JP5691129B2 - ポリイミドフィルム、その製造方法、ポリイミド金属積層体および回路基板 - Google Patents
ポリイミドフィルム、その製造方法、ポリイミド金属積層体および回路基板 Download PDFInfo
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- JP5691129B2 JP5691129B2 JP2009033775A JP2009033775A JP5691129B2 JP 5691129 B2 JP5691129 B2 JP 5691129B2 JP 2009033775 A JP2009033775 A JP 2009033775A JP 2009033775 A JP2009033775 A JP 2009033775A JP 5691129 B2 JP5691129 B2 JP 5691129B2
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- Prior art keywords
- polyimide
- polyimide film
- film
- aluminum
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001721 polyimide Polymers 0.000 title claims description 164
- 229910052751 metal Inorganic materials 0.000 title claims description 98
- 239000002184 metal Substances 0.000 title claims description 97
- 239000004642 Polyimide Substances 0.000 title claims description 67
- 238000004519 manufacturing process Methods 0.000 title claims description 34
- 229910052782 aluminium Inorganic materials 0.000 claims description 107
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 104
- 239000000243 solution Substances 0.000 claims description 83
- 238000007747 plating Methods 0.000 claims description 67
- 150000001875 compounds Chemical class 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 51
- 239000013522 chelant Substances 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000002243 precursor Substances 0.000 claims description 28
- -1 ethyl acetoacetate aluminum Chemical compound 0.000 claims description 26
- 239000000853 adhesive Substances 0.000 claims description 23
- 230000001070 adhesive effect Effects 0.000 claims description 23
- 239000004094 surface-active agent Substances 0.000 claims description 18
- 239000002736 nonionic surfactant Substances 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000011888 foil Substances 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- MQPPCKJJFDNPHJ-UHFFFAOYSA-K aluminum;3-oxohexanoate Chemical compound [Al+3].CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O MQPPCKJJFDNPHJ-UHFFFAOYSA-K 0.000 claims description 5
- 239000010410 layer Substances 0.000 description 63
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 56
- 239000010408 film Substances 0.000 description 54
- 229910052802 copper Inorganic materials 0.000 description 46
- 239000010949 copper Substances 0.000 description 46
- 238000000576 coating method Methods 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 21
- 239000003054 catalyst Substances 0.000 description 18
- 238000004544 sputter deposition Methods 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000007740 vapor deposition Methods 0.000 description 13
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000010409 thin film Substances 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 229920005575 poly(amic acid) Polymers 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 239000011889 copper foil Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 229920002120 photoresistant polymer Polymers 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000009713 electroplating Methods 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 238000007772 electroless plating Methods 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 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 6
- 229910000365 copper sulfate Inorganic materials 0.000 description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 5
- 150000004984 aromatic diamines Chemical class 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005238 degreasing Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000635 electron micrograph Methods 0.000 description 5
- 238000006358 imidation reaction Methods 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001465 metallisation Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-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
- 229910019142 PO4 Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910001120 nichrome Inorganic materials 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 2
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 2
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 description 2
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2,5-dimethylpyridine Chemical compound CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 2
- ILCOCZBHMDEIAI-UHFFFAOYSA-N 2-(2-octadecoxyethoxy)ethanol Chemical compound CCCCCCCCCCCCCCCCCCOCCOCCO ILCOCZBHMDEIAI-UHFFFAOYSA-N 0.000 description 2
- NURQLCJSMXZBPC-UHFFFAOYSA-N 3,4-dimethylpyridine Chemical compound CC1=CC=NC=C1C NURQLCJSMXZBPC-UHFFFAOYSA-N 0.000 description 2
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical compound CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 description 2
- UEJAKHGKSSMXIS-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid;dihydrate Chemical compound O.O.C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 UEJAKHGKSSMXIS-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WPMWEFXCIYCJSA-UHFFFAOYSA-N Tetraethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCO WPMWEFXCIYCJSA-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- MQQXUGFEQSCYIA-OAWHIZORSA-M aluminum;(z)-4-ethoxy-4-oxobut-2-en-2-olate;propan-2-olate Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CCOC(=O)\C=C(\C)[O-] MQQXUGFEQSCYIA-OAWHIZORSA-M 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000004712 monophosphates Chemical class 0.000 description 2
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- CSHOPPGMNYULAD-UHFFFAOYSA-N 1-tridecoxytridecane Chemical compound CCCCCCCCCCCCCOCCCCCCCCCCCCC CSHOPPGMNYULAD-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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- OWAFONKLAVPSGE-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethyl tridecyl hydrogen phosphate Chemical compound P(=O)(OCCCCCCCCCCCCC)(O)OCCOCCOCCO OWAFONKLAVPSGE-UHFFFAOYSA-N 0.000 description 1
- DVYLAOQBFOJZNX-UHFFFAOYSA-N 2-[2-[2-[2-(2,2-dimethylpropoxy)ethoxy]ethoxy]ethoxy]ethanol Chemical compound CC(C)(C)COCCOCCOCCOCCO DVYLAOQBFOJZNX-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 description 1
- RWXZXCZBMQPOBF-UHFFFAOYSA-N 5-methyl-1H-benzimidazole Chemical compound CC1=CC=C2N=CNC2=C1 RWXZXCZBMQPOBF-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- QEMOUQNHBKMHLP-UHFFFAOYSA-K C(C)(CC)CC(CC(=O)[O-])=O.C(C)(CC)CC(CC(=O)[O-])=O.C(C)(CC)CC(CC(=O)[O-])=O.[Al+3] Chemical compound C(C)(CC)CC(CC(=O)[O-])=O.C(C)(CC)CC(CC(=O)[O-])=O.C(C)(CC)CC(CC(=O)[O-])=O.[Al+3] QEMOUQNHBKMHLP-UHFFFAOYSA-K 0.000 description 1
- BSJQQSNPBJHBBE-UHFFFAOYSA-K C(CCCCC(C)C)CC(CC(=O)[O-])=O.C(CCCCC(C)C)CC(CC(=O)[O-])=O.C(CCCCC(C)C)CC(CC(=O)[O-])=O.[Al+3] Chemical compound C(CCCCC(C)C)CC(CC(=O)[O-])=O.C(CCCCC(C)C)CC(CC(=O)[O-])=O.C(CCCCC(C)C)CC(CC(=O)[O-])=O.[Al+3] BSJQQSNPBJHBBE-UHFFFAOYSA-K 0.000 description 1
- HGFCWFRSSOMWDF-UHFFFAOYSA-N C=C.P(O)(O)(O)=O.C=C Chemical compound C=C.P(O)(O)(O)=O.C=C HGFCWFRSSOMWDF-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- VNQABZCSYCTZMS-UHFFFAOYSA-N Orthoform Chemical compound COC(=O)C1=CC=C(O)C(N)=C1 VNQABZCSYCTZMS-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
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Classifications
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- H05K3/00—Apparatus or processes for manufacturing printed circuits
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- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
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- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
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- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/12—Using specific substances
- H05K2203/121—Metallo-organic compounds
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/425—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern
- H05K3/426—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern initial plating of through-holes in substrates without metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31721—Of polyimide
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Description
この自己支持性フィルムの片面または両面に、下記式(1)で表されるアルミニウムキレート化合物を含む溶液を塗布する工程と、
アルミニウムキレート化合物を含む溶液を塗布した自己支持性フィルムを加熱、イミド化する工程と
を有するポリイミドフィルムの製造方法。
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、例えば、IR(ATR)で測定し、フィルムとフルキュア品との振動帯ピーク面積の比を利用して、イミド化率を算出することができる。振動帯ピークとしては、イミドカルボニル基の対称伸縮振動帯やベンゼン環骨格伸縮振動帯などを利用できる。
1)脱脂・表面調整工程:例えば、表面調整剤で25〜80℃、15秒〜30分間浸漬処理。
2)触媒付与工程:例えば、センシタイザー、例えば塩化錫等の水溶性第1錫塩1〜50g/L、塩酸等の酸5〜100mL/Lを含有し、pH1〜5の溶液を用いてセンシタイジング、水洗、キャタリスト、例えば塩化Pd等の水溶性Pd塩0.01〜1g/L、塩酸等の酸0.01〜1mL/Lを含有し、pH1〜5のパラジウム活性化溶液に10〜50℃で5秒〜5分間浸漬、あるいは/および水溶性Ag塩(硝酸銀等)0.1〜2g/Lを含有し、pH5〜8の銀活性化溶液に10〜50℃で5秒〜5分間浸漬して、触媒付与。
3)無電解めっき用下地処理層形成工程:亜鉛イオン(硝酸亜鉛等)を0.001〜5mol/L、インジウムイオン(硝酸インジウム等)を0.00001〜0.1mol/L含有する処理液に50〜90℃で1分以上浸漬することによって処理し、亜鉛含有酸化インジウム下地層を形成。
4)触媒付与工程:例えば、水溶性Pd塩(塩化Pd等)などの水溶性金属塩0.01〜1g/Lを含有し、pH1〜5の水溶液に10〜80℃で5秒〜5分間浸漬、スプレー、塗布法で接触。
5)無電解金属めっき工程:例えば、硫酸銅等の水溶性金属塩0.01〜0.5mol/L、ホルムアルデヒド等の還元剤0.1〜1mol/L、EDTA等の錯化剤0.01〜1mol/Lを含有し、pH9〜14の溶液に10〜70℃で5〜60分間浸漬。
6)電気銅めっき工程:硫酸銅等の水溶性銅塩0.1〜0.5mol/L、硫酸等の酸1.5〜3mol/Lを含有し、pH0.1〜2の溶液に10〜30℃、陰極電流密度1〜4A/dm2で5〜60分間電解。
ポリイミドフィルム表面のアルミニウム量は、PHI社製Quantum2000走査型X線光電子分光装置により測定した。
(塗工液の調製)
サンプル瓶に、アルミニウムトリス(エチルアセトアセテート)3.80g、エチルアセトアセテートアルミニウムジイソプロピレート(ALCH)0.20g、水0.03g、シリコン系界面活性剤(東レ・ダウコーニング社製FZ−2101)0.10gおよびN,N−ジメチルアセトアミド(DMAc)96.00gを測り取り、均一になるまで攪拌して、塗工液1を得た。
(塗工液の調製)
参考例1と同様にして、表1に示す組成の塗工液2〜12を得た。
(塗工液の調製)
サンプル瓶に、アルミニウムトリス(エチルアセトアセテート)3.80g、ヘキシルアセトアセテートアルミニウムジイソプロピレート0.20g、水0.03g、シリコン系界面活性剤(東レ・ダウコーニング社製FZ−2101)0.10gおよびN,N−ジメチルアセトアミド(DMAc)96.00gを測り取り、均一になるまで攪拌して、塗工液13を得た。
(ポリアミック酸溶液Aの調製)
ポリアミック酸の合成は以下のようにして行なった。
(ポリアミック酸溶液Bの調製)
ポリアミック酸の合成は以下のようにして行なった。
(アルミニウムキレート変性層を有するポリイミドフィルムの製造)
表3に示すポリアミック酸溶液A又はポリアミック酸溶液Bをガラス基板上に流延塗布し、135℃で3分間乾燥した後、基板から剥離して自己支持性フィルムを得た。
実施例1で得られた試料1のポリイミドフィルムのアルミニウムキレート変性面のアルミニウム量(アルミニウム原子換算)をX線光電子分光により測定したところ、5.77%であった。また、このポリイミドフィルムの電子顕微鏡によるアルミニウムキレート変性面の観察結果を図5に示す。電子顕微鏡によるアルミニウムキレート変性面の観察からは、特異的な模様は見られなかった。このアルミニウムキレート変性層を有するポリイミドフィルムの機械的強度は、引張強度が390MPa、伸びが28.5%、引張弾性率が8.7GPaであった。
実施例1、2、4〜7、9〜13、参考例R3、R8で得られたアルミニウムキレート変性層を有するポリイミドフィルム(試料1〜13)のアルミニウムキレート変性面を、500倍の光学顕微鏡により表面を目視で観察した結果、図5に示す1000倍の電子顕微鏡写真と同様に、表面に網目模様など特異的な模様は認められなかった。
得られたアルミニウムキレート変性層を有するポリイミドフィルム(試料1〜13)を用いて、アルミニウムキレート変性層への湿式メッキによる金属薄膜の形成・ポリイミドフィルム金属積層体の作製は以下のようにして行なった。まず、表2に示したメッキプロセス(上村工業社製ジントラプロセス)により、得られたポリイミドフィルムのアルミニウムキレート変性面に下地層および無電解銅メッキによる銅薄膜を形成した。更に、硫酸銅系電解メッキ液を用いて、電流密度3A/dm2で30分間電解銅メッキを行なった。そして、これを200℃で60分間、150℃で24時間熱処理して、銅厚み10μmのポリイミドフィルム金属積層体(メッキ試料1〜13)を得た。この積層体(メッキ試料1〜13)の90度ピール強度、及び150℃で168時間エージングを行なった後の90度ピール強度を測定した結果を表4に示す。
(アルミニウムキレート変性層を有するポリイミドフィルムの製造)
塗工液1に代えて、表1に示した塗工液11を使用し、実施例1と同様にしてアルミニウムキレート変性層を有するポリイミドフィルムを得た。このポリイミドフィルムの電子顕微鏡によるアルミニウムキレート変性面の観察結果を図6に示す。電子顕微鏡(1000倍)によるアルミニウムキレート変性面の観察において、網目模様が認められた。
(アルミニウムキレート変性層を有するポリイミドフィルムの製造)
実施例1と同様にして得た自己支持性フィルムに、表1に示した塗工液12を塗布したところ、塗工液が弾いて均一にきれいに塗布できなかった。
試料1と金属との接着シートを介したポリイミドフィルム金属積層体を以下のようにして作製した。接着シート(デュポン社製、Pyralux LF)を介して、電解銅箔(日鉱金属株式会社製、BHY−13H−T、18μm)とポリイミドフィルムのアルミニウムキレート変性面とを重ね合わせ、これを3MPa、180℃、5分間の条件で加熱圧着した後、180℃の熱風オーブン中で1時間熱処理して、ポリイミドフィルム金属積層体を得た。この積層体の90度ピール強度は1.5N/mmであった。
回路形成は、湿式メッキによる銅薄膜形成後、セミアディティブ法により行なった。
乾式メッキによる金属薄膜の形成・ポリイミドフィルム金属積層体の作製は以下のようにして行なった。まず、試料1をスパッタリング装置内の基板フォルダーに設置し、2×10−4Pa以下の真空に排気後、アルゴンを導入して0.67Paとした後、電極に13.56MHzの高周波電力300wで10分間プラズマ処理により、アルミニウムキレート変性面のクリーニングを行なった。続いて、アルゴン0.67Pa雰囲気下、アルミニウムキレート変性面上に15nmのNiCr薄膜を形成し、さらにその上に0.4μmの銅薄膜を形成し、大気中に取り出した。さらに、酸性硫酸銅水溶液の電解メッキ液を用いて、金属膜が20μmとなるように銅メッキを施して、ポリイミドフィルム金属積層体を得た。この積層体の90度ピール強度は1.35N/mmであった。さらに、この積層体を150℃で24時間エージングを行なった後の90度ピール強度は0.57N/mmであった。
回路形成は、乾式メッキによる銅薄膜形成後、セミアディティブ法により行なった。
102 下地層形成のための触媒
103 無電解めっきによる亜鉛含有水酸化インジウム下地層
104 無電解銅めっきのための触媒
105 電解銅めっきのための電極層
106 電解銅めっきによって形成した導電金属層
206 表裏を導通させるための貫通孔
207 ドライフィルムタイプのネガ型フォトレジスト
208 回路を形成しない部位
209 電解銅めっきで形成した導電層
Claims (11)
- ポリイミド前駆体溶液の自己支持性フィルムを準備する工程と、
この自己支持性フィルムの片面または両面に、下記式(1)で表されるアルミニウムキレート化合物と、ノニオン系界面活性剤および下記式(2)で表されるアルミニウムアルコラート化合物とを含む溶液を塗布する工程と、
アルミニウムキレート化合物を含む溶液を塗布した自己支持性フィルムを加熱、イミド化する工程と
を有するポリイミドフィルムの製造方法。
- 前記ノニオン系界面活性剤が、シリコン系界面活性剤およびポリエチレングリコール系界面活性剤より選ばれる少なくとも1種である請求項1に記載のポリイミドフィルムの製造方法。
- 前記アルミニウムアルコラート化合物が、エチルアセトアセテートアルミニウムジイソプロピレートである請求項1または2に記載のポリイミドフィルムの製造方法。
- 前記アルミニウムキレート化合物が、アルミニウムトリス(エチルアセトアセテート)である請求項1〜3のいずれかに記載のポリイミドフィルムの製造方法。
- 前記自己支持性フィルムをイミド化する際の最高加熱温度が350〜520℃である請求項1〜4のいずれかに記載のポリイミドフィルムの製造方法。
- 請求項1〜5のいずれかに記載の方法により製造されるポリイミドフィルム。
- 請求項6に記載のポリイミドフィルムの、製造時にアルミニウムキレート化合物を含む溶液を塗布した面に金属層を積層してなるポリイミド金属積層体。
- 接着剤を介してポリイミドフィルムに金属箔を積層してなる請求項7に記載のポリイミド金属積層体。
- 乾式メッキまたは湿式メッキによりポリイミドフィルムに金属層を形成してなる請求項7に記載のポリイミド金属積層体。
- 請求項7〜9のいずれかに記載のポリイミド金属積層体に回路を形成してなる回路基板。
- 30μm以下のピッチの金属配線部分を含む請求項10に記載の回路基板。
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JP2009033775A JP5691129B2 (ja) | 2008-03-31 | 2009-02-17 | ポリイミドフィルム、その製造方法、ポリイミド金属積層体および回路基板 |
US12/413,917 US20090242250A1 (en) | 2008-03-31 | 2009-03-30 | Polyimide film, method for production thereof, polyimide-metal laminated product, and circuit board |
TW98110711A TW200940602A (en) | 2008-03-31 | 2009-03-31 | Polyimide film, method for production thereof, polyimide-metal laminated product, and circuit board |
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CN1910041B (zh) * | 2004-01-13 | 2012-11-07 | 宇部兴产株式会社 | 聚酰亚胺-金属层压体和聚酰亚胺电路板 |
JP5447949B2 (ja) * | 2009-11-27 | 2014-03-19 | 京セラSlcテクノロジー株式会社 | 配線基板の製造方法 |
JP5609891B2 (ja) * | 2009-12-09 | 2014-10-22 | 宇部興産株式会社 | ポリイミドフィルムの製造方法、およびポリイミドフィルム |
US8629053B2 (en) * | 2010-06-18 | 2014-01-14 | Taiwan Semiconductor Manufacturing Company, Ltd. | Plasma treatment for semiconductor devices |
US8816208B2 (en) * | 2010-09-30 | 2014-08-26 | Hitachi Metals, Ltd. | Flat cable and cable harness using the same |
US20120231258A1 (en) * | 2011-03-08 | 2012-09-13 | Xerox Corporation | Fuser member |
JP2013140856A (ja) * | 2011-12-28 | 2013-07-18 | Jx Nippon Mining & Metals Corp | キャリア付金属箔 |
JP2014027185A (ja) * | 2012-07-27 | 2014-02-06 | Toshiba Corp | 不揮発性記憶装置 |
TWI462669B (zh) * | 2013-02-08 | 2014-11-21 | Ichia Tech Inc | 多層式的軟性印刷電路板及其製造方法 |
TWI462672B (zh) * | 2013-02-08 | 2014-11-21 | Ichia Tech Inc | 前驅基板、軟性印刷電路板及其製造方法 |
US9257647B2 (en) * | 2013-03-14 | 2016-02-09 | Northrop Grumman Systems Corporation | Phase change material switch and method of making the same |
US10151195B2 (en) * | 2014-04-29 | 2018-12-11 | China Petroleum & Chemical Corporation | Electronic devices for high temperature drilling operations |
US10700270B2 (en) | 2016-06-21 | 2020-06-30 | Northrop Grumman Systems Corporation | PCM switch and method of making the same |
JP7439652B2 (ja) * | 2020-06-02 | 2024-02-28 | トヨタ自動車株式会社 | 配線基板の製造方法 |
US11546010B2 (en) | 2021-02-16 | 2023-01-03 | Northrop Grumman Systems Corporation | Hybrid high-speed and high-performance switch system |
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JP3334261B2 (ja) * | 1993-07-15 | 2002-10-15 | 東レ株式会社 | カラーフィルター |
US6129982A (en) * | 1997-11-28 | 2000-10-10 | Ube Industries, Ltd. | Aromatic polyimide film having improved adhesion |
CN1910041B (zh) * | 2004-01-13 | 2012-11-07 | 宇部兴产株式会社 | 聚酰亚胺-金属层压体和聚酰亚胺电路板 |
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