JPWO2009054273A1 - 透明導電性フィルム及びその製造方法 - Google Patents
透明導電性フィルム及びその製造方法 Download PDFInfo
- Publication number
- JPWO2009054273A1 JPWO2009054273A1 JP2009538076A JP2009538076A JPWO2009054273A1 JP WO2009054273 A1 JPWO2009054273 A1 JP WO2009054273A1 JP 2009538076 A JP2009538076 A JP 2009538076A JP 2009538076 A JP2009538076 A JP 2009538076A JP WO2009054273 A1 JPWO2009054273 A1 JP WO2009054273A1
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- Prior art keywords
- transparent conductive
- metal
- transparent
- conductive
- silver
- 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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- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- QTNLQPHXMVHGBA-UHFFFAOYSA-H hexachlororhodium Chemical compound Cl[Rh](Cl)(Cl)(Cl)(Cl)Cl QTNLQPHXMVHGBA-UHFFFAOYSA-H 0.000 description 1
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- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine group Chemical group N1=CCC2=CC=CC=C12 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
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- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- 108020004707 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
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- 150000002902 organometallic compounds Chemical class 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000005342 perphosphate group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- FURYAADUZGZUGQ-UHFFFAOYSA-N phenoxybenzene;sulfuric acid Chemical class OS(O)(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 FURYAADUZGZUGQ-UHFFFAOYSA-N 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- QWYZFXLSWMXLDM-UHFFFAOYSA-M pinacyanol iodide Chemical compound [I-].C1=CC2=CC=CC=C2N(CC)C1=CC=CC1=CC=C(C=CC=C2)C2=[N+]1CC QWYZFXLSWMXLDM-UHFFFAOYSA-M 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002850 poly(3-methoxythiophene) polymer Polymers 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
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- 239000002861 polymer material Substances 0.000 description 1
- 239000012985 polymerization agent Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
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- 229920005672 polyolefin resin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
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- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 150000003236 pyrrolines Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical class O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- UTXIVEZZTQLQDT-UHFFFAOYSA-N silver nitric acid nitrate Chemical compound [N+](=O)(O)[O-].[N+](=O)([O-])[O-].[Ag+] UTXIVEZZTQLQDT-UHFFFAOYSA-N 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229940001482 sodium sulfite Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- KICVIQZBYBXLQD-UHFFFAOYSA-M sodium;2,5-dihydroxybenzenesulfonate Chemical compound [Na+].OC1=CC=C(O)C(S([O-])(=O)=O)=C1 KICVIQZBYBXLQD-UHFFFAOYSA-M 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- WGHUNMFFLAMBJD-UHFFFAOYSA-M tetraethylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CC[N+](CC)(CC)CC WGHUNMFFLAMBJD-UHFFFAOYSA-M 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- SEACXNRNJAXIBM-UHFFFAOYSA-N triethyl(methyl)azanium Chemical compound CC[N+](C)(CC)CC SEACXNRNJAXIBM-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 125000006617 triphenylamine group Chemical class 0.000 description 1
- UPCXAARSWVHVLY-UHFFFAOYSA-N tris(2-hydroxyethyl)azanium;acetate Chemical compound CC(O)=O.OCCN(CCO)CCO UPCXAARSWVHVLY-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical class OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- C—CHEMISTRY; METALLURGY
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Abstract
Description
2 電解質層
3 銀電極
4 電源
5 スイッチ
6 アース
本発明に用いられる透明フィルム基材としては、プラスチックフィルムを用いることができる。
本発明に係る「金属導電性パターン」とは、例えば、白金、金、銀、銅、アルミニウム、亜鉛、ニッケル、チタン、ビスマス、及びそれらの合金等の金属材料を、メッシュ状、櫛形等に配置したものである。パターン形状としては特に制限はないが、例えば、三角形、正方形、長方形、菱形、平行四辺形、台形等の四角形、(正)六角形、(正)八角形等を組み合わせた幾何学図形を挙げることができる。さらに金属材料としては銀が好ましく、銀とすることにより、透明導電材料と併用する際に弊害のある黒化処理をしなくても、パターン部の着色を防ぐことが可能となる。
本願において、「静電インクジェット法」とは、帯電した液体を吐出する内部直径が30μm以下のノズルを有する液体吐出ヘッドと、前記ノズル内に溶液を供給する供給手段と、前記ノズル内の溶液に吐出電圧を印加する吐出電圧印加手段とを備えた液体吐出装置を用いてパターンを形成する方法である。
「銀塩感光材料を用いる方法」とは、ハロゲン化銀粒子を含有する層を設け、所望するパターンで露光、現像処理し、さらに物理現像処理する方法をいう。この方法により、容易に所望する導電性パターンを形成することが可能であり、また、印刷法などで問題となる交点太りによる透過率の低下も生じない。さらに物理現像処理する方法により、透明基材の平滑性を劣化させる後加熱処理がいらなくなり、好ましい導電性パターンを確保できる。
(式中、Sは粒径分布の標準偏差、Rは平均粒径を表す。)
ハロゲン化銀粒子には、さらに他の元素を含有していてもよい。例えば、写真乳剤において、硬調な乳剤を得るために用いられる金属イオンをドープすることも有用である。特に鉄イオン、ロジウムイオン、ルテニウムイオンやイリジウムイオン等の第8〜10族金属イオンは、金属銀像の生成の際に露光部と未露光部の差が明確に生じやすくなるため好ましく用いられる。
本発明に係る「透明導電材料」は、導電性高分子と、導電性繊維および導電性金属のうちの少なくとも一種を含有することを特徴とする。
本発明において用いられる導電性高分子としては、主鎖がπ共役系で構成されている有機高分子が好ましく、例えばポリピロール類、ポリチオフェン類、ポリアセチレン類、ポリフェニレン類、ポリフェニレンビニレン類、ポリアニリン類、ポリアセン類、ポリチオフェンビニレン類、及びこれらの共重合体等が挙げられる。これらの中でも、ポリピロール、ポリチオフェン、ポリ(N−メチルピロール)、ポリ(3−メチルチオフェン)、ポリ(3−メトキシチオフェン)、ポリ(3,4−エチレンジオキシチオフェン)から選ばれる重合体、又は共重合体が好適に用いられる。特にポリピロール、ポリチオフェン、ポリ(3,4−エチレンジオキシチオフェン)が好ましい。
本発明に係る「導電性繊維」とは、導電性を有し、かつ長さが幅に比べて十分に長い形状を持つものであり、概ね長さと幅の比率(アスペクト比)が5以上、好ましくは20以上のものである。形状としては中空チューブ状、ワイヤ状、ファイバー状のものがあり、例えば、カーボンナノチューブや炭素繊維、金属ナノワイヤ等がある。
本発明に係る金属ナノワイヤの金属元素としては、バルク状態での導電率が1×106S/m以上の元素を用いることができる。本発明で好ましく用いることができる金属ナノワイヤの金属元素としては、Ag,Cu,Au,Al,Rh,Ir,Co,Zn,Ni,In,Fe,Pd,Pt,Sn,Ti等を挙げることができる。本発明においては2種類以上の金属ナノワイヤを組み合わせて用いることもできるが、導電性の観点から、Ag,Cu,Au,Al,Coより選択される元素を用いることが好ましい。
導電性金属としては、金属ナノ粒子や導電性高分子により酸化され、導電性高分子内に酸化物として取り込まれた卑金属酸化物を挙げることができる。
本発明に係る金属ナノ粒子を構成する金属元素としては、金、白金、銀、銅、亜鉛、パラジウム、ロジウム、イリジウム、ルテニウム、ニッケル、アルミニウム、すず、鉛、炭素、チタンから選択される元素が好ましい。又、これらの元素を含む化合物を含有しても良い。
本願において、「卑金属による改質」とは、導電性高分子と卑金属を接触させ数時間から数日間放置させておくことにより、卑金属が導電性高分子によって酸化され、導電性高分子内に卑金属が酸化物として取り込まれることを意味する。導電性高分子を卑金属と接触させる方法としては、導電性高分子塗膜を形成し、その塗膜表面に別途形成した卑金属薄膜を密着させたり、蒸着やスパッタ法、メッキ法、電着法等で卑金属を堆積させることで可能である。
本発明に係る透明導電材料は、さらにイオン液体を含有していても良い。当該イオン液体は、常温溶融塩または単に溶融塩などとも称されるものであり、常温(室温)を含む幅広い温度域で溶融状態を呈する塩である。
[NRXH4-X]+
一般式(IV)
[PRXH4-X]+
上記の一般式(I)〜(IV)において、Rは炭素数10以下の直鎖または分枝を有するアルキル基またはエーテル結合を含み炭素と酸素の合計数が3〜12の直鎖または分枝を有するアルキル基を表し、一般式(I)において、R1は炭素数1〜4の直鎖または分枝を有するアルキル基または水素原子を表し、特に炭素数1のメチル基が好ましい。一般式(I)において、RとR1は同一ではないことが好ましい。一般式(III)および(IV)において、Xは1から4の整数である。
本発明に係る導電性組成物には、上述した各種の成分の他に、必要に応じて任意に添加剤を含有することができる。具体的には、界面活性剤、有機溶媒、紫外線吸収剤、酸化防止剤、劣化防止剤、pH調整剤、重合禁止剤、表面改質剤、脱泡剤、可塑剤、抗菌剤、などが挙げられる。これらは、1種単独で使用しても良いし、2種以上を併用しても良い。
本発明に係る透明導電材料を透明フィルム基材上に成膜して、透明導電素子を形成する方法としては、高生産性と生産コスト低減の両立、および環境負荷軽減の観点から、塗布法や印刷法などの液相成膜法を用いることが好ましい。塗布法としては、ロールコート法、バーコート法、ディップコーティング法、スピンコーティング法、キャスティング法、ダイコート法、ブレードコート法、バーコート法、グラビアコート法、カーテンコート法、スプレーコート法、ドクターコート法などを用いることができる。印刷法としては、凸版(活版)印刷法、孔版(スクリーン)印刷法、平版(オフセット)印刷法、凹版(グラビア)印刷法、スプレー印刷法、インクジェット印刷法などを用いることができる。透明導電材料層を形成した後、適宜乾燥処理を施すことができる。乾燥処理の条件として特に制限はないが、透明樹脂支持体や透明導電層が損傷しない範囲の温度で処理することが好ましい。
本発明に係る手段により、液晶ディスプレイ、エレクトロルミネッセンスディスプレイ、プラズマディスプレイ、エレクトロクロミックディスプレイ、太陽電池、電子ペーパー、タッチパネル等のフレキシビリティの高い透明導電性フィルムとその製造方法の提供が可能となるが、ここではエレクトロデポジション方式の電子ペーパーについて説明する。
添加剤 RD17643 RD18716 RD308119
頁 分類 頁 分類 頁 分類
化学増感剤 23 III 648右上 96 III
増感色素 23 IV 648〜649 996〜8 IV
減感色素 23 IV 998 IV
染料 25〜26 VIII 649〜650 1003 VIII
現像促進剤 29 XXI 648右上
カブリ抑制剤・安定剤
24 IV 649右上 1006〜7 VI
増白剤 24 V 998 V
硬膜剤 26 X 651左 1004〜5 X
界面活性剤 26〜7 XI 650右 1005〜6 XI
帯電防止剤 27 XII 650右 1006〜7 XIII
可塑剤 27 XII 650右 1006 XII
スベリ剤 27 XII
マット剤 28 XVI 650右 1008〜9 XVI
バインダー 26 XXII 1003〜4 IX
支持体 28 XVII 1009 XVII
〔金属導電性パターンA〕
反応容器内で下記溶液Aを34℃に保ち、特開昭62−160128号公報記載の混合撹拌装置を用いて高速に撹拌しながら、硝酸(濃度6%)を用いてpHを2.95に調整した。引き続き、ダブルジェット法を用いて下記溶液Bと下記溶液Cを一定の流量で8分6秒間かけて添加した。添加終了後に、炭酸ナトリウム(濃度5%)を用いてpHを5.90に調整し、続いて下記溶液Dと溶液Eを添加した。
アルカリ処理不活性ゼラチン(平均分子量10万) 18.7g
塩化ナトリウム 0.31g
溶液I(下記) 1.59ml
純水 1246ml
(溶液B)
硝酸銀 169.9g
硝酸(濃度6%) 5.89ml
純水にて317.1mlに仕上げる。
アルカリ処理不活性ゼラチン(平均分子量10万) 5.66g
塩化ナトリウム 58.8g
臭化カリウム 13.3g
溶液I(下記) 0.85ml
溶液II(下記) 2.72ml
純水にて317.1mlに仕上げる。
2−メチル−4ヒドロキシ−1,3,3a,7−テトラアザインデン 0.56g
純水 112.1ml
(溶液E)
アルカリ処理不活性ゼラチン(平均分子量10万) 3.96g
溶液I(下記) 0.40ml
純水 128.5ml
(溶液I)
界面活性剤:ポリイソプロピレンポリエチレンオキシジコハク酸エステルナトリウム塩の10質量%メタノール溶液
(溶液II)
六塩化ロジウム錯体の10質量%水溶液
上記操作終了後に、常法に従い40℃にてフロキュレーション法を用いて脱塩及び水洗処理を施し、溶液Fと防バイ剤を加えて60℃でよく分散し、40℃にてpHを5.90に調整して、最終的に臭化銀を10モル%含む平均粒子径0.09μm、変動係数10%の塩臭化銀立方体粒子乳剤を得た。
アルカリ処理不活性ゼラチン(平均分子量10万) 16.5g
純水 139.8ml
上記ハロゲン化銀乳剤に対し、チオ硫酸ナトリウムをハロゲン化銀1モル当たり20mg用い、40℃にて80分間化学増感を行い、化学増感終了後に4−ヒドロキシ−6−メチル−1,3,3a,7−テトラザインデン(TAI)をハロゲン化銀1モル当たり500mg、1−フェニル−5−メルカプトテトラゾールをハロゲン化銀1モル当たり150mg添加して、ハロゲン化銀乳剤EM−1を得た。このハロゲン化銀乳剤EM−1のハロゲン化銀粒子とゼラチンの体積比(ハロゲン化銀粒子/ゼラチン)は0.625であった。さらに硬膜剤(H−1:テトラキス(ビニルスルホニルメチル)メタン)をゼラチン1g当たり200mgの比率となるようにして添加し、また塗布助剤として、界面活性剤(SU−2:スルホ琥珀酸ジ(2−エチルヘキシル)・ナトリウム)を添加し、表面張力を調整した。こうして得られた塗布液を厚さ100μmの易接着処理済み二軸延伸透明PETフィルムの片面にGelの付量が0.13g/m2になるように塗布した後、50℃、24時間のキュア処理を実施した。
純水 500ml
メトール 2g
無水亜硫酸ナトリウム 80g
ハイドロキノン 4g
ホウ砂 4g
チオ硫酸ナトリウム 10g
臭化カリウム 0.5g
水を加えて全量を1リットルとする。
純水 750ml
チオ硫酸ナトリウム 250g
無水亜硫酸ナトリウム 15g
氷酢酸 15ml
カリミョウバン 15g
水を加えて全量を1リットルとする。
下記A液、B液を処理の直前に混合する。
純水 400ml
クエン酸 10g
リン酸水素2ナトリウム 1g
アンモニア水(28%水溶液) 1.2ml
ハイドロキノン 3g
(B液)
純水 10ml
硝酸銀 0.4g
(水洗処理及び乾燥処理)
水洗処理は、水道水で10分間洗い流した。また乾燥処理は、乾燥風(50℃)を用いてドライ状態になるまで乾燥し、金属導電性パターンAを作製した。
厚さ100μmの易接着処理済み二軸延伸透明PETフィルムの片面に、公知のノズル先端部内径10μmの静電インクジェットプリンターを用いて、Agペーストインクで、幅10μm、間隔160μmのパターンを付与した金属導電性パターンBを形成した。
厚さ100μmの易接着処理済み二軸延伸透明PETフィルムの片面に、公知のNiペーストインクを用いて印刷法により210μmピッチで、幅20μmのパターンを付与した金属導電性パターンCを形成した。
硫酸第一鉄とクエン酸ソーダを含む水溶液に、硝酸銀水溶液を添加して銀イオンを還元することにより、平均粒径が10nmの銀ナノ粒子のコロイド分散液を調製した。
3,4−エチレンジオキシチオフェンモノマーとポリスチレンスルホン酸の1:2.5水溶液に塩化金酸(HAuCl4・4H2O)と硫酸鉄水溶液をAuの含有量が1.0質量%になるように加えてポリエチレンジオキシチオフェンの重合と金ナノ粒子の形成を同時に行い、金属ナノ粒子含有導電性高分子水溶液を得た。次いでこの水溶液中の生成物を取り出し蒸留水で精製した後再度蒸留水に分散して透明導電材料2とした。
高純度単層カーボンナノチューブ(カーボン・ナノテクノロジーズ・インコーポレーテッド社製;以下「SWNT」)13質量部を、ドデシルベンゼンスルホン酸ナトリウムの20%水溶液87質量部に、100rpmの条件で撹拌しながら添加し、引き続き、超音波処理を1時間行った。次に、アクリルアミドゲルを用い、泳動用バッファーのpHを8に調整し、泳動温度20℃、印加電圧200Vの条件でゲル電気泳動を行い、カーボンナノチューブの分画を行った。続いて、泳動方向に垂直な方向に電圧を印加して繊維長約1μm以上のカーボンナノチューブのみをゲル中から回収し、10質量%のカーボンナノチューブ分散液を調製した。次いで、3,4−エチレンジオキシチオフェン(PEDOT)をポリスチレンスルホン酸(PSS)存在下で公知の方法により水系媒体中で酸化重合し、更に限外ろ過処理を行い、導電性ポリマーとしてPEDOT:PSSの20%水系分散体を得た。この段階でこの水系分散体には、50%のPSS、及び20%のエチレングリコールを含有している。一方、ドデシルベンゼンスルホン酸ナトリウムの20%水溶液にイオン液体として1−エチル−3−メチルイミダゾリウム:BF4(以下「EMIBF4」)を添加して得たEMIBF4の40%水溶液50質量部に前記PEDOT:PSSの20%水系分散体50質量部を撹拌下で添加し、10質量%の導電性ポリマー溶液を調製し、この導電性ポリマー溶液100質量部に、前記カーボンナノチューブ分散液100質量部を撹拌下で添加し、その後1時間撹拌を継続して透明導電材料3とした。
金属導電性パターンAの上に透明導電材料1を乾燥後の膜厚が40nm、銀−パラジウム複合ナノ粒子の体積分率が40%になるように塗布し、110℃で5分間加熱乾燥して透明導電性フィルム101を作製した。
透明導電性フィルム101の金属導電性パターンAをB、Cに変更した以外は同様にして透明導電性フィルム102、103を作製した。
金属導電性パターンAの上にH.C.Starck社製BaytronPH500に和光純薬社製DMSOをPEDOT/PSSに対して5質量%となるように調整した導電性ポリマー溶液を乾燥後の膜厚が100nmになるように塗布し、110℃で5分間加熱乾燥させた後、蒸着法(25℃、10-3Pa)でアルミニウム膜を10nm形成した後大気圧に戻し、室内で24時間放置して透明導電性フィルム104を作製した。
金属導電性パターンAの上に透明導電材料2を乾燥後の膜厚が100nmになるように塗布し、110℃で乾燥させた。さらに蒸着法(25℃、10−3Pa)でアルミニウム膜を10nm形成した後大気圧に戻し、室内で24時間放置して透明導電性フィルム105を作製した。
透明導電性フィルム101の透明導電材料1を透明導電材料3に変更した以外は同様にして透明導電性フィルム106を作製した。
文献1(Chem.Mater.2002,14,4736−4745)に記載の方法を参考に、平均直径60nm、平均長さ5.5μmの銀ナノワイヤを作製し、フィルターを用いて銀ナノワイヤを濾別かつ水洗処理を施した後、銀ナノワイヤーの含有量が0.5%になるようにエタノール溶液に再分散した。この銀ナノワイヤ分散液を金属導電性パターンAの上に厚さ100nmで塗布し、乾燥した。さらに、その上にH.C.Starck社製BaytronPH500に和光純薬社製DMSOをPEDOT/PSSに対して5質量%となるように調整した導電性ポリマー溶液を乾燥後の膜厚が100nmになるように塗布、乾燥して透明導電性フィルム107を作製した。
透明導電性フィルム107のBatronPH500を透明導電材料2に変更した以外は同様にして透明導電性フィルム108を作製した。
金属導電性パターンAの上に公知のスパッタリング法でITOを全面に40nmの厚さで形成し、透明導電性フィルム109を作製した。
透明導電性フィルム109の金属導電性パターンAをBに変更した以外は同様にして、透明導電性フィルム110を作製した。
金属導電性パターンAの上にH.C.Starck社製BaytronPH500に和光純薬社製DMSOをPEDOT/PSSに対して5質量%となるように調整した導電性ポリマー溶液を乾燥後の膜厚が100nmになるように塗布し、110℃で5分間加熱乾燥して透明導電性フィルム111を作製した。
透明導電膜フィルム107で、銀ナノワイヤ分散液を塗布乾燥しただけのものを透明導電性フィルム112とした。
JIS K 7361−1:1997に準拠して、スガ試験機(株)製のヘイズメーターHGM−2Bを用いて測定した。
JIS K 7194:1994(導電性プラスチックの4探針法による抵抗率試験方法)に準拠して、三菱化学社製ロレスターGP(MCP−T610型)を用いて、測定した。
ジメチルスルホキシドの2.5g中に、ヨウ化ナトリウムを90mg、ヨウ化銀を75mgを加えて完全に溶解させた後に、酸化チタン0.5gを加えて超音波分散機にて酸化チタンを分散させた。この溶液にポリビニルアルコール(ケン化度約87〜89%、重合度4500)を150mg加えて120℃に加熱しながら1時間攪拌し、電解質溶液を得た。
図1に示すように銀電極1と透明導電性フィルム2を単1電池(電源4)でつなぎ、スイッチを入れてから、目視で完全に白から黒に変わる時間を測定した。
電源のプラス、マイナスを逆転することで、白/黒変換を500回繰り返した後の応答速度を、上記と同じように求めた。
Claims (8)
- 透明フィルム基材上に金属導電性パターンと透明導電材料を有する透明導電性フィルムであって、前記透明導電材料が、導電性高分子と、導電性繊維および導電性金属のうちの少なくとも一種を含有することを特徴とする透明導電性フィルム。
- 前記導電性金属が透明金属ナノ粒子を含有することを特徴とする請求の範囲第1項に記載の透明導電性フィルム。
- 前記透明導電材料が卑金属により改質されている導電性高分子を含有することを特徴とする請求の範囲第1項又は第2項に記載の透明導電性フィルム。
- 前記導電性繊維が金属ナノワイヤを含有することを特徴とする請求の範囲第1項から第3項のいずれか一項に記載の透明導電性フィルム。
- 前記透明導電材料がイオン液体を含有することを特徴とする請求の範囲第1項から第4項のいずれか一項に記載の透明導電性フィルム。
- 前記金属導電性パターンが銀を含有することを特徴とする請求の範囲第1項から第5項のいずれか一項に記載の透明導電性フィルム。
- 請求の範囲第1項から第6項のいずれか一項に記載の透明導電性フィルムの製造方法であって、透明フィルム基材上に帯電する液体を吐出するノズルを有する液体吐出ヘッドと、前記ノズル内に溶液を供給する供給手段と、前記ノズル内の溶液に吐出電圧を印加する吐出電圧印加手段とを備えた液体吐出装置を用いて所望する金属導電性パターンを形成した後、導電性繊維および導電性金属のうち少なくとも一方を含有する透明導電材料層を形成することを特徴とする透明導電性フィルムの製造方法。
- 請求の範囲第1項から第6項のいずれか一項に記載の透明導電性フィルムの製造方法であって、透明フィルム基材上にハロゲン化銀粒子を含有する層を設け、所望するパターンで露光、現像処理することにより、所望する金属導電性パターンを形成した後、導電性繊維および導電性金属のうち少なくとも一方を含有する透明導電材料層を形成することを特徴とする透明導電性フィルムの製造方法。
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JP2005108467A (ja) | 2003-09-26 | 2005-04-21 | Mitsui Chemicals Inc | 透明導電性シートおよびそれを用いた光増感太陽電池。 |
WO2006040989A1 (ja) * | 2004-10-08 | 2006-04-20 | Toray Industries, Inc. | 導電性フィルム |
JP4688138B2 (ja) | 2005-03-11 | 2011-05-25 | 日立マクセル株式会社 | 透明導電体の製造方法 |
KR101356296B1 (ko) * | 2005-06-28 | 2014-02-06 | 이 아이 듀폰 디 네모아 앤드 캄파니 | 높은 일 함수의 투명한 도체 |
GB0518611D0 (en) * | 2005-09-13 | 2005-10-19 | Eastman Kodak Co | Transparent conductive system |
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