyl-5,5-dioxodibenzothiophene-3,7-diamine Chemical compound C12=CC(C)=C(N)C=C2S(=O)(=O)C2=C1C=C(C)C(N)=C2 OJSPYCPPVCMEBS-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- YKOLZVXSPGIIBJ-UHFFFAOYSA-N 2-Isopropylaniline Chemical compound CC(C)C1=CC=CC=C1N YKOLZVXSPGIIBJ-UHFFFAOYSA-N 0.000 description 1
- IIQLVLWFQUUZII-UHFFFAOYSA-N 2-amino-5-(4-amino-3-carboxyphenyl)benzoic acid Chemical group C1=C(C(O)=O)C(N)=CC=C1C1=CC=C(N)C(C(O)=O)=C1 IIQLVLWFQUUZII-UHFFFAOYSA-N 0.000 description 1
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- UAIUNKRWKOVEES-UHFFFAOYSA-N 3,3',5,5'-tetramethylbenzidine Chemical group CC1=C(N)C(C)=CC(C=2C=C(C)C(N)=C(C)C=2)=C1 UAIUNKRWKOVEES-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical group C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- NQZOFDAHZVLQJO-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(OC=3C=CC(OC=4C=C(N)C=CC=4)=CC=3)=CC=2)=C1 NQZOFDAHZVLQJO-UHFFFAOYSA-N 0.000 description 1
- UCQABCHSIIXVOY-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]phenoxy]aniline Chemical group NC1=CC=CC(OC=2C=CC(=CC=2)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 UCQABCHSIIXVOY-UHFFFAOYSA-N 0.000 description 1
- JERFEOKUSPGKGV-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfanylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(SC=3C=CC(OC=4C=C(N)C=CC=4)=CC=3)=CC=2)=C1 JERFEOKUSPGKGV-UHFFFAOYSA-N 0.000 description 1
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 1
- FGSUUFDRDVJCLT-UHFFFAOYSA-N 3-methylazepan-2-one Chemical compound CC1CCCCNC1=O FGSUUFDRDVJCLT-UHFFFAOYSA-N 0.000 description 1
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 1
- BQHIADYTQBPQMV-UHFFFAOYSA-N 4-(2-propylphenoxy)phthalic acid Chemical compound CCCC1=CC=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 BQHIADYTQBPQMV-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- NWIVYGKSHSJHEF-UHFFFAOYSA-N 4-[(4-amino-3,5-diethylphenyl)methyl]-2,6-diethylaniline Chemical compound CCC1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=C(CC)C=2)=C1 NWIVYGKSHSJHEF-UHFFFAOYSA-N 0.000 description 1
- CBEVWPCAHIAUOD-UHFFFAOYSA-N 4-[(4-amino-3-ethylphenyl)methyl]-2-ethylaniline Chemical compound C1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=CC=2)=C1 CBEVWPCAHIAUOD-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
- LDFYRFKAYFZVNH-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 LDFYRFKAYFZVNH-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
- SXTPNMJRVQKNRN-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfanylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1SC(C=C1)=CC=C1OC1=CC=C(N)C=C1 SXTPNMJRVQKNRN-UHFFFAOYSA-N 0.000 description 1
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 1
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- NJLBZIDFTMDFEJ-UHFFFAOYSA-N NC=1C=C(OC2=CC(=CC=C2)OC2=CC(=CC=C2)N)C=CC1.NC=1C=C(OC2=CC=C(C=C2)C2=CC=C(C=C2)OC2=CC(=CC=C2)N)C=CC1 Chemical group NC=1C=C(OC2=CC(=CC=C2)OC2=CC(=CC=C2)N)C=CC1.NC=1C=C(OC2=CC=C(C=C2)C2=CC=C(C=C2)OC2=CC(=CC=C2)N)C=CC1 NJLBZIDFTMDFEJ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- BBRLKRNNIMVXOD-UHFFFAOYSA-N bis[4-(3-aminophenoxy)phenyl]methanone Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)C(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 BBRLKRNNIMVXOD-UHFFFAOYSA-N 0.000 description 1
- LSDYQEILXDCDTR-UHFFFAOYSA-N bis[4-(4-aminophenoxy)phenyl]methanone Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 LSDYQEILXDCDTR-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000012793 heat-sealing layer Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000004962 sulfoxyl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Description
本発明は、プリント配線板、フレキシブルプリント基板、TABテープ等の電子部品の素材として用いられる片面のみに熱融着性を有する多層ポリイミドフィルム、それらの片面金属箔積層板であり、さらに詳しくは耐熱性ポリイミド層の両面に熱融着性ポリイミド層を有しさらに片面に熱融着性を有しない耐熱性ポリイミド層が積層されてなる少なくとも4層構造を有する片面のみに熱融着性を有するポリイミドフィルム、該ポリイミドフィルムを用いた片面金属箔積層板に関するものである。
本発明によれば、電子部品の実装工程で装置に張り付くことが実質的になく成形加工性が良好なオールポリイミドの片面銅張板を与える熱融着性を有する多層ポリイミドフィルムおよび片面銅張り積層板を得ることができる。
The present invention is a multilayer polyimide film having heat fusion properties only on one side used as a material for electronic components such as a printed wiring board, a flexible printed circuit board, and a TAB tape, and a single-sided metal foil laminated board. Polyimide having at least four layers structure in which heat-resistant polyimide layers are laminated on both sides and heat-resistant polyimide layers not having heat-fusibility are laminated on one side. The present invention relates to a film and a single-sided metal foil laminate using the polyimide film.
According to the present invention, a multi-layer polyimide film and a single-sided copper-clad laminate having heat-sealability that gives an all-polyimide single-sided copper-clad plate that is substantially free of sticking to an apparatus in the mounting process of electronic components and has good moldability A board can be obtained.
カメラ、パソコン、液晶ディスプレイなどの電子機器類への用途として芳香族ポリイミドフィルムは広く使用されている。
芳香族ポリイミドフィルムをフレキシブルプリント板(FPC)やテープ・オートメイティッド・ボンディング(TAB)などの基板材料として使用するためには、エポキシ樹脂などの接着剤を用いて銅箔を張り合わせる方法が採用されている。
Aromatic polyimide films are widely used as applications for electronic devices such as cameras, personal computers, and liquid crystal displays.
In order to use aromatic polyimide film as a substrate material for flexible printed circuit boards (FPC) and tape automated bonding (TAB), a method of bonding copper foil with an adhesive such as epoxy resin is adopted. Has been.
片面に熱融着性を有する多層のポリイミドフィルムとしては、特許文献1に、厚みが4〜45μmの耐熱性ポリイミド層(S1層)の両面に厚みが略等しい熱融着性ポリイミド層を有し、片面の熱融着性ポリイミド層の厚みと他面の熱融着性ポリイミド層の厚みとの合計が3〜10μmであり、該熱融着性ポリイミド層の片面に厚みが0.1〜2μmの熱融着性を有しない耐熱性ポリイミド層(S2層)が積層されてなる片面のみに熱融着性を有するポリイミドフィルムが開示されている。 As a multi-layer polyimide film having heat-fusibility on one side, Patent Document 1 has a heat-fusible polyimide layer having substantially the same thickness on both sides of a heat-resistant polyimide layer (S1 layer) having a thickness of 4 to 45 μm. The total of the thickness of the heat-sealable polyimide layer on one side and the thickness of the heat-sealable polyimide layer on the other side is 3 to 10 μm, and the thickness on one side of the heat-sealable polyimide layer is 0.1 to 2 μm. A polyimide film having a heat-fusible property only on one side obtained by laminating a heat-resistant polyimide layer (S2 layer) having no heat-welding property is disclosed.
従来の片面に熱融着性を有する多層のポリイミドフィルムでは、熱融着性ポリイミド層の片面に厚みが0.1〜2μmの熱融着性を有しない耐熱性ポリイミド層として耐熱性に優れるが、透水性の低いポリイミド素材が用いられている。そのため耐熱性ポリイミド層や熱融着性ポリイミド層に溶媒や水分が存在すると、加熱時に熱融着性ポリイミド層と熱融着性を有しない耐熱性ポリイミド層との間で発泡する場合があり、電気基板の生産性を低下させる場合がある。
本発明は、上記の改善を試み、加熱時の発泡を抑制した片面に熱融着性を有する多層のポリイミドフィルムを提供することである。
In the conventional multilayer polyimide film having heat-fusible properties on one side, the heat-fusible polyimide layer is excellent in heat resistance as a heat-resistant polyimide layer having a thickness of 0.1 to 2 μm and not having heat-fusible properties on one side. Polyimide material with low water permeability is used. Therefore, if a solvent or moisture is present in the heat-resistant polyimide layer or the heat-fusible polyimide layer, foaming may occur between the heat-fusible polyimide layer and the heat-resistant polyimide layer not having heat-fusibility during heating, There is a case where productivity of the electric substrate is lowered.
An object of the present invention is to provide a multilayer polyimide film having a heat-fusible property on one side in which the above improvement is attempted and foaming during heating is suppressed.
本発明の片面のみに熱融着性を有するポリイミドフィルムは、耐熱性ポリイミド層(S1層)の両面に熱融着性ポリイミド層(S3層)を有し、熱融着性ポリイミド層の片面に熱融着性を有しない耐熱性ポリイミド層(S2層)が積層されている片面のみに熱融着性を有するポリイミドフィルムであり、
熱融着性を有しない耐熱性ポリイミド層(S2層)は、テトラカルボン酸二無水物成分と、下記一般式(1)で表されるジアミンを0.5〜30モル%含むジアミンとから得られるポリイミドであることを特徴とする片面のみに熱融着性を有するポリイミドフィルム。
A heat-resistant polyimide layer (S2 layer) having no heat-fusibility is obtained from a tetracarboxylic dianhydride component and a diamine containing 0.5 to 30 mol% of a diamine represented by the following general formula (1). A polyimide film having a heat-sealing property only on one side, characterized in that the polyimide film is made of polyimide.
本発明の片面のみに熱融着性を有するポリイミドフィルムの好ましい態様を示し、これらは複数組み合わせることが出来る。
1)一般式(1)のジアミンは、一般式(2)に示すジアミンであること、さらに好ましくはp−フェニレンジアミンを含むこと。
2)熱融着性を有しない耐熱性ポリイミド層(S2層)は、相対透湿速度が4以上であること。
3)熱融着性を有しない耐熱性ポリイミド層(S2層)のテトラカルボン酸二無水物成分は一般式(3)に示すテトラカルボン酸二無水物であること。
1) The diamine of the general formula (1) is a diamine represented by the general formula (2), more preferably p-phenylenediamine.
2) The heat-resistant polyimide layer (S2 layer) having no heat-fusibility has a relative moisture transmission rate of 4 or more.
3) The tetracarboxylic dianhydride component of the heat-resistant polyimide layer (S2 layer) not having heat-fusibility is a tetracarboxylic dianhydride represented by the general formula (3).
本発明の片面のみに熱融着性を有するポリイミドフィルムは、耐熱性ポリイミド層(S1層)の両面に熱融着性ポリイミド層(S3層)を有し、熱融着性ポリイミド層の片面に熱融着性を有しない耐熱性ポリイミド層(S2層)が積層されている片面のみに熱融着性を有するポリイミドフィルムであり、
熱融着性を有しない耐熱性ポリイミド層(S2層)は、相対透湿速度が4以上の熱融着性を有しない耐熱性ポリイミドであることを特徴とする片面のみに熱融着性を有するポリイミドフィルムである。
The polyimide film having heat-fusibility only on one side of the present invention has a heat-fusible polyimide layer (S3 layer) on both sides of the heat-resistant polyimide layer (S1 layer), and on one side of the heat-fusible polyimide layer. A heat-resistant polyimide layer (S2 layer) having no heat-fusible property is a polyimide film having heat-fusible property only on one side,
The heat-resistant polyimide layer (S2 layer) having no heat-fusible property is a heat-resistant polyimide having no heat-fusible property having a relative moisture transmission rate of 4 or more. It is the polyimide film which has.
本発明の片面金属箔積層板は、上記の本発明の片面のみに熱融着性を有するポリイミドフィルムと金属箔とが、熱融着性を有するポリイミド層を介して熱圧着によって積層されている片面金属箔積層板である。 In the single-sided metal foil laminate of the present invention, the polyimide film having a heat-fusibility and the metal foil are laminated only on one side of the present invention by thermocompression bonding via a polyimide layer having a heat-fusibility. It is a single-sided metal foil laminate.
本発明により、加熱時の発泡を抑制した片面に熱融着性を有する多層のポリイミドフィルムを提供することができる。 According to the present invention, it is possible to provide a multilayer polyimide film having heat-fusibility on one side in which foaming during heating is suppressed.
片面のみに熱融着性を有するポリイミドフィルムでは、耐熱性ポリイミド層(S1層)、熱融着性ポリイミド層(S3層)或いは熱融着性を有しない耐熱性ポリイミド層(S2層)に含まれる水や残留する溶媒などが加熱することによりガス状になる場合がある。発生するガスは、S2層に透湿速度の遅いポリイミドを用いるとS2層側より抜け出すことが容易にできず、S3層とS2層との間、或いはS3層とS1層との間で滞留する場合があるために発泡が起きると推測できる。そのため透湿速度の高い耐熱性ポリイミドを用いることにより、発生するガスが容易にS2層側より抜け出すことができ、S3層とS2層との間、或いはS3層とS1層との間でガスの滞留を抑制することができ、その結果発泡を抑制することができると考える。 In a polyimide film having a heat-sealable property only on one side, it is included in a heat-resistant polyimide layer (S1 layer), a heat-sealable polyimide layer (S3 layer), or a heat-resistant polyimide layer (S2 layer) having no heat-sealable property. The heated water and residual solvent may become gaseous when heated. The generated gas cannot easily escape from the S2 layer side when polyimide having a low moisture transmission rate is used for the S2 layer, and stays between the S3 layer and the S2 layer, or between the S3 layer and the S1 layer. It can be inferred that foaming occurs because there are cases. For this reason, by using heat-resistant polyimide with a high moisture permeability rate, the generated gas can easily escape from the S2 layer side, and the gas can flow between the S3 layer and the S2 layer or between the S3 layer and the S1 layer. It is considered that retention can be suppressed, and as a result, foaming can be suppressed.
本発明の片面のみに熱融着性を有するポリイミドフィルムのカールを調整する方法としては、公知のどのような方法を用いてもよいが、一例として、
1)片面の熱融着性ポリイミド層と他面の熱融着性ポリイミド層の厚みをかえること、
2)片面に熱融着性を有しない耐熱性ポリイミド層(S2層)の厚みをかえること、
さらに上記1)と2)とを組み合わせること、などをあげることができる。
As a method of adjusting the curl of the polyimide film having heat-fusibility only on one side of the present invention, any known method may be used,
1) Changing the thickness of the heat-sealable polyimide layer on one side and the heat-sealable polyimide layer on the other side,
2) Change the thickness of the heat-resistant polyimide layer (S2 layer) that does not have heat-fusibility on one side,
Furthermore, the above 1) and 2) can be combined.
耐熱性ポリイミド層(S1層)は、プリント配線板、フレキシブルプリント基板、TABテープ等の電子部品の素材として用いることができるベースフィルムを構成する耐熱性ポリイミドを用いることが好ましい。
耐熱性ポリイミド層(S1層)の耐熱性ポリイミドとしては、以下の特徴を少なくとも1つ有するポリイミドを用いることができる。(これらの特徴は任意の特徴を複数組み合わせることが出来る。)
1)単独のポリイミドフィルムの場合にガラス転移温度が200℃以上、さらに好ましくは300℃以上か確認不可能であるもの、
2)、特に線膨張係数(50〜200℃)(MD)が5×10−6〜20×10−6cm/cm/℃であるもの、
3)引張弾性率(MD、ASTM−D882)は300kg/mm2以上であるもの、
4)非熱可塑性ポリイミド、などをあげることができる。
The heat-resistant polyimide layer (S1 layer) is preferably a heat-resistant polyimide that constitutes a base film that can be used as a material for electronic components such as a printed wiring board, a flexible printed circuit board, and a TAB tape.
As the heat-resistant polyimide of the heat-resistant polyimide layer (S1 layer), polyimide having at least one of the following characteristics can be used. (These features can be combined with any number of features.)
1) In the case of a single polyimide film, the glass transition temperature is 200 ° C. or higher, more preferably 300 ° C. or higher.
2), especially those having a linear expansion coefficient (50 to 200 ° C.) (MD) of 5 × 10 −6 to 20 × 10 −6 cm / cm / ° C.,
3) The tensile elastic modulus (MD, ASTM-D882) is 300 kg / mm 2 or more,
4) Non-thermoplastic polyimide can be used.
耐熱性ポリイミド層(S1層)の耐熱性ポリイミドとしては、
(1)3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、ピロメリット酸二無水物及び1,4−ヒドロキノンジベンゾエート−3,3’,4,4’−テトラカルボン酸二無水物より選ばれる成分を少なくとも1種含む酸成分、好ましくはこれらの酸成分を少なくとも70モル%以上、さらに好ましくは80モル%以上、より好ましくは90モル%以上含む酸成分と、
(2)ジアミン成分として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、m−トリジン及び4,4’−ジアミノベンズアニリドより選ばれる成分を少なくとも1種含むジアミン、好ましくはこれらのジアミン成分を少なくとも70モル%以上、さらに好ましくは80モル%以上、より好ましくは90モル%以上含むジアミン成分とから得られるポリイミドなどを用いることができる。
耐熱性ポリイミド層(S1層)を構成する酸成分とジアミン成分との組合せの一例としては、
1)3,3’,4,4’−ビフェニルテトラカルボン酸二無水物と、p−フェニレンジアミン或いはp−フェニレンジアミン及び4,4−ジアミノジフェニルエ−テル、
2)3,3’,4,4’−ビフェニルテトラカルボン酸二無水物及びピロメリット酸二無水物と、p−フェニレンジアミン或いはp−フェニレンジアミン及び4,4−ジアミノジフェニルエ−テル、
3)ピロメリット酸二無水物と、p−フェニレンジアミン及び4,4−ジアミノジフェニルエ−テル、
4)3,3’,4,4’−ビフェニルテトラカルボン酸二無水物とp−フェニレンジアミンとを主成分(合計100モル%中の50モル%以上)として得られるものが、プリント配線板、フレキシブルプリント基板、TABテープ等の電子部品の素材として用いられ、広い温度範囲にわたって優れた機械的特性を有し、長期耐熱性を有し、耐加水分解性に優れ、熱分解開始温度が高く、加熱収縮率と線膨張係数が小さい、難燃性に優れるために好ましい。
As the heat-resistant polyimide of the heat-resistant polyimide layer (S1 layer),
(1) 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride and 1,4-hydroquinone dibenzoate-3,3 ′, 4,4′-tetracarboxylic acid bis An acid component containing at least one component selected from anhydrides, preferably an acid component containing at least 70 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more of these acid components;
(2) A diamine containing at least one component selected from p-phenylenediamine, 4,4-diaminodiphenyl ether, m-tolidine, and 4,4′-diaminobenzanilide as the diamine component, preferably at least 70 of these diamine components. A polyimide obtained from a diamine component containing at least mol%, more preferably at least 80 mol%, more preferably at least 90 mol% can be used.
As an example of a combination of an acid component and a diamine component constituting the heat resistant polyimide layer (S1 layer),
1) 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, p-phenylenediamine or p-phenylenediamine and 4,4-diaminodiphenyl ether,
2) 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride, p-phenylenediamine or p-phenylenediamine and 4,4-diaminodiphenyl ether,
3) pyromellitic dianhydride, p-phenylenediamine and 4,4-diaminodiphenyl ether,
4) What is obtained by using 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and p-phenylenediamine as main components (50 mol% or more in a total of 100 mol%) is a printed wiring board, Used as a material for electronic components such as flexible printed circuit boards and TAB tapes, has excellent mechanical properties over a wide temperature range, has long-term heat resistance, excellent hydrolysis resistance, and high thermal decomposition starting temperature, It is preferable because the heat shrinkage rate and the linear expansion coefficient are small and the flame retardancy is excellent.
耐熱性ポリイミド層(S1層)の耐熱性ポリイミドを得ることができる酸成分として、上記に示す酸成分の他に本発明の特性を損なわない範囲で、
2,3,3’,4’−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、ビス(3,4−ジカルボキシフェニル)エーテル二無水物、ビス(3,4−ジカルボキシフェニル)スルフィド二無水物、ビス(3,4−ジカルボキシフェニル)スルホン二無水物、ビス(3,4−ジカルボキシフェニル)メタン二無水物、2,2−ビス(3,4−ジカルボキシフェニル)プロパン二無水物、2,2−ビス(3,4−ジカルボキシフェニル)−1,1,1,3,3,3−ヘキサフルオロプロパン二無水物、2,2−ビス[(3,4−ジカルボキシフェノキシ)フェニル]プロパン二無水物、などの酸ニ無水物成分を用いることができる。
As an acid component that can obtain the heat-resistant polyimide of the heat-resistant polyimide layer (S1 layer), in addition to the acid component shown above, the characteristics of the present invention are not impaired.
2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride Bis (3,4-dicarboxyphenyl) sulfide dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2- Bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2 Acid dianhydride components such as 2-bis [(3,4-dicarboxyphenoxy) phenyl] propane dianhydride can be used.
耐熱性ポリイミド層(S1層)の耐熱性ポリイミドを得ることができるジアミン成分として、上記に示すジアミン成分の他に本発明の特性を損なわない範囲で、
m−フェニレンジアミン、3,4’−ジアミノジフェニルエーテル、3,3’−ジアミノジフェニルスルフィド、3,4’−ジアミノジフェニルスルフィド、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、3,4’−ジアミノジフェニルスルホン、4,4’−ジアミノジフェニルスルホン、3,3’−ジアミノベンゾフェノン、4,4’−ジアミノベンゾフェノン、3,4’−ジアミノベンゾフェノン、3,3’−ジアミノジフェニルメタン、4,4’−ジアミノジフェニルメタン、3,4’−ジアミノジフェニルメタン、2,2−ジ(3−アミノフェニル)プロパン、2,2−ジ(4−アミノフェニル)プロパン、などのジアミン成分を用いることができる。
As a diamine component capable of obtaining a heat-resistant polyimide of the heat-resistant polyimide layer (S1 layer), in addition to the diamine component shown above, the characteristics of the present invention are not impaired.
m-phenylenediamine, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 4, , 4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, and the like can be used. .
熱融着性ポリイミド層(S3層)は、プリント配線板、フレキシブルプリント基板、TABテープ等の電子部品の素材として用いることができる公知の熱融着性(熱圧着性)を有するポリイミドを用いることができる。
熱融着性ポリイミド層(S3層)の熱融着性(熱圧着性)を有するポリイミドとしては、金属箔と熱融着(熱圧着)することができるポリイミドを用いることができ、好ましくは150℃〜400℃、さらに好ましくは200〜400℃、より好ましくは250〜400℃の温度で熱融着(熱圧着)できる熱可塑性ポリイミドなどのポリイミドを用いることができる。
For the heat-fusible polyimide layer (S3 layer), a polyimide having a known heat-fusible property (thermocompression bonding) that can be used as a material for electronic components such as a printed wiring board, a flexible printed circuit board, and a TAB tape is used. Can do.
As the polyimide having the heat-fusible property (thermocompression bonding property) of the heat-fusible polyimide layer (S3 layer), a polyimide that can be heat-fused (thermocompression bonding) with the metal foil can be used, preferably 150. A polyimide such as a thermoplastic polyimide that can be heat-sealed (thermocompression bonding) at a temperature of from ℃ to 400 ℃, more preferably from 200 to 400 ℃, more preferably from 250 to 400 ℃ can be used.
熱融着性ポリイミド層(S3層)の熱融着性ポリイミドは、
(1)3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、2,3,3’,4’−ビフェニルテトラカルボン酸二無水物、ピロメリット酸二無水物、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物、ビス(3,4−ジカルボキシフェニル)エーテル二無水物、ビス(3,4−ジカルボキシフェニル)スルフィド二無水物、ビス(3,4−ジカルボキシフェニル)スルホン二無水物、ビス(3,4−ジカルボキシフェニル)メタン二無水物、2,2−ビス(3,4−ジカルボキシフェニル)プロパン二無水物及び1,4−ヒドロキノンジベンゾエート−3,3’,4,4’−テトラカルボン酸二無水物などの酸ニ無水物より選ばれる成分を少なくとも1種含む酸成分、好ましくはこれらの酸成分を少なくとも70モル%以上、さらに好ましくは80モル%以上、より好ましくは90モル%以上含む酸成分と、
(2)ジアミン成分としては、1,3−ビス(4−アミノフェノキシ)ベンゼン、1,3−ビス(3−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、3,3’−ジアミノベンゾフェノン、4,4’−ビス(3−アミノフェノキシ)ビフェニル、4,4’−ビス(4−アミノフェノキシ)ビフェニル、ビス[4−(3−アミノフェノキシ)フェニル]ケトン、ビス[4−(4−アミノフェノキシ)フェニル]ケトン、ビス[4−(3−アミノフェノキシ)フェニル]スルフィド、ビス[4−(4−アミノフェノキシ)フェニル]スルフィド、ビス[4−(3−アミノフェノキシ)フェニル]スルホン、ビス[4−(4−アミノフェノキシ)フェニル]スルホン、ビス[4−(3−アミノフェノキシ)フェニル]エーテル、ビス[4−(4−アミノフェノキシ)フェニル]エーテル、2,2−ビス[4−(3−アミノフェノキシ)フェニル]プロパン、2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパンなどのジアミンより選ばれる成分を少なくとも1種含むジアミン、好ましくはこれらのジアミン成分を少なくとも70モル%以上、さらに好ましくは80モル%以上、より好ましくは90モル%以上含むジアミン成分とから得られるポリイミドなどを用いることができる。
The heat fusible polyimide of the heat fusible polyimide layer (S3 layer) is
(1) 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′ , 4,4′-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride, bis (3,4- Dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride and 1,4-hydroquinone dibenzoate An acid component containing at least one component selected from acid dianhydrides such as −3,3 ′, 4,4′-tetracarboxylic dianhydride, preferably at least 70 mol% of these acid components; Preferably 80 mol% or more, more preferably an acid component comprising 90 mol% or more,
(2) As the diamine component, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 '-Diaminobenzophenone, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4 -(4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl Sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] Ter, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] It is obtained from a diamine containing at least one component selected from diamines such as propane, preferably a diamine component containing these diamine components at least 70 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more. Polyimide or the like can be used.
熱融着性ポリイミド層(S3層)のポリイミドを得ることができる酸成分とジアミン成分との組合せの一例としては、
(1)3,3’,4,4’−ビフェニルテトラカルボン酸二無水物及び2,3,3’,4’−ビフェニルテトラカルボン酸二無水物の酸ニ無水物より選ばれる成分を少なくとも1種含む酸成分、好ましくはこれらの酸成分を少なくとも70モル%以上、さらに好ましくは80モル%以上、より好ましくは90モル%以上含む酸成分と、
(2)ジアミン成分としては、1,3−ビス(4−アミノフェノキシ)ベンゼン、1,3−ビス(3−アミノフェノキシ)ベンゼン4,4’−ビス(3−アミノフェノキシ)ビフェニル、ビス[4−(3−アミノフェノキシ)フェニル]スルホン、ビス[4−(3−アミノフェノキシ)フェニル]エーテル、2,2−ビス[4−(3−アミノフェノキシ)フェニル]プロパン、2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパンなどのジアミンより選ばれる成分を少なくとも1種含むジアミン、好ましくはこれらのジアミン成分を少なくとも70モル%以上、さらに好ましくは80モル%以上、より好ましくは90モル%以上含むジアミン成分とから得られるポリイミドなどを用いることができる。
As an example of a combination of an acid component and a diamine component that can obtain a polyimide of a heat-fusible polyimide layer (S3 layer),
(1) At least one component selected from acid dianhydrides of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride An acid component containing seeds, preferably an acid component containing at least 70 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more of these acid components;
(2) As the diamine component, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene 4,4′-bis (3-aminophenoxy) biphenyl, bis [4 -(3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4 A diamine containing at least one component selected from diamines such as-(4-aminophenoxy) phenyl] propane, preferably at least 70 mol%, more preferably 80 mol% or more, more preferably 90 mol, of these diamine components. The polyimide etc. which are obtained from the diamine component which contains% or more can be used.
熱融着性ポリイミド層(S3層)のポリイミドを得ることができるジアミン成分として、上記に示すジアミン成分の他に本発明の特性を損なわない範囲で、
m−フェニレンジアミン、3,4’−ジアミノジフェニルエーテル、3,3’−ジアミノジフェニルスルフィド、3,4’−ジアミノジフェニルスルフィド、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、3,4’−ジアミノジフェニルスルホン、4,4’−ジアミノジフェニルスルホン、3,3’−ジアミノベンゾフェノン、4,4’−ジアミノベンゾフェノン、3,4’−ジアミノベンゾフェノン、3,3’−ジアミノジフェニルメタン、4,4’−ジアミノジフェニルメタン、3,4’−ジアミノジフェニルメタン、2,2−ジ(3−アミノフェニル)プロパン、2,2−ジ(4−アミノフェニル)プロパン、などのジアミン成分を用いることができる。
As a diamine component that can obtain the polyimide of the heat-fusible polyimide layer (S3 layer), in addition to the diamine component shown above, the characteristics of the present invention are not impaired.
m-phenylenediamine, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 4, , 4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, and the like can be used. .
熱融着性を有しない耐熱性ポリイミド層(S2層)の熱融着性を有しない耐熱性ポリイミドは、テトラカルボン酸二無水物成分、好ましくは、下記一般式(3)で示すテトラカルボン酸二無水物より選ばれる少なくとも1種以上の成分、さらに好ましくは3,3’,4,4’−ビフェニルテトラカルボン酸二無水物を含むテトラカルボン酸二無水物成分と、下記一般式(1)で表されるジアミン、好ましくは下記一般式(2)で表されるジアミンから選ばれるジアミンを少なくとも1種以上を、0.5〜30モル%、好ましくは1〜29モル%、さらに好ましくは2〜28モル%、特に好ましくは7〜25モル%含むジアミン、とから得られるポリイミド、好ましくは相対透湿速度が4以上、さらに5以上、特に5〜40のポリイミドが好ましい。ポリイミドの相対透湿速度は上限値はなくてもよいが、好ましくは50以下であり、さらに好ましくは40以下である。
一般式(1)及び一般式(2)中の架橋基Aとしては、酸素原子、硫黄原子、メチレン基、カルボニル基、スルホキシル基、スルホン基、1,1’−エチリデン基、1,2−エチリデン基、2,2’−イソプロピリデン基、2,2’−ヘキサフルオロイソプロピリデン基、シクロヘキシリデン基、フェニレン基、1,3−フェニレンジメチレン基、1,4−フェニレンジメチレン基、1,3−フェニレンジエチリデン基、1,4−フェニレンジエチリデン基、1,3−フェニレンジプロピリデン基、1,4−フェニレンジプロピリデン基、1,3−フェニレンジオキシ基、1,4−フェニレンジオキシ基、ビフェニレンジオキシ基、メチレンジフェノキシ基、エチリデンジフェノキシ基、プロピリデンジフェノキシ基、ヘキサフルオロプロピリデンジフェノキシ基、オキシジフェノキシ基、チオジフェノキシ基、スルホンジフェノキシ基などを挙げる事が出来、架橋基を介することなく直接結合していても良い。 Examples of the bridging group A in the general formula (1) and the general formula (2) include an oxygen atom, a sulfur atom, a methylene group, a carbonyl group, a sulfoxyl group, a sulfone group, a 1,1′-ethylidene group, and a 1,2-ethylidene group. Group, 2,2′-isopropylidene group, 2,2′-hexafluoroisopropylidene group, cyclohexylidene group, phenylene group, 1,3-phenylenedimethylene group, 1,4-phenylenedimethylene group, 1, 3-phenylenediethylidene group, 1,4-phenylenediethylidene group, 1,3-phenylenedipropylidene group, 1,4-phenylenedipropylidene group, 1,3-phenylenedioxy group, 1,4-pheny Rangeoxy, biphenylenedioxy, methylenediphenoxy, ethylidenediphenoxy, propylidenediphenoxy, hexafluoropropiyl Denji phenoxy group, an oxy-di-phenoxy group, Chiojifenokishi group, can be mentioned such as a sulfonic di phenoxy group, it may be bonded directly without passing through the bridging group.
一般式(1)及び一般式(2)中のR1〜R4は、
1)R1〜R4の全てが、炭素数1〜6の炭化水素基、ヒドロキシル基、カルボキシル基、炭素数1〜6のアルコキシ基、カルボアルコキシ基から選ばれる置換基を表す場合、
2)R1が水素で、R2〜R4の全てが、炭素数1〜6の炭化水素基、ヒドロキシル基、カルボキシル基、炭素数1〜6のアルコキシ基、カルボアルコキシ基から選ばれる置換基を表す場合、
3)R1とR2のどちから一方が水素で他方が炭素数1〜6の炭化水素基、ヒドロキシル基、カルボキシル基、炭素数1〜6のアルコキシ基、カルボアルコキシ基から選ばれる置換基を表し、R3とR4のどちから一方が水素で他方が炭素数1〜6の炭化水素基、ヒドロキシル基、カルボキシル基、炭素数1〜6のアルコキシ基、カルボアルコキシ基から選ばれる置換基を表す場合、
4)R1とR4のどちから一方が水素で他方が炭素数1〜6の炭化水素基、ヒドロキシル基、カルボキシル基、炭素数1〜6のアルコキシ基、カルボアルコキシ基から選ばれる置換基を表し、R2とR3のどちから一方が水素で他方が炭素数1〜6の炭化水素基、ヒドロキシル基、カルボキシル基、炭素数1〜6のアルコキシ基、カルボアルコキシ基から選ばれる置換基を表す場合、
5)R2〜R4の全てが水素で、R1が炭素数1〜6の炭化水素基、ヒドロキシル基、カルボキシル基、炭素数1〜6のアルコキシ基、カルボアルコキシ基から選ばれる置換基を表す場合、をあげることができる。
R 1 to R 4 in the general formula (1) and the general formula (2) are
1) When all of R 1 to R 4 represent a substituent selected from a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 6 carbon atoms, and a carboalkoxy group,
2) A substituent in which R 1 is hydrogen and all of R 2 to R 4 are selected from a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 6 carbon atoms, and a carboalkoxy group. Represents
3) One of R 1 and R 2 is hydrogen and the other represents a substituent selected from a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 6 carbon atoms, and a carboalkoxy group. , One of R 3 and R 4 is hydrogen and the other represents a substituent selected from a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 6 carbon atoms, and a carboalkoxy group ,
4) One of R 1 and R 4 is hydrogen, and the other represents a substituent selected from a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 6 carbon atoms, and a carboalkoxy group. , One of R 2 and R 3 and the other represents a substituent selected from a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 6 carbon atoms, and a carboalkoxy group ,
5) R 2 to R 4 are all hydrogen, and R 1 is a substituent selected from a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 6 carbon atoms, and a carboalkoxy group. If so, you can mention
一般式(1)及び一般式(2)中のR1〜R4の具体的な例としては、水素、メチル基、エチル基、n−プロピル基、i−プロピル基、n−ブチル基、s−ブチル基、i−ブチル基、t−ブチル基、ペンチル基、シクロヘキシル基、フェニル基等の炭化水素基、ヒドロキシル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等のアルコキシ基、カルボキシル基、カルボメトキシ基、カルボエトキシ基、カルボプロポキシ基、カルボブトキシ基等のカルボアルコキシ基等をあげることができる。R1〜R4は全て同じでもよく、それぞれ独立に異なっていてもよい。 Specific examples of R 1 to R 4 in the general formula (1) and the general formula (2) include hydrogen, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s -Hydrocarbon group such as butyl group, i-butyl group, t-butyl group, pentyl group, cyclohexyl group, phenyl group, alkoxy group such as hydroxyl group, methoxy group, ethoxy group, propoxy group, butoxy group, carboxyl group, Examples thereof include carboalkoxy groups such as carbomethoxy group, carboethoxy group, carbopropoxy group, carbobutoxy group, and the like. R 1 to R 4 may all be the same or different from each other.
一般式(1)及び一般式(2)で表される芳香族ジアミンの具体的な例としては、3,3’−ジメチル−4,4’−ジアミノビフェニル、3,3’−ジヒドロキシ−4,4’−ジアミノビフェニル、3,3’−ジカルボキシ−4,4’−ジアミノビフェニル、3,3’−ジメトキシ−4,4’−ジアミノビフェニル、3,3’,5,5’−テトラメチル−4,4’−ジアミノビフェニル、4,4’−メチレン−ビス(2−メチルアニリン)、4,4’−メチレン−ビス(2−エチルアニリン)、4,4’−メチレン−ビス(2−イソプロピルアニリン)、4,4’−メチレン−ビス(2,6−ジメチルアニリン)、4,4’−メチレン−ビス(2,6−ジエチルアニリン)、4,4−メチレン−ビス(2,6−ジイソプロピルアニリン)、3,3’−ジヒドロキシ−4,4’−ジアミノジフェニルメタン、3,3’−ジカルボキシ−4,4’−ジアミノジフェニルメタン、3,3’−ジカルボキシ−4,4’−ジアミノ−5,5’−ジメチルジフェニルメタン、o−トリジンスルホンなどを挙げることができ、これらは単独で又は2種以上用いることができる。
熱融着性を有しない耐熱性ポリイミド層(S2層)のポリイミドを得ることができるジアミン成分として、4,4’−メチレン−ビス(2,6−ジメチルアニリン)を用いると、片面のみに熱融着性を有するポリイミドフィルムの透明性に優れるために、好適に用いることができる。
Specific examples of the aromatic diamine represented by the general formula (1) and the general formula (2) include 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dihydroxy-4, 4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3 ', 5,5'-tetramethyl- 4,4′-diaminobiphenyl, 4,4′-methylene-bis (2-methylaniline), 4,4′-methylene-bis (2-ethylaniline), 4,4′-methylene-bis (2-isopropyl) Aniline), 4,4'-methylene-bis (2,6-dimethylaniline), 4,4'-methylene-bis (2,6-diethylaniline), 4,4-methylene-bis (2,6-diisopropyl) Aniline), 3,3′-dihydroxy- , 4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diamino-5,5'-dimethyldiphenylmethane, o-tolidine sulfone These may be used alone or in combination of two or more.
When 4,4′-methylene-bis (2,6-dimethylaniline) is used as a diamine component that can obtain polyimide of a heat-resistant polyimide layer (S2 layer) that does not have heat-fusibility, heat is applied only to one side. Since it is excellent in the transparency of the polyimide film which has a melt | fusion property, it can use suitably.
熱融着性を有しない耐熱性ポリイミド層(S2層)のテトラカルボン酸二無水物成分は、一般式(3)に示すテトラカルボン酸二無水物から選ばれる成分を少なくとも1種以上を含むテトラカルボン酸二無水物を用いることができ、テトラカルボン酸二無水物100モル%中、一般式(3)に示すテトラカルボン酸二無水物を好ましくは50モル%以上、さらに好ましくは70モル%以上、より好ましくは80モル%以上、特に好ましくは90モル%以上含むことにより、本発明の特性を損なわないポリイミドを得ることができる。
一般式(3)に示すテトラカルボン酸二無水物としては、具体的には、ピロメリット酸二無水物、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物、ビス(3,4−ジカルボキシフェニル)エーテル二無水物、ビス(3,4−ジカルボキシフェニル)スルフィド二無水物、ビス(3,4−ジカルボキシフェニル)スルホン二無水物、2,2−ビス(3,4−ジカルボキシフェニル)プロパン二無水物、2,2−ビス(3,4−ジカルボキシフェニル)−1,1,1,3,3,3−ヘキサフルオロプロパン二無水物、などを挙げる事ができる。 Specific examples of the tetracarboxylic dianhydride represented by the general formula (3) include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′. , 4,4′-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride, bis (3,4- Dicarboxyphenyl) sulfone dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3 , 3,3-hexafluoropropane dianhydride, and the like.
熱融着性を有しない耐熱性ポリイミド層(S2層)の熱融着性を有しない耐熱性ポリイミドを得ることができるテトラカルボン酸二無水物成分としては、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物及びピロメリット酸二無水物より選ばれる成分を少なくとも1種含む酸成分、好ましくはこれらの酸成分を少なくとも70モル%以上、さらに好ましくは80モル%以上、より好ましくは90モル%以上含む酸成分を用いることが本発明の特性に好ましく、他のテトラカルボン酸二無水物を本発明の特性を損なわない範囲で含むことができる。 Examples of the tetracarboxylic dianhydride component that can obtain a heat-resistant polyimide having no heat-fusibility of a heat-resistant polyimide layer (S2 layer) having no heat-fusibility include 3,3 ′, 4,4 ′. -An acid component containing at least one component selected from biphenyltetracarboxylic dianhydride and pyromellitic dianhydride, preferably at least 70 mol%, more preferably 80 mol% or more, more preferably these acid components. Is preferably used for the characteristics of the present invention, and other tetracarboxylic dianhydrides can be included within a range not impairing the characteristics of the present invention.
熱融着性を有しない耐熱性ポリイミド層(S2層)の熱融着性を有しない耐熱性ポリイミドは、テトラカルボン酸二無水物成分として3,3’,4,4’−ビフェニルテトラカルボン酸二無水物を少なくとも70モル%以上、さらに好ましくは80モル%以上、より好ましくは90モル%以上含むテトラカルボン酸二無水物成分と、下記一般式(1)で表されるジアミン、好ましくは下記一般式(2)で表されるジアミンを0.5〜30モル%含むジアミンと、p−フェニレンジアミンとを含むジアミン成分から得られるポリイミドが、耐熱性に優れ、発泡の抑制に優れているために好ましい。
特に熱融着性を有しない耐熱性ポリイミド層(S2層)の熱融着性を有しない耐熱性ポリイミドは、テトラカルボン酸二無水物成分として3,3’,4,4’−ビフェニルテトラカルボン酸二無水物を少なくとも70モル%以上、さらに好ましくは80モル%以上、より好ましくは90モル%以上含むテトラカルボン酸二無水物成分と、4,4’−メチレン−ビス(2,6−ジメチルアニリン)0.5〜30モル%、好ましくは2〜28モル%、さらに好ましくは6〜25モル%と、p−フェニレンジアミンとを含むジアミン成分から得られるポリイミドが、さらに透明性に優れるために好ましい。
The heat-resistant polyimide layer having no heat-fusible property (S2 layer) and having no heat-fusible property is a 3,3 ′, 4,4′-biphenyltetracarboxylic acid as a tetracarboxylic dianhydride component. A tetracarboxylic dianhydride component containing at least 70 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more of a dianhydride, and a diamine represented by the following general formula (1), preferably A polyimide obtained from a diamine component containing 0.5 to 30 mol% of a diamine represented by the general formula (2) and p-phenylenediamine is excellent in heat resistance and excellent in suppressing foaming. Is preferred.
In particular, the heat-resistant polyimide layer having no heat-fusibility of the heat-resistant polyimide layer (S2 layer) having no heat-fusibility is 3,3 ′, 4,4′-biphenyltetracarboxylic as a tetracarboxylic dianhydride component. A tetracarboxylic dianhydride component containing at least 70 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more of acid dianhydride, and 4,4′-methylene-bis (2,6-dimethyl) Aniline) 0.5 to 30 mol%, preferably 2 to 28 mol%, more preferably 6 to 25 mol%, and polyimide obtained from a diamine component containing p-phenylenediamine is more excellent in transparency. preferable.
熱融着性を有しない耐熱性ポリイミド層(S2層)の熱融着性を有しない耐熱性ポリイミドは、上記一般式(1)、好ましくは上記一般式(2)で示されるジアミン、上記一般式(3)で示される酸成分のほかに、耐熱性ポリイミド層(S2層)の特性を損なわない範囲で公知のジアミンや酸成分を用いることができ、特にジアミンとしてはベンゼン環が1つ又は2つの芳香族ジアミンが好ましく用いることができる。 The heat-resistant polyimide layer having no heat-fusible property of the heat-resistant polyimide layer (S2 layer) having no heat-fusible property is the diamine represented by the general formula (1), preferably the general formula (2), In addition to the acid component represented by the formula (3), known diamines and acid components can be used as long as the characteristics of the heat-resistant polyimide layer (S2 layer) are not impaired. Particularly, the diamine has one benzene ring or Two aromatic diamines can be preferably used.
本発明の片面のみに熱融着性を有するポリイミドフィルムは、耐熱性ポリイミド層(S1層)の両面に熱融着性ポリイミド層(S3層)を有し、熱融着性ポリイミド層の片面に熱融着性を有しない耐熱性ポリイミド層(S2層)が積層されている片面のみに熱融着性を有するポリイミドフィルムであり、
熱融着性を有しない耐熱性ポリイミド層(S2層)は、透湿速度が4以上、さらに5以上、特に5〜40の熱融着性を有しない耐熱性ポリイミドであることを特徴とする片面のみに熱融着性を有するポリイミドフィルムである。ポリイミドの透湿速度は上限値はなくてもよいが、好ましくは50以下であり、さらに好ましくは40以下である。
The polyimide film having heat-fusibility only on one side of the present invention has a heat-fusible polyimide layer (S3 layer) on both sides of the heat-resistant polyimide layer (S1 layer), and on one side of the heat-fusible polyimide layer. A heat-resistant polyimide layer (S2 layer) having no heat-fusible property is a polyimide film having heat-fusible property only on one side,
The heat-resistant polyimide layer (S2 layer) having no heat-fusible property is characterized by being a heat-resistant polyimide having a moisture transmission rate of 4 or more, more preferably 5 or more, particularly 5 to 40, and having no heat-fusibility. It is a polyimide film having heat-fusibility only on one side. Although the upper limit of the moisture permeation rate of polyimide may not be, it is preferably 50 or less, and more preferably 40 or less.
片面のみに熱融着性を有するポリイミドフィルムにおいて、耐熱性ポリイミド層(S1層)、熱融着性ポリイミド層(S3層)及び熱融着性ポリイミド層の片面に熱融着性を有しない耐熱性ポリイミド層(S2層)の厚みは使用する目的に応じて適宜選択すればよいが、例えば厚みが4〜100μmの耐熱性ポリイミド層(S1層)の両面に厚みが略等しい熱融着性ポリイミド層を有し、片面の熱融着性ポリイミド層の厚みと他面の熱融着性ポリイミド層の厚みとの合計が3〜10μmであり、熱融着性ポリイミド層の片面に厚みが0.1〜2μmの熱融着性を有しない耐熱性ポリイミド層(S2層)が積層されている片面のみに熱融着性を有するポリイミドフィルムが好ましい。 A heat resistant polyimide layer (S1 layer), a heat-fusible polyimide layer (S3 layer), and a heat-fusible polyimide layer that has no heat-fusible property on a single-sided polyimide film. The thickness of the conductive polyimide layer (S2 layer) may be appropriately selected according to the purpose of use. For example, the heat-sealable polyimide having substantially the same thickness on both surfaces of the heat-resistant polyimide layer (S1 layer) having a thickness of 4 to 100 μm. And the total thickness of the heat-sealable polyimide layer on one side and the thickness of the heat-sealable polyimide layer on the other side is 3 to 10 μm, and the thickness is 0.1 on one side of the heat-sealable polyimide layer. A polyimide film having heat fusibility only on one side on which a heat-resistant polyimide layer (S2 layer) having no heat fusibility of 1 to 2 μm is laminated is preferable.
耐熱性ポリイミド層(S1層)のポリイミド、熱融着性ポリイミド層(S3層)のポリイミド及び熱融着性を有しない耐熱性ポリイミド層(S2層)のポリイミドは、公知の方法で合成することができ、ランダム重合、ブロック重合、或いはあらかじめ複数のポリイミド前駆体溶液或いはポリイミド溶液を合成しておき、その複数の溶液を混合後反応条件下で混合して均一溶液とする、いずれの方法によっても達成される。 The polyimide of the heat-resistant polyimide layer (S1 layer), the polyimide of the heat-fusible polyimide layer (S3 layer), and the polyimide of the heat-resistant polyimide layer (S2 layer) that does not have heat-fusible properties are synthesized by known methods. Any method of random polymerization, block polymerization, or synthesizing a plurality of polyimide precursor solutions or polyimide solutions in advance and mixing the plurality of solutions under reaction conditions to obtain a uniform solution. Achieved.
耐熱性ポリイミド層(S1層)のポリイミド、熱融着性ポリイミド層(S3層)のポリイミド及び熱融着性を有しない耐熱性ポリイミド層(S2層)のポリイミドは、酸成分とジアミン成分とを、有機溶媒中、約100℃以下、さらに80℃以下、さらに0〜60℃の温度で、特に20〜60℃の温度で、約0.2〜60時間反応させてポリイミド前駆体の溶液とし、このポリイミド前駆体溶液をドープ液として使用し、そのドープ液の薄膜を形成し、その薄膜から溶媒を蒸発させ除去すると共にポリイミド前駆体をイミド化することにより製造することができる。またポリイミド前駆体溶液に、イミド化反応触媒として各種塩基性化合物を添加することも好適に行われる。
また溶解性に優れるポリイミドでは、ポリイミド前駆体溶液を150〜250℃に加熱するか、またはイミド化剤を添加して150℃以下、特に15〜50℃の温度で反応させて、イミド環化した後溶媒を蒸発させる、もしくは貧溶媒中に析出させて粉末とした後、該粉末を有機溶液に溶解してポリイミドの有機溶媒溶液を得ることができる。
The polyimide of the heat-resistant polyimide layer (S1 layer), the polyimide of the heat-fusible polyimide layer (S3 layer), and the polyimide of the heat-resistant polyimide layer (S2 layer) having no heat-fusible properties include an acid component and a diamine component. In an organic solvent, it is reacted at a temperature of about 100 ° C. or lower, further 80 ° C. or lower, further 0 to 60 ° C., particularly 20 to 60 ° C. for about 0.2 to 60 hours to obtain a polyimide precursor solution, The polyimide precursor solution can be used as a dope solution, a thin film of the dope solution is formed, the solvent is evaporated and removed from the thin film, and the polyimide precursor is imidized. It is also preferable to add various basic compounds as an imidization reaction catalyst to the polyimide precursor solution.
Moreover, in the polyimide which is excellent in solubility, the polyimide precursor solution is heated to 150 to 250 ° C., or an imidizing agent is added and reacted at a temperature of 150 ° C. or less, particularly 15 to 50 ° C., to imide cyclization. After the solvent is evaporated or precipitated into a poor solvent to form a powder, the powder can be dissolved in an organic solution to obtain an organic solvent solution of polyimide.
ポリイミド前駆体溶液の重合反応を実施するに際して、有機極性溶媒中の全モノマ−の濃度は、使用する目的や製造する目的に応じて適宜選択すればよく、例えば耐熱性ポリイミド層(S1層)および熱融着性ポリイミド層(S3層)のポリイミド前駆体溶液は、有機極性溶媒中の全モノマ−の濃度が、好ましくは5〜40質量%、さらに好ましくは6〜35質量%、特に好ましくは10〜30質量%であることが好ましく、
耐熱性ポリイミド層(S2層)のポリイミド前駆体溶液は、有機極性溶媒中の全モノマ−の濃度が1〜15質量%、特に2〜8質量%となる割合であることが好ましい。
In carrying out the polymerization reaction of the polyimide precursor solution, the concentration of all monomers in the organic polar solvent may be appropriately selected according to the purpose of use or the purpose of production. For example, the heat-resistant polyimide layer (S1 layer) and In the polyimide precursor solution of the heat-fusible polyimide layer (S3 layer), the concentration of all monomers in the organic polar solvent is preferably 5 to 40% by mass, more preferably 6 to 35% by mass, and particularly preferably 10%. It is preferably ~ 30% by mass,
The polyimide precursor solution of the heat-resistant polyimide layer (S2 layer) is preferably in a ratio such that the concentration of all monomers in the organic polar solvent is 1 to 15% by mass, particularly 2 to 8% by mass.
ポリイミド前駆体溶液の重合反応を実施するに際して、溶液粘度は、使用する目的(塗布、流延など)や製造する目的に応じて適宜選択すればよく、ポリアミック(ポリイミド前駆体)酸溶液は、30℃で測定した回転粘度が、約0.1〜5000ポイズ、特に0.5〜2000ポイズ、さらに好ましくは1〜2000ポイズ程度のものであることが、このポリアミック酸溶液を取り扱う作業性の面から好ましい。したがって、前記の重合反応は、生成するポリアミック酸が上記のような粘度を示す程度にまで実施することが望ましい。
熱融着性ポリイミド層(S3層)及び/又は耐熱性ポリイミド層(S2層)は、上記の方法でポリイミド前駆体溶液を製造し、それに新たに有機溶媒を加え、希釈して用いることができる。
In carrying out the polymerization reaction of the polyimide precursor solution, the solution viscosity may be appropriately selected according to the purpose of use (coating, casting, etc.) and the purpose of production. The polyamic (polyimide precursor) acid solution is 30 From the viewpoint of workability in handling this polyamic acid solution, the rotational viscosity measured at ° C is about 0.1 to 5000 poise, particularly 0.5 to 2000 poise, more preferably about 1 to 2000 poise. preferable. Therefore, it is desirable to carry out the polymerization reaction to such an extent that the produced polyamic acid exhibits the above viscosity.
The heat-fusible polyimide layer (S3 layer) and / or the heat-resistant polyimide layer (S2 layer) can be used by producing a polyimide precursor solution by the above method, adding an organic solvent to the solution, and diluting it. .
耐熱性ポリイミド層(S1層)のポリイミド、熱融着性ポリイミド層(S3層)のポリイミド及び熱融着性を有しない耐熱性ポリイミド層(S2層)のポリイミドは、ジアミン成分とテトラカルボン酸二無水物の略等モル量、ジアミン成分が少し過剰な量或いは酸成分が少し過剰な量を、有機溶媒中で反応させてポリイミド前駆体の溶液(均一な溶液状態が保たれていれば一部がイミド化されていてもよい)を得ることができる。
耐熱性ポリイミド層(S1層)のポリイミド、熱融着性ポリイミド層(S3層)のポリイミド及び熱融着性を有しない耐熱性ポリイミド層(S2層)のポリイミドは、アミン末端を封止するためにジカルボン酸無水物、例えば、無水フタル酸およびその置換体、ヘキサヒドロ無水フタル酸およびその置換体、無水コハク酸およびその置換体など、特に、無水フタル酸を添加して合成することができる。
The polyimide of the heat-resistant polyimide layer (S1 layer), the polyimide of the heat-fusible polyimide layer (S3 layer), and the polyimide of the heat-resistant polyimide layer (S2 layer) having no heat-fusible properties are composed of a diamine component and a tetracarboxylic acid diester. An approximately equimolar amount of anhydride, a little excess amount of diamine component or a little excess amount of acid component are reacted in an organic solvent to give a polyimide precursor solution (if the uniform solution state is maintained, partly Can be imidized).
The polyimide of the heat-resistant polyimide layer (S1 layer), the polyimide of the heat-fusible polyimide layer (S3 layer), and the polyimide of the heat-resistant polyimide layer (S2 layer) having no heat-fusible properties seal the amine terminal. In addition, dicarboxylic acid anhydrides such as phthalic anhydride and substituted products thereof, hexahydrophthalic anhydride and substituted products thereof, succinic anhydride and substituted products thereof, in particular, phthalic anhydride can be added and synthesized.
耐熱性ポリイミド層(S1層)のポリイミド、熱融着性ポリイミド層(S3層)のポリイミド及び熱融着性を有しない耐熱性ポリイミド層(S2層)のポリイミドは、有機溶媒中、ジアミン(アミノ基のモル数として)の使用量が酸無水物の全モル数(テトラ酸二無水物とジカルボン酸無水物の酸無水物基としての総モルとして)に対する比として、0.95〜1.05、特に0.98〜1.02、そのなかでも特に0.99〜1.01であることが好ましい。ジカルボン酸無水物を使用する場合の使用量はテトラカルボン酸二無水物の酸無水物基モル量に対する比として、0.05以下であるような割合の各成分を反応させることができる。 The polyimide of the heat-resistant polyimide layer (S1 layer), the polyimide of the heat-fusible polyimide layer (S3 layer), and the polyimide of the heat-resistant polyimide layer (S2 layer) having no heat-fusible property are diamine (amino) in an organic solvent. The ratio of the amount used as the number of moles of groups) to the total number of moles of acid anhydride (as total moles of tetraacid dianhydride and dicarboxylic anhydride as acid anhydride groups) is 0.95 to 1.05. In particular, it is preferably 0.98 to 1.02, and particularly preferably 0.99 to 1.01. When the dicarboxylic acid anhydride is used, each component can be reacted at a ratio of 0.05 or less as a ratio of the tetracarboxylic dianhydride to the molar amount of the acid anhydride group.
ポリイミド前駆体のゲル化を制限する目的でリン系安定剤、例えば亜リン酸トリフェニル、リン酸トリフェニル等をポリアミック酸重合時に固形分(ポリマー)濃度に対して0.01〜1%の範囲で添加することができる。
また、イミド化促進の目的で、ドープ液中に塩基性有機化合物を添加することができる。例えば、イミダゾール、2−イミダゾール、1,2−ジメチルイミダゾール、2−フェニルイミダゾール、ベンズイミダゾール、イソキノリン、置換ピリジンなどをポリアミック酸に対して0.05〜10重量%、特に0.1〜2重量%の割合で使用することができる。これらは比較的低温でポリイミドフィルムを形成するため、イミド化が不十分となることを避けるために使用することができる。
また、接着強度の安定化の目的で、熱融着性ポリイミド用ポリアミック酸溶液に有機アルミニウム化合物、無機アルミニウム化合物または有機錫化合物を添加してもよい。例えば水酸化アルミニウム、アルミニウムトリアセチルアセトナートなどをポリアミック酸に対してアルミニウム金属として1ppm以上、特に1〜1000ppmの割合で添加することができる。
For the purpose of limiting the gelation of the polyimide precursor, a phosphorus stabilizer such as triphenyl phosphite, triphenyl phosphate, etc. is in the range of 0.01 to 1% with respect to the solid content (polymer) concentration during polyamic acid polymerization. Can be added.
For the purpose of promoting imidization, a basic organic compound can be added to the dope solution. For example, imidazole, 2-imidazole, 1,2-dimethylimidazole, 2-phenylimidazole, benzimidazole, isoquinoline, substituted pyridine and the like are 0.05 to 10% by weight, particularly 0.1 to 2% by weight, based on the polyamic acid. Can be used in proportions. Since these form a polyimide film at a relatively low temperature, they can be used to avoid insufficient imidization.
Further, for the purpose of stabilizing the adhesive strength, an organoaluminum compound, an inorganic aluminum compound or an organotin compound may be added to the polyamic acid solution for heat-fusible polyimide. For example, aluminum hydroxide, aluminum triacetylacetonate or the like can be added in an amount of 1 ppm or more, particularly 1 to 1000 ppm as an aluminum metal with respect to the polyamic acid.
ポリアミック酸製造に使用する有機溶媒は、N−メチル−2−ピロリドン、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,N−ジエチルアセトアミド、ジメチルスルホキシド、ヘキサメチルホスホルアミド、N−メチルカプロラクタム、クレゾール類などが挙げられる。これらの有機溶媒は単独で用いてもよく、2種以上を併用してもよい。 Organic solvents used for the production of polyamic acid are N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, N- Examples include methyl caprolactam and cresols. These organic solvents may be used alone or in combination of two or more.
本発明の片面のみに熱融着性を有するポリイミドフィルムの製造において、例えば上記の耐熱性ポリイミド(S1層)を与えるポリアミック酸溶液と熱融着性ポリイミド(S3層)を与えるポリアミック酸溶液を三層共押出法によって、耐熱性ポリイミド層(S1層)の厚みが4〜100μmで、両側の熱融着性ポリイミド層(S3層)の厚みの合計が3〜10μmとなるように三層押出し成形用ダイスに供給し、支持体上にキャストしてこれをステンレス鏡面、ベルト面等の支持体面上に流延塗布し、加熱および/または化学イミド化し、必要に応じてさらに100〜200℃で乾燥し、自己支持性フィルムとすることが好ましい。
本発明の片面のみに熱融着性を有するポリイミドフィルムの製造において、別な自己支持性フィルムの製造法として、熱融着性ポリイミド(S3層)を与えるポリアミック酸溶液をステンレス鏡面、ベルト面等の支持体面上に流延塗布し、必要に応じて乾燥し、さらにS3層の上面に耐熱性ポリイミド(S1層)を与えるポリアミック酸溶液を流延塗布し、必要に応じて乾燥し、さらにさらにS1層の上面に熱融着性ポリイミド(S3層)を与えるポリアミック酸溶液を流延塗布し、必要に応じて乾燥、例えば100〜200℃の温度で乾燥し、自己支持性フィルムとすることができる。
200℃を越えた高い温度で流延フィルムを処理すると、熱融着性を有するポリイミドフィルムの製造において、接着性の低下などの欠陥を来す傾向にある。
ポリアミック酸溶液をステンレス鏡面、ベルト面等の支持体面上に流延塗布し、乾燥して得られるフィルムで、支持体に接する側を自己支持性フィルムのB面とし、支持体とは反対の空気側と接する側を自己支持性フィルムのA面とする。
In the production of a polyimide film having heat fusion properties only on one side of the present invention, for example, three polyamic acid solutions that give the above heat-resistant polyimide (S1 layer) and three polyamic acid solutions that give the heat fusion polyimide (S3 layer) are used. By the layer coextrusion method, the thickness of the heat-resistant polyimide layer (S1 layer) is 4 to 100 μm, and the total thickness of the heat-fusible polyimide layers (S3 layer) on both sides is 3 to 10 μm. It is supplied to a die for casting, cast on a support, cast on a support surface such as a stainless steel mirror surface or belt surface, heated and / or chemically imidized, and further dried at 100 to 200 ° C. as necessary. It is preferable to use a self-supporting film.
In the production of a polyimide film having heat-fusibility on only one side of the present invention, as another method for producing a self-supporting film, a polyamic acid solution that gives heat-fusible polyimide (S3 layer) is made of stainless steel mirror surface, belt surface, etc. The polyamic acid solution that gives heat-resistant polyimide (S1 layer) is cast on the upper surface of the S3 layer, and is dried if necessary. A polyamic acid solution that gives a heat-fusible polyimide (S3 layer) is cast on the upper surface of the S1 layer, and if necessary, dried, for example, dried at a temperature of 100 to 200 ° C. to form a self-supporting film. it can.
When a cast film is processed at a high temperature exceeding 200 ° C., there is a tendency to cause defects such as a decrease in adhesiveness in the production of a polyimide film having heat-fusibility.
A film obtained by casting and drying a polyamic acid solution on a support surface such as a stainless steel mirror surface or a belt surface, and drying. The side in contact with the support is the B surface of the self-supporting film, and the air opposite to the support The side in contact with the side is the A side of the self-supporting film.
次いで自己支持性フィルムを支持体より剥がし、自己支持性フィルムの片面(A面あるいはB面)に、熱融着性を有しない耐熱性ポリイミド層(S2層)を与える組成のポリアミック酸溶液を該耐熱性ポリイミド層の厚みが0.1〜2μmとなるように、グラビアート法、スクリーン法、浸漬法などの塗布法で均一に塗布して均一に分布させ、その塗布フィルムを好ましくは50〜180℃、特に好ましくは60〜160℃、さらに好ましくは70〜150℃の乾燥温度で、好ましくは0.1〜20分間、特に好ましくは0.2〜15分間乾燥して固化フィルムを形成し、次いで、好ましくは(1)100gf/mm2以下、特に好ましくは80gf/mm2以下である実質的にフリーの状態ないしは低張力下、好ましくは(2)約80〜250℃、特に好ましくは100〜230℃の乾燥温度で、好ましくは約1〜200分間、特に好ましくは2〜100分間乾燥して、前記有機溶媒および生成水分が約5〜25重量%、特に10〜23重量%の割合で含有されている固化フィルムを形成することが望ましい。
熱融着性を有しない耐熱性ポリイミド層(S2層)を与える組成のポリアミック酸溶液は、自己支持性フィルムのB面に塗布することが、非融着性保持のために好ましい。
Subsequently, the self-supporting film is peeled off from the support, and a polyamic acid solution having a composition that gives a heat-resistant polyimide layer (S2 layer) having no heat-bonding property to one side (A surface or B surface) of the self-supporting film is obtained. The heat-resistant polyimide layer is uniformly coated by a coating method such as gravite, screen, or dipping so that the thickness is 0.1 to 2 μm, and the coated film is preferably 50 to 180. At a drying temperature of 60 ° C., particularly preferably 60 to 160 ° C., more preferably 70 to 150 ° C., preferably 0.1 to 20 minutes, particularly preferably 0.2 to 15 minutes to form a solidified film, Preferably (1) 100 gf / mm 2 or less, particularly preferably 80 gf / mm 2 or less, in a substantially free state or under low tension, preferably (2) about 80 to 2 Drying at a drying temperature of 50 ° C., particularly preferably 100 to 230 ° C., preferably for about 1 to 200 minutes, particularly preferably 2 to 100 minutes, the organic solvent and the generated water are about 5 to 25% by weight, in particular 10 It is desirable to form a solidified film contained in a proportion of ˜23% by weight.
The polyamic acid solution having a composition that provides a heat-resistant polyimide layer (S2 layer) having no heat-fusibility is preferably applied to the B-side of the self-supporting film in order to maintain non-fusibility.
剥離された自己支持性フィルムは、その加熱減量が20〜40質量%の範囲にあることが好ましく、イミド化率が8〜40%の範囲にあることが、自己支持性フィルムの力学的性質が十分でない場合、自己支持性フィルムの上面にポリイミド前駆体溶液をきれいに塗布しにくくなる場合、ポリイミド層(S1層)とポリイミド層(S3層)との接着強度が弱くなる場合、イミド化後に得られるポリイミドフィルムに、発泡、亀裂、クレーズ、クラック、ひびワレなどの発生が観察される場合などがあるために、好ましい。
なお、上記の自己支持性フィルムの加熱減量とは、測定対象のフィルムを420℃で20分間乾燥し、乾燥前の重量W1と乾燥後の重量W2とから次式によって求めた値である。
加熱減量(質量%)={(W1−W2)/W1}×100
また、上記の自己支持性フィルムのイミド化率は、特開平9−316199記載のカールフィッシャー水分計を用いる手法で求めることができる。
The peeled self-supporting film preferably has a weight loss on heating in the range of 20 to 40% by mass, and has an imidization ratio in the range of 8 to 40%. If it is not sufficient, it becomes difficult to apply the polyimide precursor solution cleanly on the upper surface of the self-supporting film, and if the adhesive strength between the polyimide layer (S1 layer) and the polyimide layer (S3 layer) is weakened, it is obtained after imidization. It is preferable because occurrence of foaming, cracks, crazes, cracks, cracks and the like may be observed in the polyimide film.
The loss on heating of the self-supporting film is a value obtained by drying the film to be measured at 420 ° C. for 20 minutes and calculating from the following formula from the weight W1 before drying and the weight W2 after drying.
Heat loss (mass%) = {(W1-W2) / W1} × 100
Moreover, the imidation ratio of said self-supporting film can be calculated | required by the method using the Karl Fischer moisture meter of Unexamined-Japanese-Patent No. 9-316199.
自己支持性フィルムには、必要であれば、内部または表面層に微細な無機あるいは有機の添加剤を配合することができる。無機の添加剤としては,粒子状あるいは偏平状の無機フィラーを挙げることができる。有機の添加剤としてはポリイミド粒子、熱硬化性樹脂の粒子などを挙げる事ができる。使用量および形状(大きさ,アスペクト比)については、使用目的に応じて選択することが好ましい。 In the self-supporting film, if necessary, fine inorganic or organic additives can be blended in the inside or the surface layer. Examples of inorganic additives include particulate or flat inorganic fillers. Examples of the organic additive include polyimide particles and thermosetting resin particles. The usage amount and shape (size, aspect ratio) are preferably selected according to the purpose of use.
前記溶媒および生成水分が好ましくは約25〜60重量%、特に好ましくは30〜50重量%残存している固化フィルムを乾燥温度に昇温する際には、比較的短時間内に昇温することが好ましく、例えば、10℃/分以上の昇温速度であることが好適である。乾燥する際に固化フィルム状体に対して加えられる張力を増大することによって、最終的に得られるポリイミドフィルムの線膨張係数を小さくすることができる。
そして、前述の乾燥工程に続いて、連続的または断続的に前記固化フィルムの少なくとも一対の両端縁を連続的または断続的に前記フィルムと共に移動可能な固定装置などで固定した状態で、前記の乾燥温度より高く、しかも好ましくは200〜550℃の範囲内、さらに好ましくは300〜500℃の範囲内、特に好ましくは320〜500℃の範囲内の高温度で、好ましくは1〜100分間、特に1〜10分間、前記固化フィルムを乾燥および熱処理して、好ましくは最終的に得られるポリイミドフィルム中の有機溶媒および生成水等からなる揮発物の含有量が1重量%以下になるように、固化フィルムから溶媒などを充分に除去するとともに前記フィルムを構成しているポリマーのイミド化を充分に行って、片面(B面あるいはA面)のみに熱融着性を有する多層ポリイミドフィルムを形成する。
When raising the temperature of the solidified film in which the solvent and the generated water are preferably about 25 to 60% by weight, particularly preferably 30 to 50% by weight, to a drying temperature, the temperature is raised within a relatively short time. For example, a temperature rising rate of 10 ° C./min or more is suitable. By increasing the tension applied to the solidified film body during drying, the linear expansion coefficient of the finally obtained polyimide film can be reduced.
Then, following the above-described drying step, the drying is performed in a state where at least a pair of both end edges of the solidified film is continuously or intermittently fixed with a fixing device or the like that can be moved together with the film. Higher than the temperature, preferably in the range of 200-550 ° C., more preferably in the range of 300-500 ° C., particularly preferably in the range of 320-500 ° C., preferably for 1-100 minutes, in particular 1 The solidified film is dried and heat-treated for 10 minutes for 10 minutes, so that the content of the volatile matter composed of an organic solvent and generated water in the finally obtained polyimide film is preferably 1% by weight or less. The solvent is sufficiently removed from the film and the imidation of the polymer constituting the film is sufficiently performed, so that one side (B side or A side) To form a multi-layer polyimide film having a heat-fusible to wear.
本発明の片面のみに熱融着性を有するポリイミドフィルムにおいて、多層の自己支持性フィルムを加熱、乾燥してイミド化を行い、さらに最高加熱温度320〜550℃で熱処理することにより、フィルム全体として充分な機械的性質および熱的性質に優れるフィルムを得ることができる。 In the polyimide film having heat-fusibility only on one side of the present invention, the multilayer self-supporting film is heated, dried and imidized, and further heat-treated at a maximum heating temperature of 320 to 550 ° C. A film excellent in sufficient mechanical properties and thermal properties can be obtained.
前記の固化フィルムの固定装置としては、例えば、多数のピンまたは把持具などを等間隔で備えたベルト状またはチェーン状のものを、連続的または断続的に供給される前記固化フィルムの長手方向の両側縁に沿って一対設置し、そのフィルムの移動と共に連続的または断続的に移動させながら前記フィルムを固定できる装置が好適である。また、前記の固化フィルムの固定装置は、熱処理中のフィルムを幅方向または長手方向に適当な伸び率または収縮率(特に好ましくは0.5〜5%程度の伸縮倍率)で伸縮することができる装置であってもよい。 As the fixing device for the solidified film, for example, a belt-like or chain-like one provided with a large number of pins or gripping tools at regular intervals is provided in the longitudinal direction of the solidified film supplied continuously or intermittently. A device that can be installed in a pair along both side edges and can fix the film while moving the film continuously or intermittently with the movement of the film is suitable. The solidified film fixing device can stretch or shrink the film being heat-treated in the width direction or the longitudinal direction at an appropriate elongation or contraction rate (particularly preferably about 0.5 to 5%). It may be a device.
なお、前記の工程において製造された改質されたポリイミドフィルムを、再び好ましくは400gf/mm2以下、特に好ましくは300gf/mm2以下の低張力下あるいは無張力下に、100〜400℃の温度で、好ましくは0.1〜30分間熱処理すると、特に寸法安定性が優れた片面(例えばB面)のみに熱融着性を有する多層ポリイミドフィルムとすることができる。また、製造された長尺の片面のみに熱融着性を有する多層ポリイミドフィルムは、適当な公知の方法でロール状に巻き取ることができる。 Incidentally, the polyimide film that has been modified produced in the process, again preferably 400 gf / mm 2 or less, particularly preferably under 300 gf / mm 2 or lower tension or under no tension, temperature of 100 to 400 ° C. Preferably, when heat treatment is performed for 0.1 to 30 minutes, it is possible to obtain a multilayer polyimide film having heat fusion properties only on one surface (for example, B surface) having particularly excellent dimensional stability. Moreover, the manufactured multilayer polyimide film which has heat-sealability only on the long single side | surface can be wound up in a roll shape with a suitable well-known method.
加熱処理は、熱風炉、赤外線加熱炉などの公知の種々の装置を使用して行うことができる。
自己支持性フィルムの片面にポリイミド前駆体溶液を塗布する方法としては、公知の方法を用いることができ、例えば、グラビアコート法、スピンコート法、シルクスクリーン法、ディップコート法、スプレーコート法、バーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法などの公知の塗布方法を挙げる事が出来できる。
The heat treatment can be performed using various known devices such as a hot stove and an infrared heating furnace.
As a method of applying the polyimide precursor solution to one side of the self-supporting film, a known method can be used, for example, gravure coating method, spin coating method, silk screen method, dip coating method, spray coating method, bar coating Known coating methods such as a coating method, a knife coating method, a roll coating method, a blade coating method, and a die coating method can be exemplified.
片面のみに熱融着性を有するポリイミドフィルムと金属箔とを熱圧着(熱融着することにより、熱融着性を有するポリイミド層を介して熱圧着により、片面に金属箔を積層する片面金属箔積層板を得ることができる。
金属箔(回路用)としては、銅、アルミニウム、金、合金の箔など各種金属箔を用いることができ、好適には圧延銅箔、電解銅箔などの銅箔が好ましい。
金属箔としては、どのような表面粗さでも用いることができるが、表面粗さRzが0.5μm以上であるものが好ましい。また、金属箔の表面粗さRzが7μm以下、特に5μm以下であるものが好ましい。このような金属箔、例えば銅箔はVLP、LP(またはHTE)として知られている。
金属箔の厚さは特に制限はないが、2〜35μm、特に5〜18μmであるものが好ましい。金属箔の厚みが5μm以下のものは、キャリア付き金属箔、例えばアルミニウム箔キャリア付き銅箔が使用できる。
A single-sided metal in which a metal foil is laminated on one side by thermocompression bonding via a polyimide layer having heat-sealability by heat-bonding a polyimide film and metal foil having heat-sealability only on one side A foil laminate can be obtained.
Various metal foils such as copper, aluminum, gold, and alloy foils can be used as the metal foil (for circuit), and copper foils such as rolled copper foil and electrolytic copper foil are preferable.
As the metal foil, any surface roughness can be used, but those having a surface roughness Rz of 0.5 μm or more are preferable. Further, it is preferable that the surface roughness Rz of the metal foil is 7 μm or less, particularly 5 μm or less. Such metal foils, such as copper foils, are known as VLP, LP (or HTE).
Although the thickness of metal foil does not have a restriction | limiting in particular, What is 2-35 micrometers, Especially 5-18 micrometers is preferable. When the thickness of the metal foil is 5 μm or less, a metal foil with a carrier, for example, a copper foil with an aluminum foil carrier can be used.
本発明の片面のみに熱融着性を有するポリイミドフィルムは、金属箔と熱圧着することにより、片面金属箔積層板を製造することができる。
片面金属箔積層板の製造例として、片面のみに熱融着性を有するポリイミドフィルムと金属箔を、少なくとも一対の加圧部材で連続的に、加圧部の温度が熱融着性ポリイミドのガラス転移温度より30℃以上で420℃以下の温度で加熱下に熱圧着して、長尺状の片面金属箔積層板を得ることができる。
前記の加圧部材としては、一対の圧着金属ロール(圧着部は金属製、セラミック溶射金属製のいずれでもよい)、ダブルベルトプレスおよびホットプレスが挙げられ、特に加圧下に熱圧着および冷却できるものであって、そのなかでも特に液圧式のダブルベルトプレスを好適に挙げることができる。
この発明においては、前記の加圧部材、例えば金属ロール、好適にはダブルベルトプレスを使用し、片面のみに熱融着性を有するポリイミドフィルムと金属箔と補強材とを重ね合わせて、連続的に加熱下に圧着して、長尺状の片面金属箔積層板を製造することができる。
また、片面のみに熱融着性を有するポリイミドフィルムおよび金属箔が、ロール巻きの状態で用いられ、加圧部材にそれぞれ連続的に供給され、片面金属箔積層板をロール巻きの状態で得られる場合に特に好適である。
A single-sided metal foil laminate can be manufactured by thermocompression bonding of a polyimide film having a heat-sealing property to only one side of the present invention.
As an example of manufacturing a single-sided metal foil laminate, a polyimide film and a metal foil having heat-sealability on only one side are continuously formed by at least a pair of pressure members, and the temperature of the pressure part is a heat-sealable polyimide glass. A long single-sided metal foil laminate can be obtained by thermocompression bonding under heating at a temperature of 30 ° C. or higher and 420 ° C. or lower from the transition temperature.
Examples of the pressure member include a pair of pressure-bonding metal rolls (the pressure-bonding portion may be made of metal or ceramic sprayed metal), a double belt press, and a hot press, and particularly capable of thermocompression bonding and cooling under pressure. Of these, a hydraulic double belt press is particularly preferable.
In this invention, the pressure member, for example, a metal roll, preferably a double belt press is used, and a polyimide film having a heat-fusible property on only one side, a metal foil, and a reinforcing material are overlapped to continuously It is possible to produce a long single-sided metal foil laminate by pressure bonding with heating.
Moreover, the polyimide film and metal foil which have a heat-seal property only on one side are used in the state of roll winding, and each is continuously supplied to a pressurization member, and a single side metal foil laminated board is obtained in the state of roll winding It is particularly suitable for the case.
本発明の片面金属箔積層板は、熱融着性を有する多層ポリイミドフィルムおよび金属箔が強固に、好ましくはは90°剥離強度が1.0kgf/cm以上で積層され、セラミック、耐熱性ポリイミドフィルム、金属などの他の基材と常温だけでなく300℃程度の加熱時においても接着することがなく、例えば他の耐熱性ポリイミドフィルムと300℃程度の温度で加圧下に積層しても90°剥離強度が20gf/cm以下である。
本発明の片面金属箔積層板は、成形加工性が良好で、そのまま穴あけ加工、折り曲げ加工や絞り加工、金属配線形成、配線上への電子回路の熱圧着などを行うことができる。
The single-sided metal foil laminate of the present invention comprises a multilayer polyimide film having a heat-fusible property and a metal foil that are firmly laminated, preferably 90 ° peel strength is 1.0 kgf / cm or more, and ceramic, heat-resistant polyimide film It does not adhere to other base materials such as metals not only at room temperature but also at about 300 ° C., for example, 90 ° even when laminated with other heat-resistant polyimide film under pressure at a temperature of about 300 ° C. The peel strength is 20 gf / cm or less.
The single-sided metal foil laminate of the present invention has good moldability, and can be directly subjected to drilling, bending, drawing, metal wiring formation, electronic circuit thermocompression bonding on the wiring, and the like.
本発明の片面のみに熱融着性を有するポリイミドフィルム及び本発明の片面金属箔積層板は、プリント配線板、フレキシブルプリント基板、TABテープ等の電子部品や電子機器類の素材として用いることができる。 The polyimide film having heat-fusibility on only one side of the present invention and the single-sided metal foil laminate of the present invention can be used as materials for electronic parts and electronic devices such as printed wiring boards, flexible printed boards and TAB tapes. .
以下、本発明を実施例に基づき、さらに詳細に説明する。但し、本発明は実施例により制限されるものでない。 Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited by the examples.
以下の各例において、部は質量部を意味する。
以下の各例において、物性評価および銅箔積層フィルムの剥離強度は以下の方法に従って測定した。
1)フィルムの線膨張係数:50〜200℃、5℃/分の昇温速度で測定(MD)した。
2)積層体の剥離強度:IPC−FC−2413Bに従って、90°剥離強度を測定した。
3)フィルムのHAZE:スガ試験機株式会社製Haze Computer HZ−2を使用して測定した。
4)フィルムの引張弾性率:ASTM・D882に従って測定した。
5)フィルムのガラス転移温度(℃):動的粘弾性測定(昇温速度10℃/分、周波数1Hz)tanδのピーク温度により評価した。
6)片面のみに熱融着性を有するポリイミドフィルムの熱融着性を有しない耐熱性ポリイミド層(S2層)の接着性評価:長さ20cm、幅10cmの片面のみに熱融着性を有するポリイミドフィルムの熱融着性を有しない耐熱性ポリイミド層(S2層)同士を重ね合わせた後、340℃・60MPaも条件で5分間熱圧着した。この熱圧着した試料を長さ20cm、幅1cmの短冊状に切断し、Tピール強度(温度23℃、湿度65%の条件下測定)と、熱圧着後の片面のみに熱融着性を有するポリイミドフィルムの表面の失透及び発泡の有無を目視で確認した。なお、熱圧着後のフィルム同士がピール強度を計る前に力を加えなくても剥がれる場合を自然剥離として表した。
In each of the following examples, “part” means “part by mass”.
In each of the following examples, the physical property evaluation and the peel strength of the copper foil laminated film were measured according to the following methods.
1) Linear expansion coefficient of film: 50-200 ° C., measured (MD) at a heating rate of 5 ° C./min.
2) Peel strength of laminate: 90 ° peel strength was measured according to IPC-FC-2413B.
3) HAZE of film: Measured using a Haze Computer HZ-2 manufactured by Suga Test Instruments Co., Ltd.
4) Tensile modulus of film: measured in accordance with ASTM D882.
5) Glass transition temperature (° C.) of film: Dynamic viscoelasticity measurement (temperature increase rate: 10 ° C./min, frequency: 1 Hz) Evaluation was made based on the peak temperature of tan δ.
6) Adhesive evaluation of a heat-resistant polyimide layer (S2 layer) having no heat-fusibility of a polyimide film having heat-fusibility only on one side: heat-fusible only on one side having a length of 20 cm and a width of 10 cm After superimposing the heat-resistant polyimide layers (S2 layers) having no heat fusibility of the polyimide film, thermocompression bonding was performed for 5 minutes at 340 ° C. and 60 MPa. This thermocompression-bonded sample is cut into a strip shape having a length of 20 cm and a width of 1 cm, and has a T peel strength (measured under conditions of a temperature of 23 ° C. and a humidity of 65%) and only one surface after thermocompression bonding. The presence or absence of devitrification and foaming on the surface of the polyimide film was visually confirmed. In addition, the case where it peeled without applying force before the films after thermocompression bonding measured peel strength was represented as natural peeling.
7)相対透湿速度:得られたポリイミドフィルムを乾燥窒素雰囲気下で恒量になるまで乾燥させて乾燥時のフィルム重量を測定し、その後、乾燥したポリイミドフィルムを温度27℃、湿度55%RHの雰囲気中下において1時間、重量変化を追跡し、初期の重量増加率(重量変化曲線の傾き)を透湿速度とし、下記条件Aにおける50μmフィルムの透湿速度を1とした相対値を相対透湿速度とした。
[条件A:50μmフィルムの製造法]
反応容器にN、N−ジメチルアセトアミド(DMAc)を加え、撹拌及び窒素流通下、パラフェニレンジアミン(PPD)を添加し、50℃に保温し完全に溶解させた。この溶液にジアミン成分とジカルボン酸成分とが等モル量となる割合の3,3’,4,4’−ビフェニルテトラカルボン酸二無水物(BPDA)を発熱に注意しながら徐々に添加し、添加終了後50℃を保ったまま3時間反応を続けて、モノマ−濃度18質量%のポリイミド前駆体溶液(黄色粘調液体、25℃における溶液粘度は約1000ポイズ)を得た。
ポリイミド前駆体溶液を、ガラス基板上に最終膜厚25μm及び50μmとなるように塗布し、135℃で3分(最終膜厚25μm)又は5分(最終膜厚50μm)加熱して固化フィルムを形成し、ガラス基板から剥離した後、ピンテンタ−に貼り付けて130℃で5分、180℃で5分、210℃で5分、320℃で2分間加熱した後、450℃まで5分で昇温し、450℃に2分保持して熱処理することによりポリイミドフィルムを得た。
7) Relative moisture permeation rate: The obtained polyimide film was dried to a constant weight in a dry nitrogen atmosphere, and the film weight at the time of drying was measured. Thereafter, the dried polyimide film was measured at a temperature of 27 ° C. and a humidity of 55% RH. The change in weight was traced for 1 hour in the atmosphere, the initial weight increase rate (the slope of the weight change curve) was taken as the moisture transmission rate, and the relative value with the moisture transmission rate of the 50 μm film in the following condition A as 1 was measured as relative permeability. The wet speed was used.
[Condition A: Method for producing 50 μm film]
N, N-dimethylacetamide (DMAc) was added to the reaction vessel, paraphenylenediamine (PPD) was added under stirring and nitrogen flow, and the mixture was kept at 50 ° C. and completely dissolved. To this solution, gradually add 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) in an equimolar amount of the diamine component and the dicarboxylic acid component while paying attention to heat generation. After completion, the reaction was continued for 3 hours while maintaining 50 ° C. to obtain a polyimide precursor solution having a monomer concentration of 18% by mass (yellow viscous liquid, solution viscosity at 25 ° C. was about 1000 poise).
The polyimide precursor solution is applied on a glass substrate so as to have a final film thickness of 25 μm and 50 μm, and heated at 135 ° C. for 3 minutes (final film thickness 25 μm) or 5 minutes (final film thickness 50 μm) to form a solidified film. After peeling from the glass substrate, it was attached to a pin tenter and heated at 130 ° C. for 5 minutes, 180 ° C. for 5 minutes, 210 ° C. for 5 minutes, 320 ° C. for 2 minutes, and then heated to 450 ° C. in 5 minutes. Then, a polyimide film was obtained by heat-treating at 450 ° C. for 2 minutes.
(参考例1)耐熱性ポリイミド製造用ドープ(D1)の合成例
攪拌機、窒素導入管を備えた反応容器に、N、N−ジメチルアセトアミド(DMAc)を加え、さらに、p−フェニレンジアミン(PPD)と3,3’,4,4’−ビフェニルテトラカルボン酸二無水物(s−BPDA)とを1000:998のモル比でモノマー濃度が18%(重量%、以下同じ)になるように加えた。添加終了後50℃を保ったまま3時間反応を続けた。得られたポリアミック酸溶液は褐色粘調液体であり、25℃における溶液粘度は約1500ポイズであった。この溶液を耐熱性ポリイミド用ドープ(D1)として使用した。
(Reference Example 1) Synthesis example of dope (D1) for producing heat-resistant polyimide N, N-dimethylacetamide (DMAc) was added to a reaction vessel equipped with a stirrer and a nitrogen introduction tube, and p-phenylenediamine (PPD) was further added. And 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) were added at a molar ratio of 1000: 998 so that the monomer concentration was 18% (wt%, hereinafter the same). . After completion of the addition, the reaction was continued for 3 hours while maintaining 50 ° C. The obtained polyamic acid solution was a brown viscous liquid, and the solution viscosity at 25 ° C. was about 1500 poise. This solution was used as a heat-resistant polyimide dope (D1).
(参考例2)熱融着性ポリイミド製造用ドープ(E1)の合成例
攪拌機、窒素導入管を備えた反応容器に、N、N−ジメチルアセトアミド(DMAc)を加え、さらに、2,3,3’,4’−ビフェニルテトラカルボン酸二無水物、s−BPDA、1,3−ビス(4−アミノフェノキシ)ベンゼンおよびDADEを20:80:50:50のモル比でモノマー濃度が22%になるように、またトリフェニルホスフェートをモノマー重量に対して0.1%加えた。添加終了後25℃を保ったまま1時間反応を続けた。このポリアミック酸溶液は、25℃における溶液粘度が約2000ポイズであった。この溶液を熱融着性ポリイミド用ドープ(E1)として使用した。
(Reference Example 2) Synthesis example of dope (E1) for producing heat-fusible polyimide N, N-dimethylacetamide (DMAc) was added to a reaction vessel equipped with a stirrer and a nitrogen introduction tube, and 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, s-BPDA, 1,3-bis (4-aminophenoxy) benzene and DADE at a molar ratio of 20: 80: 50: 50, resulting in a monomer concentration of 22% As such, triphenyl phosphate was also added at 0.1% based on monomer weight. After completion of the addition, the reaction was continued for 1 hour while maintaining 25 ° C. This polyamic acid solution had a solution viscosity at 25 ° C. of about 2000 poise. This solution was used as a dope for heat-fusible polyimide (E1).
(参考例3)熱融着性を有しない耐熱性ポリイミド塗工液(F1)の合成例
N、N−ジメチルアセトアミド(DMAc)に、PPDおよびs−BPDAを100:96のモル比でモノマー濃度が18%(重量%、以下同じ)になるように加えてポリアミック酸溶液を得た後、酸/ジアミンが等モルとなるように3,3’,4,4’−ビフェニルテトラカルボン酸(s−BPTA)を添加して原液を調合し、N、N−ジメチルアセトアミド(DMAc)で希釈し、モノマー濃度が5%のポリアミック酸溶液を得た。この溶液を塗工用ドープとして使用した。
(Reference example 3) Synthesis example of heat-resistant polyimide coating liquid (F1) having no heat-fusibility N, N-dimethylacetamide (DMAc), PPD and s-BPDA in a molar ratio of 100: 96 Was added so as to be 18% (% by weight, the same shall apply hereinafter) to obtain a polyamic acid solution, and then 3,3 ′, 4,4′-biphenyltetracarboxylic acid (s -BPTA) was added to prepare a stock solution and diluted with N, N-dimethylacetamide (DMAc) to obtain a polyamic acid solution having a monomer concentration of 5%. This solution was used as a coating dope.
(参考例4)熱融着性を有しない耐熱性ポリイミド塗工液(F2)の合成例
DMAcに、PPD、4,4‘−メチレン−ビス(2,6−ジメチルアニリン)およびs−BPDAを95:5:96のモル比でモノマー濃度が18%(重量%、以下同じ)になるように加えてポリアミック酸溶液を得た後、酸/ジアミンが等モルとなるように3,3’,4,4’−ビフェニルテトラカルボン酸(s−BPTA)を添加して原液を調合し、DMAcで希釈し、モノマー濃度が5%のポリアミック酸溶液を得た。この溶液を塗工用ドープとして使用した。
(Reference example 4) Synthesis example of heat-resistant polyimide coating solution (F2) having no heat-fusible properties PDM, 4,4'-methylene-bis (2,6-dimethylaniline) and s-BPDA were added to DMAc. After adding a polyamic acid solution at a molar ratio of 95: 5: 96 so that the monomer concentration is 18% (weight%, the same applies hereinafter), 3, 3 ′, so that the acid / diamine is equimolar. 4,4′-biphenyltetracarboxylic acid (s-BPTA) was added to prepare a stock solution and diluted with DMAc to obtain a polyamic acid solution having a monomer concentration of 5%. This solution was used as a coating dope.
(参考例5)熱融着性を有しない耐熱性ポリイミド塗工液(F3)の合成例
DMAcに、PPD、4,4‘−メチレン−ビス(2,6−ジメチルアニリン)およびs−BPDAを90:10:96のモル比でモノマー濃度が18%(重量%、以下同じ)になるように加えてポリアミック酸溶液を得た後、酸/ジアミンが等モルとなるように3,3’,4,4’−ビフェニルテトラカルボン酸(s−BPTA)を添加して原液を調合し、DMAcで希釈し、モノマー濃度が5%のポリアミック酸溶液を得た。この溶液を塗工用ドープとして使用した。
(Reference Example 5) Synthesis example of heat-resistant polyimide coating solution (F3) having no heat-fusible property DMAc was subjected to PPD, 4,4'-methylene-bis (2,6-dimethylaniline) and s-BPDA. After adding a polyamic acid solution at a molar ratio of 90:10:96 so that the monomer concentration is 18% (weight%, the same applies hereinafter), 3, 3 ′, so that the acid / diamine is equimolar. 4,4′-biphenyltetracarboxylic acid (s-BPTA) was added to prepare a stock solution and diluted with DMAc to obtain a polyamic acid solution having a monomer concentration of 5%. This solution was used as a coating dope.
(参考例6)熱融着性を有しない耐熱性ポリイミド塗工液(F4)の合成例
DMAcに、PPD、4,4‘−メチレン−ビス(2,6−ジメチルアニリン)およびs−BPDAを80:20:96のモル比でモノマー濃度が18%(重量%、以下同じ)になるように加えてポリアミック酸溶液を得た後、酸/ジアミンが等モルとなるように3,3’,4,4’−ビフェニルテトラカルボン酸(s−BPTA)を添加して原液を調合し、DMAcで希釈し、モノマー濃度が5%のポリアミック酸溶液を得た。この溶液を塗工用ドープとして使用した。
(Reference Example 6) Synthesis example of heat-resistant polyimide coating liquid (F4) having no heat-fusible properties PDM, 4,4'-methylene-bis (2,6-dimethylaniline) and s-BPDA were added to DMAc. After adding a polyamic acid solution at a molar ratio of 80:20:96 so that the monomer concentration is 18% (wt%, the same shall apply hereinafter), 3, 3 ′, so that the acid / diamine is equimolar. 4,4′-biphenyltetracarboxylic acid (s-BPTA) was added to prepare a stock solution and diluted with DMAc to obtain a polyamic acid solution having a monomer concentration of 5%. This solution was used as a coating dope.
(実施例1〜8、比較例2〜4)
耐熱性ポリイミド製造用ドープ(D1)と熱融着性ポリイミド製造用ドープ(E1)とを三層押出し成形用ダイス(マルチマニホールド型ダイス)を設けた製膜装置を使用し、三層押出ダイスから金属製支持体上に流延し、130℃の熱風で連続的に乾燥した後剥離して自己支持性フィルムを形成し、この自己支持性フィルムの片面(B面)に熱融着性を有しない耐熱性ポリイミド塗工液(F1〜F4)を表1に示す条件でグラビアコーターにて塗工し、加熱炉で150℃から450℃まで徐々に昇温して溶媒の除去、イミド化を行い、表1に示す厚み構成の長尺状の片面に熱融着性を有しない耐熱性ポリイミド層が積層された片面のみに熱融着性を有するポリイミドフィルムを巻き取りロールに巻き取った。
得られた片面のみに熱融着性を有するポリイミドフィルムのポリイミド層(S2層)のHAZE、接着性、失透性、発泡性の評価を行い、結果を表1に示す。
(Examples 1-8, Comparative Examples 2-4)
From a three-layer extrusion die using a film-forming apparatus provided with a three-layer extrusion die (multi-manifold die) for a heat-resistant polyimide production dope (D1) and a heat-fusible polyimide production dope (E1) Cast on a metal support, dry continuously with hot air at 130 ° C., and peel off to form a self-supporting film. One side (B surface) of this self-supporting film has heat-fusibility. Apply a heat resistant polyimide coating solution (F1 to F4) with a gravure coater under the conditions shown in Table 1, and gradually raise the temperature from 150 ° C to 450 ° C in a heating furnace to remove the solvent and imidize. The polyimide film having heat-fusible property was wound up on a take-up roll only on one surface in which a heat-resistant polyimide layer having no heat-fusible property was laminated on one side having a thickness structure shown in Table 1.
Evaluation of HAZE, adhesiveness, devitrification, and foamability of the polyimide layer (S2 layer) of the polyimide film having heat-fusibility on only one side obtained is shown in Table 1.
得られた片面のみに熱融着性を有するポリイミドフィルムは、線膨張係数(50−200℃)が、MD:18ppm/℃、TD:16ppm/℃、平均:17ppm/℃であり、引張弾性率が700kgf/mm2であった。
耐熱性ポリイミド(S1層)のガラス転移温度は400℃以下の温度で確認されず、熱融着層ポリイミド(S3層)はガラス転移温度が242℃であり、ゲル化が実質的に生じていなかった。
The polyimide film having heat-fusibility only on one side obtained has a linear expansion coefficient (50-200 ° C.) of MD: 18 ppm / ° C., TD: 16 ppm / ° C., average: 17 ppm / ° C., and tensile modulus. Was 700 kgf / mm 2 .
The glass transition temperature of the heat-resistant polyimide (S1 layer) is not confirmed at a temperature of 400 ° C. or lower, and the heat-sealable polyimide (S3 layer) has a glass transition temperature of 242 ° C., and gelation is not substantially generated. It was.
(比較例1)
耐熱性ポリイミド製造用ドープ(D1)と熱融着性ポリイミド製造用ドープ(E1)とを三層押出し成形用ダイス(マルチマニホールド型ダイス)を設けた製膜装置を使用し、三層押出ダイスから金属製支持体上に流延し、130℃の熱風で連続的に乾燥した後剥離して自己支持性フィルムを形成し、この自己支持性フィルムの片面(B面)に熱融着性を有しない耐熱性ポリイミド塗工液を塗工することなく、加熱炉で150℃から450℃まで徐々に昇温して溶媒の除去、イミド化を行い、表1に示す厚み構成を有する長尺状の両面に熱融着層を有するポリイミドフィルムを巻き取りロールに巻き取った。
得られた熱融着性を有するポリイミドフィルムのHAZEの評価を行い、結果を表1に示す。
(Comparative Example 1)
From a three-layer extrusion die using a film-forming apparatus provided with a three-layer extrusion die (multi-manifold die) for a heat-resistant polyimide production dope (D1) and a heat-fusible polyimide production dope (E1) Cast on a metal support, dry continuously with hot air at 130 ° C., and peel off to form a self-supporting film. One side (B surface) of this self-supporting film has heat-fusibility. Without applying a heat-resistant polyimide coating liquid, the temperature is gradually raised from 150 ° C. to 450 ° C. in a heating furnace to remove the solvent and imidize, and the long shape having the thickness configuration shown in Table 1 A polyimide film having a heat-sealing layer on both sides was taken up on a take-up roll.
The obtained polyimide film having heat-fusibility was evaluated for HAZE, and the results are shown in Table 1.
Claims (5)
熱融着性を有しない耐熱性ポリイミド層(S2層)は、テトラカルボン酸二無水物成分と、4,4’−メチレン−ビス(2,6−ジメチルアニリン)を含むジアミンとから得られるポリイミドであることを特徴とする片面のみに熱融着性を有するポリイミドフィルム。 A heat-resistant polyimide layer (S2 layer) that has a heat-fusible polyimide layer (S3 layer) on both sides of the heat-resistant polyimide layer (S1 layer) and has no heat-fusible property on one side of the heat-fusible polyimide layer It is a polyimide film having heat-fusibility only on one side that is laminated,
A heat-resistant polyimide layer (S2 layer) having no heat-fusibility is a polyimide obtained from a tetracarboxylic dianhydride component and a diamine containing 4,4′-methylene-bis (2,6-dimethylaniline). A polyimide film having heat-fusible properties only on one side.
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